JPS63221106A - Method for charging raw material in emulsion polymerization - Google Patents
Method for charging raw material in emulsion polymerizationInfo
- Publication number
- JPS63221106A JPS63221106A JP5305187A JP5305187A JPS63221106A JP S63221106 A JPS63221106 A JP S63221106A JP 5305187 A JP5305187 A JP 5305187A JP 5305187 A JP5305187 A JP 5305187A JP S63221106 A JPS63221106 A JP S63221106A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- parts
- weight
- diene elastomer
- emulsion polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000007720 emulsion polymerization reaction Methods 0.000 title claims abstract description 7
- 239000002994 raw material Substances 0.000 title claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 37
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims description 4
- 238000010556 emulsion polymerization method Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 abstract description 4
- 239000003995 emulsifying agent Substances 0.000 abstract description 4
- 230000000704 physical effect Effects 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000003607 modifier Substances 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 229940074404 sodium succinate Drugs 0.000 description 4
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical group CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical class CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical class CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- WWUVJRULCWHUSA-UHFFFAOYSA-N 2-methyl-1-pentene Chemical compound CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- -1 aromatic vinyl compound Chemical class 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- HLOUDBQOEJSUPI-UHFFFAOYSA-N 1-ethenyl-2,3-dimethylbenzene Chemical class CC1=CC=CC(C=C)=C1C HLOUDBQOEJSUPI-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- FSGHEPDRMHVUCQ-UHFFFAOYSA-N 2-ethoxyprop-1-ene Chemical compound CCOC(C)=C FSGHEPDRMHVUCQ-UHFFFAOYSA-N 0.000 description 1
- YOWQWFMSQCOSBA-UHFFFAOYSA-N 2-methoxypropene Chemical compound COC(C)=C YOWQWFMSQCOSBA-UHFFFAOYSA-N 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- RCBGGJURENJHKV-UHFFFAOYSA-N 2-methylhept-1-ene Chemical compound CCCCCC(C)=C RCBGGJURENJHKV-UHFFFAOYSA-N 0.000 description 1
- IRUDSQHLKGNCGF-UHFFFAOYSA-N 2-methylhex-1-ene Chemical compound CCCCC(C)=C IRUDSQHLKGNCGF-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- TWCRBBJSQAZZQB-UHFFFAOYSA-N 3-methylidenehexane Chemical compound CCCC(=C)CC TWCRBBJSQAZZQB-UHFFFAOYSA-N 0.000 description 1
- RYKZRKKEYSRDNF-UHFFFAOYSA-N 3-methylidenepentane Chemical compound CCC(=C)CC RYKZRKKEYSRDNF-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 238000007868 post-polymerization treatment Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical class C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、少なくとも一種のビニル単量体をジエンエラ
ストマーにグラフトさせることによる耐衝撃性樹脂の製
造に於ける原料装入方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method of charging raw materials in the production of impact-resistant resins by grafting at least one vinyl monomer onto a diene elastomer. .
グラフト重合体を得る方法として、乳化重合法、溶液重
合法、塊状重合法、懸濁重合法等の手法が知られている
。Techniques such as emulsion polymerization, solution polymerization, bulk polymerization, and suspension polymerization are known as methods for obtaining graft polymers.
この内、乳化重合法に於いては、急激な反応による過大
な発熱によるラテックスの崩壊の回避、モノマーの共重
合性の制御を目的として、ビニル単量体、ジエンエラス
トマー及びその他の添加剤を連続的または分割して重合
槽に添加する方法が採用される。Among these, in the emulsion polymerization method, vinyl monomers, diene elastomers, and other additives are continuously added for the purpose of avoiding latex collapse due to excessive heat generation due to rapid reaction and controlling the copolymerizability of monomers. A method is adopted in which the polymer is added to the polymerization tank in bulk or in parts.
この連続的又は分割してモノマー等を重合槽に添加する
重合方法に於いて、重合体の物性を制御する目的で分子
ｌｌ＃ＪＲ節剤を使用するが、この分子量調節剤の効果
は高いＰＨ値では小さい。その為にＰＨ３Ｐｉ節剤とし
て酸成分を混合する手法が知られている（例特開昭５２
−１３９１８７）。In this polymerization method in which monomers, etc. are added to the polymerization tank continuously or in parts, a molecular weight regulator is used for the purpose of controlling the physical properties of the polymer. Small in value. For this purpose, a method of mixing an acid component as a PH3Pi moderator is known (e.g., JP-A-52
-139187).
しかしながら上記方法でグラフト重合体が製造される場
合には、重合終了時の釜スケールが多く生産性の低下と
樹脂加工時に於ける特性の劣化、及び加工後の外見上の
悪化等の問題を生じている。However, when a graft polymer is produced by the above method, there is a lot of scale in the pot at the end of polymerization, which causes problems such as decreased productivity, deterioration of properties during resin processing, and deterioration of appearance after processing. ing.
本発明の目的は上記問題点である釜スケールを減少させ
、生産性を向上させると共に、樹脂の物性を向上させる
重合時の原料挿入方法を提供することにある。An object of the present invention is to provide a method for inserting raw materials during polymerization, which reduces the above problem of pot scale, improves productivity, and improves the physical properties of the resin.
本発明者らは、生産効率を上げる為、重合時の分子ｔｉ
＊節剤の効果を高めるべく添加するＰＨ４Ｊｉ節剤とし
ての酸成分の添加方法について鋭意検討し、本発明の完
成に到った。In order to increase production efficiency, the present inventors have determined that the molecule ti during polymerization
*The present invention was completed after intensive study on the method of adding an acid component as a PH4Ji moderator to enhance the effect of the moderator.
即ち、本発明は、ジエンエラストマーの存在下に、少な
くとも一種のモノビニル単量体を共重合させることによ
りグラフト重合体を製造する乳化重合法に於いて、ジエ
ンエラストマーを重合系の酸度を制御するｐＨ調節剤及
び他の連続又は分割装入物と分離独立した配管を用いて
別個に重合槽に装入することを特徴とする乳化重合に於
ける原料装入方法である。That is, the present invention relates to an emulsion polymerization method in which a graft polymer is produced by copolymerizing at least one monovinyl monomer in the presence of a diene elastomer. This method of charging raw materials in emulsion polymerization is characterized by charging the regulator and other continuous or divided charging materials into a polymerization tank separately using separate and independent piping.
本発明に於いて、ジエンエラストマーとは、炭素原子数
が４ないし６個の共役ジエン、例えばブタジェン、イソ
プレン、ピペリレン等のゴム状単独重合体及び共重合体
、及びこれ等のジエンの一種又はそれ以上と他の単量体
、例えばアクリロニトリル、メタクリロニトリル、α−
メチルスチレン、スチレン、アクリル酸エチル、メタク
リル酸メチル等との共重合体である。In the present invention, diene elastomers refer to conjugated dienes having 4 to 6 carbon atoms, such as rubber-like homopolymers and copolymers such as butadiene, isoprene, piperylene, and one or more of these dienes. These and other monomers, such as acrylonitrile, methacrylonitrile, α-
It is a copolymer with methylstyrene, styrene, ethyl acrylate, methyl methacrylate, etc.
好ましくは、共役ジエンとして１．３−ブタジェン及び
イソプレンであり、共重合用単量体としてアクリロニト
リル、スチレン、メタクリロニトリルがあげられる。Preferably, the conjugated diene is 1,3-butadiene and isoprene, and the monomer for copolymerization is preferably acrylonitrile, styrene, or methacrylonitrile.
特に本発明に用いるジエンエラストマーは重合したジエ
ンを５０％以上含有するのが好ましく、その製造法は通
常のラジカル開始剤を用いて乳化重合する方法によるも
のでもよく、特にその製法に制限はない。In particular, the diene elastomer used in the present invention preferably contains 50% or more of polymerized diene, and the manufacturing method thereof may be emulsion polymerization using a conventional radical initiator, and there are no particular limitations on the manufacturing method.
本発明に用いるモノビニル単量体としては、芳香族ビニ
ル化合物、不飽和ニトリル、不飽和カルボン酸エステル
、ビニルエステル、ビニルエーテル、α−オレフィン等
の１種又は２種以上からなる単量体があげられる。Examples of the monovinyl monomer used in the present invention include monomers consisting of one or more of aromatic vinyl compounds, unsaturated nitriles, unsaturated carboxylic acid esters, vinyl esters, vinyl ethers, α-olefins, etc. .
芳香族ビニル化合物としてはスチレン、α−メチルスチ
レン、ビニルトルエン類、ビニルキシレン類等があげら
れ、好ましくはスチレンである。Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluenes, and vinylxylenes, with styrene being preferred.
又不飽和ニトリルとしては、アクリロニトリル、メタク
リロニトリル、α−クロロアクリロニトリル等があげら
れ、好ましくはアクリロニトリル、メタクリロニトリル
である。Examples of the unsaturated nitrile include acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, with acrylonitrile and methacrylonitrile being preferred.
又不飽和カルボン酸エステルとしては、アクリル酸、あ
るいはメタクリル酸のメチル、エチル、プロピル、ブチ
ル等のエステルがあげることができ、好ましくはアクリ
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である。Examples of unsaturated carboxylic acid esters include esters of acrylic acid or methacrylic acid such as methyl, ethyl, propyl, butyl, and preferably methyl acrylate, ethyl acrylate, methyl methacrylate,
It is ethyl methacrylate.
ビニルエステルとしては、酢酸ビニル、フロヒオン酸ビ
ニル、ラフ酸ビニル等があげられ、好ましくは酢酸ビニ
ルである。Examples of the vinyl ester include vinyl acetate, vinyl fluohionate, vinyl fluoride, and the like, with vinyl acetate being preferred.
ビニルエーテルとしては、メチルビニルエーテル、エチ
ルビニルエーテル、プロピルビニルエーテル類、ブチル
ビニルエーテル類、メチルイソプロペニルエーテル、エ
チルイソプロペニルエーテル等あげられ、好ましくは、
メチルビニルエーテル、エチルビニルエーテル、プロピ
ルビニルエーテル類、ブチルビニルエーテル類である。Examples of the vinyl ether include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ethers, butyl vinyl ethers, methyl isopropenyl ether, ethyl isopropenyl ether, etc., and preferably,
These are methyl vinyl ether, ethyl vinyl ether, propyl vinyl ethers, and butyl vinyl ethers.
α−オレフィンとしては、イソブチン、２−メチル−１
−ブテン、２−メチル−１−ペンテン、２−メチル−１
−ヘキセン、２−メチル−１−ヘプテン、２−メチル−
１−オクテン、２−エチル−１−ブテン、２−プロピル
−１−ブテン等あげられ、好ましくは、イソブチンであ
る。α-olefins include isobutyne, 2-methyl-1
-butene, 2-methyl-1-pentene, 2-methyl-1
-hexene, 2-methyl-1-heptene, 2-methyl-
Examples include 1-octene, 2-ethyl-1-butene, 2-propyl-1-butene, and isobutene is preferred.
本発明に用いる乳化剤としては、一般に知られている動
物油脂、植物油脂、半合成油脂、合成油脂等を原料とす
るアニオン、ノニオン、カチオン界面活性剤が利用でき
る。好ましくは、アニオン界面活性剤である。As the emulsifier used in the present invention, anionic, nonionic, or cationic surfactants made from commonly known animal oils, vegetable oils, semi-synthetic oils, synthetic oils, etc. can be used. Preferably, it is an anionic surfactant.
本発明に利用し得るｐｉ（ｐｉ１節剤としては、−ＩＩ
の鉱酸、有機カルボン酸が用いられるが、好ましくは硫
酸、硝酸、亜硫酸、リン酸、ポリリン酸、酢酸、メルカ
プトプロピオン酸、プロピオン酸である。本発明に於い
て他の連続又は分割挿入物とはジエンエラストマー、ビ
ニル単量体、分子ｆｉＵ＠節剤、乳化剤等を意味する。The pi (pi1 moderating agent that can be used in the present invention is -II)
Mineral acids and organic carboxylic acids are used, preferably sulfuric acid, nitric acid, sulfurous acid, phosphoric acid, polyphosphoric acid, acetic acid, mercaptopropionic acid, and propionic acid. In the present invention, other continuous or segmented inserts refer to diene elastomers, vinyl monomers, molecular fiU@ binders, emulsifiers, and the like.
本発明に於いては、特開昭（特願昭６０−００６２０６
特願昭６Ｏ−００６２０５）に開示する重合方法を用い
ることが好ましい。この方法はジエンエラストマー１〜
４０重量部にビニル単量体の少なくとも一種をグラフト
重合させるものであり、重合物の物性、分子量等の制御
を行う為に、ジエンエラストマー、ビニル単量体、分子
！調節剤、乳化剤、ｐＨ調節剤等を連続又は分割装入す
るものである。The present invention is based on Japanese Patent Application Publication No. 60-006206.
It is preferable to use the polymerization method disclosed in Japanese Patent Application No. 6O-006205). This method uses diene elastomer 1~
40 parts by weight of at least one vinyl monomer is graft-polymerized, and in order to control the physical properties, molecular weight, etc. of the polymer, diene elastomer, vinyl monomer, molecule! Regulators, emulsifiers, pH adjusters, etc. are charged continuously or in portions.
この重合方法を利用し、本発明が示すようにジエンエラ
ストマーをｐＨｔＰ！節剤および他の連続又は分割装入
物と全く独立させるときに、重合終了時の重合釜に生成
する釜軸（スケール）は、従来の同一ヘッダで装入する
方法に比較し約１／１０となり、重合後の処理が大幅に
簡略されると同時に、生産原単位も著しく向上するもの
である。Utilizing this polymerization method, diene elastomers can be prepared at pHtP! When the moderator and other continuous or divided charges are completely independent, the scale formed in the polymerization kettle at the end of polymerization is approximately 1/10 that of the conventional method of charging with the same header. This greatly simplifies the post-polymerization treatment and at the same time significantly improves the production unit.
以下、実施例をもって本発明を具体的に説明するが、実
施例により本発明の範囲が制限されるものでないことは
いうまでもない。EXAMPLES The present invention will be specifically explained below with reference to Examples, but it goes without saying that the scope of the present invention is not limited by the Examples.
ジエンエラストマーの製造
下記組成の混合物を攪拌装置の付いた重合機に入れ、窒
素雰囲気下に５０℃で１０時間重合を行った。Production of diene elastomer A mixture having the following composition was placed in a polymerization machine equipped with a stirring device, and polymerization was carried out at 50° C. for 10 hours under a nitrogen atmosphere.
アクリロニトリル ３０重量部
１．３−ブタジェン ７０重量部脂肪酸石ケン
２．０重量部アブイソブチロニトリル ０．
３重量部（−ドデシルメルカプタン ０．５重量部イオ
ン交換水 ２００重量部出来たエラストマー
の固型分濃度は２９．８％であった。Acrylonitrile 30 parts by weight 1,3-butadiene 70 parts by weight Fatty acid soap
2.0 parts by weight Abisobutyronitrile 0.
3 parts by weight (0.5 parts by weight of -dodecyl mercaptan 200 parts by weight of ion-exchanged water) The solid content concentration of the resulting elastomer was 29.8%.
〔比較例１〕
参考例で得たジエンエラストマー７重ＩＩと下記の組成
の混合物を攪拌機付重合機に入れ窒素雰囲気下に５８℃
で重合を開始した０重合開始時のｐＨは８であった。[Comparative Example 1] A mixture of the diene elastomer 7-layer II obtained in the reference example and the following composition was placed in a polymerization machine equipped with a stirrer and heated to 58°C under a nitrogen atmosphere.
The pH at the time of polymerization initiation was 8.
アクリロニトリル １４重量部
メタクリル酸エチル ６重量部
ジオクチルスルホ ０．２重量部
コハク酸ナトリウム
ポリビニルピロリドン ０．０７重量部過硫酸カリウム
０．０６重量部イオン交換水 １２０
重量部
重合開始３０分後に重合系にリン酸を添加して重合液の
ｐｉを４とした後、下記の化合物を５時間要して連続的
に同一の投入口より添加しつつ５８℃で重合を行った。Acrylonitrile 14 parts by weight Ethyl methacrylate 6 parts by weight Dioctyl sulfo 0.2 parts by weight Sodium succinate Polyvinylpyrrolidone 0.07 parts by weight Potassium persulfate 0.06 parts by weight Ion exchange water 120
Part by weight After 30 minutes from the start of polymerization, phosphoric acid was added to the polymerization system to make the pi of the polymerization solution 4, and then the following compounds were continuously added from the same input port over a period of 5 hours and polymerized at 58°C. I did it.
アクリロニトリル ６０重量部
メタクリル酸エチル ２０重量部
ジオクチルスルホ ０．８重量部
コハク酸ナトリウム
ポリビニルピロリドン ０．３２重量部ジエンエラスト
マー ２６重１部
イオン交換水 １１０重量部
ペンタエリスリトールテトラキス
（β−メルカプトプロピオネート）
１．６５重量部
リン酸 ０．３８重量部重合終了後の釜
軸（スケール）は５．５重量部存在した。Acrylonitrile 60 parts by weight Ethyl methacrylate 20 parts by weight Dioctyl sulfo 0.8 parts by weight Sodium succinate Polyvinylpyrrolidone 0.32 parts by weight Diene elastomer 26 parts by weight 1 part Ion exchange water 110 parts by weight Pentaerythritol Tetrakis (β-mercaptopropionate) 1.65 parts by weight Phosphoric acid 0.38 parts by weight After completion of polymerization, 5.5 parts by weight of the kettle shaft (scale) was present.
〔実施例１〕
比較例１と全く同一方法で連続装入するジエンエラスト
マーを他の化合物の装入口から独立させて重合釜に添加
して重合を行った０重合終了後の釜軸（スケール）は０
．５重量部存在した。[Example 1] Diene elastomer was continuously charged in exactly the same manner as Comparative Example 1, and polymerization was carried out by adding the diene elastomer to the polymerization kettle independently from the charging port for other compounds. 0 The kettle axis (scale) after the completion of polymerization is 0
．． 5 parts by weight were present.
〔比較例２〕
参考例で得たジエンエラストマー１０重量部と下記の組
成の混合物を比較例１と同様にして反応を開始した。[Comparative Example 2] A reaction was started in the same manner as in Comparative Example 1 using 10 parts by weight of the diene elastomer obtained in the Reference Example and a mixture having the composition shown below.
アクリロニトリル １５重量部
スチレン ３重量部
アクリル酸エチル ２重量部
ジオクチルスルホ ０．２重量部
コハク酸ナトリウム
ポリビニルピロリドン ０．０７重量部過硫酸カリウム
０．０６重量部イオン交換水 １２帽
１部
重合開始３０分後に重合系に酢酸を添加して重合液のｐ
ｔ＋を４．３とした後、下記の化合物を５時間要して連
続的に同一の投入口より添加しつつ５８℃で重合を行っ
た。Acrylonitrile 15 parts by weight Styrene 3 parts by weight Ethyl acrylate 2 parts by weight Dioctylsulfo 0.2 parts by weight Sodium succinate Polyvinylpyrrolidone 0.07 parts by weight Potassium persulfate 0.06 parts by weight Ion-exchanged water 12 parts by weight 1 part 30 minutes from the start of polymerization Afterwards, acetic acid is added to the polymerization system to increase the p of the polymerization solution.
After setting t+ to 4.3, polymerization was carried out at 58° C. while continuously adding the following compounds from the same inlet over a period of 5 hours.
アクリロニトリル ５０重量部
スチレン １４１部
アクリル酸エチル ２０重量部
ジオクチルスルホ ０．８重量部
コハク酸ナトリウム
ポリビニルピロリドン ０．３２重量部ジエンエラスト
マー ２３重量部
イオン交換水 １１０重量部
ペンタエリスリトールテトラキス
（β−メルカプトプロピオネート）
１．６５重量部
酢酸 ０．２３重量部連続装入終了後
、１時間重合を行い反応を終了した。Acrylonitrile 50 parts by weight Styrene 141 parts Ethyl acrylate 20 parts by weight Dioctyl sulfo 0.8 parts by weight Sodium succinate Polyvinylpyrrolidone 0.32 parts by weight Diene elastomer 23 parts by weight Ion exchange water 110 parts by weight Pentaerythritol Tetrakis (β-mercaptopropyl) After continuously charging 1.65 parts by weight of acetic acid and 0.23 parts by weight, polymerization was carried out for 1 hour to complete the reaction.
重合終了後の釜軸（スケール）は６．３重量部存在した
。After the polymerization was completed, 6.3 parts by weight of the pot scale was present.
〔実施例２〕
比較例と全く同一方法で連続装入するジエンエラストマ
ーを他の化合物の装入口から独立させて重合釜に添加し
て重合を行った。[Example 2] Polymerization was carried out by adding continuously charged diene elastomer to the polymerization kettle independently from the charging port for other compounds in exactly the same manner as in the comparative example.
重合終了後の釜軸（スケール）は０．５重量部存在した
。After the completion of polymerization, 0.5 parts by weight of the pot shaft (scale) was present.
本発明の方法は、上記実施例で明らかなようにラテック
スの崩壊によると思われる、スケールが大幅に減少し、
原単位の約５％以上の向上を計ることが可能となり、生
産性向上及び重合ラテックスの効果が得られる。As is clear from the above examples, the method of the present invention results in a significant reduction in scale, which is probably due to the collapse of latex.
It becomes possible to measure an improvement of about 5% or more in the basic unit, and the effects of improved productivity and polymerized latex can be obtained.
Claims (1)
ニル単量体を共重合させることによりグラフト重合体を
製造する乳化重合法に於いて、ジエンエラストマーを重
合系の酸度を制御するｐＨ調節剤及び他の連続又は分割
装入物と分離独立した配管を用いて別個に重合槽に装入
することを特徴とする乳化重合に於ける原料装入方法。In the emulsion polymerization method of producing a graft polymer by copolymerizing at least one monovinyl monomer in the presence of a diene elastomer, the diene elastomer is combined with a pH regulator and other continuous or continuous polymers to control the acidity of the polymerization system. A method of charging raw materials in emulsion polymerization, which is characterized by separately charging raw materials into a polymerization tank using divided charges and separate and independent piping.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5305187A JPH075690B2 (en) | 1987-03-10 | 1987-03-10 | Raw material charging method in emulsion polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5305187A JPH075690B2 (en) | 1987-03-10 | 1987-03-10 | Raw material charging method in emulsion polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63221106A true JPS63221106A (en) | 1988-09-14 |
| JPH075690B2 JPH075690B2 (en) | 1995-01-25 |
Family
ID=12932062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5305187A Expired - Lifetime JPH075690B2 (en) | 1987-03-10 | 1987-03-10 | Raw material charging method in emulsion polymerization |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH075690B2 (en) |
-
1987
- 1987-03-10 JP JP5305187A patent/JPH075690B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH075690B2 (en) | 1995-01-25 |
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