JPH03111405A - Production of low molecular weight styrene resin - Google Patents
Production of low molecular weight styrene resinInfo
- Publication number
- JPH03111405A JPH03111405A JP24933889A JP24933889A JPH03111405A JP H03111405 A JPH03111405 A JP H03111405A JP 24933889 A JP24933889 A JP 24933889A JP 24933889 A JP24933889 A JP 24933889A JP H03111405 A JPH03111405 A JP H03111405A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- molecular weight
- low molecular
- styrene
- chain transfer
- 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.)
- Pending
Links
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229920005989 resin Polymers 0.000 title abstract description 4
- 239000011347 resin Substances 0.000 title abstract description 4
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 6
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 230000000379 polymerizing effect Effects 0.000 claims abstract 2
- 229920001890 Novodur Polymers 0.000 claims description 6
- 238000012719 thermal polymerization Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 abstract description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 abstract 1
- 239000000539 dimer Substances 0.000 abstract 1
- 239000003999 initiator Substances 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000003505 polymerization initiator Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003708 ampul Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 1
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 1
- ZOKCNEIWFQCSCM-UHFFFAOYSA-N (2-methyl-4-phenylpent-4-en-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)CC(=C)C1=CC=CC=C1 ZOKCNEIWFQCSCM-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 1
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 description 1
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 1
- 229930006722 beta-pinene Natural products 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 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
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 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
- 229920002223 polystyrene Polymers 0.000 description 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 150000003505 terpenes Chemical class 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、低分子量スチレン系樹脂の製造方法に関する
。低分子量スチレン系樹脂は電子写真用のトナー、ホッ
トメルト型コーティング剤の基剤、顔料分散剤、樹脂改
質剤、タッキファイヤ−などに用いられる。又流動性の
よい成形用スチレン系樹脂としても用いられる。Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for producing a low molecular weight styrenic resin. It is used as a dispersant, resin modifier, tackifier, etc. It is also used as a styrene resin for molding with good fluidity.
〈従来の技術〉
従来低分子量スチレン系樹脂を製造する方法としては、
原料モノマーを比較的低温分解性の重合開始剤を多量に
用いて重合させる方法（特公昭５６−３４１６３号公報
）、溶剤存在下で溶液重合させる方法（特開昭６３−２
７３６０６）などが知られている。<Conventional technology> Conventional methods for producing low molecular weight styrenic resins include:
A method in which raw material monomers are polymerized using a large amount of a relatively low-temperature decomposable polymerization initiator (Japanese Patent Publication No. 56-34163), a method in which solution polymerization is carried out in the presence of a solvent (Japanese Patent Publication No. 63-2
73606) are known.
〈発明が解決しようとする課題〉 前記従来法は夫々法のような問題点があった。<Problem that the invention seeks to solve> Each of the above conventional methods has the same problems.
即ち特公昭５６−３４１６３号公報に示された方法は多
量の重合開始剤を必要とし経済的に不利であり、又重合
熱のコントロールが難しいという難点があった。又特開
昭６３−２７３６０６号公報に示された方法は溶媒除去
の操作が必要であり経済的に不利である。That is, the method disclosed in Japanese Patent Publication No. 56-34163 requires a large amount of polymerization initiator, which is economically disadvantageous, and also has the disadvantage that it is difficult to control the polymerization heat. Furthermore, the method disclosed in Japanese Patent Application Laid-Open No. 63-273606 requires an operation for removing the solvent, which is economically disadvantageous.
又熱重合で分子量を低下させるためにはできるだけ高温
にする必要があるが、高温では重合速度が大きくなりす
ぎ反応の制御が容易ではない。Furthermore, in order to lower the molecular weight by thermal polymerization, it is necessary to raise the temperature as high as possible, but at high temperatures the polymerization rate becomes too high and it is not easy to control the reaction.
〈課題を解決するための手段〉
本発明者らは、上記の従来法に比し優れた低分子量スチ
レン系樹脂の製造法を開発する目的で長期に亘って研究
した結果、原料単量体を連鎖移動剤の存在下で熱重合さ
せることにより低分子量の重合体を経済的に得ることを
見出して本発明を完成した。<Means for Solving the Problems> As a result of long-term research aimed at developing a method for producing low molecular weight styrenic resins that is superior to the conventional methods described above, the present inventors have found that the raw material monomer The present invention was completed by discovering that a low molecular weight polymer can be obtained economically by thermal polymerization in the presence of a chain transfer agent.
即ち本発明は、スチレン単量体単独、又はそれと共重合
可能なビニル単量体との混合物を重合させる際に、連鎖
移動剤の存在下１２０〜２２０℃の条件下で熱重合させ
ることを特徴とする低分子量スチレン系樹脂の製造方法
に関する。That is, the present invention is characterized in that when styrene monomer alone or a mixture of styrene monomer and a vinyl monomer copolymerizable with it is polymerized, thermal polymerization is carried out under conditions of 120 to 220°C in the presence of a chain transfer agent. The present invention relates to a method for producing a low molecular weight styrenic resin.
本発明に用いられる重合用原料単層体はスチレン単独、
或いはそれと共重合可能なビニル単量体との混合物であ
り、スチレンと共重合可能なビニル単量体としては、た
とえばアクリル酸メチル、アクリル酸エチル、アクリル
酸ブチル、アクリル酸オクチルなどのアクリル酸エステ
ル類、メタクリル酸メチル、メタクリル酸エチル、メタ
クリル酸ブチル、メタクリル酸オクチルなどのメタクリ
ル酸エステル類、アクリロニトリル等である。The polymerization raw material monolayer used in the present invention is styrene alone,
Alternatively, it is a mixture with a vinyl monomer copolymerizable with styrene. Examples of vinyl monomers copolymerizable with styrene include acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and octyl acrylate. methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, and octyl methacrylate, and acrylonitrile.
そして重合用原料単量体中スチレンは少なくとも２０重
量％、通常４０重量％以上であることが必要である。The content of styrene in the raw material monomer for polymerization must be at least 20% by weight, usually 40% by weight or more.
本発明方法においては連鎖移動剤を用いることに特徴が
ある。この連鎖移動剤を用いることにより、熱重合であ
るにもが＼わらず、重合速度が低下するのである。The method of the present invention is characterized by the use of a chain transfer agent. By using this chain transfer agent, the polymerization rate is reduced even though the polymerization is thermal.
本発明において使用される連鎖移動剤はα−メチルスチ
レンダイマー（２，４−ジフェニル−４−メチル−１−
ペンテン）またはターピノーレン、ミルセン、リモネン
、α−ピネン、β−ピネン、などの各種テルペノイド類
、ｎ−ドデシルメルカプタンなどメルカプタン類などで
ある。その中でα−メチルスチレンダイマー及びタービ
ノーレンが分子量低下の効果が太き（若干重合速度を低
下させる効果も有する。The chain transfer agent used in the present invention is α-methylstyrene dimer (2,4-diphenyl-4-methyl-1-
pentene) or various terpenoids such as terpinolene, myrcene, limonene, α-pinene, β-pinene, and mercaptans such as n-dodecylmercaptan. Among them, α-methylstyrene dimer and turbinolene have the greatest effect of lowering the molecular weight (they also have the effect of slightly lowering the polymerization rate).
又、メルカプタン類は重合初期においては低分子量化の
効果は大きいが中期以後では効果が小さ（なる傾向にあ
る。連鎖移動剤の使用量は原料単量体に対して０．０５
〜１５重量％である。In addition, mercaptans have a large effect on lowering the molecular weight in the early stage of polymerization, but the effect tends to be small after the middle stage.The amount of chain transfer agent used is 0.05% of the raw material monomer.
~15% by weight.
０．０５％重量未満ではその効果が小さく、又１５重量
％を越えてその効果の向上は小さく経済的でない。If it is less than 0.05% by weight, the effect is small, and if it exceeds 15% by weight, the improvement in the effect is small and is not economical.
本発明の方法は、基本的には重合開始剤を用いない熱重
合であるが、重合初期において重合速度を促進するため
の重合開始剤をいわゆるキック剤として用いてもよい。Although the method of the present invention is basically thermal polymerization without using a polymerization initiator, a polymerization initiator may be used as a so-called kicking agent to accelerate the polymerization rate at the initial stage of polymerization.
その場合、重合開始剤の濃度は重合の初期（重合転化率
２０％以下）において実質的に消失する条件で行なう。In this case, the concentration of the polymerization initiator is set such that it substantially disappears at the initial stage of polymerization (polymerization conversion rate of 20% or less).
又重合転化率７０％以上においては重合を完結させる目
的で重合開始剤を追い触媒として使用してもよい。Further, at a polymerization conversion rate of 70% or more, a polymerization initiator may be used as a follower catalyst for the purpose of completing the polymerization.
本発明で用いられる重合温度は１２０℃〜２２０℃であ
り、好ましくは１３０℃〜１８０℃である。１２０℃未
満では重合速度が小さく、又２２０℃を越えると反応の
制御が困難である。The polymerization temperature used in the present invention is 120°C to 220°C, preferably 130°C to 180°C. If the temperature is lower than 120°C, the polymerization rate will be low, and if it exceeds 220°C, it will be difficult to control the reaction.
（発明の効果〉
特定の条件で連鎖移動剤を用いる本発明は、以下に述べ
る特徴を有している。(Effects of the Invention) The present invention, which uses a chain transfer agent under specific conditions, has the following features.
即ち本発明により、多量の溶剤あるいは重合開始剤を必
要としないで、低分子量の重合体を経済的に製造するこ
とができる。That is, according to the present invention, low molecular weight polymers can be economically produced without requiring large amounts of solvents or polymerization initiators.
〈実 施 例、比 較 例〉
以下、本発明を実施例、比較例により具体的に説明する
。尚、例中に用いる連鎖移動剤の略号は以下の化合物を
意味する。<Examples and Comparative Examples> The present invention will be specifically explained below using Examples and Comparative Examples. In addition, the abbreviations of chain transfer agents used in the examples mean the following compounds.
ＭＳＤ；α−メチルスチレンダイマー（日本油脂製、ノ
フマーＭＳＤ）
Ｔ Ｐ；タービノーレン（日本油脂製、ノフマーＴＰ）
ＮＤＭ；ｎ−ドデシルメルカプタン
重合により得られた生成物の分子量はすべてゲルパーミ
ネーションクロマトグラフィー（ＧＰＣ）を用いポリス
チレン換算で測定した。MSD: α-methylstyrene dimer (Nofumar MSD, NOF Corporation) TP: Turbinolene (Nofumar TP, NOF Corporation) NDM: The molecular weight of the product obtained by n-dodecylmercaptan polymerization was determined by gel permeation chromatography ( GPC) and measured in terms of polystyrene.
Ｍｎは数平均分子量を表わしＭｗは重合平均分子量を表
わす。重合転化率はガスクロマトグラフィーによる残存
モノマーの量より算出した。Mn represents the number average molecular weight, and Mw represents the polymerization average molecular weight. The polymerization conversion rate was calculated from the amount of residual monomer determined by gas chromatography.
実施例 １
容量２０ｍｆｆ１のガラスアンプルにスチレン１０ｇ及
びＭＳＤｏ、５ｇを入れ窒素置換した後溶融封管した。Example 1 10 g of styrene and 5 g of MSDo were placed in a glass ampoule with a capacity of 20 mff1, and after purging with nitrogen, the ampoule was melt-sealed.
それを恒温油槽中で１６０℃で４時間、重合させた。重
合物を分析した結果、重合転化率は８３％、分子量はＭ
ｎ ＝ １４，０００、Ｍ ｗ ＝ ２８．０００、
Ｍｗ／Ｍｎ＝２．０であった。It was polymerized in a constant temperature oil bath at 160°C for 4 hours. As a result of analyzing the polymer, the polymerization conversion rate was 83%, and the molecular weight was M.
n = 14,000, Mw = 28.000,
Mw/Mn=2.0.
実施例２〜１１
実施例１と同じアンプルを用いスチレン１０ｇと連鎖移
動剤として第１表に示したものを使用し、第１表に示し
た重合条件で重合した後、重合物を分析した。その結果
は第１表の通りであった。Examples 2 to 11 Using the same ampoule as in Example 1 and using 10 g of styrene and the chain transfer agent shown in Table 1, polymerization was carried out under the polymerization conditions shown in Table 1, and then the polymerized product was analyzed. The results were as shown in Table 1.
比較例 １〜５
実施例１と同じアンプルを用いスチレン１０ｇを入れ、
連鎖移動剤を用いないで第２表に示した重合条件でを重
合した後、重合物を分析した。その結果は第２表に示す
。Comparative Examples 1 to 5 Using the same ampoule as in Example 1, add 10 g of styrene,
After polymerization under the polymerization conditions shown in Table 2 without using a chain transfer agent, the polymer was analyzed. The results are shown in Table 2.
実施例１２
実施例１と同じアンプルを用いスチレン５ｇとメタクリ
ル酸メチル５ｇ及びＭＳＤｏ、２ｇを入れ窒素置換した
後溶融封管した。それを恒温油槽中で１４０℃で１０時
間、重合させた。重合物を分析した結果、重合転化率は
９４％、分子量はＭｎ＝２８、０００、Ｍ ｗ ＝ ６
４．０００、Ｍｗ／Ｍｎ＝２．３であった。Example 12 Using the same ampoule as in Example 1, 5 g of styrene, 5 g of methyl methacrylate, and 2 g of MSDo were put therein, and after purging with nitrogen, the tube was melt-sealed. It was polymerized in a constant temperature oil bath at 140°C for 10 hours. As a result of analyzing the polymer, the polymerization conversion rate was 94%, the molecular weight was Mn = 28,000, and Mw = 6.
4.000, Mw/Mn=2.3.
比較例６
実施例１２においてＭＳＤを用いないで実施例１１と同
じ重合を行なった。その結果は、重合転化率は９６％、
分子量はＭ 、ｎ ＝ １３０，０００ 、 Ｍ ｗ
＝２８０．０００ 、 Ｍｗ／Ｍｎ＝２．２であった。Comparative Example 6 In Example 12, the same polymerization as in Example 11 was carried out without using MSD. The results showed that the polymerization conversion rate was 96%.
The molecular weight is M, n = 130,000, M w
=280.000, Mw/Mn=2.2.
実施例１３
実施例１と同じアンプルを用いスチレン８ｇとアクリル
酸ブチル２ｇ及びＭＳＤｏ、５ｇを入れ窒素置換した後
溶融封管した。それを恒温油槽中で１２０〜１８０℃に
昇温させながら５時間、重合させた。重合物を分析した
結果、重合転化率は９１％、分子量はＭ ｎ ＝ １１
．０００、Ｍｗ ＝２０，０００． Ｍｗ／Ｍｎ＝１．
８であった。Example 13 Using the same ampoule as in Example 1, 8 g of styrene, 2 g of butyl acrylate, and 5 g of MSDo were put therein, and after purging with nitrogen, the tube was melt-sealed. This was polymerized for 5 hours while raising the temperature to 120 to 180°C in a constant temperature oil bath. As a result of analyzing the polymer, the polymerization conversion rate was 91%, and the molecular weight was M n = 11.
．． 000, Mw =20,000. Mw/Mn=1.
It was 8.
比較例７
実施例１３においてＭＳＤを用いないで実施例１２と同
じ重合を行なった。その結果は、重合転化率は９３％、
分子量はＭ ｎ ＝ ９５．０００． Ｍ ｗ ＝１８
０．０００ 、 Ｍ ｗ／ Ｍ ｎ ＝ １．９であっ
た。Comparative Example 7 In Example 13, the same polymerization as in Example 12 was carried out without using MSD. The results showed that the polymerization conversion rate was 93%.
The molecular weight is M n = 95.000. M w =18
0.000, Mw/Mn=1.9.
脂１１ｊく
同一の重合条件である実施例２と比較例１、実施例３と
比較例２、実施例６．７．１０．１１と比較例３、実施
例４，８と比較例４、実施例５．９と比較例５、実施例
１２と比較例６、実施例１３と比較例７とを比較すれば
、重合に際して連鎖移動剤を存在させることにより低分
子量のスチレン系樹脂を得ることができるという本発明
の効果は明らかである。Example 2 and Comparative Example 1, Example 3 and Comparative Example 2, Example 6.7.10.11 and Comparative Example 3, Examples 4 and 8 and Comparative Example 4, and the same polymerization conditions. Comparing Example 5.9 and Comparative Example 5, Example 12 and Comparative Example 6, and Example 13 and Comparative Example 7, it is found that a low molecular weight styrenic resin can be obtained by the presence of a chain transfer agent during polymerization. The effect of the present invention is obvious.
Claims (1)
体との混合物を重合させる際に、連鎖移動剤の存在下１
２０〜２２０℃の条件下で熱重合させることを特徴とす
る低分子量スチレン系樹脂の製造方法。When polymerizing styrene monomer alone or a mixture of styrene monomer and copolymerizable vinyl monomer, 1 in the presence of a chain transfer agent.
A method for producing a low molecular weight styrenic resin, characterized by carrying out thermal polymerization under conditions of 20 to 220°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24933889A JPH03111405A (en) | 1989-09-27 | 1989-09-27 | Production of low molecular weight styrene resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24933889A JPH03111405A (en) | 1989-09-27 | 1989-09-27 | Production of low molecular weight styrene resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03111405A true JPH03111405A (en) | 1991-05-13 |
Family
ID=17191534
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24933889A Pending JPH03111405A (en) | 1989-09-27 | 1989-09-27 | Production of low molecular weight styrene resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03111405A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998016561A1 (en) * | 1996-10-11 | 1998-04-23 | Nippon Carbide Kogyo Kabushiki Kaisha | Polymer obtained by emulsion polymerization method |
| JP2002091067A (en) * | 2000-09-12 | 2002-03-27 | Konica Corp | Electrostatic charge image developing toner and method for manufacturing electrostatic charge image developing toner |
-
1989
- 1989-09-27 JP JP24933889A patent/JPH03111405A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998016561A1 (en) * | 1996-10-11 | 1998-04-23 | Nippon Carbide Kogyo Kabushiki Kaisha | Polymer obtained by emulsion polymerization method |
| US6197907B1 (en) | 1996-10-11 | 2001-03-06 | Nippon Carbide Kogyo Kabushiki Kaisha | Polymer obtained by emulsion polymerization method |
| JP3390991B2 (en) * | 1996-10-11 | 2003-03-31 | 日本カーバイド工業株式会社 | Polymer obtained by emulsion polymerization method |
| JP2002091067A (en) * | 2000-09-12 | 2002-03-27 | Konica Corp | Electrostatic charge image developing toner and method for manufacturing electrostatic charge image developing toner |
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