JPH0240362A - Diacyl type polymeric peroxide - Google Patents
Diacyl type polymeric peroxideInfo
- Publication number
- JPH0240362A JPH0240362A JP18959188A JP18959188A JPH0240362A JP H0240362 A JPH0240362 A JP H0240362A JP 18959188 A JP18959188 A JP 18959188A JP 18959188 A JP18959188 A JP 18959188A JP H0240362 A JPH0240362 A JP H0240362A
- Authority
- JP
- Japan
- Prior art keywords
- diacyl
- peroxide
- type polymeric
- formula
- chloride
- 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
- 150000002978 peroxides Chemical class 0.000 title claims abstract description 50
- 239000000126 substance Substances 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 17
- 239000003505 polymerization initiator Substances 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 8
- 239000000178 monomer Substances 0.000 abstract description 7
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004793 Polystyrene Substances 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 4
- 229920002223 polystyrene Polymers 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 abstract description 4
- LSLYHQZLPNQHAA-UHFFFAOYSA-N 8,13-dimethylicosa-8,12-dienedioyl dichloride Chemical compound ClC(=O)CCCCCCC(C)=CCCC=C(C)CCCCCCC(Cl)=O LSLYHQZLPNQHAA-UHFFFAOYSA-N 0.000 abstract description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 229920001400 block copolymer Polymers 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000007870 radical polymerization initiator Substances 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 229920006248 expandable polystyrene Polymers 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000005502 peroxidation Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 3
- 239000004135 Bone phosphate Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000002843 carboxylic acid group Chemical group 0.000 description 3
- 239000012933 diacyl peroxide Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000004965 peroxy acids Chemical group 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 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 description 1
- SNDRGIMRDVEXJF-UHFFFAOYSA-N 8-ethyloctadecanedioyl dichloride Chemical compound ClC(=O)CCCCCCC(CC)CCCCCCCCCC(Cl)=O SNDRGIMRDVEXJF-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- -1 acrylic ester Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004794 expanded polystyrene Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011076 safety test Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyethers (AREA)
- Polymerization Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、新規なジアシル型ポリメリックペルオキシド
に関するものである。また、エチレン性不飽和単量体の
遊離基重合開始剤（以後、重合開始剤と略称）として有
効なジアシル型ポリメリックペルオキシドである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel diacyl type polymeric peroxide. It is also a diacyl-type polymeric peroxide that is effective as a free radical polymerization initiator (hereinafter abbreviated as polymerization initiator) for ethylenically unsaturated monomers.
（従来の技術）
従来、三塩基性酸塩化物と過酸化す） ＩＪウムとを重
縮合反応させて得られるジアシル型ポリメリックペルオ
キシドが、ベリヒテ・デル・ドイチェン・ヘミジエン・
ゲゼルシャフト、第２７巻、 第１５１０頁（１８９４
）に、また直鎖飽和三塩基性酸塩化物と過酸化ナトリウ
ムとの反応から得られるジアシル型ポリメリックペルオ
キシドが、ケミカルアブストラクト、第６０巻、 ５２
９３ｄ （１９４０）に記載されている。(Prior art) Conventionally, diacyl-type polymeric peroxides obtained by polycondensation reaction of tribasic acid chlorides and peroxides,
Gesellschaft, Volume 27, Page 1510 (1894
), and diacyl-type polymeric peroxides obtained from the reaction of linear saturated tribasic acid chlorides with sodium peroxide are published in Chemical Abstracts, Vol. 60, 52.
93d (1940).
これらジアシル型ポリメリックペルオキシドは、衝撃と
摩擦に対して敏感であり、また各種有機溶媒やエチレン
性不飽和単量体に対し殆ど或は全く溶解しない欠点があ
った。These diacyl type polymeric peroxides have the drawback of being sensitive to impact and friction, and having little or no solubility in various organic solvents and ethylenically unsaturated monomers.
これらの欠点を解決するために、分子内に分岐した長鎖
炭化水素基を構成単位に有するジアシル型ポリメリック
ペルオキシドが、特開昭５９−８７２６号公報、特開昭
５９−１７６３２０号公報、特開昭５９−３８２３３号
公報で提案されている。In order to solve these drawbacks, diacyl-type polymeric peroxides having a branched long-chain hydrocarbon group as a constituent unit in the molecule have been proposed in JP-A-59-8726, JP-A-59-176320, and JP-A-59-176320. This was proposed in Publication No. 59-38233.
しかし、これらジアシル型ポリメリックペルオキシドは
、開始剤効率の面で十分ではなく、また従来のものと同
様、三塩基性酸塩化物と過酸化剤との反応によって得ら
れることからその末端基は過酸基またはカルボン酸基で
あり、経日安定性に問題が残されていた。However, these diacyl-type polymeric peroxides do not have sufficient initiator efficiency, and like conventional ones, they are obtained by the reaction of a tribasic acid chloride and a peroxidant, so their terminal groups are group or carboxylic acid group, and there remained a problem in stability over time.
これらの欠点を解決するために、次式で表される特定の
末端基を有するジアシル型ポリメリックペルオキシドが
、即ち
（式中Ｘはｎが１のとき−Ｈ，−ＣＩ、 −０−Ｃｆ１
３．−ｍ−ＣＨ，、。In order to solve these drawbacks, a diacyl type polymeric peroxide having a specific terminal group represented by the following formula, namely (where X is -H, -CI when n is 1, -0-Cf1
3. -m-CH,.
ＣＨ２ＣＨ３，−Ｃ（ＣＨ３）３をしめし、ｎが２のと
き、２．４位のＣ１をしめし、ｍは２〜１５である）が
、特公昭６３−１５２６７号公報に、また特公昭６３−
１５２６８号公報にて
（式中Ｘは炭素原子数１〜１９のアルキル基を示し、ｎ
は２〜１５である）
が開示されている。CH2CH3, -C(CH3)3, when n is 2, C1 at the 2.4th position is shown, and m is 2 to 15) is disclosed in Japanese Patent Publication No. 63-15267, and
No. 15268 (in the formula, X represents an alkyl group having 1 to 19 carbon atoms, and n
is 2 to 15) is disclosed.
（発明が解決しようとする問題点）
前述の特定の末端基を有するジアシル型ポリメリックペ
ルオキシドによって、安全性、溶解性、開始剤効率、そ
して特に経口安定性が改良されてきた。しかし、これら
ジアシル型ポリメリックペルオキシドも開始剤効率にお
いてはいまだ十分とはいえず、重合時のサイクルアップ
の点からも、より高いものが望まれており、さらに優れ
たジアシル型ポリメリックペルオキシドが求められてい
た。Problems to be Solved by the Invention The diacyl-type polymeric peroxides having the specific terminal groups described above have improved safety, solubility, initiator efficiency, and especially oral stability. However, these diacyl-type polymeric peroxides are still not sufficient in terms of initiator efficiency, and from the viewpoint of cycle-up during polymerization, even higher diacyl-type polymeric peroxides are desired. Ta.
発明者らは、この欠点を解決するため種々研究を行った
結果、新規なジアシル型ポリメリックペルオキシドによ
り、即ち構成単位中の分子内２ケ所に分岐した炭化水素
基を有し、また特定の末端基を有する新規なジアシル型
ポリメリックペルオキシドにより、経口安定性、溶解性
、更には安全性を低下させることなしに、開始剤効率が
改良されることを見いだし本発明を完成するに至った。As a result of various studies conducted by the inventors in order to solve this drawback, the inventors discovered that a new diacyl type polymeric peroxide, which has a hydrocarbon group branched at two locations within the molecule in the structural unit, and a specific terminal group. The present inventors have discovered that a novel diacyl-type polymeric peroxide having the following properties improves initiator efficiency without deteriorating oral stability, solubility, or even safety, leading to the completion of the present invention.
（問題を解決するための手段）
本発明は、次の一般式
（式中Ｘはｎが１のとき−Ｈ，−ＣＩ、 −ＣＨ３，−
ＣＨ２ＣＨ３゜Ｃ（ＣＨ，）３を示し、ｎが２のとき、
２．４位の−Ｃ１を示し、ｍは２〜１５である）
で表される新規なジアシル型ポリメリックペルオキシド
である。(Means for solving the problem) The present invention is based on the following general formula (wherein, when n is 1, X is -H, -CI, -CH3, -
CH2CH3°C(CH,)3, when n is 2,
-C1 at the 2.4-position, m is 2 to 15) This is a novel diacyl type polymeric peroxide.
本発明の新規なジアシル型ポリメリックペルオキシドは
、前述の一般式で示されるが、式中の両末端のベンゼン
環のＸｎで表される置換基の種類及び数は、同一または
異なるものであってもよい。The novel diacyl-type polymeric peroxide of the present invention is represented by the above-mentioned general formula, and the type and number of substituents represented by Xn on both terminal benzene rings in the formula may be the same or different. good.
本発明の新規なジアシル型ポリメリックペルオキシドは
、例えば次のようにして製造することができる。The novel diacyl type polymeric peroxide of the present invention can be produced, for example, as follows.
即ち、７，１２−ジメチルオクタデカン−７，１１−ジ
エン−１，１８−ジカルボン酸塩化物と前記（１）式の
末端基に相当する一塩基性酸塩化物との混合物を過酸化
ナトリウムまたは過酸化カリウム等の過酸化剤の水溶液
中に撹拌しながら少しづつ加え反応させ、反応終了後、
反応廃液と分離することにより容易に製造できる。That is, a mixture of 7,12-dimethyloctadecane-7,11-diene-1,18-dicarboxylic acid chloride and a monobasic acid chloride corresponding to the terminal group of formula (1) above is heated with sodium peroxide or peroxide. Add it little by little to an aqueous solution of a peroxidant such as potassium oxide while stirring and let it react, and after the reaction is complete,
It can be easily produced by separating it from the reaction waste liquid.
７．１２−ジメチルオクタデカン−７，１１−ジエン−
１，１８ジカルボン酸塩化物に対する一塩基性酸のモル
比は、前者を１とすると０．０７〜１である。０．０７
未満では、ｍ（平均縮合度）は１５より大きくはなるが
、ペルオキシドの末端基に過酸基またはカルボン酸基が
残り、経日安定性に悪影響を及ぼす。また１を越えると
通常の一官能性ジアシルペルオキシドの副生によヘポリ
メリックペルオキシドとしての特異的な効果が発揮でき
ない。7.12-dimethyloctadecane-7,11-diene-
The molar ratio of monobasic acid to 1,18 dicarboxylic acid chloride is 0.07 to 1, assuming that the former is 1. 0.07
If m (average degree of condensation) is less than 15, m (average degree of condensation) will be greater than 15, but a peracid group or a carboxylic acid group will remain at the end group of the peroxide, which will have an adverse effect on stability over time. Moreover, when it exceeds 1, the specific effect as a hepolymeric peroxide cannot be exhibited due to the by-product of normal monofunctional diacyl peroxide.
また過酸化剤の使用量は原料酸化物の混合物の塩素量に
対して約０．５〜１．５当量である。The amount of peroxidant used is about 0.5 to 1.5 equivalents based on the amount of chlorine in the mixture of raw oxides.
反応条件は通常のジアシルペルオキシドとＩｎであって
反応温度は約−１０〜４０℃好ましくは約−５〜−１５
℃であり、反応時間は約０．１〜５時間好ましくは約０
．２５〜２時間である。The reaction conditions are ordinary diacyl peroxide and In, and the reaction temperature is about -10 to 40°C, preferably about -5 to -15°C.
℃, and the reaction time is about 0.1 to 5 hours, preferably about 0.
．． 25 to 2 hours.
以上のようにして製造した本発明の新規なジアシル型ポ
リメリックペルオキシドは、無色透明な語調液体である
。The novel diacyl-type polymeric peroxide of the present invention produced as described above is a colorless and transparent liquid.
このジアシル型ポリメリックペルオキシドは、赤外線吸
収スペクトルにより、ジアシルのＣ＝ＯＭ合とペルオキ
シドの０−０結合が確認され、核磁気共鳴スペクトルに
より−ＣＨ，、−ＣＨ２、フＣＨ，−ＣＯＣＨ２−置を
使用）によりその平均分子量が決定され、その値から平
均縮合度ｍが求められる。In this diacyl type polymeric peroxide, the C=OM combination of diacyl and the 0-0 bond of the peroxide were confirmed by infrared absorption spectrum, and the -CH,, -CH2, -CH, -COCH2- configuration was confirmed by nuclear magnetic resonance spectrum. ), the average molecular weight is determined, and the average degree of condensation m is determined from that value.
さらにヨード滴定法により活性酸素量が求められる。Furthermore, the amount of active oxygen is determined by iodometric titration.
このジアシル型ポリメリックペルオキシドは、エチレン
性不飽和単量体の重合開始剤として有用である。エチレ
ン性不飽和単量体は例えば、スチレン、酢酸ビニル、ア
クリル酸エステル、メタクリル酸エステル、アクリロニ
トリル、メタクリル酸） ＩＪル、塩化ビニリデン、塩
化ビニノペエチレン等である。さらにまた発泡ポリスチ
レン、耐衝撃性ポリスチレンまたはブロック共重合体の
製造のための重合開始剤としても有用である。This diacyl type polymeric peroxide is useful as a polymerization initiator for ethylenically unsaturated monomers. Examples of the ethylenically unsaturated monomer include styrene, vinyl acetate, acrylic ester, methacrylic ester, acrylonitrile, methacrylic acid, vinylidene chloride, and vinylidene chloride. It is also useful as a polymerization initiator for the production of expanded polystyrene, high impact polystyrene or block copolymers.
（発明の効果）
本発明の新規なジアシル型ポリメリックペルオキシドは
、従来の分子内に分岐した炭化水素基を有し、また特定
の末端基を有するジアシル型ポリメリックペルオキシド
に比べ、同等の優れた経日安定性を有し、また開始剤効
率は一段と高くなり重合時におけるサイクルアップを可
能にした。(Effects of the Invention) The novel diacyl-type polymeric peroxide of the present invention has a branched hydrocarbon group in the molecule, and has an equally excellent aging property compared to the conventional diacyl-type polymeric peroxide that has a specific terminal group. It has stability, and further increases initiator efficiency, making it possible to cycle up during polymerization.
また従来の分子内に分岐した炭化水素基を有するジアシ
ル型ポリメリックペルオキシドと同様に有機溶媒に対す
る溶解性及びエチレン性不飽和単量体に対する溶解性に
優れているため、エチレン性不飽和単量体の重合開始剤
として使用した場合には、その作業性を大幅に向上させ
うる。また衝撃及び摩擦に対しては、従来のジアシル型
ポリメリックペルオキシド１ご上ヒベてさら１こ３屯感
であり、取扱時の安定性が非常に高い。さらにまたエチ
レン性不飽和単量体の重合開始剤として使用した場合に
は、通常の一官能性のジアシルペルオキシドを用いた場
合に比べ、従来のジアシル型ポリメリックペルオキシド
と同様に約２倍の分子量を有する重合体が得られる。In addition, like conventional diacyl-type polymeric peroxides having a branched hydrocarbon group in the molecule, they have excellent solubility in organic solvents and ethylenically unsaturated monomers. When used as a polymerization initiator, its workability can be greatly improved. In addition, it is 1 to 3 times more resistant to impact and friction than conventional diacyl-type polymeric peroxide, and has very high stability during handling. Furthermore, when used as a polymerization initiator for ethylenically unsaturated monomers, the molecular weight is approximately twice as high as that of conventional diacyl type polymeric peroxides compared to when ordinary monofunctional diacyl peroxides are used. A polymer having the following properties is obtained.
（実施例）
次に本発明のジアシル型ポリメリックペルオキシドを実
施例につき、さらに詳細に説明する。(Example) Next, the diacyl type polymeric peroxide of the present invention will be described in more detail with reference to Examples.
実施例１
撹拌機及び温度計を備えた四つロフラスコ中で７％水酸
化ナトリウム水溶液１６６ｇ （０，２９モル）５０％
過酸化水素水９．９ｇ （０，１４５モル）とを混合し
、過酸化ナトリウム水溶液をｍ製した。次に７，１２−
ジメチルオクタデカン−７，１１−ジエン１，１８−ジ
カルボン酸塩化物（純度９９％）４０．８ｇ （０，１
モル）と安息香酸塩化物５．６ｇ （０，０４モル）と
トルエン５０ｇとの混合液を撹拌下で０〜５℃の温度で
少しづつ加えた。Example 1 166 g (0.29 mol) 50% 7% aqueous sodium hydroxide solution in a four-bottle flask equipped with a stirrer and a thermometer
9.9 g (0,145 mol) of hydrogen peroxide solution was mixed to prepare m aqueous sodium peroxide solution. Then 7,12-
Dimethyloctadecane-7,11-diene 1,18-dicarboxylic acid chloride (99% purity) 40.8g (0,1
A mixture of 5.6 g (0.04 mol) of benzoic acid chloride and 50 g of toluene was added in portions under stirring at a temperature of 0 to 5°C.
この温度で３０分間撹拌した後、希塩酸によりｐＨ７ま
で中和した。次いで有機層を取り出し、これを水で２回
洗浄した後、無水硫酸マグネシウムで乾燥した。濾過に
より固形物を取り除きその後減圧下でトルエンを留去す
ることにより３５ｇの無色透明な語調液体を得た。After stirring at this temperature for 30 minutes, the mixture was neutralized to pH 7 with dilute hydrochloric acid. The organic layer was then taken out, washed twice with water, and then dried over anhydrous magnesium sulfate. Solid matter was removed by filtration, and toluene was distilled off under reduced pressure to obtain 35 g of a colorless and transparent liquid.
この語調液体について通常のヨード滴定法により活性酸
素量を求めたところ４．１９％であった。The active oxygen content of this tone liquid was determined to be 4.19% by the usual iodometric titration method.
この語調液体の赤外線吸収スペクトルにおける特性吸収
波長は１７８０ｃｍ−’、１８１０ｃｍ−’ （ジアシ
ル基のＣ＝Ｏ結合）及び８９０ ａｍ−’（［１−［１
結合）であり、またカルボン酸基に基づりＣ＝０結合に
よる１７１０ｃｍ−’の吸収とＤＨ結合による２６００
〜３２００ｃｍ ’の吸収及び過酸基に基づ＜Ｃ・０の
結合による１７５０ｃｍ−’の吸収及びＤＨ結合による
３３００ｃｍ−’の吸収は見られなかった。核磁気共鳴
吸収スペクトルのδ値及び強度は、（ａ） １．２０
ｐｐｍ（６０Ｈ）
（ｂ） １．５１１）ｐｍ（２０Ｈ）
（ｃ） １．６５ ｐｐｍ（３０）１）（ｄ） ２．０
１ ｐｐｍ（４０８）
（ｅ） ２．１８ ｐｐｍ（２ＯＮ）
（ｆ） ５．１０ ｐｐｍ（１０ｆｔ）（ｇ） ７．３
６ ｆｌｐｍ（６Ｈ）
（ｈ） ７．９０ ｐｐｍ（４Ｈ）
であり、ｖＰＯ法により測定した平均分子量は２０６４
であることから次式で表されるジアシル型ポリメリック
ペルオキシドであることが確Ｓ忍された。The characteristic absorption wavelengths in the infrared absorption spectrum of this tone liquid are 1780 cm-', 1810 cm-' (C=O bond of diacyl group) and 890 am-' ([1-[1
bond), and based on the carboxylic acid group, absorption at 1710 cm-' due to C=0 bond and absorption at 2600 cm-' due to DH bond.
Absorption at ~3200 cm', absorption at 1750 cm-' due to <C·0 bond based on peracid groups, and absorption at 3300 cm-' due to DH bond were not observed. The δ value and intensity of the nuclear magnetic resonance absorption spectrum are (a) 1.20
ppm (60H) (b) 1.511) pm (20H) (c) 1.65 ppm (30) 1) (d) 2.0
1 ppm (408) (e) 2.18 ppm (2ON) (f) 5.10 ppm (10ft) (g) 7.3
6 flpm (6H) (h) 7.90 ppm (4H), and the average molecular weight measured by the vPO method is 2064
Therefore, it was confirmed that it was a diacyl type polymeric peroxide represented by the following formula.
■■
実施例２〜９
一塩基性酸塩化物と７％水酸化ナトリウムそして５０％
過酸化水素水の量を後掲の第１表に示す看に変えたこと
以外は、実施例１と同様にしてジアシル型ポリメリック
ペルオキシドを製造し、その構造を実施例１と同様の方
法で確認した。結果を第２表に示す。■■ Examples 2-9 Monobasic acid chloride and 7% sodium hydroxide and 50%
Diacyl type polymeric peroxide was produced in the same manner as in Example 1, except that the amount of hydrogen peroxide solution was changed to the amount shown in Table 1 below, and its structure was confirmed in the same manner as in Example 1. did. The results are shown in Table 2.
比較例１
７．１２−ジメチルオクタデカン−７，１１−ジエン−
１゜１８−ジカルボン酸塩化物と過酸化ナトリウムとを
反応させ、公知のジアシル型ポリメリックペルオキシド
を製造した。このペルオキシドは赤外線吸収スペクトル
の特性吸収波長及び核磁気共鳴スペクトルのδ値及び強
度から次式
の構成単位からなるペルオキシドであることが確認され
た。平均分子量はｖＰＯ法による測定結果から７６００
（平均縮合度２０．８）であった。Comparative Example 1 7.12-dimethyloctadecane-7,11-diene-
A known diacyl type polymeric peroxide was produced by reacting 1°18-dicarboxylic acid chloride with sodium peroxide. This peroxide was confirmed to be a peroxide consisting of the structural unit of the following formula from the characteristic absorption wavelength of the infrared absorption spectrum and the δ value and intensity of the nuclear magnetic resonance spectrum. The average molecular weight is 7600 from the measurement results by vPO method.
(average degree of condensation 20.8).
比較例２
７−エチルヘキサデカン−１，１６−ジカルボン酸塩化
物及び安息香酸塩化物の混合物（モル比５：２）と過酸
化ナトリウムとを反応させ、公知のジアシル型ポリメリ
ックペルオキシドを製造した。このペルオキシドは赤外
線吸収スペクトルの特性吸収波長及び核磁気共鳴スペク
トルのδ値及び強度から次式
の構成単位からなるペルオキシドであることが確認され
た。平均分子量はＶＰＯ法による測定結果から１９９０
（平均縮合度５．１）であった。Comparative Example 2 A known diacyl-type polymeric peroxide was produced by reacting a mixture of 7-ethylhexadecane-1,16-dicarboxylic acid chloride and benzoic acid chloride (molar ratio 5:2) with sodium peroxide. This peroxide was confirmed to be a peroxide consisting of the structural unit of the following formula from the characteristic absorption wavelength of the infrared absorption spectrum and the δ value and intensity of the nuclear magnetic resonance spectrum. The average molecular weight is 1990 from the measurement results by the VPO method.
(average degree of condensation 5.1).
参考例１
〔スチレンの重合（塊状重合）と重合開始剤効率の測定
〕
スチレン各１１に重合開始剤として実施例１〜９及び比
較例１．２で製造したジアシル型ポリメリックペルオキ
シド０．０２モルをそれぞれ溶解して調製した試料５ｍ
１ｌ！を、内径１２ｍｍのガラスアンプルに封入し、６
０℃で重合を行い、それぞれの重合開始剤について開始
剤効率を求めた。Reference Example 1 [Polymerization of styrene (bulk polymerization) and measurement of polymerization initiator efficiency] 0.02 mol of the diacyl type polymeric peroxide produced in Examples 1 to 9 and Comparative Example 1.2 was added to each 11 styrene as a polymerization initiator. 5 m of sample prepared by dissolving each
1l! was sealed in a glass ampoule with an inner diameter of 12 mm, and 6
Polymerization was performed at 0°C, and the initiator efficiency was determined for each polymerization initiator.
開始剤効率の測定方法は「ビニル重合実験法」（共立出
版）第２５６頁に記載の方法に基づいて測定した。The initiator efficiency was measured based on the method described in "Vinyl Polymerization Experimental Method" (Kyoritsu Shuppan), page 256.
・得られたそれぞれについての測定結果を次の第３表に
示す。- The measurement results obtained for each are shown in Table 3 below.
前掲の第３表より明らかに、本発明のジアシル型ポリメ
リックペルオキシドは従来のジアシル型ポリメリックペ
ルオキシドに比べ、開始剤効率カ優れていることを示し
ている。Table 3 above clearly shows that the diacyl type polymeric peroxide of the present invention has superior initiator efficiency compared to the conventional diacyl type polymeric peroxide.
参考例２
〔スチレンの重合（塊状重合）と平均分子量の測定〕
スチレン１βに重合開始剤として実施例１で製造したジ
アシル型ポリメリックペルオキシド０．０９モルを溶解
して調製した試料５ｍｌを、内径１２＋ｎｍのガラスア
ンプルに封入し、７０℃で７時間重合を行った。しかる
後、反応液を取り出し、５０−の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り未反応
のスチレンモノマーを定量して重合転化率を求めた。Reference Example 2 [Polymerization of styrene (bulk polymerization) and measurement of average molecular weight] 5 ml of a sample prepared by dissolving 0.09 mole of the diacyl type polymeric peroxide produced in Example 1 as a polymerization initiator in styrene 1β was mixed with an inner diameter of 12 + nm. The mixture was sealed in a glass ampoule, and polymerization was carried out at 70°C for 7 hours. After that, the reaction solution was taken out and dissolved in 50-benzene,
The polymerization conversion rate was determined by quantifying unreacted styrene monomer by gas chromatography using an internal standard method.
次いで５００−のメチルアルコール中に投じてポリスチ
レンの白色沈殿を析出させた。この白色沈澱を乾燥した
後、ＧＰＣ（東洋曹達工業■製高速液体クロマトグラフ
ＨＬＣ−８０２ＵＲ型）によりポリスチレンの平均分子
量を求めた。Then, the mixture was poured into 500 ml of methyl alcohol to precipitate a white polystyrene precipitate. After drying this white precipitate, the average molecular weight of the polystyrene was determined by GPC (high performance liquid chromatograph model HLC-802UR manufactured by Toyo Soda Kogyo ■).
比較のため、通常の過酸化ラウロイルをジアシル型ポリ
メリックペルオキシドの代わりに用い、同様な操作を行
って重合転化率及びポリスチレンの平均分子量を求めた
。これらの結果を次の第４表に示す。For comparison, ordinary lauroyl peroxide was used in place of the diacyl type polymeric peroxide, and the same operation was performed to determine the polymerization conversion rate and the average molecular weight of polystyrene. These results are shown in Table 4 below.
前掲の第４表より明らかなように、本発明のジアシル型
ポリメリックペルオキシドは従来から用いられている過
酸化ラウロイルに比べてスチレンの平均分子量を約２倍
にすることができ、重合開始剤として優れていることを
示している。As is clear from Table 4 above, the diacyl-type polymeric peroxide of the present invention can approximately double the average molecular weight of styrene compared to conventionally used lauroyl peroxide, making it an excellent polymerization initiator. It shows that
参考例３
〔経日安定性、安全度、溶解性〕
実施例１及び比較例１，２で製造したジアシル型ポリメ
リックペルオキシドについて、下記の方法で経日安定性
、安全度及び各種溶媒に対する溶解度を測定した。得ら
れた結果を後掲の第５表、第６表及び第７表にそれぞれ
示す。Reference Example 3 [Stability over time, safety, solubility] Regarding the diacyl-type polymeric peroxides produced in Example 1 and Comparative Examples 1 and 2, the stability over time, safety, and solubility in various solvents were evaluated using the following method. It was measured. The obtained results are shown in Tables 5, 6 and 7 below, respectively.
＝経日安定性＝
５℃において２５日後、５０日後、１００日後の分解率
として求めた。また５℃においても同様に１０日後、２
０日後、３０日後の分解率を求めた。=Daily stability= It was determined as the decomposition rate after 25 days, 50 days, and 100 days at 5°C. Similarly, after 10 days at 5℃, 2
The decomposition rate was determined after 0 days and 30 days.
−安全度試験＝
「安全工学」第４巻第２号第１８１頁（１９６５）に記
載の方法で落鎚感度、摩擦感度、弾道臼砲、圧力容器試
験を行った。-Safety test = Drop sensitivity, friction sensitivity, ballistic mortar, and pressure vessel tests were conducted using the methods described in "Safety Engineering", Vol. 4, No. 2, p. 181 (1965).
１溶解度試験＝
２５℃におけるベンゼン、トルエン、スチレン、クロロ
ロホルム及び酢酸エチルの各１００ｇに溶解するｇ数を
測定した。1 Solubility test = The number of grams dissolved in 100 grams each of benzene, toluene, styrene, chloroform, and ethyl acetate at 25° C. was measured.
前掲の第５表、第６表、及び第７表より明らかなように
、本発明のジアシル型ポリメリックペルオキシドは従来
のジアシル型ポリメリックペルオキシドに比べ、経口安
定性及び溶解性においてなんら変わりのないこと、更に
安全度では若干の向上がみられることがわかる。As is clear from the above-mentioned Tables 5, 6, and 7, the diacyl-type polymeric peroxide of the present invention has no difference in oral stability and solubility compared to conventional diacyl-type polymeric peroxides, Furthermore, it can be seen that there is a slight improvement in safety.
Claims (1)
、−ｍ−ＣＨ＿３、−ＣＨ＿２ＣＨ＿３、−Ｃ（ＣＨ＿
３）＿３を示し、ｎが２のとき、２、４位の−Ｃｌを示
し、ｍは２〜１５である）で表される新規なジアシル型
ポリメリックペルオキシド。[Claims] 1. The following general formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, when n is 1, X is -H, -Cl, -o-CH_3
, -m-CH_3, -CH_2CH_3, -C(CH_
3) A novel diacyl-type polymeric peroxide represented by _3, when n is 2, it represents -Cl at the 2 and 4 positions, and m is 2 to 15).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18959188A JPH0240362A (en) | 1988-07-30 | 1988-07-30 | Diacyl type polymeric peroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18959188A JPH0240362A (en) | 1988-07-30 | 1988-07-30 | Diacyl type polymeric peroxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0240362A true JPH0240362A (en) | 1990-02-09 |
Family
ID=16243881
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18959188A Pending JPH0240362A (en) | 1988-07-30 | 1988-07-30 | Diacyl type polymeric peroxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0240362A (en) |
-
1988
- 1988-07-30 JP JP18959188A patent/JPH0240362A/en active Pending
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