JPH0124805B2 - - Google Patents
Info
- Publication number
- JPH0124805B2 JPH0124805B2 JP55004142A JP414280A JPH0124805B2 JP H0124805 B2 JPH0124805 B2 JP H0124805B2 JP 55004142 A JP55004142 A JP 55004142A JP 414280 A JP414280 A JP 414280A JP H0124805 B2 JPH0124805 B2 JP H0124805B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- methylstyrene
- copolymer
- vinyl
- monomer
- 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
- 238000006116 polymerization reaction Methods 0.000 claims description 62
- 239000000178 monomer Substances 0.000 claims description 52
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 25
- 229920001577 copolymer Polymers 0.000 claims description 18
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 17
- 229920002554 vinyl polymer Polymers 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 6
- -1 N-substituted maleimide Chemical class 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 2
- KYPOHTVBFVELTG-OWOJBTEDSA-N (e)-but-2-enedinitrile Chemical compound N#C\C=C\C#N KYPOHTVBFVELTG-OWOJBTEDSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 2
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 claims description 2
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-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
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004945 emulsification 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
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- HSJXWMZKBLUOLQ-UHFFFAOYSA-M potassium;2-dodecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HSJXWMZKBLUOLQ-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Description
本発明はα−メチルスチレン、シアン化ビニル
単量体およびこれらと共重合可能なビニル単量体
を水性乳化重合するに際し、重合初期よりシアン
化ビニル単量体を制御された速度で重合系中に添
加して重合を完結することにより色調、耐衝撃性
及び耐熱性が著しく改善された共重合体の製法に
関する。
従来から芳香族ビニル単量体およびシアン化ビ
ニル単量体を主成分とする単量体混合物を重合す
る際、重合後期にシアン化ビニル単量体及び／又
は芳香族ビニル単量体を添加して重合を完結させ
る方法が種々提案されており、例えば特公昭45−
33661号や特公昭47−46472号などがある。
しかしこれらの方法によつて得られた共重合体
はその分子量及び単量体組成に分布を生じ、色
調、耐衝撃性及び耐熱性に劣る共重合体となるの
でこれをABS樹脂に配合しても色調、耐衝撃性
及び耐熱性が十分な樹脂組成物とはならない。
特にシアン化ビニル単量体を単独で重合後期に
添加した共重合体をABS樹脂に配合した場合は
色調が著しく劣化する欠点がある。
本発明者はこれら欠点を改良するため鋭意検討
を行なつた結果、重合初期よりシアン化ビニル単
量体を制御された速度で重合系中に添加して重合
を完結することにより色調、耐衝撃性及び耐熱性
の著しく改善された共重合体を製造する方法を見
い出し本発明に到達した。
すなわち、本発明は、α−メチルスチレン65〜
80重量％、シアン化ビニル単量体15〜30重量％お
よびこれらと共重合可能なビニル単量体０〜20重
量％からなる単量体を水性乳化重合して共重合体
を製造する方法において、α−メチルスチレンは
その全量を重合開始時に存在させ、シアン化ビニ
ル単量体はその一部を重合開始時に存在させて重
合を開始し、重合開始から重合終了するまでの間
に残りのシアン化ビニル単量体をα−メチルスチ
レンの消費速度より実質的に遅い速度で重合系に
添加し、しかも重合が実質的に終了するまでの
間、重合系中の未反応単量体の組成比がシアン化
ビニル単量体のモル数に対し、α−メチルスチレ
ンおよび前記共重合可能なビニル単量体の合計モ
ル数を1.3〜３倍とするように保持して重合を実
質的に完結させることを特徴とする共重合体の製
法である。
水性乳化重合は乳化剤を含む水性の系で遊離基
発生開始剤を用いて行なうのが好ましく、重合系
中に分子量調節剤、乳化助剤あるいは滑剤等の添
加剤を添加してもよい。
本発明の方法においては、重合に供する単量体
のうち、α−メチルスチレンは最初から全てを重
合系に入れておき、シアン化ビニル単量体はその
一部のみを重合開始時に入れておき、残りのシア
ン化ビニル単量体は重合途中で連続的に、または
１回ないし２回以上に分けて添加して、重合系中
の未反応単量体の組成比を特定範囲に保つように
する。すなわち、重合系中の未反応単量体の組成
比を、α−メチルスチレンと前記共重合可能なビ
ニル単量体の合計モル数がシアン化ビニル単量体
のモル数に対し、常に1.3〜３倍、特に好ましく
は1.7〜2.5倍になるように保つて重合を実質的に
完結させることが重要である。この未反応シアン
化ビニル単量体に対するモル数が３倍をこえる場
合は高分子量の重合体が得られにくく耐衝撃性に
劣り、また重合速度が著しく遅くなり高収率で重
合体を得ることは非常に困難になる。一方未反応
シアン化ビニル単量体に対するモル数が1.3倍未
満の場合は得られる重合体の色調が著しく劣化す
るとともに耐熱性も低下する。
なお、α−メチルスチレンおよびシアン化ビニ
ル単量体と共重合可能な単量体は、重合開始時に
その全量を重合系に入れておいてよい。しかし、
場合によつては重合開始時には、それを全く入れ
ておかず、又はその一部のみを入れておき、重合
途中において添加してもよい。
α−メチルスチレンおよびシアン化ビニル単量
体と共重合可能なビニル単量体の具体例として
は、α−メチルスチレン以外の芳香族ビニル単量
体、アセナフチレン、フマロニトリル、マレイミ
ド、Ｎ−置換マレイミド、メタクリル酸、アクリ
ル酸、メタクリル酸エステル、アクリル酸エステ
ルなどの公知の各種ビニル単量体から選ばれた１
種以上のものがあげられる。α−メチルスチレン
以外の芳香族ビニル単量体としては、スチレン、
ビニルトルエン、ｔ−ブチルスチレン、ハロゲン
置換スチレンなどがあげられる。シアン化ビニル
単量体としてはアクリロニトリル、メタアクリロ
ニトリル、α−クロロアクリロニトリルなどがあ
げられる。
本発明における水性乳化重合は水溶性遊離基発
生開始剤を用いて行なうのが好ましい。水溶性遊
離基発生開始剤代表例として過硫酸塩があり、そ
の具体例としては過硫酸カリウム、過硫酸ナトリ
ウム、過硫酸アンモニウム等があげられる。また
乳化剤としてはドデシルベンゼンスルホン酸ソー
ダ塩（以下DBSNと略記）、ドデシルベンゼンス
ルホン酸カリウム塩等のアルキルベンゼンスルホ
ン酸金属塩、ステアリン酸ソーダ又はカリウム
塩、オレイン酸ソーダ又はカリウム塩等の脂肪酸
金属塩やラウリル酸エステルソーダ塩などの従来
公知の各種乳化剤があげられる。
本発明における乳化重合の媒体として用いる水
の量は前記単量体の合計100重量部に対し、100〜
500重量部好ましくは150〜250重量部である。水
の量が少なすぎると重合系の乳化液の安定性が低
下するとともに重合熱の除去が困難となり、また
多すぎると共重合体の生産効率が低下する。
以下に本発明を実施例によつて具体的に説明す
るが、これ等は本発明の範囲を限定するものでは
ない。なお、単量体の略号は次のものを示す。
αMSM：α−メチルスチレン
SM ：スチレン
AN ：アクリロニトリル
実施例 １
撹拌機付１のガラス製オートクレーブ中に窒
素ガスを吹き込みながら第１表の物質を添加し
た。
In the present invention, when carrying out aqueous emulsion polymerization of α-methylstyrene, vinyl cyanide monomers, and vinyl monomers copolymerizable with these, vinyl cyanide monomers are introduced into the polymerization system at a controlled rate from the initial stage of polymerization. It relates to a method for producing a copolymer whose color tone, impact resistance, and heat resistance are significantly improved by adding the copolymer to the copolymer and completing the polymerization. Conventionally, when polymerizing a monomer mixture containing aromatic vinyl monomers and vinyl cyanide monomers as main components, vinyl cyanide monomers and/or vinyl aromatic monomers are added in the late stage of polymerization. Various methods have been proposed to complete the polymerization.
These include No. 33661 and Special Publication No. 47-46472. However, the copolymers obtained by these methods have a distribution in molecular weight and monomer composition, resulting in copolymers with poor color tone, impact resistance, and heat resistance, so they cannot be blended with ABS resin. However, a resin composition with sufficient color tone, impact resistance, and heat resistance cannot be obtained. In particular, when a copolymer in which vinyl cyanide monomer is added alone in the late stage of polymerization is blended with ABS resin, there is a drawback that the color tone is significantly deteriorated. As a result of intensive studies to improve these drawbacks, the inventors of the present invention found that by adding vinyl cyanide monomer to the polymerization system at a controlled rate from the initial stage of polymerization to complete the polymerization, color tone and impact resistance can be improved. The present invention has been accomplished by discovering a method for producing a copolymer with significantly improved properties and heat resistance. That is, the present invention provides α-methylstyrene 65~
In a method for producing a copolymer by aqueous emulsion polymerization of monomers consisting of 80% by weight, 15 to 30% by weight of vinyl cyanide monomer, and 0 to 20% by weight of vinyl monomer copolymerizable with these monomers. , α-methylstyrene is present in its entirety at the start of polymerization, and a portion of vinyl cyanide monomer is present at the start of polymerization to initiate polymerization, and the remaining cyanide monomer is present at the start of polymerization. The vinyl monomer is added to the polymerization system at a rate substantially slower than the consumption rate of α-methylstyrene, and the composition ratio of unreacted monomers in the polymerization system is maintained until the polymerization is substantially completed. The total number of moles of α-methylstyrene and the copolymerizable vinyl monomer is maintained at 1.3 to 3 times the number of moles of the vinyl cyanide monomer to substantially complete the polymerization. This is a method for producing a copolymer characterized by the following. The aqueous emulsion polymerization is preferably carried out in an aqueous system containing an emulsifier using a free radical generating initiator, and additives such as a molecular weight regulator, an emulsification aid or a lubricant may be added to the polymerization system. In the method of the present invention, among the monomers to be subjected to polymerization, all α-methylstyrene is added to the polymerization system from the beginning, and only a portion of the vinyl cyanide monomer is added at the start of polymerization. , the remaining vinyl cyanide monomer is added continuously during the polymerization, or in one or more portions to maintain the composition ratio of unreacted monomers in the polymerization system within a specific range. do. That is, the composition ratio of unreacted monomers in the polymerization system is such that the total number of moles of α-methylstyrene and the copolymerizable vinyl monomer is always from 1.3 to the number of moles of vinyl cyanide monomer. It is important to maintain the polymerization ratio at 3 times, particularly preferably 1.7 to 2.5 times, to substantially complete the polymerization. If the number of moles exceeds 3 times the unreacted vinyl cyanide monomer, it is difficult to obtain a polymer with high molecular weight, resulting in poor impact resistance, and the polymerization rate becomes extremely slow, making it difficult to obtain a polymer in high yield. becomes very difficult. On the other hand, if the number of moles is less than 1.3 times the amount of unreacted vinyl cyanide monomer, the color tone of the obtained polymer will be significantly deteriorated and the heat resistance will also be reduced. In addition, the monomer copolymerizable with α-methylstyrene and vinyl cyanide monomer may be added in its entirety to the polymerization system at the time of initiation of polymerization. but,
In some cases, it may not be added at all or only a portion thereof at the start of polymerization, and may be added during the polymerization. Specific examples of vinyl monomers copolymerizable with α-methylstyrene and vinyl cyanide monomers include aromatic vinyl monomers other than α-methylstyrene, acenaphthylene, fumaronitrile, maleimide, N-substituted maleimide, 1 selected from various known vinyl monomers such as methacrylic acid, acrylic acid, methacrylic ester, and acrylic ester
There is more to it than seeds. Aromatic vinyl monomers other than α-methylstyrene include styrene,
Examples include vinyltoluene, t-butylstyrene, and halogen-substituted styrene. Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile. The aqueous emulsion polymerization in the present invention is preferably carried out using a water-soluble free radical generating initiator. A typical example of a water-soluble free radical generation initiator is a persulfate, and specific examples thereof include potassium persulfate, sodium persulfate, ammonium persulfate, and the like. Examples of emulsifiers include alkylbenzenesulfonic acid metal salts such as dodecylbenzenesulfonic acid sodium salt (hereinafter abbreviated as DBSN), dodecylbenzenesulfonic acid potassium salt, fatty acid metal salts such as sodium stearate or potassium salt, sodium oleate or potassium salt, etc. Examples include various conventionally known emulsifiers such as lauric acid ester sodium salt. The amount of water used as a medium for emulsion polymerization in the present invention is 100 to 100 parts by weight, based on 100 parts by weight of the monomers in total.
The amount is 500 parts by weight, preferably 150 to 250 parts by weight. If the amount of water is too small, the stability of the emulsion of the polymerization system will be reduced and it will be difficult to remove the heat of polymerization, and if the amount is too large, the production efficiency of the copolymer will be reduced. EXAMPLES The present invention will be specifically explained below using Examples, but these are not intended to limit the scope of the present invention. The monomer abbreviations are as follows. αMSM: α-methylstyrene SM: Styrene AN: Acrylonitrile Example 1 The substances listed in Table 1 were added into a glass autoclave equipped with a stirrer while blowing nitrogen gas.
【表】
オートクレーブを加熱し、内容物を温度70℃に
昇温させた後に過硫酸カリウム１％水溶液20mlを
添加し重合を開始した。また同様の水溶液を６時
間後にも10ml添加した。重合開始より１時間後の
重合率は12.3重量％であつた。この時点より微量
定量ポンプを用いANを毎時5.0ｇの割合で総計30
ｇを６時間かけて重合系中に添加した。途中重合
率および未反応モノマーの組成経時変化を見るた
めにオートクレーブ中より乳化液を数mlづつサン
プリングした。重合は10時間で停止させた。その
時の重合率は96.8重量％であつた。途中サンプリ
ングした重合乳化液をガスクロマトグラフイーで
分析した。その結果を第２表に示す。[Table] After heating the autoclave and raising the temperature of the contents to 70°C, 20 ml of a 1% aqueous solution of potassium persulfate was added to initiate polymerization. Further, 10 ml of the same aqueous solution was added 6 hours later. The polymerization rate one hour after the start of polymerization was 12.3% by weight. From this point, use a micro-metering pump to administer AN at a rate of 5.0 g/hour for a total of 30 g.
g was added to the polymerization system over 6 hours. Several ml of the emulsion was sampled from the autoclave in order to observe changes in the polymerization rate and composition of unreacted monomers over time. Polymerization was stopped in 10 hours. The polymerization rate at that time was 96.8% by weight. The polymer emulsion sampled during the process was analyzed by gas chromatography. The results are shown in Table 2.
【表】
このようにして得られた重合乳化液を塩化カル
シウムにより凝固させ、脱水、乾燥させて白色粉
末状の重合体を得た。
上記重合体粉末とポリブタジエン100重量部に
対し、SMとANの比が70：30である混合物150重
量部をグラフト重合させた重合体粉末を、樹脂組
成物中のポリブタジエン含量が16重量％になるよ
う配合し、これをペレツトとした後射出成形して
その物性を測定した。これらの結果を第７表に示
す。
比較例 １
実施例１と同様のオートクレーブに窒素ガスを
吹き込みながら第３表の物質を添加した。[Table] The polymer emulsion thus obtained was coagulated with calcium chloride, dehydrated and dried to obtain a white powdery polymer. The above polymer powder and 100 parts by weight of polybutadiene are graft-polymerized with 150 parts by weight of a mixture in which the ratio of SM and AN is 70:30, and the polybutadiene content in the resin composition is 16% by weight. The pellets were made into pellets, which were then injection molded and their physical properties were measured. These results are shown in Table 7. Comparative Example 1 The substances listed in Table 3 were added to the same autoclave as in Example 1 while blowing nitrogen gas.
【表】
重合法は重合開始７時間後よりANを毎時15ｇ
の割合で総計15ｇを１時間かけて重合系に添加し
た以外は実施例１と同様の操作を行なつた。[Table] In the polymerization method, 15g of AN is added per hour from 7 hours after the start of polymerization.
The same operation as in Example 1 was carried out except that a total of 15 g was added to the polymerization system over 1 hour at a ratio of 15 g.
【表】【table】
【表】
このようにして得られた重合乳化液は実施例１
と同様の処理を行ない物性を測定した。
実施例 ２
実施例１においてSMの代りにメタクリル酸15
ｇを用いた以外は同様に行つた。
実施例 ３
実施例１において、SMの代りにＮ−フエニル
マレイミド15ｇを用いた以外は同様に行つた。
実施例 ４
実施例１と同様のオートクレーブに窒素ガスを
吹き込みながら第５表の物質を添加した。[Table] The polymer emulsion obtained in this way is Example 1
The same treatment as above was performed and the physical properties were measured. Example 2 Methacrylic acid 15 was used instead of SM in Example 1.
The same procedure was carried out except that g was used. Example 3 The same procedure as in Example 1 was carried out except that 15 g of N-phenylmaleimide was used instead of SM. Example 4 The substances listed in Table 5 were added to an autoclave similar to Example 1 while blowing nitrogen gas.
【表】【table】
【表】
重合法は過硫酸カリウム１％水溶液20mlを添加
した直後、すなわち重合開始直後よりANを毎時
約5.43ｇの割合で総計38ｇを７時間かけて重合系
に添加した以外は実施例１と同様の操作を行なつ
た。[Table] The polymerization method was the same as Example 1 except that AN was added to the polymerization system at a rate of about 5.43 g per hour over a period of 7 hours immediately after adding 20 ml of a 1% potassium persulfate aqueous solution, that is, immediately after the start of polymerization. A similar operation was performed.
【表】
このようにして得られた重合乳化液は実施例１
と同様の処理を行ない物性を測定した。[Table] The polymer emulsion obtained in this way is Example 1
The same treatment as above was performed and the physical properties were measured.
【表】【table】
【表】
比較例 ２
実施例１と同様のオートクレーブに窒素ガスを
吹き込みながら第３表の物質を添加した。重合法
は、重合開始後はANの添加を実施せずに、その
まま重合を10時間続け、10時間経過したとき停止
させた以外は実施例１と同様の操作を行なつた。
重合結果を第８表に示す。このようにして得ら
れた重合液の最終重合率は90％に達せず、この重
合は工業的製造としては不利であることがわか
る。
ここで単離した共重合体の色相は良好であつ
た。[Table] Comparative Example 2 The substances shown in Table 3 were added to an autoclave similar to Example 1 while blowing nitrogen gas. The polymerization method was carried out in the same manner as in Example 1, except that after the start of the polymerization, AN was not added, the polymerization was continued for 10 hours, and then stopped after 10 hours. The polymerization results are shown in Table 8. The final polymerization rate of the polymerization solution thus obtained did not reach 90%, indicating that this polymerization is disadvantageous for industrial production. The copolymer isolated here had a good hue.
Claims (1)
ビニル単量体15〜30重量％およびこれらと共重合
可能なビニル単量体０〜20重量％からなる単量体
を水性乳化重合して共重合体を製造する方法にお
いて、α−メチルスチレンはその全量を重合開始
時に存在させ、シアン化ビニル単量体はその一部
を重合開始時に存在させて重合を開始し、重合開
始から重合終了するまでの間に残りのシアン化ビ
ニル単量体をα−メチルスチレンの消費速度より
実質的に遅い速度で重合系に添加し、しかも重合
が実質的に終了するまでの間、重合系中の未反応
単量体の組成比がシアン化ビニル単量体のモル数
に対し、α−メチルスチレンおよび前記共重合可
能なビニル単量体の合計モル数を1.3〜３倍とす
るように保持して重合を実質的に完結させること
を特徴とする共重合体の製法。 ２ シアン化ビニル単量体がアクリロニトリルお
よび／またはメタクリロニトリルである特許請求
の範囲第１項記載の共重合体の製法。 ３ 共重合可能なビニル単量体がα−メチルスチ
レン以外の芳香族ビニル単量体、アセナフチレ
ン、フマロニトリル、マレイミド、Ｎ−置換マレ
イミド、メタクリル酸、アクリル酸、メタクリル
酸エステルおよびアクリル酸エステルより選ばれ
た１種以上である特許請求の範囲第１項記載の共
重合体の製法。[Claims] 1 Monomers consisting of 65 to 80% by weight of α-methylstyrene, 15 to 30% by weight of vinyl cyanide monomer, and 0 to 20% by weight of vinyl monomer copolymerizable with these. In the method of producing a copolymer by aqueous emulsion polymerization, the entire amount of α-methylstyrene is present at the beginning of polymerization, and a portion of the vinyl cyanide monomer is present at the beginning of polymerization to initiate polymerization, The remaining vinyl cyanide monomer is added to the polymerization system at a rate substantially slower than the consumption rate of α-methylstyrene during the period from the start of polymerization to the end of polymerization, and until the polymerization is substantially completed. , the composition ratio of unreacted monomers in the polymerization system is such that the total number of moles of α-methylstyrene and the copolymerizable vinyl monomer is 1.3 to 3 times the number of moles of vinyl cyanide monomer. A method for producing a copolymer, which comprises holding the copolymer in such a manner that the polymerization is substantially completed. 2. The method for producing a copolymer according to claim 1, wherein the vinyl cyanide monomer is acrylonitrile and/or methacrylonitrile. 3. The copolymerizable vinyl monomer is selected from aromatic vinyl monomers other than α-methylstyrene, acenaphthylene, fumaronitrile, maleimide, N-substituted maleimide, methacrylic acid, acrylic acid, methacrylic ester, and acrylic ester. A method for producing a copolymer according to claim 1, wherein the copolymer is one or more kinds of copolymers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP414280A JPS56103211A (en) | 1980-01-18 | 1980-01-18 | Preparation of copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP414280A JPS56103211A (en) | 1980-01-18 | 1980-01-18 | Preparation of copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56103211A JPS56103211A (en) | 1981-08-18 |
| JPH0124805B2 true JPH0124805B2 (en) | 1989-05-15 |
Family
ID=11576521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP414280A Granted JPS56103211A (en) | 1980-01-18 | 1980-01-18 | Preparation of copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56103211A (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5861108A (en) * | 1981-10-06 | 1983-04-12 | Kanegafuchi Chem Ind Co Ltd | Thermoplastic resin and its preparation |
| JPS5986613A (en) * | 1982-11-10 | 1984-05-18 | Ube Saikon Kk | Production of alpha-methylstyrene copolymer |
| JPS60248760A (en) * | 1984-05-23 | 1985-12-09 | Kanegafuchi Chem Ind Co Ltd | Heat-resistant and impact-resistant resin composition |
| JPH0699492B2 (en) * | 1984-06-05 | 1994-12-07 | 日本合成ゴム株式会社 | Method for manufacturing heat resistant resin |
| US4659790A (en) * | 1984-06-05 | 1987-04-21 | Japan Synthetic Rubber Co., Ltd. | Heat-resistant copolymer of alpha-methylstyrene and acrylonitrile, process for preparing the same, and thermoplastic resin composition containing the same |
| DE3431194A1 (en) * | 1984-08-24 | 1986-03-06 | Bayer Ag, 5090 Leverkusen | COPOLYMERISATE MADE OF (DELTA) METHYL STYRENE AND ACRYLNITRILE |
| JPS61155409A (en) * | 1984-12-28 | 1986-07-15 | Mitsubishi Rayon Co Ltd | Productin of alpha-alkyl-substituted aromatic vinyl copolymer |
| JPS61296011A (en) * | 1985-06-24 | 1986-12-26 | Japan Synthetic Rubber Co Ltd | Production of maleimide based copolymer |
| JPS6399508U (en) * | 1986-12-18 | 1988-06-28 | ||
| US6153712A (en) * | 1996-06-03 | 2000-11-28 | Nippon Shokubai Co., Ltd. | Thermoplastic copolymer and process for the production thereof |
| JP5164557B2 (en) * | 2007-12-26 | 2013-03-21 | テクノポリマー株式会社 | Thermoplastic resin composition and molded article |
| JP5242154B2 (en) * | 2007-12-26 | 2013-07-24 | テクノポリマー株式会社 | α-methylstyrene copolymer and process for producing the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4920074A (en) * | 1972-06-16 | 1974-02-22 | ||
| JPS5465756A (en) * | 1977-11-05 | 1979-05-26 | Mitsubishi Monsanto Chem Co | Resin composition having improved releasability containing glass fiber |
| JPS54103456A (en) * | 1978-01-31 | 1979-08-14 | Sumitomo Naugatuck Co Ltd | Thermoplastic resin composition having improved thermal cycle properties and metallized article |
| JPS5578007A (en) * | 1978-12-06 | 1980-06-12 | Sumitomo Naugatuck Co Ltd | Preparation of thermoplastic resin |
-
1980
- 1980-01-18 JP JP414280A patent/JPS56103211A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4920074A (en) * | 1972-06-16 | 1974-02-22 | ||
| JPS5465756A (en) * | 1977-11-05 | 1979-05-26 | Mitsubishi Monsanto Chem Co | Resin composition having improved releasability containing glass fiber |
| JPS54103456A (en) * | 1978-01-31 | 1979-08-14 | Sumitomo Naugatuck Co Ltd | Thermoplastic resin composition having improved thermal cycle properties and metallized article |
| JPS5578007A (en) * | 1978-12-06 | 1980-06-12 | Sumitomo Naugatuck Co Ltd | Preparation of thermoplastic resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56103211A (en) | 1981-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0124805B2 (en) | ||
| US2746943A (en) | Polymer compositions and methods for producing the same | |
| CA1049175A (en) | Styrene-butadiene copolymer latices containing carboxyl groups | |
| US4623678A (en) | Method for shear coagulation of latex resins | |
| US4427832A (en) | Thermoplastic resin compositions | |
| JP3137752B2 (en) | Method for producing resin for toner | |
| JPS6239173B2 (en) | ||
| JPS6261048B2 (en) | ||
| JPS61155416A (en) | Thermoplastic molding composition having high notch impact strength | |
| MXPA02008381A (en) | Method for producing caoutchouc particles. | |
| JP2701245B2 (en) | Thermoplastic mixture | |
| US2775567A (en) | Method of preparing dyeable copolymers | |
| KR100419230B1 (en) | Manufacturing method of thermoplastic resin with excellent whiteness and impact resistance | |
| US3655828A (en) | Process for preparing a polymer composition having improved gloss and color | |
| KR940011156B1 (en) | Process for producing a heat resistant copolymer | |
| MXPA03000461A (en) | Agglomeratable rubber latex. | |
| KR100188529B1 (en) | The preparation of thermoplastic resin composition having high glossness and high impact strength at low temperature | |
| JPS6321682B2 (en) | ||
| JPS6328461B2 (en) | ||
| SU439494A1 (en) | Method for producing latex | |
| JPH0580935B2 (en) | ||
| JPS63189401A (en) | Production of maleimide copolymer | |
| US4035564A (en) | Polymerization process for producing polychloroprene particles | |
| KR19980029660A (en) | Method for producing a thermoplastic resin composition excellent in natural color and impact resistance. | |
| JPH075685B2 (en) | Method for producing nitrile copolymer |