WO1998033770A1 - Peroxide compositions with improved safety characteristics - Google Patents
Peroxide compositions with improved safety characteristics Download PDFInfo
- Publication number
- WO1998033770A1 WO1998033770A1 PCT/EP1998/000391 EP9800391W WO9833770A1 WO 1998033770 A1 WO1998033770 A1 WO 1998033770A1 EP 9800391 W EP9800391 W EP 9800391W WO 9833770 A1 WO9833770 A1 WO 9833770A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- peroxide
- ketone
- phlegmatizer
- compositions
- boiling
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C409/00—Peroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
- C07C407/003—Separation; Purification; Stabilisation; Use of additives
- C07C407/006—Stabilisation; Use of additives
Definitions
- the present invention relates to liquid formulations of peroxides that need to be phlegmatized in order to fulfill safety requirements.
- peroxides Numerous peroxides are known that need to be phlegmatized with an inert diluent or solvent in order to permit their safe handling and use.
- concentration of active oxygen in the final formulation must be very low.
- such formulations with low peroxide concentrations are mostly undesirable, since the application of the formulation will lead to high levels of undesired inert diluent or solvent in the resulting material.
- U.K. Patent 1 ,072,728 discloses specific ketone peroxides formulations comprising at least one particular hydrophilic solvent that renders the formulation safe. It is not suggested that other combinations of solvents, not being the hydrophilic solvents in suit, would permit safe peroxide compositions with an even higher active oxygen content.
- U.S. Patent 3,649,546 relates to non-hazardous ketone peroxide polymerization initiators wherein ketone peroxides are formulated in esters with boiling points in the range of 140-250°C. Such compositions may also contain another compatible diluent. No reference is made to any requirements in respect of the boiling point of the additional diluent, nor to any advantages that specific combinations of phlegmatizer and diluent may have.
- ketone peroxide formulations as described in both U.K. Patent 1 ,072,728 and U.S. Patent 3,649,546 suffer from the fact that the esters and hydrophilic phlegmatizers that are used therein, have a negative effect on the unsaturated polyester resins wherein they are typically applied for curing. More particularly, in gel coats, the disclosed ketone peroxide formulations will often lead to an increased osmosis and to the related blistering problems, because of the compatibility of the phlegmatizer and water.
- U.K. Patent 1 ,470,012 discloses specific ketone formulations that are considered to be safe and whereof the specified solvent system must boil smoothly over a range of at least 40°C at temperatures of at least 175°C. Also in this reference, the solvents of choice are glycols and phosphates, that can be classified as hydrophilic materials.
- U.S. Patent 4,052,464 discloses the preparation of di-tert.butylperoxy ketals using ethylbenzene as a reaction medium to enable the azeotropic removal of water. Additionally, the reaction medium may contain a diluent having a boiling point higher than that of ethylbenzene. However, no benefits of such a combination are given.
- a combination of phlegmatizers with boiling points that are at least 20°C, preferably more than 50°C, apart permits the formulation of safer peroxide compositions.
- One of the phlegmatizers may be a solid or wax, provided that the final composition including peroxide, the phlegmatizers and optional other additives is in liquid form at handling temperatures.
- the liquid composition is homogeneous, although one of the phlegmatizers may also be in a finely dispersed form, for example in suspension, emulsion, or vesicle form.
- the present invention provides in a first aspect, safer peroxide compositions comprising at least two phlegmatizers that have boiling points more than 20°C, preferably more than 50°C, apart, with an active oxygen concentration greater than the active oxygen concentration of compositions with acceptable characteristics based on one phlegmatizer or two phlegmatizers not satisfying the boiling point requirement.
- the present invention relates to the use of these compositions in radical polymerization processes, including curing reactions of unsaturated polyester resins, cross-linking reactions, polymer modification processes, and other reactions involving peroxides, like the synthesis of certain chemicals.
- the present invention relates to, preferably non-cyclic, ketone peroxide compositions that comprise no hydrophilic phlegmatizers or reduced levels thereof, but mainly so-called apolar phlegmatizers.
- Such formulations allow the production of unsaturated polyester resin articles with increased resistance to osmosis.
- the present invention relates to safe, preferably non- cyclic, ketone peroxides having a reduced viscosity for use in spray-on processes of unsaturated polyester resins.
- compositions of the present invention are safer than compositions of the same peroxide with the same peroxide concentration in which use is made of only one phlegmatizer or of two phlegmatizers not satisfying the boiling point requirement as specified herein.
- “safer” is meant that the compositions of the present invention show an improvement in at least one of the following tests: deflagration test (deflagration), the time pressure test (deflagration), the Koenen test (heating under defined confinement), and the pressure vessel test (heating under defined confinement).
- Improvement means a lower rating in the test result; or , alternatively, for the deflagration test a change from "yes, rapidly” to “yes, slowly” or from “yes, slowly” to “no”; for heating under defined confinement a change from "violent” to "medium”, from “medium” to “low”, or from “low” to “no".
- the peroxide compositions according to the invention are characterized by the use of at least two phlegmatizers, with the conditions that 1) for at least one out of all possible pairs of phlegmatizers the difference in boiling point is more than 20°C, preferably more than 50°C and 2) the final composition shows no or slow deflagration in the deflagration test and the time pressure test and no violent thermal explosion effects are observed in the pressure vessel test and/or the Koenen test.
- the phlegmatizer with the lowest boiling point should have a boiling point such that no or slow deflagration of the peroxide composition occurs in the deflagration and time pressure test.
- the boiling point lies between 30°C and 300°C, more preferably between 100°C and 250°C. Most preferred are boiling points between 100°C and 200°C.
- Acceptable boiling points for the low-boiling phlegmatizer will depend on the peroxide to be formulated, the concentration of the peroxide in the composition, and the concentration of the low-boiling phlegmatizer.
- the concentration of the peroxide has to be decreased, the concentration of the low-boiling phlegmatizer has to be increased, or a phlegmatizer with a lower boiling point has to be used.
- the peroxide concentration in the composition may be increased, the concentration of the low-boiling phlegmatizer may be decreased, or a phlegmatizer with a higher boiling point may be used.
- the low- boiling phlegmatizer is to be limited to apolar materials.
- Apolar phlegmatizers are all solvents that have little affinity for water.
- apolar phlegmatizers are defined to be solvents that are not alcohols, including glycols, esters, and/or cyclic amides.
- the phlegmatizer with the highest boiling point is selected such that the composition passes both the pressure vessel test (PVT) and the Koenen test, i.e., no violent thermal explosion effect is observed in any of these tests under any of the circumstances.
- This high-boiling phlegmatizer should have a boiling point at least 20°C, preferably 50°C, above that of the phlegmatizer with the lowest boiling point.
- the boiling point of the high-boiling phlegmatizer lies between 100°C and 700°C, more preferably between 200°C and 600°C.
- Acceptable boiling points for the high-boiling phlegmatizer will depend on the peroxide to be formulated, the concentration of the peroxide, and the concentration of the high-boiling phlegmatizer. Whenever the composition does not pass the PVT or the Koenen test, the peroxide concentration has to be decreased, the concentration of high-boiling phlegmatizer has to be increased, or a phlegmatizer with a higher boiling point has to be selected. Similarly, whenever the composition passes both the PVT and Koenen tests, the peroxide concentration may be increased, or the high-boiling phlegmatizer concentration decreased or a phlegmatizer with a lower boiling point may be selected in order to obtain the desired composition.
- any weight ratio between low- and high-boiling phlegmatizer in the composition can be applied. Preferred are weight ratios of low- and high-boiling phlegmatizers between 20:1 and 1 :20. More preferred are weight ratios between 10:1 and 1 :10. Most preferred are weight ratios between 5:1 and 1 :5.
- existing combinations of peroxides with one phlegmatizer can be improved by applying a second phlegmatizer that has a boiling point that differs more than 20°C, preferably more than 50°C, from the boiling point of the first phlegmatizer.
- a second phlegmatizer that has a boiling point that differs more than 20°C, preferably more than 50°C, from the boiling point of the first phlegmatizer.
- higher peroxide concentrations can be used while safety characteristics are not regressed.
- Peroxides that can be formulated according to the invention include peroxyesters, percarbonates, peroxydicarbonates, diacylperoxides, peroxyketals, hydroperoxides, and ketone peroxides. These peroxides are either liquid at room temperature or dissolved in the phlegmatizers according to the invention.
- peroxides examples include tertiary alkyl peracetates, peroxyketals derived from linear, branched or cyclic C 3 -C 13 ketones or C 4 - C 20 diketones, and ketone peroxides derived from linear, branched or cyclic C 3 -C 13 ketones or C 4 -C 20 diketones.
- the hydroperoxide that is used in the preparation of the peroxide may not only be aliphatic, but may, optionally, be unsaturated and may also comprise one or more cycloaliphatic or aromatic groups. Also, the hydroperoxide may contain one or more hydroperoxy groups.
- the invention pertains to compositions of ketone peroxides that contain at least two phlegmatizers.
- the ketone peroxides may be either cyclic or non-cyclic.
- at least the lowest boiling phlegmatizer therein is apolar.
- the ketone peroxides can be made by reacting a ketone with hydrogen peroxide as is described in U.S. Patent 3,003,000; Uhlmann. 3rd Edition, Vol. 13, pp. 256-57 (1962); the article, "Studies in Organic Peroxides. XXV.
- Suitable ketones for use in the synthesis of ketone peroxides include, for example, acetone, acetophenone, methyl-n-amyl ketone, ethylbutyl ketone, ethylpropyl ketone, methylisoamyl ketone, methylheptyl ketone, methylhexyl ketone, ethylamyl ketone, diethylketone, dipropyl ketone, methylethyl ketone, methylisobutyl ketone, methylisopropyl ketone, methylpropyl ketone, methyl-n-butyl ketone, methyl-t-butyl ketone, isobutylheptyl ketone, diisobutyl ketone, cyclohexanone, 2-methyl cyclohexanone, 3,3,5-trimethyl cyclohexanone, methylbenzyl ketone
- Suitable peroxides for use in accordance with the present invention are the (cyclic) ketone peroxides derived from acetone, acetylacetone, methylethyl ketone, methylpropyl ketone, methylisopropyl ketone, methylbutyl ketone, methylisobutyl ketone, methylamyl ketone, methylisoamyl ketone, methylhexyl ketone, methylheptyl ketone, diethyl ketone, ethylpropyl ketone, ethylamyl ketone, methyloctyl ketone, methylnonyl ketone, methyldecyl ketone, methylundecyl ketone, cyclopentanone, cyclohexanone, 2-methylcyclohexanone, 3,3,5-trimethyl cyclohexanone, and mixtures thereof.
- Cyclic ketone peroxides are composed of at least two ketone peroxide entities which may be the same or different.
- cyclic ketone peroxides may be in the form of dimers, trimers, etc.
- a mixture is formed which predominantly consists of the dimeric and trimeric forms. The ratio between the various forms mainly depends on the reaction conditions during the preparation. If so desired, the mixture may be separated into the individual cyclic ketone peroxide compounds.
- the cyclic ketone peroxide trimers are less volatile and more reactive than the corresponding dimers. Preference for certain compositions or individual compounds may depend on differences in physical properties or requirements in application of the peroxides, e.g.
- cyclic ketone peroxides e.g. oligomeric compounds or mixtures
- the cyclic ketone peroxide is produced using an apolar solvent like a hydrocarbon.
- Most preferred phlegmatizers used in the production of the cyclic ketone peroxide are selected from white oils and isoaliphatic hydrocarbons.
- useful liquid phlegmatizers that can be used in the compositions according to the invention include various solvents, diluents and oils. More particularly, useful liquids include alkanols, cycloalkanols, alkylene glycols, alkylene glycol monoalkyl ethers, cyclic ether substituted alcohols, cyclic amides, aldehydes, ketones, epoxides, esters, hydrocarbon solvents, halogenated hydrocarbon solvents, paraffinic oils, white oils, and silicone oils.
- hydrophilic esters include, but are not limited to, monocarboxylic esters of mono- and dihydric alcohols, esters of dicarboxylic acids and monohydric alcohols, carbonates of monohydric alcohols, alkoxyalkyl esters, ⁇ -keto esters, phthalates, phosphates, benzoates, adipates, and citrates.
- esters useful in most of the compositions of the present invention are dimethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, diallyl phthalate, n-pentyl acetate, isopentyl acetate, n-hexyl acetate, 2- ethylhexyl acetate, benzyl acetate, methyl benzoate, ethyl benzoate, isopropyl benzoate, n-octyl benzoate, isodecyl benzoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, propylene glycol dibenzoate, n- butyl pivalate, isoamyl pivalate, sec-amyl pivalate, n-hexyl pivalate, diethyl adipate,
- Preferred useful hydrocarbon solvents include, but are not limited to, hydrogenated oligomers of alkanes, pentane, heptane, isododecane, toluene, ethylbenzene, xylene (o, m, p, or mixtures thereof), mesithylene, amyl benzene, isoamyl benzene, decalin, o-diisopropyl benzene, m- diisopropyl benzene, p-diisopropyl benzene, n-dodecane, 2,4,5,7- tetramethyl octane, n-amyl toluene, 1 ,2,3,4-tetramethyl benzene, 3,5- diethyl toluene, hexahydronaphthalene, and mixtures thereof.
- More preferred hydrocarbon solvents include Isopar® B, Isopar C, Isopar E, Isopar H, Isopar J, Isopar K, Isopar L, Isopar M, Isopar V, Exxsol® hexane, Exxsol heptane, Exxsol D145/160, Exxsol D40, Varsol® 40, Varsol 60, Solvesso® 100, Solvesso 150, Solvesso 200, Shellsol® T, Shellsol TD, Shellsol D40, Shellsol D60, Shellsol D70, Shellsol D90, Shellsol D100 and mixtures thereof.
- Useful halogenated hydrocarbons include phenyl trichloride, 3-bromo-o- xylene, 4-bromo-o-xylene, 2-bromo-m-xylene, 4-bromo-m-xylene, 5-bromo- m-xylene, o-dibromobenzene, p-dibromobenzene, 1 ,4-dibromobutane, 1 ,1- dibromo-2,2-dichloroethane, bromooctane, tetrabromoethylene, 1 ,2,3- trichlorobenzene, 1 ,2,4-trichlorobenzene, and mixtures thereof.
- aldehydes useful in the compositions of the present invention include n-chlorobenzaldehyde and decanal.
- ketones useful in the compositions of the present invention include acetophenone, isophorone, isobutyl ketone, methylphenyl diketone, diamyl ketone, diisoamyl ketone, ethyloctyl ketone, ethylphenyl ketone, acetone, methyl-n-amyl ketone, ethylbutyl ketone, ethylpropyl ketone, methylisoamyl ketone, methylheptyl ketone, methylhexyl ketone, ethylamyl ketone, diethyl ketone, dipropyl ketone, methylethyl ketone, methylisobutyl ketone, methylisopropyl ketone, methylpropyl ketone, methyl-t-butyl ketone, isobutylheptyl ketone, diisobutyl
- cyclic amides examples include 2-pyrrolidone, N-methyl pyrrolidone, 1 ,5- dimethyl-2-pyrrolidone, and 3,3-dimethyl-2-pyrrolidone.
- an epoxide which may be employed in the compositions of the present invention is styrene oxide.
- useful alcohols are n-butyl alcohol, capryl alcohol, octyl alcohol, dodecyl alcohol, tetrahydrofurfuryl alcohol, 1 ,4-dihydroxymethyl cyclohexane, cyclohexanol, glycerol, ethylene glycol, diethylene glycol, polyethylene glycols with molecular weights under 20,000, propylene glycol, dipropylene glycol, neopentyl glycol, hexylene glycol, 1 ,4-butylene glycol, 2,3-butylene glycol, butene diol, 1 ,5-pentane diol, 3,6- dimethyloctane-3,6-diol, 2,5-dimethyl-hex-3-yne-2,5-diol, 2,4,7,9- tetra
- paraffinic oils useful in the compositions of the present invention include, but are not limited to, halogenated paraffinic oils and paraffinic diesel oil.
- white oils include, but are not limited to, Marcol® 52, Marcol 82, Marcol 172, Primol® 352, and Bayol® 82.
- Soluble solid or waxy materials that can be employed in the compositions of the present invention include solid paraffins, polyethylene glycol, polypropylene glycol, polytetrahydrofuran, and polycaprolactone.
- compositions of the present invention may also contain optional other additives as long as these additives do not have a significant negative effect on the safety, transportability and/or storage stability of the formulations.
- additives may be mentioned: antiozonants, antioxidants, antidegradants, UN. stabilizers, coagents, fungicides, antistatic agents, pigments, dyes, coupling agents, dispersing aids, blowing agents, lubricants, process oils and mould-release agents.
- additives may be employed in their usual amounts.
- compositions in accordance with the present invention contain 10-90% by weight of one or more of the (cyclic) ketone peroxides, and most preferably these compositions contain 20-70% by weight of the (cyclic) ketone peroxides.
- compositions of the present invention are useful in conventional radical (co)polymerization processes as well as for curing unsaturated polyester resins and for cross-linking, degradation or other types of modification processes of (co)polymers.
- An important advantage is obtained by using the compositions according to the invention because they are safer and/or they show a higher peroxide content. When using compositions with a higher peroxide content, there will be less contamination of the polymer with the phiegmatizing agents that are used. Hence polymers of improved quality are attainable.
- the peroxides are preferably selected from cyclic or non-cyclic ketone peroxides
- the phlegmatizers are preferably selected from apolar products such as aldehydes, ketones, epoxides, (halogenated) hydrocarbon solvents, paraffinic oils, white oils, silicone oils, and combinations thereof.
- the phlegmatizers are selected from (halogenated) hydrocarbon solvents, paraffinic oils, white oils, and combinations thereof. The use of such apolar compounds in the composition is observed to improve the resistance of the cured resin to osmosis.
- Osmosis is the process where water penetrates the surface of the cured resin product, often a gel coat, and forms sub-surface pockets that are visible on the surface as "blisters". Osmosis is known to be a very serious problem for polyester resin based boat hulls.
- the apolar phlegmatizer is combined with one phlegmatizer that is more hydrophilic in nature, so that at least one of the phlegmatizers is apolar.
- this apolar phlegmatizer is the low- boiling one.
- the compositions when used in the curing process of unsaturated polyester resins, will result in cured resins that hardly suffer from osmosis.
- compositions according to the invention have a reduced viscosity compared with commercial ketone peroxide formulations comprising a conventional hydrophilic phlegmatizer.
- a reduced viscosity is highly desired in processes where an unsaturated polyester resin is used in spray-on techniques.
- at least one of the phlegmatizers of the composition is apolar, since such compositions showed substantially reduced viscosities and very good blending into unsaturated polyester resin.
- Total active oxygen contents of peroxide compositions can be determined with conventional techniques.
- the determination of the dimer/trimer ratio (D/T) in cyclic-ketone peroxides can be accomplished by GC techniques as described in European Patent Application 94202136.1. Procedures and criteria in respect of the time pressure test, the deflagration test, the Koenen test, and the pressure vessel test are disclosed in UN test C.1 , UN test C.2, UN test E.1 , and UN test E.2, respectively, in "United Nations Recommendations on the Transport of Dangerous Goods, Manual of Tests and Criteria, ST/SG/AC.10/11/Rev.2", United Nations, New York and Geneva, 1995.
- Phlegmatizer A is Primol®352 Phlegmatizer B is Isododecane.
- Phlegmatizer C is Isopar V.
- Phlegmatizer D is Isopar E.
- the PVT rating of the peroxide formulation with Isopar E is not acceptable.
- the composition according to the invention has an improved performance in the deflagration test when compared with the formulation with only Isopar V.
- Phlegmatizer E is Isopar V.
- Phlegmatizer F is Isopar E.
- the formulation of TBPA with Isopar V shows unacceptable PVT and deflagration test ratings.
- the composition according to the invention has improved PVT and TPT ratings compared to the formulation of TBPA with just Isopar E.
- Phlegmatizer H is Xylene. Phlegmatizer G is Dimethylphthalate.
- Example 7 An accelerated blistering test was carried out at 50°C using the ASTM D714-56 method.
- Use was made of a turtle box which is a box with portholes closed off by means of a gel coated laminate, with the gel coat side facing the water in the box. The water in the box is stirred and controlled at the testing temperature.
- the gel coated laminate was produced by first casting a 400 ⁇ m (when dried) gel coat based on a commercial iso/npg unsaturated polyester resin system as supplied by De IJssel, and then a 2 mm lamination resin consisting of 70% ortho resin and 30% glass fibre. Both the gel coat system and the lamination resin were cured using 2% by weight of MEKP, based on the system and the resin, respectively.
- both the gel coat system and the lamination resin comprised 1% xylene.
- Example 8 Example 7 was repeated except that the xylene was replaced by diethylene glycol. The amount of blistering is reported below.
- Example 7 representing a curing system in which one of the phlegmatizers of the peroxide composition is apolar, showed an improved resistance to blistering.
- Example 9 and Comparative Example H representing a curing system in which one of the phlegmatizers of the peroxide composition is apolar, showed an improved resistance to blistering.
- Example 9 a composition was made consisting of methylethyl ketone peroxide and two phlegmatizers, viz. DMP and xylene (mixture of isomers).
- the two phlegmatizers were used in a ratio of 56 % by weight and 44 % by weight, respectively, based on the total weight of the two phlegmatizers.
- Comparative Example H only one conventional phlegmatizer was used, viz. DMP.
- the products were evaluated for their viscosity using a thermostatted cone-plate type viscometer with a cone diameter of 28 mm and a cone angle of 3° ex Tokyo Keiki Co. Ltd. Japan (type E) as well as their mixing behaviour with an unsaturated polyester resin at a temperature of 5°C (visual). The following results were obtained.
- composition according to the invention clearly shows great advantages when used in processes where low viscosity and fast mixing with an unsaturated resin are required, such as in spray-on applications.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polymerization Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP53251198A JP2001511201A (en) | 1997-02-03 | 1998-01-21 | Peroxide composition with improved safety properties |
AU60971/98A AU6097198A (en) | 1997-02-03 | 1998-01-21 | Peroxide compositions with improved safety characteristics |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP97200283.6 | 1997-02-03 | ||
EP97200283 | 1997-02-03 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998033770A1 true WO1998033770A1 (en) | 1998-08-06 |
Family
ID=8227978
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1998/000391 WO1998033770A1 (en) | 1997-02-03 | 1998-01-21 | Peroxide compositions with improved safety characteristics |
Country Status (6)
Country | Link |
---|---|
JP (1) | JP2001511201A (en) |
KR (1) | KR20000069953A (en) |
AU (1) | AU6097198A (en) |
TW (1) | TW528776B (en) |
WO (1) | WO1998033770A1 (en) |
ZA (1) | ZA98832B (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0987299A1 (en) * | 1998-09-18 | 2000-03-22 | Elf Atochem Deutschland GmbH | Compositions containing radical-generating agents and phlegmatizers, use and process for the preparation of such compositions |
WO2000023434A1 (en) * | 1998-10-16 | 2000-04-27 | Akzo Nobel N.V. | Improved phlegmatization of cyclic ketone peroxides |
EP1219602A1 (en) * | 2000-12-29 | 2002-07-03 | Akzo Nobel N.V. | Methyl isopropyl ketone peroxide formulations and their use for curing unsaturated polyesters |
WO2002053531A2 (en) * | 2000-12-29 | 2002-07-11 | Akzo Nobel N.V. | Methyl propyl ketone peroxide formulations and their use for curing unsaturated polyesters |
WO2003070699A1 (en) * | 2002-02-22 | 2003-08-28 | Akzo Nobel N.V. | Ketone peroxide compositions |
US7252784B2 (en) | 2002-12-06 | 2007-08-07 | Akzo Nobel N.V. | Cyclic ketone peroxide formulations |
WO2014086692A1 (en) | 2012-12-05 | 2014-06-12 | Akzo Nobel Chemicals International B.V. | Masterbatch comprising a cyclic ketone peroxide |
US20140350167A1 (en) * | 2007-12-06 | 2014-11-27 | Matthias Freese | Peroxide composition |
US9527967B2 (en) | 2012-12-05 | 2016-12-27 | Akzo Nobel Chemicals International B.V. | Peroxide masterbatch based on bioresin |
EP3116865B1 (en) | 2014-03-11 | 2017-11-15 | Akzo Nobel Chemicals International B.V. | Cyclic ketone peroxide composition |
WO2020007820A1 (en) | 2018-07-04 | 2020-01-09 | Fischerwerke Gmbh & Co. Kg | Phthalate-free kit, use for securing anchoring elements in consturction area |
EP3712184B1 (en) | 2019-03-18 | 2023-04-26 | MKT Metall-Kunststoff-Technik GmbH & Co. KG | Fastening system comprising a curing component with at least one benzoate |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4797178B2 (en) * | 2002-12-06 | 2011-10-19 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Cyclic ketone peroxide formulation, improved cyclic ketone peroxide formulation |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1072728A (en) * | 1965-11-17 | 1967-06-21 | Wallace & Tiernan Inc | Stabilised ketone peroxide compositions |
US3649546A (en) * | 1967-05-15 | 1972-03-14 | Norac Co | Non-hazardous ketone peroxide polymerization initiators |
GB1470012A (en) * | 1973-09-10 | 1977-04-14 | Chinook Chem Corp | Ketone peroxide composition |
-
1998
- 1998-01-21 WO PCT/EP1998/000391 patent/WO1998033770A1/en not_active Application Discontinuation
- 1998-01-21 KR KR1019997006166A patent/KR20000069953A/en not_active Application Discontinuation
- 1998-01-21 AU AU60971/98A patent/AU6097198A/en not_active Abandoned
- 1998-01-21 JP JP53251198A patent/JP2001511201A/en not_active Withdrawn
- 1998-02-02 ZA ZA98832A patent/ZA98832B/en unknown
- 1998-02-09 TW TW087101713A patent/TW528776B/en not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1072728A (en) * | 1965-11-17 | 1967-06-21 | Wallace & Tiernan Inc | Stabilised ketone peroxide compositions |
US3649546A (en) * | 1967-05-15 | 1972-03-14 | Norac Co | Non-hazardous ketone peroxide polymerization initiators |
GB1470012A (en) * | 1973-09-10 | 1977-04-14 | Chinook Chem Corp | Ketone peroxide composition |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CZ298322B6 (en) * | 1998-09-18 | 2007-08-29 | Elf Atochem Deutschland Gmbh | Composition in the form of a solution containing substances providing radicals and phlegmatizing agent |
EP0987299A1 (en) * | 1998-09-18 | 2000-03-22 | Elf Atochem Deutschland GmbH | Compositions containing radical-generating agents and phlegmatizers, use and process for the preparation of such compositions |
WO2000023434A1 (en) * | 1998-10-16 | 2000-04-27 | Akzo Nobel N.V. | Improved phlegmatization of cyclic ketone peroxides |
US6358435B1 (en) | 1998-10-16 | 2002-03-19 | Akzo Nobel N.V. | Phlegmatization of cyclic ketone peroxides |
EP1219602A1 (en) * | 2000-12-29 | 2002-07-03 | Akzo Nobel N.V. | Methyl isopropyl ketone peroxide formulations and their use for curing unsaturated polyesters |
WO2002053531A2 (en) * | 2000-12-29 | 2002-07-11 | Akzo Nobel N.V. | Methyl propyl ketone peroxide formulations and their use for curing unsaturated polyesters |
WO2002053531A3 (en) * | 2000-12-29 | 2003-04-10 | Akzo Nobel Nv | Methyl propyl ketone peroxide formulations and their use for curing unsaturated polyesters |
US6642287B2 (en) | 2000-12-29 | 2003-11-04 | Akzo Nobel N.V. | Methyl propyl ketone peroxide formulations and their use in processes to cure unsaturated polyester resins |
WO2003070699A1 (en) * | 2002-02-22 | 2003-08-28 | Akzo Nobel N.V. | Ketone peroxide compositions |
US7252784B2 (en) | 2002-12-06 | 2007-08-07 | Akzo Nobel N.V. | Cyclic ketone peroxide formulations |
US20140350167A1 (en) * | 2007-12-06 | 2014-11-27 | Matthias Freese | Peroxide composition |
US9109107B2 (en) * | 2007-12-06 | 2015-08-18 | Dsm Ip Assets B.V. | Peroxide composition |
WO2014086692A1 (en) | 2012-12-05 | 2014-06-12 | Akzo Nobel Chemicals International B.V. | Masterbatch comprising a cyclic ketone peroxide |
US9527967B2 (en) | 2012-12-05 | 2016-12-27 | Akzo Nobel Chemicals International B.V. | Peroxide masterbatch based on bioresin |
US10316162B2 (en) | 2012-12-05 | 2019-06-11 | Akzo Nobel Chemicals International B.V. | Masterbatch comprising a cyclic ketone peroxide |
EP3116865B1 (en) | 2014-03-11 | 2017-11-15 | Akzo Nobel Chemicals International B.V. | Cyclic ketone peroxide composition |
WO2020007820A1 (en) | 2018-07-04 | 2020-01-09 | Fischerwerke Gmbh & Co. Kg | Phthalate-free kit, use for securing anchoring elements in consturction area |
EP3818026B1 (en) | 2018-07-04 | 2022-08-31 | fischerwerke GmbH & Co. KG | Phthalate-free kit, use for securing anchoring elements in consturction area |
EP3712184B1 (en) | 2019-03-18 | 2023-04-26 | MKT Metall-Kunststoff-Technik GmbH & Co. KG | Fastening system comprising a curing component with at least one benzoate |
Also Published As
Publication number | Publication date |
---|---|
TW528776B (en) | 2003-04-21 |
KR20000069953A (en) | 2000-11-25 |
ZA98832B (en) | 1998-08-05 |
AU6097198A (en) | 1998-08-25 |
JP2001511201A (en) | 2001-08-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO1998033770A1 (en) | Peroxide compositions with improved safety characteristics | |
EP0772609B1 (en) | Cyclic ketone peroxide formulations | |
RU97102726A (en) | COMPOSITIONS BASED ON CYCLIC KETONE PEROXIDES | |
JP2004516310A (en) | Organic peroxide compositions containing reactive desensitizers that are transportable and safely packaged | |
EP0813550B1 (en) | Cyclic ketone peroxides as polymer initiators | |
JP2011173895A (en) | Storage stable cyclic ketone peroxide composition | |
EP1347954B1 (en) | Methyl propyl ketone peroxide formulations and their use for curing unsaturated polyesters | |
ZA200304681B (en) | Peroxide compositions with reactive diluents. | |
US6642287B2 (en) | Methyl propyl ketone peroxide formulations and their use in processes to cure unsaturated polyester resins | |
US7456212B2 (en) | Storage stable cyclic ketone peroxide compositions | |
AU2002237230A1 (en) | Methyl propyl ketone peroxide formulations and their use for curing unsaturated polyesters | |
Weatherhead | Catalysts, accelerators and inhibitors for unsaturated polyester resins | |
JPH1143618A (en) | Curing agent composition | |
EP3249005A1 (en) | Peroxide formulation |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE GH GM GW HU ID IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW SD SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 1019997006166 Country of ref document: KR |
|
ENP | Entry into the national phase |
Ref country code: JP Ref document number: 1998 532511 Kind code of ref document: A Format of ref document f/p: F |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
122 | Ep: pct application non-entry in european phase | ||
WWP | Wipo information: published in national office |
Ref document number: 1019997006166 Country of ref document: KR |
|
WWR | Wipo information: refused in national office |
Ref document number: 1019997006166 Country of ref document: KR |