WO2013014050A1 - Di-(tert-butyl cyclohexyl) peroxydicarbonate composition - Google Patents
Di-(tert-butyl cyclohexyl) peroxydicarbonate composition Download PDFInfo
- Publication number
- WO2013014050A1 WO2013014050A1 PCT/EP2012/064132 EP2012064132W WO2013014050A1 WO 2013014050 A1 WO2013014050 A1 WO 2013014050A1 EP 2012064132 W EP2012064132 W EP 2012064132W WO 2013014050 A1 WO2013014050 A1 WO 2013014050A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- butyl ether
- tert
- peroxydicarbonate
- composition according
- peroxide composition
- 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
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
Definitions
- the present invention relates to di-(tert-butylcyclohexyl) peroxydicarbonate suspensions, their use and their preparation.
- Di-(tert-butylcyclohexyl) peroxydicarbonate is solid at room temperature and tends to be rather dusty and, therefore, difficult to handle. As a result, this peroxide is preferably handled in the form of a suspension and/or paste instead of its pure form.
- WO 2008/125591 discloses 40 wt% di-(tert-butylcyclohexyl) peroxydicarbonate suspensions comprising polyethylene glycol, (di-)ethylene glycol, and a silica (Aerosil 200).
- the invention therefore relates to a process for the preparation of a suspension comprising di-(tert-butylcyclohexyl) peroxydicarbonate comprising the steps of: a) preparing a pre-mix comprising di-(tert-butylcyclohexyl) peroxydicarbonate, one or more organic solvents, a hydrophilic silica, and a polyalkoxylated butyl ether , and
- the invention also relates to a peroxide composition
- a peroxide composition comprising di-(tert- butylcyclohexyl) peroxydicarbonate, silica, one or more organic solvents, and a polyalkoxylated butyl ether.
- the peroxide is preferably present in the composition of the invention in an amount of at least 10 wt%, more preferably at least 15 wt%, even more preferably at least 20 wt%, and most preferably at least 30 wt%, based on the total weight of the composition, and generally at most 90 wt%, preferably at most 70 wt%, and most preferably at most 50 wt%, based on the total weight of the composition.
- a hydrophilic silica is defined as a silica which has not been treated with organic compounds to increase its hydrophobicity. Examples of such silicas are fumed or pyrogenic silica, precipitated silica, and silica gel.
- the silica is preferably used in the process and the composition of the invention in an amount of at least 0.5 wt%, more preferably at least 1.0 wt%, based on the total weight of the composition, and generally of at most 5 wt%, preferably at most 3 wt%, and most preferably at most 2 wt%, based on the total weight of the composition.
- the one or more organic solvents used in the process and the composition according to the present invention should be able to disperse the di-(tert- butylcyclohexyl) peroxydicarbonate.
- the organic solvent(s) do/does not dissolve the peroxide.
- At least one of the organic solvents used comprises at least one hydroxyl group and/or at least one -OR group, wherein R is a substituent comprising from 1 to 20 carbon atoms.
- the R-group may contain one or more heteroatoms like O, N, or S.
- organic solvent generally does not react with the peroxide or with itself in the presence of the peroxide. For this reason, organic solvents comprising a nitrogen atom are less preferred.
- Suitable examples of organic solvents include glycols such as ethylene glycol, glycerol, diethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol; and phosphorus-containing compounds such as diethyl phosphate, dibutyl phosphate, tributyl phosphate, triethyl phosphate, dibutyl phosphite, and triethyl phosphite.
- Preferred organic solvents are selected from the group consisting of ethylene glycol, glycerol, diethylene glycol, dipropylene glycol, polyethylene glycol, and triethyl phosphate.
- the one or more organic solvents is/are preferably used in the process and the composition of the invention in a total amount of at least 20 wt%, more preferably at least 30 wt%, even more preferably at least 40 wt%, and most preferably at least 50 wt%, based on the total weight of the composition, and generally of at most 90 wt%, preferably at most 70 wt%, and most preferably at most 60 wt%, based on the total weight of the composition.
- the peroxide composition of the present invention preferably comprises less than 20 wt% of water, based on the total weight of the composition.
- the composition comprises less than 10 wt% of water, more preferably less than 5 wt%, and most preferably the composition is free of water.
- water may influence the curing properties - the compositions may not cure at all - and water may impair the mechanical properties of the resulting polymer.
- water is not compatible with apolar organic polymer systems, and will separate out.
- the polyalkoxylated butyl ether is a non-ionic surfactant.
- the polyalkoxylated butyl ether is a polyethoxylated and/or a polypropoxylated butyl ether, more preferably of any of the formulae C H 9 0-(CH 2 CH 2 0) m - (CH 2 CH(CH 3 )0) n H, C 4 H 9 0-(CH 2 CH(CH 3 )0)n-(CH 2 CH 2 0) m H, C 4 H 9 0- (CH 2 CH(CH 3 )0) n H and C 4 H 9 0-(CH 2 CH 2 0) m H, wherein m and n are individually selected from the range 1 -20, more preferably 1 -5.
- the total number of alkoxylate groups is preferably at least 2.
- the polyalkoxylated butyl ether is a polyethoxylated butyl ether. Also mixtures of one or more polyalkoxylated butyl ethers can be used.
- the amount of polyalkoxylated butyl ether used in the process and the composition of the present invention preferably ranges from 0.1 -5.0 wt%, more preferably 0.2- 3.0 wt%, and most preferable 0.3-1.0 wt%, based on the weight of the entire composition.
- the amount of polyalkoxylated butyl ether used depends on the desired viscosity of the composition. If the composition is desired to have the form of a paste, the amount of polyalkoxylated butyl ether is preferably in the range 0.1 -0.5 wt%, more preferably 0.2-0.4 wt%, based on the weight of the entire composition.
- additional compounds may be used in the process and the composition according to the present invention.
- additional compounds include anti-freezing agents, protective colloids, pH-adjusting agents such as calcium oxide or phosphate buffers, sequestering agents, inhibitors, radical scavengers, chain transfer agents, and, if desired, biocides, e.g. fungicides.
- concentration of these compounds will depend on the desired effect and the other ingredients in the composition. Less preferred compounds are phthalates and benzoates like 2-ethylhexyl benzoate, as these generally form an undesirable environmental burden and/or are carcinogenic.
- the additional compounds are present in an amount of at least 0.1 wt%, preferably at least 0.5 wt%, and most preferably at least 1 wt%, based on the total weight of the composition, and generally of at most 20 wt%, preferably at most 10 wt%, and most preferably at most 5 wt%, based on the total weight of the composition.
- the first step of the process according to the present invention is the preparation of a pre-mix comprising di-(tert-butylcyclohexyl) peroxydicarbonate, the one or more organic solvents, the silica, the polyalkoxylated butyl ether, and any optional additional compounds.
- the solvent, the silica, and any additional compounds are first mixed to form a homogenous suspension, after which the di-(tert- butylcyclohexyl) peroxydicarbonate is added and mixed to form a homogeneous suspension, followed by the addition of the polyalkoxylated butyl ether.
- This preparation of the pre-mix can be done in any suitable mixing apparatus, such as a conical mixer (e.g. a Nauta Mixer), a dissolver, a Drais® mixer, or an Ultra- turrax.
- a conical mixer e.g. a Nauta Mixer
- dissolver e.g. a dissolver
- Drais® mixer e.g. a Drais® mixer
- the pre-mix is preferably prepared at room temperature or lower, e.g. -10-25°C, more preferably -5-20°C, and most preferably 0-12°C.
- milling is defined in this specification as a mechanical action resulting in the particle size (d90) of di-(tert- butylcyclohexyl) peroxydicarbonate to be reduced to 200 microns or less, as measured by laser light diffraction using a wet dispersing unit without ultrasonic treatment (e.g. using a Sympatec QUIXEL) in combination with a He-Ne laser (632.8 nm) diffraction sensor (e.g. Sympatec HELOS H0148).
- Milling can be performed in various types of mills, including horizontal grinding mills, vertical grinding mills, ball mills, bead mills, sand mills, high-shear mixers, colloid mills, and electrical transducers that can introduce ultrasound waves into a suspension. It is important to control the temperature of the mixture during milling to below 35°C in order to prevent decomposition of the peroxide.
- a preferred type of mill is a dispax® reactor, which is an inline ultra high shear dispersing machine, which contains one or more rotor-stator combinations (generators) in series. In order to control the temperature, the mixture can be cooled during milling. Alternatively, a dispax® reactor with only one rotor-stator combination can be used, and/or the flow through the dispax® is adjusted to achieve this temperature control.
- the composition of the present invention can have the form of a paste or of a less viscous suspension/slurry.
- the less viscous suspensions preferably have a viscosity less than 10,000 mPa-s.
- composition of the invention can be used in polymer modification processes, cross-linking reactions, mass polymerization processes, and curing processes of, for example, unsaturated polyester, vinyl ester, and acrylate resins, including ortho- resins, iso-resins, iso-npg resins, and dicyclopentadiene (DCPD) resins.
- unsaturated polyester, vinyl ester, and acrylate resins including ortho- resins, iso-resins, iso-npg resins, and dicyclopentadiene (DCPD) resins.
- DCPD dicyclopentadiene
- a variety of monomers and/or polymers can be reacted, including, for example, acrylates, vinyl esters, vinyl halides, vinyl ethers, vinyl aromatic compounds, such as styrene, lower alkenes, polybutadiene, unsaturated imides, methacrylate-butadiene-styrene copolymers, and the like.
- composition of the invention is suitably used in mass polymerization processes, and in particular in the curing of unsaturated polyester resins, acrylate, or vinyl ester resins.
- Di-(tert-butylcyclohexyl) peroxydicarbonate (Perkadox® 16, ex Akzo Nobel; 8,4 kg) was introduced slowly into the mixture within a period of 34 minutes.
- Ethylan NS500 LQ polyalkoxylated butyl ether, ex AkzoNobel
- Example 1 was repeated, except that after the addition of the polyalkoxylated butyl ether, the mixture was stirred at 2°C and this mixture was cooled to -1 °C and then milled. Milling resulted in a temperature increase of 31 °C.
- Example 1 was repeated, except that 140 g Ethylan NS500 LQ was added to a pre-mix of 1 °C and that milling was performed with a flow rate of 325 kg/h.
- Milling resulted in a temperature increase of 25°C; from 1 °C to 26°C).
- Example 3 was repeated except that no polyalkoxylated butyl ether was added. Milling resulted in a temperature increase of 36°C (from -6°C to 30°C).
- Example 5
- Example 3 was repeated except that the temperature of the premix was adjusted to 4°C and milling was performed using a 1 -stage Dispax® reactor. This milling resulted in a temperature increase of only 14°C (from 2°C to 16°C).
- Example 6
- Example 3 was repeated except that the temperature of the premix was adjusted to 3°C and milling was performed using a 2-stage Dispax® reactor. Milling resulted in a temperature increase of 24°C (from -3°C to 21 °C).
- Example 7
- Example 3 was repeated except that different types of surfactants were used.
- the viscosity of the resulting pastes was determined by a pourability test.
- the pourability test consisted of placing 100 g of the paste in an LDPE beaker, turning the beaker upside down for 10 seconds and determining the amount of paste leaving the beaker. If more than 80 wt% of paste left the beaker, the paste was considered 'pourable'. If 10-80 wt% of paste left the beaker, the paste was considered 'slightly pourable'.
- Example 7 was repeated, except that dibenzoyl peroxide was used instead of Di- (tert-butylcyclohexyl) peroxydicarbonate. None of the surfactants listed above turned out to lower the viscosity in a significant way, i.e. all of the formulations remained 'not pourable' as explained in example 7.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Detergent Compositions (AREA)
- Polymerization Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA2841844A CA2841844A1 (en) | 2011-07-22 | 2012-07-19 | Di-(tert-butyl cyclohexyl) peroxydicarbonate composition |
BR112014000886A BR112014000886A2 (en) | 2011-07-22 | 2012-07-19 | process for preparing a composition, peroxide composition and use of the peroxide composition |
US14/232,329 US20140135466A1 (en) | 2011-07-22 | 2012-07-19 | Di-(tert-butyl cyclohexyl) peroxydicarbonate composition |
KR1020147003541A KR20140048969A (en) | 2011-07-22 | 2012-07-19 | Di-(tert-butyl cyclohexyl) peroxydicarbonate composition |
RU2014105594/05A RU2014105594A (en) | 2011-07-22 | 2012-07-19 | COMPOSITION DI- (TER-BUTYL CYCLOGEXYL) -PEROXIDICARBONATE |
JP2014520659A JP5829334B2 (en) | 2011-07-22 | 2012-07-19 | Di- (tert-butylcyclohexyl) peroxydicarbonate composition |
CN201280034863.XA CN103649198A (en) | 2011-07-22 | 2012-07-19 | Di-(tert-butyl cyclohexyl) peroxydicarbonate composition |
MX2014000668A MX2014000668A (en) | 2011-07-22 | 2012-07-19 | Di-(tert-butyl cyclohexyl) peroxydicarbonate composition. |
EP12735573.3A EP2734582A1 (en) | 2011-07-22 | 2012-07-19 | Di-(tert-butyl cyclohexyl) peroxydicarbonate composition |
AU2012289040A AU2012289040B2 (en) | 2011-07-22 | 2012-07-19 | Di-(tert-butyl cyclohexyl) peroxydicarbonate composition |
ZA2014/00179A ZA201400179B (en) | 2011-07-22 | 2014-01-09 | Di-(tert-butyl cyclohexyl) peroxydicarbonate composition |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP11175032 | 2011-07-22 | ||
EP11175032.9 | 2011-07-22 | ||
US201161511179P | 2011-07-25 | 2011-07-25 | |
US61/511,179 | 2011-07-25 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013014050A1 true WO2013014050A1 (en) | 2013-01-31 |
Family
ID=44900884
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2012/064132 WO2013014050A1 (en) | 2011-07-22 | 2012-07-19 | Di-(tert-butyl cyclohexyl) peroxydicarbonate composition |
Country Status (13)
Country | Link |
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US (1) | US20140135466A1 (en) |
EP (1) | EP2734582A1 (en) |
JP (1) | JP5829334B2 (en) |
KR (1) | KR20140048969A (en) |
CN (1) | CN103649198A (en) |
AR (1) | AR087283A1 (en) |
AU (1) | AU2012289040B2 (en) |
BR (1) | BR112014000886A2 (en) |
CA (1) | CA2841844A1 (en) |
MX (1) | MX2014000668A (en) |
RU (1) | RU2014105594A (en) |
WO (1) | WO2013014050A1 (en) |
ZA (1) | ZA201400179B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN111386098B (en) * | 2017-09-28 | 2023-01-03 | 阿科玛股份有限公司 | Delivery system for peroxide compounds and uses thereof |
CN110294973A (en) * | 2018-03-22 | 2019-10-01 | 深圳Tcl工业研究院有限公司 | A kind of ink |
KR20210068519A (en) * | 2018-10-12 | 2021-06-09 | 누리온 케미칼즈 인터내셔널 비.브이. | Solid organic peroxide composition |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998018835A1 (en) * | 1996-10-30 | 1998-05-07 | Akzo Nobel N.V. | Process to make initiator compositions comprising polyvinyl alcohol and surfactant |
WO2008125591A1 (en) | 2007-04-13 | 2008-10-23 | Akzo Nobel N.V. | Peroxide composition |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04117405A (en) * | 1990-05-11 | 1992-04-17 | Atochem Yoshitomi Kk | Aqueous emulsion composition of organic peroxide and its use |
EP1893684B1 (en) * | 2005-06-21 | 2016-08-24 | Akzo Nobel N.V. | Process for modifying inorganic oxygen-containing particulate material, product obtained therefrom, and use thereof |
EP1978493A1 (en) * | 2007-04-05 | 2008-10-08 | Siemens Schweiz AG | Flashing light and combined acoustic/optical alarm for alarm systems |
-
2012
- 2012-07-19 MX MX2014000668A patent/MX2014000668A/en unknown
- 2012-07-19 CA CA2841844A patent/CA2841844A1/en not_active Abandoned
- 2012-07-19 KR KR1020147003541A patent/KR20140048969A/en not_active Application Discontinuation
- 2012-07-19 CN CN201280034863.XA patent/CN103649198A/en active Pending
- 2012-07-19 EP EP12735573.3A patent/EP2734582A1/en not_active Withdrawn
- 2012-07-19 WO PCT/EP2012/064132 patent/WO2013014050A1/en active Application Filing
- 2012-07-19 JP JP2014520659A patent/JP5829334B2/en not_active Expired - Fee Related
- 2012-07-19 BR BR112014000886A patent/BR112014000886A2/en not_active IP Right Cessation
- 2012-07-19 US US14/232,329 patent/US20140135466A1/en not_active Abandoned
- 2012-07-19 AU AU2012289040A patent/AU2012289040B2/en not_active Ceased
- 2012-07-19 RU RU2014105594/05A patent/RU2014105594A/en not_active Application Discontinuation
- 2012-07-20 AR ARP120102664A patent/AR087283A1/en not_active Application Discontinuation
-
2014
- 2014-01-09 ZA ZA2014/00179A patent/ZA201400179B/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998018835A1 (en) * | 1996-10-30 | 1998-05-07 | Akzo Nobel N.V. | Process to make initiator compositions comprising polyvinyl alcohol and surfactant |
WO2008125591A1 (en) | 2007-04-13 | 2008-10-23 | Akzo Nobel N.V. | Peroxide composition |
Also Published As
Publication number | Publication date |
---|---|
ZA201400179B (en) | 2015-06-24 |
KR20140048969A (en) | 2014-04-24 |
CA2841844A1 (en) | 2013-01-31 |
CN103649198A (en) | 2014-03-19 |
AR087283A1 (en) | 2014-03-12 |
AU2012289040B2 (en) | 2015-09-10 |
AU2012289040A1 (en) | 2014-01-16 |
JP5829334B2 (en) | 2015-12-09 |
RU2014105594A (en) | 2015-08-27 |
BR112014000886A2 (en) | 2017-04-18 |
JP2014520942A (en) | 2014-08-25 |
US20140135466A1 (en) | 2014-05-15 |
EP2734582A1 (en) | 2014-05-28 |
MX2014000668A (en) | 2014-03-21 |
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