TW528776B - Peroxide compositions with improved safety characteristics - Google Patents

Abstract

Safe peroxide compositions are provided which comprise two phlegmatizers having boiling points that are more than 20 DEG C, preferably more than 50 DEG C, apart. These compositions are safer than peroxide compositions with the same peroxide concentration containing only one phlegmatizer or phlegmatizers not fulfilling the boiling point requirement. The compositions are particularly useful in radical polymerization processes, cross-linking reactions, polymer modification processes, and other reactions involving peroxides, for example the preparation of certain chemicals.

Description

528776 V. Description of the invention The present invention relates to liquid peroxides that require desensitization to meet safety requirements. BACKGROUND OF THE INVENTION It is known that a variety of peroxides need to be desensitized with an inert diluent or solvent to allow safe handling and use. For some peroxides, in order to comply with all safety regulations and to store, transport, and handle in an acceptable and safe manner, the active oxygen concentration in the final formulation must be low. However, this low peroxide concentration The formulation is the last thing the industry wants, because the use of this formulation results in high levels of unwanted inert diluents or solvents in the resulting material. The British Patent No. 1,072,728 discloses a specific ketone peroxide formulation which contains at least one specific hydrophilic solvent which keeps the formulation safe. Even if the active oxygen content is high, the present invention suggests that other solvent compositions should not be used as safe peroxide compositions, and these solvents are not suitable hydrophilic solvents. Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (read first read the back note > one department > and then write this page) Agents, in which ketone peroxides are formulated with esters, have a boiling point in the range of 140-250 C. These compositions may also contain other compatible diluents. There is no reference to the boiling point of other diluents in this invention, nor to any possible advantages of sensitizers and diluents for a particular composition. The foot ketone peroxide formulations described in British Patent No. 1,072,728 and U.S. Patent No. 3,649,546 are adversely affected due to the negative effects of the esters and hydrophilic desensitizing agents used on the unsaturated polyester resin. Among them, unsaturated polyester resin is usually used for curing. In summary, the -4-528776 Λ 7 Β7 disclosed here _ ----- ------ V. Description of the invention (2) _ The ketone peroxidation formulations are often due to the compatibility of desensitizers with water The problem is that gel coat penetration increases and causes foaming problems. British Patent No. I, 470,012 discloses a specific ketone formulation which is considered safe by the industry. This particular solvent system must be at least 175. (: Above mild boiling, the temperature range is at least 40 C. In this reference, the solvents selected are diols and phosphates that can be classified as hydrophilic substances. US Patent No. 4,052,464 series discloses di-tertiary butyl peroxide Preparation of oxidized ketals, in which ethylbenzene is used as a reaction medium for azeotropic removal of water. In addition, the 'reaction medium may contain a diluent with a boiling point greater than ethylbenzene. However, this patent does not describe such a composition U.S. Patent Nos. 4,13 1,72 8 and 4,178,263 disclose ways to desensitize vibration-sensitive peroxides by using at least one heterogeneous I-comonomer (copolymerization) monomer for dilution. However, it is stated in International Patent Application No. WO93 / 25615 that these peroxides use oligomers of styrene and a comonomer as a diluent. These patents do not disclose or suggest this specific What kind of advantages can the thinner composition bring. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, rw (read the precautions on the back before filling out this page)-1- i. European Unpublished Patent Application No. 942 ( j2135.3, 942〇21361, and 9: > 2 005 42 · 9, which are transportable and storage stable cyclic ketone peroxide groups & products, wherein the composition contains one of 1.0-90% by weight Or a kind of ketone peroxide, and one or more dilutions of 10-99% by weight. The diluent in 〃 is selected from liquid desensitizers, plasticizers, solid polymerization carriers = inorganic carriers, organic peroxides. Oxides and their compositions for the use of such cyclic ketone peroxide compositions in (co) polymerization processes and (co) polymer modification. The first two patent applications are filed in 7994 @ 2 夏The third is filed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs and printed 528776. V. Invention Description (3 on March 6, 1995. It can be clearly understood from the above description that the peroxide formula has long been quite considerable. Note: The main objective of this patent is to formulate a composition that can be safely manufactured, transported, stored, and handled. In addition, the present invention also intends to formulate a peroxide composition with a content of active oxygen as much as possible, so that Adverse effects of peroxide compositions A diluent is a good basis. Summary of the Invention _ The inventor of the present invention has inadvertently found that "a desensitizing agent with a boiling point difference of at least 20 or more may allow a safer peroxy compound composition formulation, where the difference is greater than 50 C Che Fu Jia. Assuming that the final composition contains peroxides, one of the desensitizers may be a solid or wax, and the desensitizer and the other adducts selected are liquid at 2 temperature. Although one of the desensitizers is also It may be a finely divided phase, such as a suspending agent, emulsifier, or foaming agent, but the liquid composition is still preferably in a homogeneous state. Therefore, the present invention first provides a safer peroxide composition containing at least two kinds of Desensitizers with a point difference greater than 20τ, and a difference of more than 50j is preferred. The active oxygen concentration is higher than that with 'acceptable characteristics, but with: one desensitizer or two that do not meet the stagnation point requirements. Desensitizer-based composition. The invention of human Γ is related to the radical polymerization process, the cross-linking reaction, the polymerization and exemption process, and others such as the synthesis of specific chemical substances, including peroxidation, and these compositions. According to the present invention, by using various peroxide compositions, the amount of the desensitizer can be reduced to increase the loading of the U compound 'or produce a product with improved characteristics. -6- (Please read the note t. On the back before filling in this page; > IIJτν 、-口-528776 Λ 7 Β7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (4) Second 'The present invention relates to non-cyclic ketone peroxide compositions, which mainly contain non-polar sensitizers, but contain little or no hydrophilic sensitizers. These formulations can make unsaturated polyester resin substances Less permeation occurs during manufacture. These and other objects of the present invention will be clearly understood from the following summary and detailed description of the invention. DESCRIPTION OF THE INVENTION The composition of the present invention has an equivalent peroxide concentration but only one desensitization Agent, or the same peroxide composition that contains two desensitizing agents but does not meet the special boiling point requirements herein. "Safer" here means that the combination of the present invention is shown in at least one of the following tests The properties have been improved:-Deflagration test (deflagration),-Time dust test (detonation),-Koenen test (heating under specific conditions), and _ pressure valley as test (heating under specific conditions) ). Reform means that the level of the test result is low. In other words, in the deflagration test, it changed from "yes, rapid" to "yes, slow", or from "yes, slow" to "none", and in In the test of heating under specific conditions, it changed from "intense" to "medium", from "medium" to "low i ya" and horse I low ", or from" low "to" none ". Full test Fe and related standards are passed on to "people of money, ikf knowledge + Department of Green" in "United Nations Recommendations, Test Manuals and Standards for Transport of Dangerous Goods ST / SG / ΑΓ 10 / 1W Di, Card WMWAC.10 / 11 / Revision Edition No. "Second Edition", Lian Shiguo's New York, New York, New York, and New York, ^ > '^ years, including time pressure test, deflagration test, Conan test and pressure capacity crying M " Λ Gang * Dair " The hard work is to know that it is recorded in the United Nations military. ¾ younger C · 1, united ρ σ national heart younger C.2, United Nations test No. E.1 -7- This paper standard applies to the Chinese national standard隼 (f Please read the following: /JE.*. Matters • Fill out this page}

528776 Λ 7 Β7 V. Description of the invention (5) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs and UN Test No. E. 2. According to the present invention, the peroxide composition is characterized by the use of at least two desensitizing agents under the following conditions: 1) among all possible desensitizing agent pairs, at least one of which has a boiling point difference of more than 20 ° C, and The difference is 50X: the above is better; 2) In the deflagration test and the time pressure test, the final composition showed no or slow deflagration, and in the pressure vessel test and / or the Conan test, no intense thermal explosion effect was observed . The desensitizing agent with the lowest boiling point should have a boiling point that will not cause or slowly detonate the peroxide composition during the deflagration and time pressure tests. The boiling point is at 30. It is preferably between 0 and 3 00 C 'and more preferably between 100 X: and 250 ° C. The best boiling point is between 100 C and 200 C. For low boiling point sensitizers, the acceptable boiling point will depend on the concentration of peroxides, peroxides in the composition and the concentration of low boiling point sensitizers. In the deflagration or time pressure test, the peroxide concentration must be reduced every time a rapid deflagration occurs, and the low-boiling point desensitizer concentration must be increased, or a lower-boiling point desensitizer must be used. Similarly, whenever the composition passes a deflagration or time pressure test, the peroxide concentration in the composition may be increased, and the concentration of the low stagnation point desensitizer may be reduced, or a higher boiling point may be used Desensitizer. When the non-mounting ketone peroxide is desensitized, it is preferable to limit the low boiling point desensitizer to non-polar substances. Non-polar desensitizers are all agents that have little affinity for water. In this patent, a non-polar desensitizer is defined as a solvent that is not an alcohol, an ester, and / or a cyclic amine. Select the desensitizing agent with the highest boiling point to make the composition pass the pressure vessel test (PVT) and Conan test, that is, under no circumstances will this be observed: This paper rule is applicable (please read the note on the back first) Matters re_fill this page

In 1 * " --- · Is --- --a = --- --..... ^ 衣 ---. 、-口 ——. Tm · mu m inm · 528776 Λ 7 ---_ Β7 5. Description of the invention (δ) The test has an intense hot explosion effect. The boiling point of this high boiling point desensitizer should be at least 20 ° C higher than the lowest boiling point desensitizing agent, and the difference is preferably above 50 ° C. The boiling point of the South and 'Fu point sensitizer is 100 ° C and 700. (: Is better, between 200 C and 600 ° C. For high-boiling point desensitizers, it is acceptable.) Epoxy point will be adjusted according to the peroxide, peroxide concentration and high boiling point Depending on the concentration of the sensitizer. Whenever the composition does not pass the PVT or Conan test, the concentration of peroxide must be reduced and the concentration of high boiling point desensitizing agent must be increased 'or a higher boiling point desensitizing agent must be used When a substance passes the PVT or Conan test, it may be necessary to increase the concentration of peroxide and reduce the concentration of the high Buddha point desensitizer, or use a lower boiling point desensitizer. Under the knowledge of this information, if the technician understands these materials, if only one desensitizer 'or two or more desensitizers that do not meet the boiling point requirements are used, the peroxide composition will be formulated with a peroxide concentration that is less than an acceptable level. No problem at all. The weight ratio of all low boiling point to high boiling point desensitizers in the composition can be patented. The weight ratio of the low boiling point and high boiling point desensitizers is preferably between 20: 1 and 1:20. The weight ratio is more preferably between 10: 1 and 1: i0. The best weight ratio is between 5: 1 and 1 ·· 5. ‘'The median boiling range U 1¾ is replaced whenever the desensitizing agent does not show a specific boiling point. In a further specific embodiment of the present invention, the existing peroxide composition containing a desensitizing agent can be improved by using a second desensitizing agent whose boiling point is different from the first desensitizing agent by 20 X: Above, and with a difference of 50 X: Above is good. In these novel compositions, higher peroxide concentrations can be used as long as the safety characteristics have not deteriorated. ___ -9- Size of this paper: Standard ((: μΓΓ ^ 4 Specification (2 丨 〇: < 297 Gongyi-(Please read the precautions on the back before filling in this page — —m m

1T printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 528776 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 衮 Λ 7 -----_________ B7 V. Description of the Invention (7) — ~~ --- '^ 本本 明 配 配The peroxides include peroxide esters, percarbonates, oxybicarbonates, difluorenyl peroxides, peroxyketals, organic peroxides, and ketone peroxides. According to the present invention, these peroxides are liquid when they are combined with a desensitizing agent at room temperature. Illustrative examples of these peroxides are tertiary peracetates' from linear, branched, and cyclic C3_Ci3 ketones or c4_c2O diisocyanates (over shrinkage), and from linear, branched, and cyclic c3_c13 酉 ketone peroxides derived from the same or C4-C2Q dione. Organic peroxides used for the preparation of peroxides are not only hydrocarbons, but also unsaturated smoke, which may also contain one or more cyclic hydrocarbon groups or aryl groups. Moreover, the organic peroxide may contain one or more organic peroxide groups. The invention relates more preferably to ketone peroxides comprising at least two desensitizing agents. The ketone peroxide may be cyclic or acyclic. Desensitizers with at least the lowest boiling point are non-polar cars. Ketone peroxides can be made by reacting ketones with hydrogen peroxide as described in the following documents; these disclosures are incorporated herein by reference: U.S. Patent No. 3,003,000; Uhlmann, Third Edition, No. Volume 13, pp. 256-57 (1962); thesis "Research on Organic Peroxides. Χχν. Preparation, Separation and Identification of Peroxy 'Compounds Derived from Fluorenyl Ethyl Ketone and Hydrogen Peroxide", Milas (Milas), NA, Golubovic, A., L Am. Chejn ^ Soc., Vol. 81, pp. 5824-26 (1959), Organic peroxides, Swern, D. ed. , Wiley-Interscience, New York (1970), and Houben-Weyl Methoden der Orgam, che Chemie, £ 13, Vol. 1, p. 736. Appropriate ketones used in the synthesis of the preferred non-cyclic ketone peroxides include, for example, C--10- this paper is sized to the Chinese National Standard (CNS) Λ4 (210x 297 gong)! 1 UJ!?--»15 s Hi I—! In φ (please read the note on the back first and then • fill in this page) Clothing --- i 'T II 、 \' '口 • I--· 1 · Ι lil-i am 1,- --1 · 1 Ilf-I I 1 -11 i— -1 528776 Λ 7 B7 V. Description of the invention (8) Ketone, acetophenone, methyl-n-pentyl ketone, ethyl butyl ketone, ethyl Propyl ketone, methyl isoamyl ketone, methyl heptyl ketone, methyl hexyl ketone, ethyl amyl ketone, monoethyl ketone, dipropyl ketone, methyl ethyl ketone, methyl isobutyl ketone , Methyl Xipropyl, isopropylpropyl hydrazone, methyl-n-butyl ketone, methyl-tertiary butyl ketone, isobutyl heptyl ketone, diisobutyl ketone, cyclohexanone, 2_ Fluorenylcyclohexanone 1, 3, 3, 5-trimethylcyclohexanone, methylfluorenone, phenylmethylketone, phenylethylketone, methylchloromethylketone, methylbromomethyl Ketones, phenylphenyl-pyridine bis._2,4-cyclohexanetrione-1,4_, coupled with their products. Two or more different ketone compositions are also used here. An example of a better peroxide used in the present invention is a cyclic ketone peroxide, in which the equivalent peroxide system is derived from acetone, ethylacetone, fluorenylethyl ketone, methylpropylS, methylisopropyl Ketone, methylbutyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, methyl hexyl ketone, methyl heptyl ketone, diethyl S, hexyl propyl ketone, Ethylpentyl ketone, methyl octyl ketone, methyl nonyl ketone, methyl decyl ketone, methyl undecyl ketone, cyclopentyl ketone, cyclohexanone, 2-methyl cyclohexanone, 3, 3% trimethylcyclohexanone and its composition. The cyclic ketone peroxide is composed of at least two kinds of ketone peroxide ', which may be the same or different in nature. Therefore, the cyclic ketone peroxide may be in the form of a dimer or a trimer. In the preparation of cyclic ketone peroxides, a composition is generally formed, which is mainly composed of dimer and trimer forms. The proportion of each form depends on the reaction conditions at the time of preparation. If urgently needed, this composition can be separated into individual cyclic ketone peroxides. Generally, terpolymers of cyclic ketone peroxides are less volatile and more reactive than dimers. Prefer to use a specific composition or individual compound, depending on the physical properties of the peroxide and the application requirements, _____-11-This paper ⑤ Applicable ^ ~ Please read the note on the back-Matters-^ Fill out this page, ^, 1τ Economy Printed by the Consumer Cooperative of the Ministry of Standards, Ministry of Standards, 528776 V. Description of the invention (9 / $ such as storage stability, half-life and temperature, volatility, boiling point ', solubility, etc. The printer also needs to understand that any form of cyclic ketone peroxidation All materials are included in this article such as oligomers or compositions. Cycloketone peroxides are preferably produced using non-polar solvents such as hydrocarbons. The production of cyclic ketone peroxides is selected from white oil or heteroaliphatic Hydrocarbons are more preferred. Examples of liquid desensitizers that can be used in the composition according to the present invention include various agents, diluents, and oils. In summary, useful liquids include alkanols,% alcohols, alkenyl glycols, Alkenyl glycol monoesters, cyclic ester-substituted alcohols, cyclic amidines, acids, amidines, epoxidized compounds, esters, hydrocarbon-based solvents, halogenated hydrocarbon-based solvents, paraffinic oils, white oils and silicone oils. Examples of hydrophilic g Monoisopropyl vinegar containing monohydric alcohols and dihydric alcohols, diyl 1¾: g-groups with monohydric alcohols, linoleic acid g-groups with monohydric alcohols, alkoxylated vinegars, β-ketoesters, acid esters, phosphoric acid Ester, benzoate, adipate, and citrate, but not limited to this. Among the useful esters of the large-size composition of the present invention printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs, the special esters Examples are: dimethyl acid ester, dibutyl acid ester, diisobutyl acid ester, dioctyl vinegar, diphenyl acid, butyl phenyl ester, 'diacetate, n -Pentyl acetate, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, phenyl acetate, methyl benzoate, ethyl benzoate, cumene benzoate , N-octyl benzoate, isodecyl benzoate, diethylene glycol dibenzoate, monopropanediol dibenzyl § intent, propylene glycol monobenzyl acid Methyl neopentanoic acid, isopentylvaleric acid S purpose, secondary-pentylvaleric acid purpose, n-hexylvaleric acid purpose, diethyladipate g purpose, dioctyl adipate @ Purpose, Diisodecyl adipic acid g, methyl neodecanoate N-butyl neodecanoic acid vinegar, propanediol diacetic acid vinegar, -12- The standard of this paper is applicable to the Chinese National Standard (CNS) Λ4 gauge Luo (210X297 public 528776 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Λ 7 B7 V. Description of the invention (10) Monoacetic acid glycol diacetate, cyclohexyl acetate, neopentyl acetate, methyl-2-ethylhexanoate, n-heptylformate, n- Octyl formate, dipropyl carbonate, dibutyl carbonate, isoamyl propionate, secondary-pentyl propionate, phenyl propionate, butylhexanoate, ethylene glycol di Propionate, heptylpropionate, methylphenyl acetate, octyl acetate, 2-ethylhexyl acetate, propyl caprylate, triethyl phosphate, tricresyl phosphate, trimethyl Fluorenyl phosphate, tolyl diphenyl phosphate, 2-ethylhexyl-diphenyl phosphate, isodecyl-diphenyl phosphate, tri < 2-ethylhexyl) phosphate, dimethyl Methylmethyl phosphonate, chlorinated phosphate, tributyl phosphate, tributoxyethyllinate, methyldecanoate, dimethylsuccinate, diethylsuccinate Ester, dimethylmalonate, diethylmalonate, methylethylsuccinate, diisobutylnylonate, 2,2,4-trimethyl-1,3-pentane Diol-diisobutyrate, diethyl oxalate, methyl p-toluate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate Dibasic acid esters, dibutyl butyl butyl ether, ethyl succinic acid, dibutyl volatile acid g, and dibutyl maleate, such as dibutyl maleate. Examples of more useful hydrocarbon solvents include ':' hydrogenated oligomers such as pentane, pentane, heptane, isodecane, toluene, xylene, 1, pentylbenzene, isopentylbenzene, alkane, o- -Diisopropylbenzene, m-diisopropylbenzene, p-diisopropylbenzene, n-decane, 2,4,5,7-tetramethyloctane, n-pentylmethylbenzyl, 1 , 2,3,4_tetramethylbenzene, 3,5 · diethyltoluene, hexane, and combinations thereof, but not limited thereto. Useful hydrogenated hydrocarbons, including: trichlorobenzene, 3-bromo-meta-xylene, 4-bromo-o-xylene, 2-bromo_m-xylene, 4_bromo-m-xylene, 5 -Bromo-m-xylene, o-dibromobenzene, p-dibromobenzene, 14-dibromobutane j— In —I · 111 I— 1 -i I:-H-- Pack-4 ( Please read the note on the back first, “fill this page m · ^ n ^ n tmv * order -13-528776 A 7 ______ B7 V. Description of the invention (11) — Γ, 1, 1-2 &> stinky _ 2, 2-Gas diacetylene, bromoxin, tetrabromoacetamidine, 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, and combinations thereof. More preferred hydrocarbon solvents include isoparaffins (Isopar ®) B, isoparaffin c, isoparaffin E, isoparaffin Η, isoparaffin J, isoparaffin K, isoparaffin L, isoparaffin M, isoparaffin V, Axor (Exxsol® ) Hexane, Axor heptane, Axor D145 / 160, Axor D40, Varsol® 40, Vasso 60, Solvesso® 100, Solvaso 150, Shuttle Weissaw 200, Shellsol® T, Shellsol TD 'Shellsol-D40, Shellsol D60, Shellsol D70, Shellsol D90, Shell D100 and its composition. Examples of aldehydes used in the composition of the present invention include n-chlorobenzaldehyde and decanal. Examples of ketones used in the composition of the present invention include phenyl methyl ketone and isophorone , Isobutyl ketone, methylphenyl dione, dipentyl ketone, diisoamyl ketone, ethyl octyl ketone, ethyl phenyl ketone, acetone, methyl-n-pentyl ketone, ethyl butane Ethyl ketone, ethyl propyl ketone, methyl isoamyl ketone, methyl heptyl ketone, methyl hexyl ketone, ethyl amyl ketone, diethyl ketone, dipropyl ketone, methyl ethyl ketone, methyl ethyl ketone Methyl isobutyl hydrazone, methyl isopropyl g, methyl propyl ketone, methyl-tertiary-butyl ketone, isobutyl heptyl ketone, iso-isobutyl ketone, 2,4-pentanediamine Printed by the Standards Bureau's Consumer Cooperatives' (please read the note on the back-the matter before filling out this page) Different, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 3,5-octanedione, 5-methyl-2,4-hexanedione, 2,6-dimethyl-3,5-heptanedione, 2,4-octanedione, 5,5-di Methyl-2,4-hexamethylene difluoride, 6-methyl-2,4-heptanedione, 1-phenyl-1,3-butanedione, ^ phenyl-1,3-benzodione, 1 , 3-diphenyl-1,3-propanedione, 1-phenyl-2,4-pentanedione, cyclohexanedione-1,4, methyl ethyl ketone, phenyl ethyl ketone, methyl chloride Methyl ketone, methyl bromomethyl ketone and their coupling products. Examples of cyclamidine include 2-pyrrolidone, N-methylpyrrolidone, it dimethyl_ -14- This paper applies the China National Standard (CNS) ) Λ4 size (210X 297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 528776 Λ 7

Each is the same as 3,3-dimethyl-2-carbone. An example of an epoxy compound used in the composition of the present invention is styrene oxide. -Examples of useful alcohols are n-butanol, secondary octanol, octanol, decanol, tetrakisanol, 1,4-dimethylolcyclohexane, cyclohexanol, glycerol, ethylene glycol, Polyethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, hexanediol, 1,4-butanediol, 2,3-butanediol, butanol,丨, 5-pentanediol, 3,6-dimethyloctane_3,6_diol, 2,5_dimethyl_ • hexane block_2,5_diol, 2,4, 7 > Tetrafluorenyldecane'7-diol earth, 2'2,4,4-tetramethyl-1,3 · cyclobutane alcohol, ethylene glycol monoethanol, ethylene glycol monobutyl ether, two Glycol monoethyl ether, diethylene glycol monobutyl ether. The chain in the composition of the present invention; ^ Smoke oil includes self-chemical chain burning hydrocarbon oil and paraffin diesel oil, but is not limited thereto. Other fats including white oil, epoxidized soybean oil and silicone oil can also be used in the composition of the present invention. Preferred white oils include Marco 52, Marco 82, Marco 172, Primo (Pnm〇1 @) 352, and Beyond (β '), but not limited thereto. Used in the combination of the present invention Soluble solids or waxy substances in the substance include solid chains, polyethylene glycol, polypropylene glycol, polytetrahydro and polycaprolactone. = To = the safety, transportability of the product to the formulation and / Or storage stability / has a serious negative effect, the composition of the present invention may also include other optional adducts. 纟 patents may mention the following adducts; for example: anti-odor oxidants, antioxidants, Antidegradants, UV stabilizers, active auxiliaries, fungicides, antistatic agents, pigments, dyes, coupling agents, dispersing aids, foaming agents, lubricants, process oils and release agents. Appropriate amounts can be used in the industry_ ____ -15- The size of this paper is suitable for towels (CNS) size 8 (21Qx; 297 public) (please read the notes on the back first? Matters, and then fill out this page}

528776 Λ 7 Β7

Adduct. According to the present invention, more preferred compositions include 10-90% by weight of one or more cyclic ketone peroxides, and these compositions include 20-70% by weight of cyclic ketone peroxides. . The composition of the present invention can be used in a general free radical (co) polymerization process to mature unsaturated polyester resins, or to crosslink, degrade, or modify other types of (co) polymers. -The present invention further illustrates the following examples, but is not limited thereto. Examples of rabbits only:-Cyclomethyl ethyl ketone peroxide (cyclo-MEKP), the total active oxygen concentration of which is 10.63%-2,2-bis (tertiary-butyl peroxy) butane (DTBPB), 80%-tertiary-butyl peroxyacetate (TBPA), 70%-methyl ethyl ketone peroxide (MEKP), active oxygen 11.63% (please read the note on the back first) Each entry on this page} Pei · Sensitizer printed by the Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs: Boiling point (° c) 'Flash point (° C)-isoparaffin E 125 7-xylene 140 28-isodecyl Alkanes 185 45-Isoparaffins V 292 132-Dimethyl esters 284 200-Putramol® white oil (such as Exo) 477 250 -16- Standards are applicable to China National Standard (CNS) 8 4 specifications (210x ' 297 公 楚) 528776 Λ 7 ίΠ &quot; ------______ V. Description of the invention (14)-The total active oxygen content in the peroxide composition of other materials can be determined by general techniques. Related ring S is the same as peroxide For the analysis of active oxygen (ac t. 〇) content, please refer to the procedure described in European Patent Application No. 94202 136.1. Regarding the dimer / trimer ratio (D / T), which can be determined by gas chromatography (GC) technology as described in European Patent Application No. 94202 136.1. Procedures and standards for time pressure test, deflagration test,-Conan test and pressure tolerance test , Revealed separately, United Nations Test No. cj in "United Nations Recommendations, Test Manuals and Standards for Transport of Dangerous Goods ST / SG / AC.10 / 11 / Rev. 2nd Edition" (United Nations, New York and Geneva, 1995) United Nations Test No. C.2, United Nations Test No. ej, and United Nations Test E · 2. (Please read the notes on the back -fr to fill out this page-I -US * ...... II 1- 1-¾ -.......-!-!-. · Contact: Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs --- 17- This paper applies to this standard} (528776 Λ 7 Β7 V. Description of the Invention (15) Examples 1 -3 and Comparative Examples A and B Example 1 Example 2 Example 3 Example A Example B Ring MEKP content (active oxygen) 6% 6% 6% 6% 6% D / T 9.5 / 90.5 10 / 90 6/94 17/82 25/75 Desensitizer, weight ratio A: B = 1: 1 A: B = 3: 1 A: B = 9: 1 AB PVT, series 2 mm, lower 2 mm, 3 millimeters low, 8 millimeters medium Medium 14 mm, intense Conan test, series <1 mm, low &lt; 1 mm, low &lt; 1 mm, low &lt; 1 mm, low &lt; 1 mm, low deflagration test, series 0.21 mm / s 7 No 0.24 mm / s' No 4.34 mm / s Yes, slow 3.9 mm / slow Yes, slow 0.02 mm / s, no TPT, stages &lt; 20.7 bar, no &lt; 20.7 bar, no 770 ms, yes, slow &lt; 20.7 bar, none &lt; 20.7 bar, none (please read the note on the back to fill out this page first) Desensitizer A is Primo® 352 Desensitizer B is isodecyl. * 'Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs According to the present invention, this formula has accepted safety characteristics, while a solvent-based formula does not. -18- This paper size is applicable to China National Standards (CNS) Λ4 specification (210X 297) 528776 7 7 Λ Β Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (16)

Example 4 and Comparative Examples C and D Example 4 Example C Example D DTBPB content 60% 60% 60% Desensitizer, weight ratio C: D = 1: 1 CD PVT, stage 6 mm, medium 6 mm, medium 22 Mm, intense Conan test, stage 1.5 mm, medium 1.5 mm, medium 10 mm, intense deflagration test 'stage 0.289 mm / sec, no 0.694 mm / sec, yes, slow 0 mm / sec', TPT, stage 1997 Millisecond, yes, slow 2227 milliseconds, yes, slow &lt; 20.7 bar, without desensitizer C is isoparaffin V. Desensitizer D is isoparaffin E. Peroxide formulations containing isoparaffin E have failed PVT stages. According to the present invention, the characteristics of the composition in the deflagration test have been improved compared to the formulation containing isoparaffin V. -19- The national standard of this paper is applicable to a national standard, CNS) Λ4 specification (2l0X 297 gigabytes) (Please read the notes and notices on the back -r to fill out this page)

528776 Λ 7 Β V. Description of the invention (17) 111 ·· I— I i · Example 5 and Comparative Examples E and F Example 5 Example E Example F TPA content 60% 60% 60% Desensitizer, weight ratio + E : F = 1: 3 CD PVT, stage 6 mm, medium &gt; 24 mm, intense 7 mm, medium Conan test 'stage 1 mm, lower 1 mm, lower 1 mm, low deflagration test, stage 0.146 mm / Second, no 16.7mm / s, fast 0.105mm / s, no TPT, stage 1668ms, yes, 467ms slow, yes, 3557ms slow, yes, please read the note f on the back first; Η: fill in This page ii-.s. Ϊ— I —ill Desensitizer E is isoparaffin V. The desensitizer F is isoparaffin E. TBPA formulations containing isoparaffin V failed PVT and deflagration test stages. According to the present invention, the PVT and TPT stages of the composition have been improved compared to a formulation containing only isoparaffin E. Ding ---,-> \ 口 I--. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs -20- This paper size applies to the Chinese National Standard (CNS) Λ4 specification (210 × 297 public epidemic) 528776 '\ Ί ----- Β7 V. Description of the invention (18) l ^ n In n ^ — ni m · Repeated] 6 and comparative ^ Q Example 6 Example G--_... · &quot; μεκρ content (active oxygen ) 8.92 8.92 Desensitizer, weight ratio * H: G 2 0.69: 1 G PVT, series 1 mm, lower 4 mm, middle Conan test, series 1 mm, lower 2 mm, intense deflagration test, series 0.318 mm / S, no 0.190 mm / s, no TPT, 2140 milliseconds, slow 820 milliseconds, slow i &quot; (Please read the notes, precautions, and then fill out this page on the back) The desensitizer is xylene. Desensitizer G is a dimethyl ester. Examples show that the commercially available MEKP formulations based on MEKP can be modified by adding low boiling point desensitizing agents such as xylene. In particular, the negative effects of the 'heating composition' in the limited second room can be greatly reduced. 1 mm i * -I--1-1-Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. -21-) 8 size 4 (210X 297 公 # ·)

Claims (1)

528776 Patent Application No. 087101713 Amendment to Chinese Patent Application Park (September 91) A8 B8 C8 D8 6. Application for a patent Fan Yuan 1. A peroxide composition that is liquid at room temperature and has a grade of "low" or "medium" in the pressure vessel and Koenen test. And there is no deflagration or very low deflagration, which is characterized by containing at least two desensitizing agents with a boiling point difference of more than 20%, and at least one of which is non-polar. Tributyl peroxyketal with ethylbenzene and a high boiling point diluent, and &amp; and contains at least one peroxide selected from the group consisting of cyclofluorene peroxides, peroxyesters, difluorene peroxides, peroxides Oxydicarbonate, peroxocarbonate, peroxocondensation, dialkyl peroxide, organic peroxide, and competing compounds. 2. The composition according to the scope of the patent application, page j, characterized in that it is characterized by at least one peroxide-based acyclic ketone peroxide. 3. The composition according to item 1 or 2 of the scope of the patent application, wherein at least one of the sensitizers is a hydrocarbon. 4. According to the patent scope of the request! &amp; The composition of item 2, wherein the boiling point of the low stagnation point desensitizing agent is lower than 200 t. 5. According to the group 1 or 2 of the scope of the patent application, Yagan Ganshan, and the mouthpiece, wherein the peroxide is a ketone peroxide. The series in the pressure vessel and Conan test is "low $" Shi... _ &Amp; Medium ", not right A desensitizing agent is non-polar 6.-A peroxide composition in the urban state at room temperature, [Composition in , Peroxy carbonic acid has a very low deflagration or deflagration with a boiling point difference of 20 ° C K, and a plant containing at least -peroxy esters, dioxane, 528776 A8 B8. 8 &quot; &quot; &quot; --------- D8 VI. Patent Application ^ ---, peroxyketal, dialkyl peroxide, organic peroxide and their blends , It is used for curing unsaturated polyester resin, or used in the production process involving (co) polymer cross-linking, degradation or other modification. 7. The peroxide composition according to item 6 of the scope of the patent application, wherein the non-polar desensitizer is a low-boiling point, which is used to mature the unsaturated polyester resin. 8. The peroxide composition according to item 6 or 7 of the scope of the patent application, wherein the peroxide is an acyclic ketone peroxide, which is used for spraying unsaturated polyester resins. 9. The peroxide composition according to any one of claims 1 or 2 of the scope of patent application, which is used in a radical (co) polymerization method. -2- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)