JPH03143902A - Polymerization of vinyl monomer - Google Patents
Polymerization of vinyl monomerInfo
- Publication number
- JPH03143902A JPH03143902A JP28172389A JP28172389A JPH03143902A JP H03143902 A JPH03143902 A JP H03143902A JP 28172389 A JP28172389 A JP 28172389A JP 28172389 A JP28172389 A JP 28172389A JP H03143902 A JPH03143902 A JP H03143902A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- vinyl monomer
- polymer
- mixture
- polymerizing
- 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
- 239000000178 monomer Substances 0.000 title claims abstract description 25
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 title description 40
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 150000001451 organic peroxides Chemical class 0.000 abstract description 6
- NXOILCGRBHWREZ-UHFFFAOYSA-N (5-acetylperoxy-2,5-dimethylhexan-2-yl) ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)CCC(C)(C)OOC(C)=O NXOILCGRBHWREZ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 5
- 229920005990 polystyrene resin Polymers 0.000 description 5
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-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
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- UYKQBCCHYMNDCF-UHFFFAOYSA-N ethyl hydroxy carbonate Chemical compound CCOC(=O)OO UYKQBCCHYMNDCF-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- 235000019731 tricalcium phosphate Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NPZMPTRRBKWDBG-UHFFFAOYSA-N (2,5-dimethyl-5-propanoylperoxyhexan-2-yl) propaneperoxoate Chemical compound CCC(=O)OOC(C)(C)CCC(C)(C)OOC(=O)CC NPZMPTRRBKWDBG-UHFFFAOYSA-N 0.000 description 1
- -1 2 ,5-dimethyl-2,5-di(butyrylperoxy)hexane Chemical compound 0.000 description 1
- HFGHRUCCKVYFKL-UHFFFAOYSA-N 4-ethoxy-2-piperazin-1-yl-7-pyridin-4-yl-5h-pyrimido[5,4-b]indole Chemical compound C1=C2NC=3C(OCC)=NC(N4CCNCC4)=NC=3C2=CC=C1C1=CC=NC=C1 HFGHRUCCKVYFKL-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- WDENQIQQYWYTPO-IBGZPJMESA-N acalabrutinib Chemical compound CC#CC(=O)N1CCC[C@H]1C1=NC(C=2C=CC(=CC=2)C(=O)NC=2N=CC=CC=2)=C2N1C=CN=C2N WDENQIQQYWYTPO-IBGZPJMESA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000021152 breakfast Nutrition 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- WHLQSCBTLNMDDR-UHFFFAOYSA-N butan-2-yl hydroxy carbonate Chemical compound CCC(C)OC(=O)OO WHLQSCBTLNMDDR-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JSKZWIGBDHYSGI-UCSXVCBISA-L disodium;(6r,7r)-7-[[(2e)-2-(2-amino-1,3-thiazol-4-yl)-2-[1-[2-(3,4-dihydroxybenzoyl)hydrazinyl]-2-methyl-1-oxopropan-2-yl]oxyiminoacetyl]amino]-3-[(2-carboxylato-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-yl)sulfanylmethyl]-8-oxo-5-thia-1-azabicyclo[4.2. Chemical compound [Na+].[Na+].N([C@H]1[C@@H]2N(C1=O)C(=C(CS2)CSC1=CC(=NC2=NC(=NN21)C([O-])=O)C)C([O-])=O)C(=O)C(\C=1N=C(N)SC=1)=N\OC(C)(C)C(=O)NNC(=O)C1=CC=C(O)C(O)=C1 JSKZWIGBDHYSGI-UCSXVCBISA-L 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- JPYSCRRXQGAHBU-UHFFFAOYSA-N hydroxy methyl carbonate Chemical compound COC(=O)OO JPYSCRRXQGAHBU-UHFFFAOYSA-N 0.000 description 1
- ZSDPJPHNMOTSQZ-UHFFFAOYSA-N hydroxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OO ZSDPJPHNMOTSQZ-UHFFFAOYSA-N 0.000 description 1
- IBUDOENFVGHGFQ-UHFFFAOYSA-N hydroxy propyl carbonate Chemical compound CCCOC(=O)OO IBUDOENFVGHGFQ-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野ン
本発明は、特定の有機過酸化物を重合開始剤として用い
るビニル系単量体の２４、塊状或いは溶液重合プロセス
でのホモ重合もしくは共電合方？去に関するものであり
、特に、機械的強度に優れる重合体を経済的に製造する
方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Fields> The present invention is directed to homopolymerization or copolymerization of vinyl monomers using specific organic peroxides as polymerization initiators, in bulk or solution polymerization processes. Match? In particular, the present invention relates to a method for economically producing a polymer having excellent mechanical strength.
〈従来の技術〉
ビニル単量体の重合によって得られる重合体の機械的強
度は、重合体の分子量に比例することが知られている一
１ｌ！ｎ甑 ４ヱ爵＾（＋卦／ント１）−件す。<Prior Art> It is known that the mechanical strength of a polymer obtained by polymerizing vinyl monomers is proportional to the molecular weight of the polymer. n 甑 4ヱ士＾(+卦／NT 1) - す.
重合体成形物の引張り強度、曲げ強度及び衝撃６度等の
機械的強度は強くなる。従って、各種ビ。The mechanical strength of the polymer molded product, such as tensile strength, bending strength, and 6 degree impact, becomes stronger. Therefore, various bis.
ル単量体より高分子量の重合体を製造する方法番ついて
検討されている。Methods for producing polymers with higher molecular weight than monomers are being studied.
例えば、スチレンの高分子量重合体を得る方ンとして次
のような方法が知られている。即ち、イ）重合時に架橋
剤を併用し、生成する重合体ｎを架橋することによって
高分子量化する方法。For example, the following method is known to obtain a high molecular weight polymer of styrene. That is, a) a method in which a crosslinking agent is used in combination during polymerization to crosslink the resulting polymer n to increase its molecular weight.
口）重合速度と生成する重合体の数平均分子ｍ。) Polymerization rate and number average molecule m of the produced polymer.
関係は、近代工業化学、第１６巻、高分子工業イ：学、
Ｉ上、第８０頁（朝食書店）に示されるよ亡に、次式に
よって表わされる。Related: Modern Industrial Chemistry, Volume 16, Polymer Industry: Science,
I, page 80 (Breakfast Bookstore), it is expressed by the following formula.
１／Ｐｎ＝ＡＲ＋ＣＭ Ｐｎ ： 数平均分子量 Ｒ： 全重合速度 Ａ及びＣＭ： 定数項 即ち重合速度と重合度の間には、反比例の関裔がある。1/Pn=AR+CM Pn: Number average molecular weight R: Total polymerization rate A and CM: Constant term That is, there is an inverse relationship between polymerization rate and degree of polymerization.
それ故、反応温度を下げたり、重合開虹剤の添加量を減
少させＲを小さくすることによってＰｎを大きくする方
法がある。Therefore, there is a method of increasing Pn by lowering the reaction temperature or decreasing the amount of polymerization rainbow opener added to decrease R.
〈発明が解決しようとする課題〉
前記イ）、口）の各方法には、次のような問題点がある
。即ち、イ）の方法の場合、得られた樹脂の流動性が悪
く、成形加工性に欠け、且つ成形品にフラッシュ現象や
フローマーク現象が発生し、物性を著しく低下させ好ま
しくない。<Problems to be Solved by the Invention> Each of the above methods (a) and (g) has the following problems. That is, in the case of the method (a), the obtained resin has poor fluidity and lacks moldability, and flash phenomena and flow mark phenomena occur in the molded product, which significantly deteriorates the physical properties, which is undesirable.
又、口）の方法では、重合速度を低下させるために単位
時間当たりの重合体収量が大きく低下し、経済的に有利
な方法でない。従って、速い重合速度、即ち、単位時間
当たりの重合体収量が多く、成形加工性の良い高分子量
体の製造法の開発が強く要望されていた。In addition, in the method (2), the polymer yield per unit time is greatly reduced due to the lowering of the polymerization rate, and it is not an economically advantageous method. Therefore, there has been a strong demand for the development of a method for producing polymers that have a high polymerization rate, that is, a large yield of polymer per unit time, and have good moldability.
〈課題を解決するための手段〉
かかる観点から、本発明者らは、種々研究を重ねた結果
、ビニル単量体の重合開始剤として下記の式（１）及び
式（ＩＩ）で表わされる有機過酸化物を用いることによ
って上記問題が解決されることを確認し、本発明を完成
した。<Means for Solving the Problems> From this point of view, the present inventors have conducted various studies and found that organic compounds represented by the following formulas (1) and (II) are used as polymerization initiators for vinyl monomers. The present invention was completed by confirming that the above problems could be solved by using peroxide.
（但し、
１
は、
炭素数１〜３の直鎖アルキル基
を示す）
（但し、Ｒ２ば、炭素数１〜４のアルキル基を示す）
即ち、本発明は、ビニル単量体単独、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、上記
式（１）及び式（ＩＩ）で表わされる有機過酸化物の少
なくとも１種を重合開始剤として使用することによって
、速い重合速度で成形加工性の良い高分子量体を得る重
合方法である。(However, 1 represents a linear alkyl group having 1 to 3 carbon atoms.) (However, R2 represents an alkyl group having 1 to 4 carbon atoms.) That is, the present invention is directed to vinyl monomers alone or together with vinyl monomers. When polymerizing a mixture with a copolymerizable vinyl monomer, rapid polymerization can be achieved by using at least one of the organic peroxides represented by the above formulas (1) and (II) as a polymerization initiator. This is a polymerization method that yields high-molecular weight materials with good moldability at a high speed.
上記一般式で示される重合開始剤として使用される有機
過酸化物としては２．５−ジメチル−２，５−ジ（アセ
チルパーオキシ）ヘキサン、２．５−ジメチル−２，５
−ジ（プロピオニルパーオキシ）ヘキサン、２，５−ジ
メチル−２゜５−ジ（ブチリルパーオキシ）ヘキサン、
２゜５−ジメチルヘキサン−２，５−ジ（メチルパーオ
キシカーボネート）、２．５−ジメチルヘキサン−２，
５−ジ（エチルパーオキシカーボネート）、２．５−ジ
メチルヘキサン−２，５−ジ（ｎ−プロピルパーオキシ
カーボネート）、２゜５−ジメチルヘキサン−２，５−
ジ（イソプロピルパーオキシカーボネート）、２．５−
ジメチルヘキサン−２，５−ジ（ｓｅｃ−ブチルパーオ
キシカーボネート）等を例示することができ、本発Ｒ日
し＋セＩＸアｍｒ＼ニレ−＋１．山渓ｌ＋し１イｊ斗
に■「為ば、スチレン、α−メチルスチレン、アクリロ
ニトリル、メタクリル酸メチル等があり、又、それらの
（共）重合時にゴム状重合体、例えばポリブタジェン、
スチレン−ブタジェン共重合体、エチレン−プロピレン
共重合体とを存在させても良い。Organic peroxides used as polymerization initiators represented by the above general formula include 2,5-dimethyl-2,5-di(acetylperoxy)hexane, 2,5-dimethyl-2,5
-di(propionylperoxy)hexane, 2,5-dimethyl-2゜5-di(butyrylperoxy)hexane,
2゜5-dimethylhexane-2,5-di(methylperoxycarbonate), 2.5-dimethylhexane-2,
5-di(ethyl peroxycarbonate), 2,5-dimethylhexane-2,5-di(n-propylperoxycarbonate), 2゜5-dimethylhexane-2,5-
Di(isopropyl peroxycarbonate), 2.5-
Dimethylhexane-2,5-di(sec-butylperoxycarbonate) and the like can be exemplified. Sankei l + Shi1 Ijto
``There are styrene, α-methylstyrene, acrylonitrile, methyl methacrylate, etc., and when they are (co)polymerized, rubbery polymers such as polybutadiene, etc.
A styrene-butadiene copolymer or an ethylene-propylene copolymer may also be present.
有機過酸化物はその内の少なくとも一種を用い、又その
使用量は、ビニル系単量体に対して０、ＯＩ〜０．５重
量％である。０．０１重量％未満では実質的な効果が少
なく、０．５重量％を超えると重合反応が速すぎ反応熱
の除去等の制御が困難で且つ高分子量体を得ることに難
がある。本発明の実施における重合方法は、懸濁、塊状
及び溶７夜のいずれの方法も採用できる。At least one of these organic peroxides is used, and the amount used is 0.0I to 0.5% by weight based on the vinyl monomer. If it is less than 0.01% by weight, there will be little substantial effect, and if it exceeds 0.5% by weight, the polymerization reaction will be too rapid, making it difficult to control the removal of reaction heat, etc., and making it difficult to obtain a high molecular weight product. As the polymerization method in carrying out the present invention, any of suspension, bulk and dissolution methods can be employed.
本発明の実施における重合温度は、通常８０℃以上１５
０℃以下である。８０℃未滴の温度では、高分子量を得
るには適するが、重合反応を完結するのに時間がかかり
、単位時間当たりの収量が低く経済的に好ましくない。The polymerization temperature in carrying out the present invention is usually 80°C or higher and 15°C.
The temperature is below 0°C. A temperature of 80° C. is suitable for obtaining a high molecular weight, but it takes time to complete the polymerization reaction and the yield per unit time is low, which is economically undesirable.
１５０℃を超える温度では、重合速度が著しく大きく
なり円滑な重合制御が難しく、又、所望する高分子量体
を得ることが困難である。If the temperature exceeds 150°C, the polymerization rate becomes extremely high, making it difficult to smoothly control the polymerization and also making it difficult to obtain the desired polymer.
〈発明の効果〉
以上述べたように前述の式（１）、（ｒｌ）で示される
有機過酸化物を重合開始剤として用いるビニル単量体の
（共）重合方法は、短時間に成形加工性の良い高分子量
体を製造することができ工業的に有用である。<Effects of the Invention> As described above, the method for (co)polymerizing vinyl monomers using the organic peroxides represented by formulas (1) and (rl) described above as polymerization initiators enables molding and processing in a short time. It can produce high molecular weight substances with good properties and is industrially useful.
〈実 施 例〉
次に本発明を実施例及び比較例により具体的に説明する
。尚例中に用いる重合開始剤の略号は以下の化合物を意
味する。<Examples> Next, the present invention will be specifically explained using Examples and Comparative Examples. The abbreviations of polymerization initiators used in the examples mean the following compounds.
２．５−Ａ ： ２，５−ジメチル−２，５−ジ（
アセチルパーオキシ）ヘキサン２．５−Ｂ ： ２
，５−ジメチル−２，５−ジ（ブチリルパーオキシ）ヘ
キサン２．５−Ｅ ： ２，５−ジメチルヘキサン
−２，５−ン（エチルパーオキシカーボネート）実施例
−１
容量７ｅのオートクレーブ中に純水２
ｋｇ、
第三
りん酸カルシウム１５ｇを加え、 １５０ｒｐｍで撹拌
し、次いでスチレン２．５ｋｇ、９８％純度の２゜５−
Ａ７．０ｇを加え、容器内をＮ２ガスで置換してから密
閉した。昇温しで１１０℃で４時間重合し、その後冷却
し、常法に従い中和、脱水、乾燥した。これをさらに押
出機により通常のペレット形状としてポリスチレン樹脂
とした。ポリスチレン樹脂の収量は、２．４５ｋｇで仕
込モノマーに対する収率は、９８．０％であった。又、
このポリスチレン樹脂１ｋｇを射出成形機により成形し
、試験片をつくり機械的強度等を測定した。結果を表−
１に示す。2.5-A: 2,5-dimethyl-2,5-di(
Acetylperoxy)hexane 2.5-B: 2
,5-dimethyl-2,5-di(butyrylperoxy)hexane 2.5-E: 2,5-dimethylhexane-2,5-one (ethylperoxycarbonate) Example-1 In an autoclave with a capacity of 7e Add 2 kg of pure water and 15 g of tribasic calcium phosphate, stir at 150 rpm, then add 2.5 kg of styrene and 98% pure 2°5-
7.0 g of A was added, the inside of the container was replaced with N2 gas, and then the container was sealed. Polymerization was carried out at 110° C. for 4 hours, followed by cooling, neutralization, dehydration, and drying according to conventional methods. This was further shaped into regular pellets using an extruder to produce polystyrene resin. The yield of polystyrene resin was 2.45 kg, and the yield based on the monomer charged was 98.0%. or,
1 kg of this polystyrene resin was molded using an injection molding machine, a test piece was made, and its mechanical strength and other properties were measured. Display the results -
Shown in 1.
３）メルトフローインデクサ−にて測定４）目視による
比較例−１
架橋剤としてジビニルベンゼン７．５ｇ添加し重合１ｍ
度１２０℃で３時間重合した以外は、実施例＝１に準じ
て重合及びベレット化した。得られたポリスチレン樹脂
の収量は、２．４６ｋｇで仕込モノマーに対する収率は
、９８．１％であった。又、実施例−１と同様にして、
試験片をつくり機械的強度等を測定した。結果を表−２
に示す。3) Measured with a melt flow indexer 4) Visual observation Comparative Example 1 Added 7.5 g of divinylbenzene as a crosslinking agent and polymerized 1 m
Polymerization and pelletization were carried out in the same manner as in Example 1, except that the polymerization was carried out at 120° C. for 3 hours. The yield of the obtained polystyrene resin was 2.46 kg, and the yield based on the monomer charged was 98.1%. Also, in the same manner as Example-1,
Test pieces were made and mechanical strength etc. were measured. Table 2 of the results
Shown below.
表−１と表−２の結果を比較すると明らかなように、架
橋剤を併用して得た高分子量体は、Ｍｌ値が小さく加工
性に欠け、且つ成形品にフラッシュ現象及びフローマー
ク現象が生じ、好ましくないことがわかる。As is clear from comparing the results in Table 1 and Table 2, the polymer obtained by using a crosslinking agent has a small Ml value, lacks processability, and causes flash and flow mark phenomena on molded products. This can be seen as undesirable.
実施例−２〜４
実施例−１の２．５−Ａの代わりに、表−３に示す重合
開始剤及び重合温度・時間を用いた以外は、実施例−１
に準じて重合を行なった。又、以後の試験片作成と機械
的強度等の測定も実施例−１に準じて行なった。結果を
表−４に示す。Examples-2 to 4 Example-1 except that the polymerization initiator and polymerization temperature and time shown in Table-3 were used instead of 2.5-A of Example-1.
Polymerization was carried out according to . In addition, subsequent preparation of test pieces and measurements of mechanical strength, etc., were conducted in accordance with Example-1. The results are shown in Table 4.
１）
０、 ０１ｍｏｌ／スチレン１ｋｇ使用実施例１とは譬
同様の物性の共重合体を得ることができた。1) Using 0.01 mol/1 kg of styrene A copolymer with physical properties similar to those in Example 1 could be obtained.
実施例−５
スチレン８０重量％とα−メチルスチレン２０重量％と
の混合物１ｋｇに重合開始剤として、９８％純度の２．
５−Ａ １．４ｇを溶解して調整した試料５ｍｆｆを内
径１２ｍｍのガラスアンプルに封入し、 １２０°Ｃで
重合を行なった。所定時間ごとにガラスアンプルを取り
出し、内容物をベンゼンに溶解させ、内部標準法による
ガスクロマトグラフィーによって未反応単量体を定量し
て重合転化率を算出した。Example-5 1 kg of a mixture of 80% by weight of styrene and 20% by weight of α-methylstyrene was added with 2.5% of purity as a polymerization initiator.
A sample of 5 mff prepared by dissolving 1.4 g of 5-A was sealed in a glass ampoule with an inner diameter of 12 mm, and polymerization was performed at 120°C. A glass ampoule was taken out at predetermined time intervals, the contents were dissolved in benzene, and unreacted monomers were quantified by gas chromatography using an internal standard method to calculate the polymerization conversion rate.
又、重合転化率が９８〜１００％となる重合体をつくり
、その物性を測定した。それらの結果を表−５及び表−
６に示す。In addition, a polymer with a polymerization conversion rate of 98 to 100% was prepared and its physical properties were measured. The results are shown in Table-5 and Table-
6.
ｉ二二二ｊΣ
比較例−２〜３
重合開始剤の使用量をｏ、 ｏｏｇ％、０．７０％とし
た以外は実施例５と同様に処理し、重合転化率、重合体
の物性を測定した。i222jΣ Comparative Examples-2 to 3 The same process as in Example 5 was carried out except that the amount of polymerization initiator used was o, oog%, 0.70%, and the polymerization conversion rate and physical properties of the polymer were measured. did.
前者の重合時間２時間後、後者の重合時間７時間後の共
重合体の重合転化率、重合体の諸物性を表７に示す。Table 7 shows the polymerization conversion rate of the copolymer and various physical properties of the copolymer after 2 hours of polymerization time in the former case and 7 hours after polymerization time in the latter case.
ｚＬ＝二二
表−６と表−７の結果から明らかなように、２．５−Ａ
添加量が０．０１重量％未満では、より高分子量体を得
ることはできるが重合を完結するのに長時間要し、経済
的でない。又、０．５重量％を超えた場合は重合は速や
かに完結するが機（酸強度に優れる重合体を得ることが
できない。zL=22As is clear from the results in Table-6 and Table-7, 2.5-A
If the amount added is less than 0.01% by weight, a higher molecular weight product can be obtained, but it takes a long time to complete the polymerization, which is not economical. If the amount exceeds 0.5% by weight, the polymerization will be completed quickly, but it will not be possible to obtain a polymer with excellent acid strength.
比較例−４〜５
従来から用いられる重合開始剤であるｔ−ブチルペルオ
キシベンゾエートを用い、単量体に対する添加量を０，
２０重量％、０．０１重量％にした以外実施例５と同様
に処理し、重合転化率、重合体の物性を測定した。前者
の重合時間５時間後、後者の重合時間７時間後の共重合
体の重合転化率、重合体の物性を表８に示す。Comparative Examples 4 to 5 Using t-butyl peroxybenzoate, which is a conventionally used polymerization initiator, the amount added to the monomer was 0,
The same treatment as in Example 5 was carried out except that the proportions were 20% by weight and 0.01% by weight, and the polymerization conversion rate and physical properties of the polymer were measured. Table 8 shows the polymerization conversion rate and physical properties of the copolymer after 5 hours of polymerization time for the former and 7 hours for the latter.
即ち比較例４では重合速度は早い高分子体は得られず、
又、比較例５では重合速度が遅く実用的ではない。That is, in Comparative Example 4, a polymer with a high polymerization rate could not be obtained;
Moreover, in Comparative Example 5, the polymerization rate is slow and is not practical.
実施例−６
冷却機、温度計、撹拌機を備えたフラスコ中にトルエン
１２０ ｇ、メタクリル酸メチル８０ｇ、２゜５− Ｉ
Ｏ，４ｇ （０，００１モル）を仕込み９０℃で８時
間重合を行なった。得られたポリマー溶ｌ夜の粘度平均
分子ｉｔ （Ｍｖ）及び残存モノマー量を調べた所、夫
々９５．０００と２．３％であった。Example-6 120 g of toluene, 80 g of methyl methacrylate, 2°5-I in a flask equipped with a cooler, thermometer, and stirrer.
4 g (0,001 mol) of O was charged and polymerization was carried out at 90° C. for 8 hours. The viscosity average molecular weight (Mv) of the resulting polymer solution and the amount of residual monomer were examined and found to be 95.000 and 2.3%, respectively.
比較例−６
２，５−Ｉの代わりに、ｔ−ブチルペルオキシベンゾエ
ートを０．３９ｇ （０，００２モル）を用いた以外は
実施例−６に準じて重合を行なった。得られたポリマー
溶ｌ夜のＭｖは、６７、０００で残存モノマーば、３．
４％であった。Comparative Example 6 Polymerization was carried out according to Example 6 except that 0.39 g (0,002 mol) of t-butyl peroxybenzoate was used instead of 2,5-I. The Mv of the obtained polymer solution was 67,000, and the residual monomer was 3.
It was 4%.
実施例−７
容Ｍ７１のオートクレーブ中に、ポリブタジェン０、２
４ｋｇを溶解したスチレン溶酸４ｋｇ、２゜５−５Ｂ７
．２ｇを加え、 ２００ｒｐｍで撹拌した。容器内をＮ
２ガスで置換してから密閉し昇温した。Example-7 In an autoclave with a volume of M71, polybutadiene 0, 2
4 kg of styrene dissolved acid, 2゜5-5B7
．． 2g was added and stirred at 200 rpm. N inside the container
After replacing with 2 gases, it was sealed and the temperature was raised.
１００℃で２時間重合した後、冷却し、予備重合を終え
た。次いで、容１１１５ｆｆのオートクレーブ中に純水
４ｋｇ、第三リン酸カルシウム３２ｇを加え、１５０ｒ
ｐｍで撹拌して、そこに新たに２．５−３Ｂ７．２ｇを
加えた前記の予備重合を夜を入れ、Ｎ２ガスで置換後、
密閉し、昇温して１１０℃で３時間重合し冷却した。以
後、実施例−１に準じて耐衝撃性ポリスチレン樹脂を得
た。この樹脂のＩ ｚｏｄ衝撃純度は、９．７ ｋｇ−
ｃｍ／ｃｍ２であった。After polymerizing at 100° C. for 2 hours, the mixture was cooled to complete the preliminary polymerization. Next, 4 kg of pure water and 32 g of tribasic calcium phosphate were added to an autoclave with a capacity of 1115 ff, and the mixture was heated for 150 r.
After stirring at pm and adding 7.2 g of 2.5-3B, the above prepolymerization was carried out overnight, and after replacing with N2 gas,
The container was sealed, heated to 110° C. for 3 hours, and then cooled. Thereafter, an impact-resistant polystyrene resin was obtained according to Example-1. The Izod impact purity of this resin is 9.7 kg-
cm/cm2.
比較例−７
２，５−３Ｂの代わりにｔ−ブチルペルオキシベンゾエ
ートを用いた以外は、
実施例−７に準じ
で重合した。Comparative Example 7 Polymerization was carried out in the same manner as in Example 7, except that t-butyl peroxybenzoate was used instead of 2,5-3B.
得られた樹脂のＩｚｏｄ衝撃強度は、 ４．６ ｋｇ−ｃｆｆｌ／ｃ−であった。The Izod impact strength of the obtained resin is: 4.6 kg-cffl/c-.
Claims (1)
との混合物を重合させる際に、下記の式（ I ）及び式
（II）で表わされる有機過酸化物の少なくとも一種を重
合開始剤として単量体に対して０．０１〜０．５重量％
使用することを特徴とするビニル単量体の重合方法。 ▲数式、化学式、表等があります▼（ I ） （但し、Ｒ＿１は、炭素数１〜３の直鎖アルキル基を示
す） ▲数式、化学式、表等があります▼（II） （但し、Ｒ＿２は、炭素数１〜４のアルキル基を示す）[Claims] When polymerizing a vinyl monomer alone or a mixture of a vinyl monomer copolymerizable with the vinyl monomer, at least 0.01 to 0.5% by weight of one type of polymerization initiator based on the monomer
A method for polymerizing a vinyl monomer, characterized in that it is used. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (However, R_1 represents a straight-chain alkyl group having 1 to 3 carbon atoms) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (However, R_2 is , represents an alkyl group having 1 to 4 carbon atoms)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28172389A JPH03143902A (en) | 1989-10-31 | 1989-10-31 | Polymerization of vinyl monomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28172389A JPH03143902A (en) | 1989-10-31 | 1989-10-31 | Polymerization of vinyl monomer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03143902A true JPH03143902A (en) | 1991-06-19 |
Family
ID=17643084
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28172389A Pending JPH03143902A (en) | 1989-10-31 | 1989-10-31 | Polymerization of vinyl monomer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03143902A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009003438A (en) * | 2007-05-21 | 2009-01-08 | Canon Inc | Method for producing polymerized toner, polymerized toner, method for producing binder resin for toner and binder resin for toner |
-
1989
- 1989-10-31 JP JP28172389A patent/JPH03143902A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009003438A (en) * | 2007-05-21 | 2009-01-08 | Canon Inc | Method for producing polymerized toner, polymerized toner, method for producing binder resin for toner and binder resin for toner |
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