JPH0410481B2 - - Google Patents
Info
- Publication number
- JPH0410481B2 JPH0410481B2 JP58160074A JP16007483A JPH0410481B2 JP H0410481 B2 JPH0410481 B2 JP H0410481B2 JP 58160074 A JP58160074 A JP 58160074A JP 16007483 A JP16007483 A JP 16007483A JP H0410481 B2 JPH0410481 B2 JP H0410481B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- weight
- emulsifier
- present
- alkylstyrene
- 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 - Lifetime
Links
- 239000000178 monomer Substances 0.000 claims description 17
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 16
- 239000003995 emulsifying agent Substances 0.000 claims description 15
- QUUCYKKMFLJLFS-UHFFFAOYSA-N Dehydroabietan Natural products CC1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 QUUCYKKMFLJLFS-UHFFFAOYSA-N 0.000 claims description 7
- NFWKVWVWBFBAOV-UHFFFAOYSA-N Dehydroabietic acid Natural products OC(=O)C1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 NFWKVWVWBFBAOV-UHFFFAOYSA-N 0.000 claims description 7
- NFWKVWVWBFBAOV-MISYRCLQSA-N dehydroabietic acid Chemical compound OC(=O)[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 NFWKVWVWBFBAOV-MISYRCLQSA-N 0.000 claims description 7
- 229940118781 dehydroabietic acid Drugs 0.000 claims description 7
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- -1 alkali metal salt Chemical class 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 4
- 235000011613 Pinus brutia Nutrition 0.000 description 4
- 241000018646 Pinus brutia Species 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 238000007323 disproportionation reaction Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- MHVJRKBZMUDEEV-UHFFFAOYSA-N (-)-ent-pimara-8(14),15-dien-19-oic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)C=C1CC2 MHVJRKBZMUDEEV-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- MXYATHGRPJZBNA-KRFUXDQASA-N isopimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@@](C=C)(C)CC2=CC1 MXYATHGRPJZBNA-KRFUXDQASA-N 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- MHVJRKBZMUDEEV-APQLOABGSA-N (+)-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-APQLOABGSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical group CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- MXYATHGRPJZBNA-UHFFFAOYSA-N 4-epi-isopimaric acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)CC1=CC2 MXYATHGRPJZBNA-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- KGMSWPSAVZAMKR-UHFFFAOYSA-N Me ester-3, 22-Dihydroxy-29-hopanoic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(=C(C)C)C=C1CC2 KGMSWPSAVZAMKR-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- KGMSWPSAVZAMKR-ONCXSQPRSA-N Neoabietic acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CCC(=C(C)C)C=C2CC1 KGMSWPSAVZAMKR-ONCXSQPRSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical group CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 229940043264 dodecyl sulfate Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006902 nitrogenation reaction Methods 0.000 description 1
- XRRONFCBYFZWTM-UHFFFAOYSA-N octadecanoic acid;sodium Chemical compound [Na].CCCCCCCCCCCCCCCCCC(O)=O XRRONFCBYFZWTM-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Description
本発明は特定の化合物を乳化剤として用いるエ
チレン系不飽和単量体の乳化重合法に関する。
従来よりスチレン、（メタ）アクリル酸エステ
ル、アクリロニトリル等に代表されるエチレン系
不飽和単量体の重合用乳化剤として、ステアリン
酸、オレイン酸などの高級脂肪酸ナトリウム、不
均化ロジン酸ナトリウム、ラウリル硫酸ナトリウ
ム、アルキルベンゼンスルホン酸ナトリウムが広
く用いられているが、乳化重合の製法上、最終製
品中に使用された乳化剤が残留する。最終製品の
透明性、着色性、耐光変色性および吸湿性の点に
おいてロジン酸石ケンは他の乳化剤より優れた性
質を示すが、ロジン酸石ケンは一般に重合性が悪
く、現実には、重合性に乏しい単量体では使用さ
れていない。
例えば、α−アルキルスチレン等の（共）重合
性に劣る単量体を用いた重合系においては、重合
終了後の未反応単量体が多いため生産性に劣り、
また、得られた（共）重合体の耐熱性低下など物
性上の問題を有している。
このため、一般的には重合後、得られた重合体
ラテツクスをスチームストリツピングによつて未
反応体を除去しているが膨大なエネルギーを必要
とする。
本発明者らは、かかる状況に鑑み乳化重合にお
ける重合性につき鋭意研究した結果、ある特定量
以上のデヒドロアビエチン酸を含有する不均化ロ
ジン酸からなる乳化剤を用いることにより、（共）
重合性に劣る単量体を用いた重合系においても、
優れた重合性が得られると共に、得られる製品も
透明性、着色性、耐光変色性および吸湿性に優れ
ることを見出し、本発明に到達したものである。
すなわち、本発明は、デヒドロアビエチン酸含
有量が65重量％以上である不均化ロジン酸からな
る不均化ロジン酸アルカリ金属塩および／または
アンモニウム塩を乳化剤として用いることによ
り、安定性に優れ、かつ、未反応単量体の少ない
生産性に優れる乳化重合法を提供するものであ
り、得られる製品（樹脂）の透明性、着色性、耐
光変色性および吸湿性に優れる。
以下に本発明に関し詳細に説明する。
一般にロジン酸とは、松の生立木から採用され
る生松脂から得られるガムロジン酸(i)、松の切株
から石油系溶剤にて抽出して得られるウツドロジ
ン酸(ii)及びクラフトパルプ製造時の蒸解廃液から
得られるトール油ロジン酸(iii)に分類されるが、い
ずれも天然物を原料とするためアビエチン酸を主
成分とするものであり、少量成分としてネオアビ
エチン酸、パラストリン酸、デヒドロアビエチン
酸、ピマル酸、イソピマル酸等を含む。不均化反
応により不均化ロジン酸が得られているが、現
在、工業的に得られている不均化ロジン酸中のデ
ヒドロアビエチン酸含有量はせいぜい55重量％で
ある。
しかしながら、本発明における不均化ロジン酸
とは、デヒドロアビエチン酸含有量が65重量％以
上、好ましくは70重量％以上のものである。65重
量％未満では本発明の目的が達せられない。
本発明において限定される乳化剤を用いること
により、（共）重合性に劣るα−アルキルスチレ
ンを含むエチレン系不飽和単量体の（共）重合に
おいて著しい改善効果が得られる。該エチレン系
不飽和単量体に占めるα−アルキルスチレンの含
有量については特に制限はなく、α−アルキルス
チレン含有量の増加と共にその改善効果も向上す
るが、好ましくは30重量％以上、特に好ましくは
50重量％以上である。
デヒドロアビエチン酸含有量が65重量％以上で
ある不均化ロジン酸は、不均化反応時の触媒量、
温度等を特定化することによつて得られる。
本発明において用いられる乳化剤とは、デヒド
ロアビエチン酸を主成分とする不均化ロジン酸を
ナトリウム、カリウムなどのアルカリ金属または
アンモニアで中和した不均化ロジン酸石ケンであ
り、１種又は２種以上用いることができる。
かかる乳化剤の使用割合には特に制限はなく、
重合すべき単量体の種類等により適宜決定される
ものであるが、通常エチレン系不飽和単量体100
重量部当り、0.01〜10重量部である。
本発明の乳化重合に供されるエチレン系不飽和
単量体にはα−アルキルスチレンが含まれる。α
−アルキルスチレンの代表例としてα−メチルス
チレンが挙げられる。
α−アルキルスチレン以外のエチレン系不飽和
単量体としては、スチレンに代表される芳香族ビ
ニル（α−アルキルスチレン除く）、アクリロニ
トリル、メタクリロニトリル等のシアン化ビニ
ル、アクリル酸メチル、アクリル酸エチル、メタ
クリル酸メチル、メタクリル酸エチル、ヒドロキ
シメタクリル酸エチル等の不飽和カルボン酸アル
キルエステル、アクリル酸、メタクリル酸等の不
飽和カルボン酸等々が挙げられ、一種以上用いら
れる。
単量体は、本発明で述べられる特定の乳化剤の
存在下重合され、単一重合体、または共重合体を
形成するが、さらにゴム質重合体の存在下におけ
る重合により、グラフト重合体をも形成すること
ができる。
具体的には、α−メチルスチレン−アクリロニ
トリル共重合体、α−メチルスチレン−アクリロ
ニトリル−メチルメタクリレート共重合体、アク
リロニトリル−ジエン系ゴム−α−メチルスチレ
ン重合体、アクリロニトリル−オレフイン系ゴム
−α−メチルスチレン重合体等が挙げられる。
本発明の特定化合物を乳化剤として用いる乳化
重合法を実施するにあたり、公知の重合開始剤、
分子量調整剤等を用いることができる。さらに公
知の乳化剤を併用することもできる。
以下に実施例を挙げて説明するが、本発明はこ
れらによつて何ら制限されるものでない。
実施例および比較例
窒素置換した反応器に、表−１に示す乳化剤全
量、過硫酸カリウム全量、水全量および単量体混
合物の30重量％を入れ70℃で１時間重合を行い、
残りの単量体混合物（70重量％）をその後３時間
で連続添加し、更に２時間熟成を行い重合を完了
した。
得られた共重合体ラテツクスは塩化カルシウム
で塩析し、乾燥後共重合体パウダーを作成した。
パウダーをバンバリーミキサーで混練し、ペレツ
トを作成した。
なお、着色性および耐光変色性評価に際して
は、バンバリーミキサー混練時顔料を添加した。
The present invention relates to a method for emulsion polymerization of ethylenically unsaturated monomers using a specific compound as an emulsifier. Traditionally, sodium stearic acid, higher fatty acids such as oleic acid, disproportionated sodium rosinate, and lauryl sulfate have been used as emulsifiers for polymerizing ethylenically unsaturated monomers such as styrene, (meth)acrylic acid esters, and acrylonitrile. Sodium and sodium alkylbenzene sulfonate are widely used, but due to the emulsion polymerization process, the emulsifier used remains in the final product. Although rosin acid soap exhibits superior properties to other emulsifiers in terms of transparency, coloration, light discoloration resistance, and hygroscopicity of the final product, rosin acid soap generally has poor polymerizability, and in reality, it is difficult to polymerize. It is not used in monomers with poor properties. For example, in a polymerization system using a monomer with poor (co)polymerizability such as α-alkylstyrene, there is a large amount of unreacted monomer after polymerization, resulting in poor productivity.
Furthermore, the obtained (co)polymer has problems in terms of physical properties such as a decrease in heat resistance. For this reason, unreacted substances are generally removed from the resulting polymer latex by steam stripping after polymerization, but this requires a huge amount of energy. In view of this situation, the present inventors conducted extensive research on the polymerizability in emulsion polymerization, and found that by using an emulsifier consisting of a disproportionated rosin acid containing a certain amount or more of dehydroabietic acid, (co-)
Even in polymerization systems using monomers with poor polymerizability,
The present invention was achieved based on the discovery that not only excellent polymerizability can be obtained, but also that the resulting product has excellent transparency, colorability, light discoloration resistance, and hygroscopicity. That is, the present invention provides excellent stability by using as an emulsifier an alkali metal salt and/or ammonium salt of disproportionated rosin acid comprising disproportionated rosin acid having a dehydroabietic acid content of 65% by weight or more. In addition, the present invention provides an emulsion polymerization method with excellent productivity with less unreacted monomers, and the resulting product (resin) has excellent transparency, colorability, light discoloration resistance, and hygroscopicity. The present invention will be explained in detail below. In general, rosin acid is gum rosin acid (i) obtained from raw pine resin taken from living pine trees, uddrosin acid (ii) obtained by extraction from pine stumps with a petroleum solvent, and rosin acid (ii) obtained from pine resin during the production of kraft pulp. Tall oil obtained from cooking waste liquor is classified as rosin acid (III), but since all of them are made from natural products, the main component is abietic acid, with minor components including neoabietic acid, parastric acid, and dehydroabietin. Acids, including pimaric acid, isopimaric acid, etc. Disproportionation rosin acids have been obtained by disproportionation reactions, but the content of dehydroabietic acid in the disproportionation rosin acids currently obtained industrially is at most 55% by weight. However, the disproportionated rosin acid in the present invention has a dehydroabietic acid content of 65% by weight or more, preferably 70% by weight or more. If it is less than 65% by weight, the object of the present invention cannot be achieved. By using the emulsifier defined in the present invention, a remarkable improvement effect can be obtained in the (co)polymerization of ethylenically unsaturated monomers containing α-alkylstyrene, which has poor (co)polymerizability. There is no particular restriction on the content of α-alkylstyrene in the ethylenically unsaturated monomer, and the improving effect improves as the content of α-alkylstyrene increases, but it is preferably 30% by weight or more, particularly preferably teeth
It is 50% by weight or more. Disproportionated rosin acid with a dehydroabietic acid content of 65% by weight or more has a catalyst amount during the disproportionation reaction,
It can be obtained by specifying temperature, etc. The emulsifier used in the present invention is a disproportionated rosin acid soap prepared by neutralizing a disproportionated rosin acid containing dehydroabietic acid as a main component with an alkali metal such as sodium or potassium or ammonia, and is one or two types of emulsifier. More than one species can be used. There are no particular restrictions on the proportion of such emulsifiers used;
It is determined appropriately depending on the type of monomer to be polymerized, but usually 100% of the ethylenically unsaturated monomer is used.
It is 0.01 to 10 parts by weight per part by weight. The ethylenically unsaturated monomer used in the emulsion polymerization of the present invention includes α-alkylstyrene. α
-A typical example of alkylstyrene is α-methylstyrene. Examples of ethylenically unsaturated monomers other than α-alkylstyrene include aromatic vinyl represented by styrene (excluding α-alkylstyrene), vinyl cyanides such as acrylonitrile and methacrylonitrile, methyl acrylate, and ethyl acrylate. , unsaturated carboxylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, and hydroxyethyl methacrylate, and unsaturated carboxylic acids such as acrylic acid and methacrylic acid, and one or more of them may be used. The monomers are polymerized in the presence of the specific emulsifiers mentioned in the present invention to form a homopolymer or a copolymer, but they can also be polymerized in the presence of a rubbery polymer to form a graft polymer. can do. Specifically, α-methylstyrene-acrylonitrile copolymer, α-methylstyrene-acrylonitrile-methylmethacrylate copolymer, acrylonitrile-diene rubber-α-methylstyrene polymer, acrylonitrile-olefin rubber-α-methyl Examples include styrene polymers. In carrying out the emulsion polymerization method using the specific compound of the present invention as an emulsifier, a known polymerization initiator,
Molecular weight regulators and the like can be used. Furthermore, a known emulsifier can also be used in combination. Examples will be described below, but the present invention is not limited thereto. Examples and Comparative Examples The total amount of emulsifier shown in Table 1, the total amount of potassium persulfate, the total amount of water, and 30% by weight of the monomer mixture were placed in a reactor purged with nitrogen, and polymerization was performed at 70°C for 1 hour.
The remaining monomer mixture (70% by weight) was then continuously added over the next 3 hours, and the mixture was aged for an additional 2 hours to complete the polymerization. The obtained copolymer latex was salted out with calcium chloride, and after drying, a copolymer powder was prepared.
The powder was kneaded with a Banbury mixer to create pellets. In addition, when evaluating colorability and light discoloration resistance, pigments were added during kneading with a Banbury mixer.
【表】【table】
Claims (1)
である不均化ロジン酸からなる不均化ロジン酸ア
ルカリ金属塩および／またはアンモニウム塩を乳
化剤として用いることを特徴とするα−アルキル
スチレンを含むエチレン系不飽和単量体の乳化重
合法。1. An ethylene-based product containing α-alkylstyrene, characterized in that an alkali metal salt and/or ammonium salt of a disproportionated rosin acid containing a dehydroabietic acid content of 65% by weight or more is used as an emulsifier. Emulsion polymerization of unsaturated monomers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58160074A JPS6051704A (en) | 1983-08-31 | 1983-08-31 | Emulsion polymerization of ethylenically unsaturated monomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58160074A JPS6051704A (en) | 1983-08-31 | 1983-08-31 | Emulsion polymerization of ethylenically unsaturated monomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6051704A JPS6051704A (en) | 1985-03-23 |
| JPH0410481B2 true JPH0410481B2 (en) | 1992-02-25 |
Family
ID=15707317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58160074A Granted JPS6051704A (en) | 1983-08-31 | 1983-08-31 | Emulsion polymerization of ethylenically unsaturated monomer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6051704A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5254622A (en) * | 1988-12-09 | 1993-10-19 | Asahi Kasei Kogyo Kabushiki Kaisha | ABS resin compositions and molded articles thereof having improved coating performances |
| CA2004925C (en) * | 1988-12-09 | 1997-09-23 | Atsushi Nanasawa | Abs resin compositions and molded articles thereof having improved coating performances |
| CN1067696C (en) * | 1996-12-27 | 2001-06-27 | 中国科学院广州化学研究所 | Vinyl disproportionated rosin resinate/vinyl cyanide copolymer and its preparation |
| JP2003026742A (en) * | 2001-07-16 | 2003-01-29 | Nippon A & L Kk | Method for manufacturing graft copolymer latex |
| CN105797644B (en) * | 2016-04-20 | 2017-10-10 | 江南大学 | A kind of intelligent foam of photoresponse type formed by dehydroabietic acid based surfactants |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS528276A (en) * | 1976-07-06 | 1977-01-21 | Tadano Tekkosho:Kk | Oil-pressure cylinder with detector of axially directed stress |
| JPS5754067A (en) * | 1980-09-18 | 1982-03-31 | Ietatsu Ono | Vibrating barrel polishing apparatus |
-
1983
- 1983-08-31 JP JP58160074A patent/JPS6051704A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS528276A (en) * | 1976-07-06 | 1977-01-21 | Tadano Tekkosho:Kk | Oil-pressure cylinder with detector of axially directed stress |
| JPS5754067A (en) * | 1980-09-18 | 1982-03-31 | Ietatsu Ono | Vibrating barrel polishing apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6051704A (en) | 1985-03-23 |
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