US3853957A - Oxy substituted peroxyketals - Google Patents

Oxy substituted peroxyketals Download PDF

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Publication number
US3853957A
US3853957A US00727336A US72733668A US3853957A US 3853957 A US3853957 A US 3853957A US 00727336 A US00727336 A US 00727336A US 72733668 A US72733668 A US 72733668A US 3853957 A US3853957 A US 3853957A
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US
United States
Prior art keywords
bis
butylperoxy
peroxyketals
mole
ether
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US00727336A
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English (en)
Inventor
Angelo A D
W Mckellin
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Arkema Inc
Pennwalt Corp
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Pennwalt Corp
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Filing date
Publication date
Application filed by Pennwalt Corp filed Critical Pennwalt Corp
Priority to US00727336A priority Critical patent/US3853957A/en
Priority to DE19691923085 priority patent/DE1923085A1/de
Priority to NL6907012A priority patent/NL6907012A/xx
Priority to FR6914528A priority patent/FR2007986A1/fr
Priority to GB1251427D priority patent/GB1251427A/en
Application granted granted Critical
Publication of US3853957A publication Critical patent/US3853957A/en
Assigned to ATOCHEM NORTH AMERICA, INC., A PA CORP. reassignment ATOCHEM NORTH AMERICA, INC., A PA CORP. MERGER AND CHANGE OF NAME EFFECTIVE ON DECEMBER 31, 1989, IN PENNSYLVANIA Assignors: ATOCHEM INC., A DE CORP. (MERGED INTO), M&T CHEMICALS INC., A DE CORP. (MERGED INTO), PENNWALT CORPORATION, A PA CORP. (CHANGED TO)
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/28—Oxygen or compounds releasing free oxygen
    • C08F4/32—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C409/00—Peroxy compounds
    • C07C409/20—Peroxy compounds the —O—O— group being bound to a carbon atom further substituted by singly—bound oxygen atoms
    • C07C409/22—Peroxy compounds the —O—O— group being bound to a carbon atom further substituted by singly—bound oxygen atoms having two —O—O— groups bound to the carbon atom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
    • C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms

Definitions

  • substituted'peroxyketals of the invention have the formula:
  • R and R are aliphatic or cycloaliphatic biradicals
  • R CR together may form a ring
  • ganic bromine compounds in flame retardant compositions as crosslinking or curing agents in unsaturated polyester resin compositions; as crosslinking agents; and as chemical intermediates in the general manner of known peroxyketals.
  • R and R are the same or different aliphatic or cycloaliphatic biradicals.
  • R C,R together may form a ring which is substituted by Y, Z, and two peroxy (-00-) groups.
  • R ' is an aliphatic, cycloaliphatic or aryl radical.
  • R and R are the same or different H, aliphatic or cycloaliphatic radicals.
  • the aliphatic radical includes substitution by aryl radicals araliphatic radicals and cycloaliphatic radicals.
  • the cycloaliphatic radical includes substitution by aliphatic and by aryl radicals.
  • the aryl radicals may be substituted by aliphatic and by cycloaliphatic radicals. Both cycloaliphatic and aryl radicals may be single ring, such as, phenyland cyclohexyl, or connected rings, such as biphenyl, binaphthyl, bicyclopropyl, bicyclopentyl, or fused rings such as naphthyl, decahydronaphthyl. It is to be understood that the sustituents should not interfere with the desired reaction. In general halogen, oxygen, sulfur and nitrogen substituents or groups containing these do not interfere.
  • R and R each have 1-10 carbon atoms in the aliphatic biradical and 3-12 carbon atoms in the cycloaliphatic biradical.
  • R and R are alkylene, phenalkylene, and cycloalkylene and the corresponding halo substituted radicals.
  • R has 1-18 carbon atoms in the aliphatic radical, 3-12 carbon atoms in the cycloaliphatic radical, or 6-12 carbon atoms in the aryl radical.
  • R is alkyl having 1-12 carbon atoms, phenalkyl having 7-12 carbon atoms, cycloalkyl having 4-8 carbon atoms, or phenyl having 6-12 carbon atoms and c.
  • Y is H, OH or fl h VO Rii;
  • Z is OH or O 40 j f ff e.
  • the compounds of this invention are useful as sources of free radicals which can be used to initiate the polymerization of monomers; as synergists with orthe corresponding halo substituted radicals.
  • R and R are the same or different radicals H, aliphatic having 4-12 carbon atoms, or cycloaliphatic radicals having 4-12 carbon atoms.
  • R and R are the same or different radicals H, aliphatic hydrocarbon having 4-10 carbon atoms, or cycloaliphatic hydrocarbon having 4-10 carbon atoms and each radical affords a tertiary carbon atom which t-carbon atom is joined to a peroxy oxygen atom, for example
  • the hydroxyproducts of this invention can be prepared by the reduction of peroxyketalcarboxylic acids and esters and by the saponification of aceyloxyperoxyketals.
  • the acyloxyperoxyketals are also a new class of peroxy compounds which can be prepared by the reaction of acyloxyketones with hydrogen peroxide or hytone,
  • Acidic catalysts typical of those useful in preparing the peroxyketalesters include: sulfuric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, perchloric acid and strong acid ion exchange resins such as Amberlite 200 and Amberlyst 15.
  • peroxyketals When the peroxyketals are prepared using hydroperoxides they can be reacted further to produce the alcoholic products of this invention where Yd-l or OH, Z OH. If the .ESEWWE!
  • the hydroxyperoxyketal can be obtained by treating the peroxyketalester with a reducing agent of the complex metal hydride type such as lighium aluminum hydride and its chemical equivalents (Reduction With Complex Metal Hydrides, Norman G. Gaylord, Interscience Publishers Inc., N.Y., 1956) which are known to reduce esters to alcohols under mild conditions.
  • a reducing agent of the complex metal hydride type such as lighium aluminum hydride and its chemical equivalents (Reduction With Complex Metal Hydrides, Norman G. Gaylord, Interscience Publishers Inc., N.Y., 1956) which are known to reduce esters to alcohols under mild conditions.
  • the peroxyketal group is in the part of the ester linked to the carbonyl carbon atome thru an oxygen atom, then the hydroxyperketal can be obtained either by simple hydrolysis or saponification or if desired, by reductive cleavage of the ester with the reducing agents indicated above.
  • Typical hydroperoxides which can be used to prepare the products of this invention include t-butyl hydroperoxide, t-arnyl hydroperoxide, chloro-t-butyl hydroperoxide, l,'l,3,3-tetramethylbutyl hydroperoxide, cumyl hydropemxid, P-mntl. '!x .hy!qwr 2 de P n 5 hydroperoxide, diisopropylbenzene hydroperoxide, 2- methyl-2-hydroperoxy-4-hydroxypentane.
  • EXAMPLE I A. PREPARATION OF ACETONYL CAPROATE A mixture of 30.2g. (0.22 mole) of sodium caproate, 25 ml. of caproic acid and 18.5g. (0.20 mole) of chloroacetone was stirred and heated at 110-120 C for 5 hours. After cooling to 30C, 25 ml. of pentane was added, the pentane layer decanted and washed with water and 5% sodium hydroxide solution. After drying over anhydrous magnesium sulfate, the pentane was removed under reduced pressure. The product weighing 16.7g. was obtained in 48.5% yield.
  • the product weighed 6.46g. contained 21.6% of the calculated amount of active oxygen by iodometric assay, and was obtained in 15.1% yield.
  • a reaction mixture containing 17.4g. (0.1 mole) of 1,3-diacetoxyacetone, 21.7g. (0.22 mole) of 90% tbu'tyl hydroperoxide and ml. of benzene was stirred at 0C, while 108g. 77% sulfuric acid was added slowly.
  • the reaction mixture was then stirred at 0C for 4 hours, and the organic layer separated.
  • the organic layer was washed with water, 2% sodium hydroxide solution and finally with 'water, and then dried over anhydrous magnesium sulfate.
  • the product weighed 20.0g. assayed 101.3% of the calculated amount of active oxygen by iodometric assay.
  • reaction mixture was stirred for an additional hour at 0C, the ether layer separated, washed with cold 40% ammonium sulfate solution and then treated with solid sodium bicarbonate to adjust the pH of the aqueous layer to pH 5.
  • the ether layer was separated, dried over anhydrous magnesium sulfate and the ether removed under reduced pressure, leaving 15.57g. of product assaying 7.01% active oxygen by iodometric titration (43.5% of the calculated active oxygen for the desired product).
  • the formulated styrene was self-extinguishing in 2.4 seconds, showing that the peroxidic product was a good flame retardant synergist.
  • EXAMPLE XIV Crosslinking 'of Polyethylene The peroxide crosslinking of polyethylene (Union Carbide DYNH-1)* was carried out by mixing 0.01 equivalent of peroxide with 100g. of polyethylene, on a roll mill and curing the samples in a heated press for 30 minutes to .crosslink the polyethylene. The extent of crosslinking was determined by extracting the crosslinked sampleswith hot xylene, the undissolved. fraction being the crosslinked material.
  • R and R are C -C3 alkylene, C -C -phenaIkyIene or C -C -cycloalkylene; or -R,-CR is a cyclohexylene ring; Yis H or Y is attached to a carbon atom of R which carbon atom also contains an attached hydrogen atom;
  • R is C C -alkyl, C C, -cycloalkyl; C C, phenylalkyl; phenyl, naphthyl, chlorophenyl or nitrophenyl; R and R are H, C -C -alkyl or C -C -cycloalkyl;
  • a peroxyketal of claim 1 having the formula 3. 3,3-Dihydroperoxy-2-methylbutyl pivalate. 4. 1 ,3-Diacetoxy-2,2-bis( t-butylperoxy )pro'pane.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymerization Catalysts (AREA)
US00727336A 1968-05-07 1968-05-07 Oxy substituted peroxyketals Expired - Lifetime US3853957A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US00727336A US3853957A (en) 1968-05-07 1968-05-07 Oxy substituted peroxyketals
DE19691923085 DE1923085A1 (de) 1968-05-07 1969-05-06 Peroxyketale
NL6907012A NL6907012A (enrdf_load_stackoverflow) 1968-05-07 1969-05-07
FR6914528A FR2007986A1 (enrdf_load_stackoverflow) 1968-05-07 1969-05-07
GB1251427D GB1251427A (enrdf_load_stackoverflow) 1968-05-07 1969-05-07

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US00727336A US3853957A (en) 1968-05-07 1968-05-07 Oxy substituted peroxyketals

Publications (1)

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US3853957A true US3853957A (en) 1974-12-10

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US00727336A Expired - Lifetime US3853957A (en) 1968-05-07 1968-05-07 Oxy substituted peroxyketals

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US (1) US3853957A (enrdf_load_stackoverflow)
DE (1) DE1923085A1 (enrdf_load_stackoverflow)
FR (1) FR2007986A1 (enrdf_load_stackoverflow)
GB (1) GB1251427A (enrdf_load_stackoverflow)
NL (1) NL6907012A (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4267109A (en) * 1975-06-30 1981-05-12 Argus Chemical Corporation Cyclic perketals and their use for cross-linking high density polyethylene
US4271279A (en) * 1975-06-30 1981-06-02 Argus Chemical Corporation Cyclic perketals and their use for cross-linking high density polyethylene
US5312997A (en) * 1992-05-11 1994-05-17 Bayer Aktiengesellschaft Surface-active pereoxides and their use
US5866712A (en) * 1996-12-30 1999-02-02 Elf Atochem North America, Inc. Oxalic acid peroxide compositions and uses
US5981787A (en) * 1996-12-30 1999-11-09 Elf Atochem North America, Inc. Peroxyoxalates derived from hydroxy-hydroperoxides

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4285866A (en) 1976-05-21 1981-08-25 Argus Chemical Corporation Cyclic perketals and their use for cross-linking high density polyethylene

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2455569A (en) * 1948-07-20 1948-12-07 Shell Dev Reaction products of tertiary organic hydroperoxides with aldehydes or ketones
US3296184A (en) * 1963-02-14 1967-01-03 Montedison Spa Vulcanizable compositions of olefin polymers or copolymers and vulcanized articles obtained therefrom

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2455569A (en) * 1948-07-20 1948-12-07 Shell Dev Reaction products of tertiary organic hydroperoxides with aldehydes or ketones
US3296184A (en) * 1963-02-14 1967-01-03 Montedison Spa Vulcanizable compositions of olefin polymers or copolymers and vulcanized articles obtained therefrom

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4267109A (en) * 1975-06-30 1981-05-12 Argus Chemical Corporation Cyclic perketals and their use for cross-linking high density polyethylene
US4271279A (en) * 1975-06-30 1981-06-02 Argus Chemical Corporation Cyclic perketals and their use for cross-linking high density polyethylene
US5312997A (en) * 1992-05-11 1994-05-17 Bayer Aktiengesellschaft Surface-active pereoxides and their use
US5866712A (en) * 1996-12-30 1999-02-02 Elf Atochem North America, Inc. Oxalic acid peroxide compositions and uses
US5981787A (en) * 1996-12-30 1999-11-09 Elf Atochem North America, Inc. Peroxyoxalates derived from hydroxy-hydroperoxides

Also Published As

Publication number Publication date
NL6907012A (enrdf_load_stackoverflow) 1969-11-11
FR2007986A1 (enrdf_load_stackoverflow) 1970-01-16
DE1923085A1 (de) 1969-11-27
GB1251427A (enrdf_load_stackoverflow) 1971-10-27

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Owner name: ATOCHEM NORTH AMERICA, INC., A PA CORP.

Free format text: MERGER AND CHANGE OF NAME EFFECTIVE ON DECEMBER 31, 1989, IN PENNSYLVANIA;ASSIGNORS:ATOCHEM INC., ADE CORP. (MERGED INTO);M&T CHEMICALS INC., A DE CORP. (MERGED INTO);PENNWALT CORPORATION, A PA CORP. (CHANGED TO);REEL/FRAME:005496/0003

Effective date: 19891231