JPS5926627B2 - organic peroxide composition - Google Patents
organic peroxide compositionInfo
- Publication number
- JPS5926627B2 JPS5926627B2 JP8935476A JP8935476A JPS5926627B2 JP S5926627 B2 JPS5926627 B2 JP S5926627B2 JP 8935476 A JP8935476 A JP 8935476A JP 8935476 A JP8935476 A JP 8935476A JP S5926627 B2 JPS5926627 B2 JP S5926627B2
- Authority
- JP
- Japan
- Prior art keywords
- composition
- diperaromatic
- organic peroxide
- water
- dibasic acid
- 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
- 239000000203 mixture Substances 0.000 title claims description 50
- 150000001451 organic peroxides Chemical class 0.000 title claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000002253 acid Substances 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 150000002978 peroxides Chemical class 0.000 description 9
- 239000000178 monomer Substances 0.000 description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 229920006337 unsaturated polyester resin Polymers 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- 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
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 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 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical compound CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 description 1
- RXNOYRCWKRFNIM-UHFFFAOYSA-N 2-carbonochloridoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(Cl)=O RXNOYRCWKRFNIM-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-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
- 229920004552 POLYLITE® Polymers 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- -1 peracid esters Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- FQFILJKFZCVHNH-UHFFFAOYSA-N tert-butyl n-[3-[(5-bromo-2-chloropyrimidin-4-yl)amino]propyl]carbamate Chemical compound CC(C)(C)OC(=O)NCCCNC1=NC(Cl)=NC=C1Br FQFILJKFZCVHNH-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerization Catalysts (AREA)
Description
【発明の詳細な説明】
本発明は、ジ過芳香族二塩基性酸−ｔ−アルキルエステ
ルと水とからなる組成物、すなわち、エチレン性単量体
の遊離基重合開始剤としで使用される、取り扱いが簡単
でかつ安全な、粉体の有機過酸化物組成物に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition comprising a diperaromatic dibasic acid t-alkyl ester and water, which is used as a free radical polymerization initiator for ethylenic monomers. , relates to a powdered organic peroxide composition that is easy and safe to handle.
従来から用いられている有機過酸化物たとえばジ過フタ
ル酸のｔ−ブチルエステルは、純品の状態では熱、衝撃
、摩擦などに対して敏感であり、爆発的分解の危険性が
ある。Conventionally used organic peroxides, such as t-butyl ester of diperphthalic acid, are sensitive to heat, impact, friction, etc. in their pure state, and there is a risk of explosive decomposition.
そのため、フタル酸ジブチルで希釈したものが製造され
ているが、この溶液は、粘度が高くその製造に困難をと
もなう。また、単量体に対する溶解性が悪く結晶が分離
しやすいために使用しにくいなどの欠点がある。このジ
過フタル酸のｔ−ブチルエステルは、また、ベンゼン、
トルエンなどの芳香族炭化水素の溶液とすることもでき
るが、これらの希釈剤は揮発性があるため、溶液製造時
および取り扱い時の作業環境を悪化させるおそれがあり
、さらに、スチレンの重合開始剤として用いた場合、希
釈剤が重合体中に残存するので、重合体品質悪化の原因
となる。本発明の目的は、製造や取り扱いが簡便でかつ
安全なジ過芳香族二塩基性酸−ｔ−アルキルエステルの
組成物を提供することにある。Therefore, a solution diluted with dibutyl phthalate has been manufactured, but this solution has a high viscosity and is difficult to manufacture. Furthermore, it has the disadvantage that it is difficult to use because it has poor solubility in monomers and easily separates into crystals. This diperphthalic acid t-butyl ester can also be used for benzene,
Solutions of aromatic hydrocarbons such as toluene can also be used, but these diluents are volatile and may worsen the working environment during solution preparation and handling.Additionally, styrene polymerization initiators When used as a diluent, the diluent remains in the polymer, causing deterioration in the quality of the polymer. An object of the present invention is to provide a diperaromatic dibasic acid t-alkyl ester composition that is easy to manufacture and handle and is safe.
本発明の他の目的は、重合体の品質を悪化させるおそれ
のないジ過芳香族二塩基性酸−ｔ−アルキルエステルの
組成物を提供することにある。Another object of the present invention is to provide a composition of diperaromatic dibasic acid t-alkyl ester that does not cause deterioration in the quality of the polymer.
本発明のさらにもう一つの目的は、重合開始剤としてビ
ニル単量体に添加した場合、単量体に溶解しやすいジ過
芳香族二塩基性酸−ｔ−アルキルエステルの組成物を提
供することにある。これらの目的は、以下に詳述するよ
うに、本発明のジ過芳香族二塩基性酸−ｔ−アルキルエ
ステルと水との組成物によつて初めて達成された。Yet another object of the present invention is to provide a composition of a diperaromatic dibasic acid t-alkyl ester that is easily soluble in the vinyl monomer when added to the monomer as a polymerization initiator. It is in. These objectives have been achieved for the first time by the compositions of diperaromatic dibasic acid-t-alkyl esters and water of the present invention, as detailed below.
従来、有機過酸化物と水との組成物については、過酸化
ベンゾイルと水との組成物が知られていたが、このもの
は、不飽和ポリエステル樹脂の硬化触媒としては、樹脂
単量体に対する溶解速度が遅いために使用できず、かわ
つて、過酸化ベンゾイルとフタル酸ジオクチルとのペー
スト状の組成物が用いられていた。したがつて、本発明
のジ過芳香族二塩基性酸一ｔ−アルキルエステルと水と
の組成物が、ビニル単量体、不飽和ポリエステル樹脂に
対する溶解性にすぐれ、しかも、取り扱い上、使用上種
々の利点を有することは、従来の技術からはとうてい予
期できないことであつた。Conventionally, a composition of benzoyl peroxide and water was known as a composition of organic peroxide and water, but this composition was used as a curing catalyst for unsaturated polyester resin. It could not be used because of its slow dissolution rate, and instead a paste-like composition of benzoyl peroxide and dioctyl phthalate was used. Therefore, the composition of the diperaromatic dibasic acid monot-alkyl ester of the present invention and water has excellent solubility in vinyl monomers and unsaturated polyester resins, and is easy to handle and use. Having various advantages was completely unexpected from the prior art.
本発明の組成物は、次のいずれの方法によつても製造す
ることができる。The composition of the present invention can be manufactured by any of the following methods.
（１）油溶性溶媒を加えない条件下に、芳香族二塩基性
酸ハライドとｔ−アルキルヒドロペルオキシドとをアル
カリ水溶液中で、公知の過酸エステルの製造条件で反応
させて製造する。(1) Produced by reacting an aromatic dibasic acid halide and a t-alkyl hydroperoxide in an alkaline aqueous solution under conditions known for producing peracid esters without adding an oil-soluble solvent.
（２）純品のジ過芳香族二塩基性酸−ｔ−アルキルエス
テルと水とを混合して製造する。(2) Produced by mixing pure diperaromatic dibasic acid t-alkyl ester and water.
この内、（１）の方法は、危険性の高い高純度の過酸化
物を取り扱う必要のないこと、製造工程が簡単であるこ
とから、より好ましい方法である。Among these methods, method (1) is more preferable because it does not require handling highly dangerous high-purity peroxides and the manufacturing process is simple.
本発明におけるジ過芳香族二塩基性酸−ｔ−ア ，′ル
キルエステルと水との組成比は、６０〜９５重量部：４
０〜５重量部、好ましくは７０〜８０重量部：３０〜２
０重量部であり、この範囲内で任意に調製できる。水が
４０重量部以上になると、水が分離して来るため、実質
的に均一な組成物と ４はならず好ましくない。また、
水が５重量部以下になると、熱、衝撃、摩擦などに対す
る感度が大きくなり好ましくな〜・。本発明の組成物に
使用されるジ過芳香族二塩基性酸−ｔ−アルキルエステ
ルは、次の一般式（式中Ｒは、炭素数４から８までの第
３級アルキル基を表わす）で示すことができ、水との組
成物としたときに、夏期においても溶融せず、また、水
の分離や固化の原因とならないように、その融点が４０
℃以上のものが特に好ましい。In the present invention, the composition ratio of diperaromatic dibasic acid t-a,'alkyl ester and water is 60 to 95 parts by weight: 4
0-5 parts by weight, preferably 70-80 parts by weight: 30-2
0 part by weight, and can be arbitrarily adjusted within this range. If the amount of water exceeds 40 parts by weight, the water will separate and the composition will not be substantially uniform, which is not preferable. Also,
If the water content is less than 5 parts by weight, the sensitivity to heat, impact, friction, etc. will increase, which is undesirable. The diperaromatic dibasic acid t-alkyl ester used in the composition of the present invention has the following general formula (wherein R represents a tertiary alkyl group having 4 to 8 carbon atoms). When it is made into a composition with water, it has a melting point of 40% so that it does not melt even in summer and does not cause separation or solidification of water.
℃ or higher is particularly preferred.
具体的な化合物としては、 などをあげることができる。As a specific compound, etc. can be given.
本発明の有機過酸化物組成物は、ビニル単量体特にスチ
レンの重合開始剤として、また、不飽和ポリエステル樹
脂の硬化剤として有効である。The organic peroxide composition of the present invention is effective as a polymerization initiator for vinyl monomers, particularly styrene, and as a curing agent for unsaturated polyester resins.
ここで不飽和ポリエステル樹脂とは、無水フタル酸のよ
うな飽和二塩基酸、および無水マレイン酸やフマル酸の
ような不飽和二塩基酸と、グリコール類とを重縮合した
鎖状ポリエステルを、スチレンやフタル酸ジアリルのよ
うな重合性ビニルモノマ一で希釈した溶液をいう。以上
のように、本発明の有機過酸化物組成物は、その製造や
取り扱いが簡便で安全性も高く、さらに、重合開始剤と
して用いた場合、ビニル単量体に溶解しやすく、しかも
、重合体の品質を悪化させるおそれもないという特徴を
もつものである。Here, the unsaturated polyester resin is a chain polyester obtained by polycondensing a saturated dibasic acid such as phthalic anhydride, an unsaturated dibasic acid such as maleic anhydride or fumaric acid, and glycols. A solution diluted with a polymerizable vinyl monomer such as diallyl phthalate or diallyl phthalate. As described above, the organic peroxide composition of the present invention is easy to manufacture and handle, and is highly safe.Furthermore, when used as a polymerization initiator, it is easily soluble in vinyl monomers, and has polymerization properties. It has the characteristic that there is no risk of deteriorating the quality of the merging.
次に、実施例、参考例により本発明を説明する。実施例
１（ジ過イソフタル酸−ｔ−ブチルエステルと水との
組成物の製造）かきまぜ機を備えた４つロフラスコに１
０％カセイソーダ水溶液９６７（０．２４モル）を入れ
、攪拌下にｔ−ブチルヒドロペルオキシド（工業用、純
度８１．３％）２３．３ｙ（０．２１モル）を２０℃で
徐々に加え、同温度で２０分間反応させて、ｔブチルヒ
ドロペルオキシドのナトリウム塩水溶液を得た。Next, the present invention will be explained with reference to Examples and Reference Examples. Example 1 (Preparation of a composition of diperisophthalic acid-t-butyl ester and water) In a four-loaf flask equipped with a stirrer, one
A 0% caustic soda aqueous solution 967 (0.24 mol) was added, and while stirring, 23.3y (0.21 mol) of t-butyl hydroperoxide (industrial grade, purity 81.3%) was gradually added at 20°C. After reacting at temperature for 20 minutes, an aqueous solution of sodium salt of t-butyl hydroperoxide was obtained.
ついで、このｔ−ブチルヒドロペルオキシドのナトリウ
ム塩水溶液に、攪拌下にイソフタル酸クロリド２０．３
７（０．１０モル）を１５℃で１０分間にわたつて少し
ずつ加え、徐々に昇温して反応温度２５〜３０℃で２時
間反応させた。Next, 20.3 ml of isophthalic acid chloride was added to this aqueous sodium salt solution of t-butyl hydroperoxide while stirring.
7 (0.10 mol) was added little by little over 10 minutes at 15°C, and the temperature was gradually raised to allow reaction at a reaction temperature of 25 to 30°C for 2 hours.
その後粉体の生成物を沢取し、５％カセイソーダ水溶液
で１回、水で２回、洗浄、▲過をくりかえして、ジ過イ
ソフタル酸−ｔ−ブチルエステルと水との組成物３２．
７ｙを得た。ヨード滴定法により活性酸素量を測定して
純度を求め、過酸化物と水との組成比を決定した。Thereafter, the powdered product was collected, washed once with a 5% caustic soda aqueous solution and twice with water, and filtered repeatedly to form a composition of diperisophthalic acid t-butyl ester and water.32.
Got 7y. Purity was determined by measuring the amount of active oxygen by iodometry, and the composition ratio of peroxide and water was determined.
ヨード滴定法による純度は８２．４％（収率８６．９％
）、組成比（重量比）は過酸化物：水一８２．４：１７
．６であつた。実施例 ２
（ジ過テレフタル酸−ｔ−ブチルエステルと水との組成
物の製造）イソフタル酸クロリドの代わりにテレフタル
酸クロリドを用いる以外は、実施例１に述べたと同様の
方法で操作し、ジ過テレフタル酸−ｔ−ブチルエステル
との組成物３２．３７を得た。Purity by iodometry was 82.4% (yield 86.9%)
), the composition ratio (weight ratio) is peroxide: water - 82.4:17
．． It was 6. Example 2 (Production of a composition of diperterephthalic acid-t-butyl ester and water) The same procedure as described in Example 1 was used except that terephthalic acid chloride was used instead of isophthalic acid chloride. Composition 32.37 with perterephthalic acid tert-butyl ester was obtained.
ヨード滴定法により活性酸素量を測定して純度を求め、
過酸化物と水との組成比を決定した。Purity is determined by measuring the amount of active oxygen using iodometric titration method.
The composition ratio of peroxide and water was determined.
ヨード滴定法による純度は８１，８％（収率８５．１％
）、組成比（重量比）は過酸化物：水一８１．８：１８
．２であつた。実施例 ３
（ジ過フタル酸−ｔ−ブチルエステルと水との組成物の
製造）かきまぜ機を備えた４つロフラスコに１０％カセ
イソーダ水溶液９６７（０．２４モル）を入れ、攪拌下
にｔ−ブチルヒドロペルオキシド（工業用、純度８１．
３％）２３．３ｙ（０．２１モル）を２０℃で徐々に加
え、同温度で２０分間反応させて、ｔブチルヒドロペル
オキシドのナトリウム塩水溶液を得た。Purity by iodometry is 81.8% (yield 85.1%)
), the composition ratio (weight ratio) is peroxide:water 81.8:18
．． It was 2. Example 3 (Production of a composition of diperphthalic acid t-butyl ester and water) A 10% caustic soda aqueous solution 967 (0.24 mol) was placed in a four-bottle flask equipped with a stirrer, and t-butyl diperphthalate was added under stirring. Butyl hydroperoxide (industrial grade, purity 81.
3%) 23.3y (0.21 mol) was gradually added at 20°C and reacted at the same temperature for 20 minutes to obtain an aqueous solution of sodium salt of t-butyl hydroperoxide.
ついで、このｔ−ブチルヒドロペルオキシドのナトリウ
ム塩水溶液に、撹拌下に、・゛１５０ｍ１のエーテルに
フタル酸クロリド２０．３ｔ（０４１０モル）を溶解し
た溶液を、１５℃で１０分間にわたつて少しずつ加え、
徐々に昇温して反応温度２５〜３０′Ｃで２時間反応さ
せた。Then, a solution of 20.3 t (0,410 mol) of phthalic acid chloride dissolved in 150 ml of ether was added little by little to this aqueous sodium salt solution of t-butyl hydroperoxide over 10 minutes at 15°C while stirring. In addition,
The temperature was gradually increased and the reaction was carried out for 2 hours at a reaction temperature of 25-30'C.
その後有機層を分離し、５％カセイソーダ水溶液で１回
、水で２回洗浄した。ついで、これを無水硫酸マグネシ
ウムで乾燥し、石油エーテル１００ｍ１を加え、ドライ
アイス−アセトンで冷却して結晶を析出させた。その後
この結晶を▲取し、真空下に乾燥して、ジ過フタル酸−
ｔ−ブチルエステル２１。３７を得た。Thereafter, the organic layer was separated and washed once with a 5% aqueous solution of caustic soda and twice with water. Next, this was dried over anhydrous magnesium sulfate, 100 ml of petroleum ether was added, and the mixture was cooled with dry ice-acetone to precipitate crystals. Thereafter, the crystals were collected ▲, dried under vacuum, and diperphthalic acid
21.37 t-butyl esters were obtained.
（純度９８，５％、収率６７。５％）
次に、このジ過フタル酸−ｔ−ブチルエステル２１．３
７を１００ｍ１の水に分散させ、一夜放置した後▲過し
て、ジ過フタル酸−ｔ−ブチルエステルと水との組成物
２５．４ｙを得た。(Purity 98.5%, yield 67.5%) Next, 21.3% of this diperphthalic acid-t-butyl ester
7 was dispersed in 100 ml of water, left overnight, and then filtered to obtain 25.4y of a composition of diperphthalic acid t-butyl ester and water.
以下実施例１に述べたと同様の方法で、過酸化物と水と
の組成比を決定した。ヨード滴定法による純度は８２．
５％、組成比（重量比）は過酸化物：水−８２．５：１
７．５であつた。The composition ratio of peroxide and water was determined in the same manner as described in Example 1 below. Purity by iodometry is 82.
5%, composition ratio (weight ratio): peroxide: water - 82.5:1
It was 7.5.
実施例 ４〜７
（その他のジ過芳香族二塩基性酸−ｔ−アルキルエステ
ルと水との組成物の製造）相当する芳香族二塩基性酸ク
ロリドとｔ−アルキルヒドロペルオキシドとを用い、芳
香族二塩基性酸クロリド添加後に、３５〜４０℃で３時
間反応させる以外は、実施例１に述べたと同様の方法で
操作して、相当するジ過芳香族二塩基性酸−ｔ−アルキ
ルエステルと水との組成物を製造した。Examples 4 to 7 (Production of compositions of other diperaromatic dibasic acid-t-alkyl esters and water) Using the corresponding aromatic dibasic acid chloride and t-alkyl hydroperoxide, aromatic The corresponding diperaromatic dibasic acid-t-alkyl ester was prepared in the same manner as described in Example 1, except that after addition of the group dibasic acid chloride, the reaction was carried out at 35-40°C for 3 hours. and water.
その結果を表−１に示す。参考例 １
（有機過酸化物組成物の安全度）
本発明のジ過芳香族二塩基性酸のｔ−ブチルエステルと
水とからなる組成物の安全度を試験し、それぞれの過酸
化物の純品と比較した。The results are shown in Table-1. Reference Example 1 (Safety level of organic peroxide composition) The safety level of a composition consisting of t-butyl ester of diperaromatic dibasic acid of the present invention and water was tested, and the safety level of each peroxide composition was tested. Compared with pure product.
その結果を表−２に示すが、試験法は北川氏ほかが「安
全工学」（４．（２）、１３１（１９６５））に記載し
た方法によつた。表−２から、本発明のジ過芳香族二塩
基性酸のｔ−ブチルエステルと水との組成物が、それぞ
れの過酸化物の純品と比較して大幅に安全度が向上して
いることがわかる。The results are shown in Table 2, and the test method was the method described by Mr. Kitagawa et al. in "Safety Engineering" (4. (2), 131 (1965)). Table 2 shows that the composition of the t-butyl ester of diperaromatic dibasic acid of the present invention and water has significantly improved safety compared to pure products of each peroxide. I understand that.
参考例 ２
（不飽和ポリエステル樹脂への溶解性）
本発明の組成物と、過酸化ベンゾイルと水との組成物を
用い、不飽和ポリエステル樹脂への溶解性を比較した。Reference Example 2 (Solubility in unsaturated polyester resin) The solubility in unsaturated polyester resin was compared using the composition of the present invention and a composition of benzoyl peroxide and water.
試験法は、不飽和ポリエステル樹脂（大日本インキ化学
工業（株）製、商品名ポリライト８０１０）５０７に対
して組成物１ｙを添加し、２５℃の温度においてガラス
棒で撹拌をつづけ完全に溶解するのに要した時間を測定
した。The test method is to add composition 1y to unsaturated polyester resin (manufactured by Dainippon Ink & Chemicals Co., Ltd., trade name Polylite 8010) 507, and continue stirring with a glass rod at a temperature of 25°C until it completely dissolves. The time required for this was measured.
その結果を表−３に示す。表−３から、本発明の組成物
の溶解性が、過酸化ベンゾイルと水との組成物よりはる
かにすぐれていることがわかる。The results are shown in Table-3. From Table 3, it can be seen that the solubility of the composition of the present invention is much better than that of the composition of benzoyl peroxide and water.
Claims (1)
表わす）で示されるジ過芳香族二塩基性酸−ｔ−アルキ
ルエステル６０〜９５重量部と水５〜４０重量部とから
なる有機過酸化物組成物。 ２ ジ過芳香族二塩基性酸−ｔ−アルキルエステルが、
式▲数式、化学式、表等があります▼ で示される化合物である特許請求の範囲第１項記載の有
機過酸化物組成物。 ３ ジ過芳香族二塩基性酸−ｔ−アルキルエステルが、
式▲数式、化学式、表等があります▼ で示される化合物である特許請求の範囲第１項記載の有
機過酸化物組成物。 ４ ジ過芳香族二塩基性酸−ｔ−アルキルエステルが、
式▲数式、化学式、表等があります▼ で示される化合物である特許請求の範囲第１項記載の有
機過酸化物組成物。 ５ ジ過芳香族二塩基性酸−ｔ−アルキルエステルが、
式▲数式、化学式、表等があります▼ で示される化合物である特許請求の範囲第１項記載の有
機過酸化物組成物。 ６ ジ過芳香族二塩基性酸−ｔ−アルキルエステルが、
式▲数式、化学式、表等があります▼ で示される化合物である特許請求の範囲第１項記載の有
機過酸化物組成物。 ７ ジ過芳香族二塩基性酸−ｔ−アルキルエステルが、
式▲数式、化学式、表等があります▼ で示される化合物である特許請求の範囲第１項記載の有
機過酸化物組成物。 ８ ジ過芳香族二塩基性酸−ｔ−アルキルエステルが、
式▲数式、化学式、表等があります▼ で示される化合物である特許請求の範囲第１項記載の有
機過酸化物組成物。[Claims] 1. A diperaromatic dibasic compound represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, R represents a tertiary alkyl group having 4 to 8 carbon atoms) An organic peroxide composition comprising 60 to 95 parts by weight of an acid t-alkyl ester and 5 to 40 parts by weight of water. 2 diperaromatic dibasic acid-t-alkyl ester,
The organic peroxide composition according to claim 1, which is a compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 3 diperaromatic dibasic acid-t-alkyl ester,
The organic peroxide composition according to claim 1, which is a compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 4 diperaromatic dibasic acid-t-alkyl ester,
The organic peroxide composition according to claim 1, which is a compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 5 diperaromatic dibasic acid-t-alkyl ester,
The organic peroxide composition according to claim 1, which is a compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 6 diperaromatic dibasic acid-t-alkyl ester,
The organic peroxide composition according to claim 1, which is a compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 7 Diperaromatic dibasic acid-t-alkyl ester is
The organic peroxide composition according to claim 1, which is a compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 8 Diperaromatic dibasic acid-t-alkyl ester is
The organic peroxide composition according to claim 1, which is a compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8935476A JPS5926627B2 (en) | 1976-07-27 | 1976-07-27 | organic peroxide composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8935476A JPS5926627B2 (en) | 1976-07-27 | 1976-07-27 | organic peroxide composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5315333A JPS5315333A (en) | 1978-02-13 |
| JPS5926627B2 true JPS5926627B2 (en) | 1984-06-29 |
Family
ID=13968364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8935476A Expired JPS5926627B2 (en) | 1976-07-27 | 1976-07-27 | organic peroxide composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5926627B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4937585B2 (en) * | 2006-01-05 | 2012-05-23 | 三菱電機株式会社 | Polymer actuator unit |
-
1976
- 1976-07-27 JP JP8935476A patent/JPS5926627B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5315333A (en) | 1978-02-13 |
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