JPH0370705A - Polyvinylacetal and its production - Google Patents
Polyvinylacetal and its productionInfo
- Publication number
- JPH0370705A JPH0370705A JP20839589A JP20839589A JPH0370705A JP H0370705 A JPH0370705 A JP H0370705A JP 20839589 A JP20839589 A JP 20839589A JP 20839589 A JP20839589 A JP 20839589A JP H0370705 A JPH0370705 A JP H0370705A
- Authority
- JP
- Japan
- Prior art keywords
- polyvinyl
- vinyl
- pva
- aldehyde
- syndiotacticity
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000006359 acetalization reaction Methods 0.000 claims abstract description 9
- 229920001577 copolymer Polymers 0.000 claims abstract description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 37
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 25
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 25
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 25
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 22
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 229920001289 polyvinyl ether Polymers 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 229920001290 polyvinyl ester Polymers 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 150000001299 aldehydes Chemical class 0.000 description 7
- 239000005340 laminated glass Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000007127 saponification reaction Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 6
- -1 sgc-butyl Chemical group 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- LGYNIFWIKSEESD-UHFFFAOYSA-N 2-ethylhexanal Chemical compound CCCCC(CC)C=O LGYNIFWIKSEESD-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- FPSPPRZKBUVEJQ-UHFFFAOYSA-N 4,6-dimethoxypyrimidine Chemical compound COC1=CC(OC)=NC=N1 FPSPPRZKBUVEJQ-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- ZBGRMWIREQJHPK-UHFFFAOYSA-N ethenyl 2,2,2-trifluoroacetate Chemical compound FC(F)(F)C(=O)OC=C ZBGRMWIREQJHPK-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- JEYLQCXBYFQJRO-UHFFFAOYSA-N 2-[2-[2-(2-ethylbutanoyloxy)ethoxy]ethoxy]ethyl 2-ethylbutanoate Chemical compound CCC(CC)C(=O)OCCOCCOCCOC(=O)C(CC)CC JEYLQCXBYFQJRO-UHFFFAOYSA-N 0.000 description 1
- PGYJSURPYAAOMM-UHFFFAOYSA-N 2-ethenoxy-2-methylpropane Chemical compound CC(C)(C)OC=C PGYJSURPYAAOMM-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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000011354 acetal resin Substances 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- HFTNNOZFRQLFQB-UHFFFAOYSA-N ethenoxy(trimethyl)silane Chemical compound C[Si](C)(C)OC=C HFTNNOZFRQLFQB-UHFFFAOYSA-N 0.000 description 1
- CMDXMIHZUJPRHG-UHFFFAOYSA-N ethenyl decanoate Chemical compound CCCCCCCCCC(=O)OC=C CMDXMIHZUJPRHG-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- BLZSRIYYOIZLJL-UHFFFAOYSA-N ethenyl pentanoate Chemical compound CCCCC(=O)OC=C BLZSRIYYOIZLJL-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 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
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001650 tertiary alcohol group Chemical group 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Joining Of Glass To Other Materials (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】 人、産業上の利用分野 本発明は新規なポリビニルアセタールに関する。[Detailed description of the invention] Human and industrial applications The present invention relates to a novel polyvinyl acetal.
さらに詳しくは電線用エナメル、接着材、スポンジの基
材、バインダーや安全合わせガラス用中間膜の主材、セ
ラミックスバインダー、接着材、塗料等に用いられるポ
リビニルアセタールに関スる。More specifically, it relates to polyvinyl acetal used in electric wire enamel, adhesives, sponge base materials, binders and interlayer films for safety laminated glass, ceramic binders, adhesives, paints, etc.
Ｂ、従来の技術
これまで、ポリビニルアセタールについては、原料ポリ
ビニルアルコールに関しては重合度やけん化度さらには
ビニルアルコール単位および酢酸ビニル単位以外の第３
戒分の導入が検討されており、アセタール化反応に関し
てはアルデヒドの種類はもちろんのことアセタール化度
、反応方法および反応条件が詳細に検討されている。B. Conventional technology Up until now, for polyvinyl acetal, the degree of polymerization and saponification of the raw material polyvinyl alcohol, as well as the degree of tertiary alcohol units other than vinyl alcohol units and vinyl acetate units, have been
The introduction of precepts is being considered, and regarding the acetalization reaction, not only the type of aldehyde but also the degree of acetalization, reaction method, and reaction conditions are being studied in detail.
しかしながら、ポリビニルアセタール樹脂の高性能化に
対する要求、たとえば安全合わせガラスの強度性能に対
する要求はすすます高くなり％これまでの通常のポリビ
ニルアルコールからのボリビニルアセタールではしだい
に対応が困難になってきているのが現状である。However, the demands for higher performance of polyvinyl acetal resins, such as demands for strength performance of safety laminated glass, are getting higher and higher, and it is becoming increasingly difficult to meet the demands with conventional polyvinyl acetal made from polyvinyl alcohol. is the current situation.
Ｃ１発明が解決しようとする課題
かかる状況下１本発明は耐熱性および強度性能、特に高
温時における強度性能に優れた新規なポリビニルアセタ
ールを提供せんとするものである。C1 Problems to be Solved by the Invention Under these circumstances, the present invention seeks to provide a novel polyvinyl acetal that is excellent in heat resistance and strength performance, particularly strength performance at high temperatures.
０９課題を解決するための手段
本発明者らは、上記課題解決に向けて鋭意検討した結果
、シンジオタクテイシテイ−が５５モル多以上のポリビ
ニルアルコールをアセタール化して得られるポリビニル
アセタールが浚れた耐熱性と強度性能を有することを見
い出し、本発明を完成したものである。09 Means for Solving the Problems As a result of intensive studies aimed at solving the above problems, the present inventors found that polyvinyl acetal obtained by acetalizing polyvinyl alcohol with a syndiotacticity of 55 moles or more was obtained. It was discovered that it has heat resistance and strength performance, and the present invention was completed.
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セタールは、シンジオタクテイシ
テイ−が５５モル多以上のポリビニルアルコールをアセ
タール化することによう得られた下記の一般式（１）お
よび（ＩＩ）で表される単位を必須成分とした構造を有
する。The polyvinyl acetal of the present invention has as an essential component units represented by the following general formulas (1) and (II) obtained by acetalizing polyvinyl alcohol having a syndiotacticity of 55 moles or more. It has a structure that
（ここで、Ｒは水素量たは炭素数１から１８會での炭化
水素基を表す）
本発明によれば、シンジオタクテイシテイ−が５５モル
嘩以上のポリビニルアルコールをアセタール化して得ら
れるポリビニルアセタールは、従来のアタクテイツクな
ポリビニルアルコールをベースにしたポリビニルアセタ
ールに比べて、耐熱性と強度特性に優れる。この性能は
、原料ポリビニルアルコールのシンジオタクテイシテイ
−が高い方が良好であることから１原料ポリビニルアル
コールのシンジオタクテイシテイ−は５５モル多以上で
あることが必要であり１好筐しくは５８モル多以上であ
う、さらに好ましくは６０モル傅以上である。(Here, R represents the amount of hydrogen or a hydrocarbon group having 1 to 18 carbon atoms.) According to the present invention, polyvinyl alcohol obtained by acetalizing polyvinyl alcohol having a syndiotacticity of 55 mol or more Acetal has superior heat resistance and strength properties compared to polyvinyl acetal, which is based on conventionally aggressive polyvinyl alcohol. This performance is better when the syndiotacticity of raw material polyvinyl alcohol is higher, so the syndiotacticity of one raw material polyvinyl alcohol needs to be 55 moles or more, and 1 is preferably 58 moles or more. The molar amount is more than 60 molar, more preferably 60 molar or more.
ところて、この様な高シンジオタクテイシテイ−のポリ
ビニルアルコールはｓ通常ｏポリビニルアルコールの製
造法である酢酸ビニルのけん化からは得られない。本発
明で用いられるような高シンジオタクテイシテイ−のポ
リビニルアセタールハ、ヒバリン酸ビニル、トリフロロ
酢酸ビニル。However, such high syndiotactic polyvinyl alcohol cannot be obtained by saponification of vinyl acetate, which is the usual method for producing polyvinyl alcohol. High syndiotactic polyvinyl acetals, vinyl hybarate, vinyl trifluoroacetate as used in the present invention.
トリクロロ酢酸ビニル、１蟻酸ビニルのごとき側鎖の嵩
高いビニルエステル！たは極性の高いビニルエステルの
重合体の加水分解、もしくはｔ−ブチルビニルエーテル
やトリメチルシリルビニルエーテルのごときポリビニル
エーテルの加水分解によって得られる。この中で、得ら
れるポリマーの性質、重合や加水分解反応の容易さから
、ビバリン酸ビニルの単独重合体または共重合体からの
ポリビニルアルコールが好ｔＬい。Vinyl esters with bulky side chains such as vinyl trichloroacetate and vinyl monoformate! or by hydrolysis of highly polar vinyl ester polymers, or by hydrolysis of polyvinyl ethers such as t-butyl vinyl ether and trimethylsilyl vinyl ether. Among these, polyvinyl alcohol made from a vinyl bivalate homopolymer or copolymer is preferred from the viewpoint of the properties of the resulting polymer and the ease of polymerization and hydrolysis reactions.
本発明に用いるポリビニルアルコールのタフティシティ
−以外の性質については特に制限はないが、アセタール
化反応時の取り扱い性や目的とするポリビニルアセター
ルの性質によって決定される。重合度は通常１０〜２０
０００ 、好筐しくは２０−１５０００である。けん化
度は６０−１００モル多である。重合度およびけん化度
は該ポリビニルアセタールの用途によう適宜選択される
。There are no particular limitations on the properties of the polyvinyl alcohol used in the present invention other than toughness, but they are determined by the ease of handling during the acetalization reaction and the intended properties of the polyvinyl acetal. The degree of polymerization is usually 10-20
000, preferably 20-15000. The degree of saponification is 60-100 molar. The degree of polymerization and the degree of saponification are appropriately selected depending on the use of the polyvinyl acetal.
本発明のポリビニルアセタールは、一般式（１）で表さ
れるビニルアセタール構造によって特定され、Ｒとして
水素、メチル、エチル、ｎ−プロピル、ｉ−プロピル、
ｎ−ブチル、ｓｇｃ−ブチル、ｉ−ブチル、ｔ−ブチル
、アミル、ヘキシル、ヘプチル、オクチル、２−エチル
ヘキシル、デシル、ドデシル、セチル、ステアリル等の
各炭化水素基が含まれる。一般式（１）および（Ｉｆ）
で表される単位の該ポリビニルアセタール中のモル分ｉ
をそれぞれＭ （Ｉ）およびＭ（Ｉｆ）とすると、 Ｃ
Ｍ（１）／（Ｍ（１） ＋Ｍ（ＩＩ）））ｘｔｏｏで定
義されるアセタール化＆は、５〜８０モル弾であシ、好
ましくは３０〜８０モル嘩、さらに好ましくは５０〜８
００〜８０モル弾ら選ばれる。The polyvinyl acetal of the present invention is specified by the vinyl acetal structure represented by the general formula (1), where R is hydrogen, methyl, ethyl, n-propyl, i-propyl,
Hydrocarbon groups such as n-butyl, sgc-butyl, i-butyl, t-butyl, amyl, hexyl, heptyl, octyl, 2-ethylhexyl, decyl, dodecyl, cetyl, and stearyl are included. General formula (1) and (If)
The mole content i of the unit represented by in the polyvinyl acetal
are M (I) and M (If), respectively, then C
Acetalization defined as M(1)/(M(1) +M(II)))
Selected from 00 to 80 moles.
本発明のポリビニルアセタールは、本発明の趣旨を損な
わない範囲において、上記一般式（１）および（ｎ）以
外の単位を含有することも差し支えない。この様な単位
として、たとえばビバリン酸ビニル、トリフロロ酢酸ビ
ニル、トリクロロ酢酸ビニル、ギ酸ビニル、酢酸ビニル
、プロピオン酸ビニル、バレリン酸ビニル、カプリン酸
ビニル、ラウリン酸ビニル等のビニルエステル類をはじ
めとして、エチレン、プロピレン、インブチレン、ｌ−
オクテン、１−ドデセン、ｌ−オクタデセン等のオレフ
ィン類、アクリル酸、メタクリル酸、クロトン酸、無水
マレイン酸、イタコン酸等の不飽和酸類、あるいはその
塩、あるいはモノまたはジアルキルエステル類、アクリ
ロニトリル、メタクリロ＝トリル等の二、トリル類、ア
クリルアミド。The polyvinyl acetal of the present invention may contain units other than the above general formulas (1) and (n) as long as the spirit of the present invention is not impaired. Examples of such units include vinyl esters such as vinyl bivalate, vinyl trifluoroacetate, vinyl trichloroacetate, vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl caprate, and vinyl laurate; , propylene, imbutylene, l-
Olefins such as octene, 1-dodecene, and l-octadecene, unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, and itaconic acid, or salts thereof, mono- or dialkyl esters, acrylonitrile, methacryloyl Tolyl, etc., tolyl, acrylamide.
メタクリルアミド等のアミド類、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ィン
スルホン酸類、あるいはその塩類。Amides such as methacrylamide, ethylene sulfonic acid,
Olefin sulfonic acids such as allyl sulfonic acid and methallyl sulfonic acid, or their salts.
アルキルビニルエーテル類、ポリオキシアルキルアリル
エーテル類、アルキルアリルエーテル類。Alkyl vinyl ethers, polyoxyalkyl allyl ethers, alkyl allyl ethers.
飽和カルボン酸アリルエステル類、ビニルケトン。Saturated carboxylic acid allyl esters, vinyl ketones.
Ｎ−ビニルピロリドン、塩化ビニル、塩化ビニリデン、
オキシアルキレン基含有不飽和モノマー。N-vinylpyrrolidone, vinyl chloride, vinylidene chloride,
Unsaturated monomer containing oxyalkylene group.
アミン筐たは第四級アンモニウム塩含有不飽和ビニルモ
ノマー等があげられる。Examples include unsaturated vinyl monomers containing amine casings or quaternary ammonium salts.
本発明のポリビニルアセタールは、通常、シンジオタク
テイシテイ−が５５５モル％上のポリビニルアルコール
とアルデヒドとを触媒を用いて反応させることによって
得られる。アルデヒドとしては、ホルムアルデヒド、ア
セトアルデヒド、プロピルアルデヒド、ブチルアルデヒ
ド、ヘキシルアルデヒド、オクチルアルデヒド、２−エ
チルヘキシルアルデヒド、ベンジルアルデヒド等が用い
られ、触媒としては硫酸、塩酸、硝酸、燐！！！！％蟻
ａｓｐ−トルエンスルホン酸の如き酸類あるいは塩化カ
ルシウム、塩化亜鉛、塩化第２鉄のような塩類も用いら
れる。この場合、反応の進め方や溶媒の選択によって溶
解法、均−系法、沈殿法、エマルジョン法、粉末法等の
プロセスが選択される。The polyvinyl acetal of the present invention is usually obtained by reacting polyvinyl alcohol having a syndiotacticity of 555 mol % with an aldehyde using a catalyst. As the aldehyde, formaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, hexylaldehyde, octylaldehyde, 2-ethylhexylaldehyde, benzylaldehyde, etc. are used, and as the catalyst, sulfuric acid, hydrochloric acid, nitric acid, phosphorus! ! ! ! Acids such as % asp-toluenesulfonic acid or salts such as calcium chloride, zinc chloride, ferric chloride may also be used. In this case, processes such as a dissolution method, a homogeneous system method, a precipitation method, an emulsion method, a powder method, etc. are selected depending on how the reaction proceeds and the selection of a solvent.
シンジオタクテイシテイ−が５５５モル％上のポリビニ
ルアルコールとアルデヒドとの反応条件は特に制限はな
いが、好１しくは該ポリビニルアルコール濃度３〜２０
重量傅、アルデヒド濃度ｌ〜３０重量那、触媒０．５〜
３０重量優、反応温度ｌＯ〜１００℃、さらに好筐しく
は６０〜９０℃、反応時間１〜４８時間である。上記の
反応条件はポリビニルアルコールの重合鷹およびけん化
度。There are no particular restrictions on the reaction conditions of polyvinyl alcohol with a syndiotacticity of 555 mol% or more and an aldehyde, but preferably the polyvinyl alcohol concentration is 3 to 20%.
Weight range, aldehyde concentration 1~30 weight range, catalyst 0.5~
The reaction temperature is 10 to 100°C, more preferably 60 to 90°C, and the reaction time is 1 to 48 hours. The above reaction conditions are the polymerization level and saponification degree of polyvinyl alcohol.
さらに得られるポリビニルアセクールのアセタール化度
によう適宜選択される。Furthermore, it is appropriately selected depending on the degree of acetalization of the polyvinyl acecool to be obtained.
！たポリビニルアルコールの製造工程で、ポリビニルエ
ステルもしくはポリビニルエーテルの加水分解と上述の
アセタール化を同時に実施することも可能である。! In the process for producing polyvinyl alcohol, it is also possible to simultaneously carry out the hydrolysis of polyvinyl ester or polyvinyl ether and the above-mentioned acetalization.
Ｅ、実施例
以下、実施例により本発明をさらに具体的に説明するが
１本発明は実施例によシなんら限定されるものではない
。なお実施例中の「部」は、特にことわジのない限シ「
重量部」を表す。E. Examples The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples in any way. Note that "part" in the examples refers to "part" unless otherwise specified.
Parts by weight.
実施例１
ビバリン酸ビニルの重合体なけん化し、ビバリン酸ビニ
ル単位のけん化度が９８．７モル％で、シンジオタクテ
イシテイ−６１，２モル％、再酢化物のポリ酢酸ビニル
換算で重合度１５００のポリビニルアルコールを得た。Example 1 A polymer of vinyl bivalate was saponified, and the degree of saponification of the vinyl bivalate unit was 98.7 mol%, the syndiotacticity was -61.2 mol%, and the degree of polymerization was calculated in terms of polyvinyl acetate of the reacetate. 1500 polyvinyl alcohol was obtained.
次にこのポリビニルアルコール１０部を蒸留水９０部に
いれ、攪拌下で加熱溶解した後、４０℃まで冷却した。Next, 10 parts of this polyvinyl alcohol was added to 90 parts of distilled water, heated and dissolved under stirring, and then cooled to 40°C.
４０℃で攪拌しながら３５俤濃度の塩酸６．５部を添加
し、さらにブチルアルデヒド５．２部を加えると、ポリ
ビニルブチラールの白色沈殿が生成した。４０℃でさら
に４時間熟成を行なった後、反応を終了し、樹脂を中和
、水洗して前記の定義によるブチラール化度が６２モル
優のポリビニルブチラール樹脂を得た。While stirring at 40° C., 6.5 parts of 35% hydrochloric acid were added, and further 5.2 parts of butyraldehyde were added to form a white precipitate of polyvinyl butyral. After further aging at 40° C. for 4 hours, the reaction was terminated, and the resin was neutralized and washed with water to obtain a polyvinyl butyral resin having a degree of butyralization as defined above of 62 moles.
比較例１
ポリビニルアルコールとして重合度１７５０、けん化１
ｔ９Ｂ、５％％シンジオタクテイシテイ−５３多のもの
を使用する以外は実施例１と同様にして、ブチラール化
度が６４ｑ６のポリビニルブチラールを得た。Comparative Example 1 Polyvinyl alcohol with polymerization degree of 1750 and saponification of 1
Polyvinyl butyral having a degree of butyralization of 64q6 was obtained in the same manner as in Example 1 except that t9B, 5% syndiotacticity -53 was used.
実施例工および比較例工で示したポリビニルブチラール
１００部に、トリエチレングリコール−ジー２−エチル
ブチレート５０部を加えて可塑化し、さらに１４０℃、
５０ｋｆ／−の条件下で厚さ０．７５−の中間膜を作成
した。このフィルムをガラス板（厚さ３ｃｒＩＫ、巾３
ｏ Ｑｓｉ、長さ３００ｍ）２枚の間に挾んで１２０
℃、１Ｏｋｆ／ｃｆＡの条件で張す合わせ、安全合わせ
ガラスを得た。得られた安全合わせガラスについて耐貫
通強度を落球高さから測定した。結果を表１に示す。実
施例１で得たポリビニルブチラールの優位性が明らかで
ある。50 parts of triethylene glycol-di-2-ethyl butyrate was added to 100 parts of the polyvinyl butyral shown in the example work and comparative example work to plasticize it, and the mixture was further heated at 140°C.
An interlayer film having a thickness of 0.75 mm was produced under the condition of 50 kf/-. Spread this film on a glass plate (thickness 3crIK, width 3
o Qsi, length 300m) sandwiched between two pieces 120
A safety laminated glass was obtained which was laminated under the conditions of ℃ and 1 Okf/cfA. The penetration resistance strength of the obtained safety laminated glass was measured from the falling ball height. The results are shown in Table 1. The superiority of polyvinyl butyral obtained in Example 1 is clear.
実施例２〜４
実施例１に示したポリビニルアセクールヲ用いて、アル
デヒドの種類と使用量を変える以外は実施例１と同様の
条件で反応し、各種ポリビニルアセタールを得た。反応
条件と得られたポリビニルアセタールのアセタール化度
を表２に示す。Examples 2 to 4 Using the polyvinyl acetyl shown in Example 1, reactions were carried out under the same conditions as in Example 1 except that the type and amount of aldehyde used were changed to obtain various polyvinyl acetals. Table 2 shows the reaction conditions and the degree of acetalization of the obtained polyvinyl acetal.
表 ２
１）安全合わせガラス試料（３００Ｘ３００ｍ）を支持
枠に固定して水平に保持し、その上から２．２６陣の鋼
球を試験片の中央に自由落下させる。鋼球の高さを０．
５ｍ単位で変化させ、一定高さでの繰す返し試験でその
試験数の５０−において鋼球の貫通が妨げられる最高の
落球高さを測定した。Table 2 1) A safety laminated glass sample (300 x 300 m) is fixed to a support frame and held horizontally, and 2.26 steel balls are freely dropped from above to the center of the test piece. Set the height of the steel ball to 0.
The height of the ball was varied in 5 m increments, and the highest falling ball height at which penetration of the steel ball was prevented was measured in 50 repeated tests at a constant height.
１）ＦＡ；ホルマリン（３７多）
２）ＡＣＡ；アセトアルデヒド
ａ） ２−ＥＨＡ ； ２−エチルヘキシルアルデヒ
ドＦ１発明の効果
本発明によれば、これまでのポリビニルアセクールに比
べて特に耐熱性と強度特性に優れたポリビニルアセクー
ルが得られる。これは原料ポリビニルアルコールとして
シンジオタクテイシテイ−が５５モル優以上のものを用
いることによってはじめて達成されたもので、おそらく
長いシンジオ連鎖部の水酸基が他の部分の水酸基に比べ
てアセタール化され難く、残存水酸基分布や水酸基間の
相互作用が変化したことによるものと推察される。1) FA; formalin (37%) 2) ACA; acetaldehyde a) 2-EHA; 2-ethylhexylaldehyde Excellent polyvinyl acecool can be obtained. This was achieved for the first time by using a raw material polyvinyl alcohol with a syndiotacticity of 55 moles or more, and it is probably because the hydroxyl groups in the long syndiotactic chain are less likely to be acetalized than the hydroxyl groups in other parts. This is presumed to be due to changes in the distribution of residual hydroxyl groups and interactions between hydroxyl groups.
本発明で得られたポリビニルアセタールは上記の特徴を
生かした分野に用いられ、例えばポリビニルホルマール
は耐熱性の電線エナメル、接着材、塗料、スポンジ基材
、バインダーに、ポリビニルアセトアセタールは耐熱性
のワニス、ラッカー成分や接着剤として、ポリビニルブ
チラールは耐熱性の塗料、接着剤、各種バインダー グ
リーン強度の大きいセラミックスバインダーとして用い
られるほかとくに安全合わせガラスの中間膜用基材とし
て有用であり、該ポリビニルブチラールを基材とした安
全合わせガラス用中間膜は、低温から高温！で広い温度
領域において優れた耐貫通強度を有し、同時にガラスと
の接着性にも優れる。またヘキシルアルデヒド、オクチ
ルアルデヒド、２−エチルヘキシルアルデヒド等の高級
アルデヒドを用いたポリビニルアセタールは、柔軟性を
有するとともに高強度であることから接着剤や粘着剤と
して用いられる。The polyvinyl acetal obtained in the present invention is used in fields that take advantage of the above characteristics. For example, polyvinyl formal is used in heat-resistant wire enamel, adhesives, paints, sponge base materials, and binders, and polyvinyl acetoacetal is used in heat-resistant varnishes. Polyvinyl butyral is used as a lacquer component and adhesive, in heat-resistant paints, adhesives, and various binders.In addition to being used as a ceramic binder with high green strength, it is particularly useful as a base material for interlayer films in safety laminated glass. The interlayer film for safety laminated glass used as a base material can be used from low to high temperatures! It has excellent penetration resistance over a wide temperature range and also has excellent adhesion to glass. Moreover, polyvinyl acetal using a higher aldehyde such as hexylaldehyde, octylaldehyde, 2-ethylhexylaldehyde, etc. is flexible and has high strength, so it is used as an adhesive or a pressure-sensitive adhesive.
Claims (4)
リビニルアルコールをアセタール化してなる分子量が４
５０〜３×１０＾６であり、かつアセタール化度が５〜
８０モル％のポリビニルアセタール。(1) Polyvinyl alcohol with syndiotacticity of 55 mol% or more is acetalized and has a molecular weight of 4.
50~3×10^6, and the degree of acetalization is 5~
80 mol% polyvinyl acetal.
重合体または共重合体の加水分解物である請求項１記載
のポリビニルアセタール。(2) The polyvinyl acetal according to claim 1, wherein the polyvinyl alcohol is a hydrolyzate of a homopolymer or copolymer of vinyl bivalate.
リビニルアルコールをアルデヒドと反応させることを特
徴とする請求項１または２記載のポリビニルアセタール
の製造方法。(3) The method for producing polyvinyl acetal according to claim 1 or 2, characterized in that polyvinyl alcohol having a syndiotacticity of 55 mol % or more is reacted with an aldehyde.
リビニルエステルまたはポリビニルエーテルの加水分解
反応とアルデヒドとの反応を同時に併行して行うことを
特徴とする請求項１または２記載のポリビニルアセター
ルの製造方法。(4) The method for producing polyvinyl acetal according to claim 1 or 2, characterized in that the hydrolysis reaction of a polyvinyl ester or polyvinyl ether having a syndiotacticity of 55 mol% or more and the reaction with an aldehyde are carried out simultaneously. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20839589A JP2710838B2 (en) | 1989-08-11 | 1989-08-11 | Polyvinyl acetal and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20839589A JP2710838B2 (en) | 1989-08-11 | 1989-08-11 | Polyvinyl acetal and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0370705A true JPH0370705A (en) | 1991-03-26 |
| JP2710838B2 JP2710838B2 (en) | 1998-02-10 |
Family
ID=16555548
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20839589A Expired - Fee Related JP2710838B2 (en) | 1989-08-11 | 1989-08-11 | Polyvinyl acetal and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2710838B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011102197A1 (en) * | 2010-02-16 | 2011-08-25 | 株式会社クラレ | Polyvinyl acetal resin for ceramic green sheets, process for production thereof, slurry composition, ceramic green sheets, and laminted ceramic capacitor |
| JP2015189803A (en) * | 2014-03-27 | 2015-11-02 | 積水化学工業株式会社 | polyvinyl acetal resin |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102517400B1 (en) * | 2017-06-21 | 2023-04-03 | 주식회사 엘지생활건강 | Water soluble poly(vinyl alcohol)-derived copolymer having stability |
-
1989
- 1989-08-11 JP JP20839589A patent/JP2710838B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011102197A1 (en) * | 2010-02-16 | 2011-08-25 | 株式会社クラレ | Polyvinyl acetal resin for ceramic green sheets, process for production thereof, slurry composition, ceramic green sheets, and laminted ceramic capacitor |
| JP2015189803A (en) * | 2014-03-27 | 2015-11-02 | 積水化学工業株式会社 | polyvinyl acetal resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2710838B2 (en) | 1998-02-10 |
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