WO1993017054A1 - Initiateurs de peroxygene inorganique et procedes d'utilisation - Google Patents

Initiateurs de peroxygene inorganique et procedes d'utilisation Download PDF

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Publication number
WO1993017054A1
WO1993017054A1 PCT/US1993/001767 US9301767W WO9317054A1 WO 1993017054 A1 WO1993017054 A1 WO 1993017054A1 US 9301767 W US9301767 W US 9301767W WO 9317054 A1 WO9317054 A1 WO 9317054A1
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Prior art keywords
peroxygen compound
organic
unsaturated polyester
peroxide
inorganic
Prior art date
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PCT/US1993/001767
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English (en)
Inventor
James M. Self
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Abco Industries, Inc.
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Filing date
Publication date
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Publication of WO1993017054A1 publication Critical patent/WO1993017054A1/fr

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    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/04—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters
    • C08F299/0442—Catalysts
    • C08F299/045—Peroxy-compounds

Definitions

  • Unsaturated polyester resin syrups formulated according to the present invention may be employed in the production of coatings, molded or cast, spray-layup and hand-layup products such as flat and profiled building sheets, automobile fenders and other shaped components, furniture, plumbing fixtures such as tub and shower inserts, duct work, 0 boats, electrical component housings, electrical circuit boards, and the like.
  • Unsaturated polyester resins may additionally be used as adhesives, potting compounds, moldings and composites reinforced with fibrous fillers. Such reinforcing materials may include fibers of graphite, glass, aramid and blends.
  • the resins may be extended with inert particuiate 5 fillers and aggregates such as wood flour, silica, glass beads, clay, calcium carbonate and the like. See Bjorksten et al., Polyesters and Their Applications. (Reinhold Publishing Corporation, New York 1960).
  • Unsaturated polyester resins are customarily produced by polyesterification of polycarboxylic acids or polycarboxylic acid anhydrides o and polyols, particularly glycols.
  • the polyester contains at least one ethylenic unsaturation which is customarily present due to the polycarboxylic acid.
  • Unsaturated polyester resins such as polyethylene maleate may be cured, or cross-linked, by mixing the polyester with a suitable vinyl 5 monomer such as styrene. On heating in the presence of an initiator, polymerization takes place so that the vinyl monomer polymerizes at the site of the polyester double bonds and a cross-linked network of polyester chains is produced thereby.
  • the rate of such addition polymerization may be accelerated as explained herein by the addition of promoters such as o organic metal complexes, for example, cobalt napthenate, vanadium octoate, or lithium napthenate and/or amines, for example, phenoidiethanoiamine or triethanolamine.
  • Typical prior art initiators for curing unsaturated polyester resin syrups include the organic peroxygen compounds, of which 5 methylethylketone peroxide and benzoyl peroxide are the most widely used.
  • Other known initiators for curing unsaturated polyester resins include lauroyl peroxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, hydroheptyl peroxide, succinic acid peroxide, butyl peroctoate, df-t-butyl peroxide, di-t-butyl perbenzoate, isopropyl procarbonate, t-butyl 5 perbenzoate, acetyl peroxides, t-butyf peracetate, t-butyl hydroperoxides, di-t-butyl diperphthalate, benzoin, cumene hydroperoxide, cyclohexanone peroxide, the ozonides including di-isopropylene ozonide, and
  • Such initiators have generally been employed as a paste-like mixture of a plast ⁇ cizer and initiator. Additionally, a finely divided, partially soluble, thermoplastic such as polystyrene or polymethylmethacrylate may be added thereto to reduce shrinkage during polymerization, thus resulting in a smoother composite surface. 5
  • the initiator and a promoter, if any, are selected so that the initiation of polymerization of the unsaturated polyester resin syrup can be controlled by the operator. The initiator must be compatible with the promoter and the unsaturated polyester resin to be cured.
  • polyester resin and the processing system will o dictate the promoter, or accelerator, and the particular catalyst, or initiator, that will be used. Cure times may be adjusted, for example, from 72 hours to 10 seconds by proper selection of the types and amounts of various promoters. Gel times may be adjusted, for example, from 24 hours to 3 seconds, depending entirely on the temperature, the reactivity of the resin, 5 and promoter selection.
  • inorganic peroxides have not been so used.
  • Inorganic peroxides such as the peroxydisulphates (also known as persulphates) perborate tetrahydrates (also known as perborates), carbonate peroxyhydrates (also known as percabonates), and other inorganic peroxides such as zinc peroxide and calcium peroxide have, 5 however, been widely used as initiators for emulsion polymerizations of monomers such as vinyl acetate.
  • polymers which have been made using emulsion polymerization techniques employing inorganic peroxygen compounds as initiators include the polyvinylacetates, poly- styrenebutydienes, polymethylmethacrylates, polyvinylchlorides, and 0 polyacrylonitriles, acrylics, polystyrenes, and neoprenes.
  • the inorganic peroxides Prior to the present invention, the inorganic peroxides have not been used to cure unsaturated polyester resins. Moreover, prior to the present invention, it was not known in the art that inorganic peroxygen compounds could be combined with organic peroxygen compounds. 5 Although some initial investigations into combining organic and inorganic peroxygen compounds was done during the 1960's relative to solid rocket fuels research, such combinations generally failed due to their highly explosive nature and incompatability.
  • Another advantage of the present invention is to provide an initiator for curing unsaturated polyester resins wherein an inorganic peroxygen composition is utilized.
  • Yet another advantage of the present invention is to provide an 5 initiator for unsaturated polyester resins comprising inorganic and organic peroxygen compounds.
  • initiators for curing unsaturated polyester resins 5 comprise an inorganic peroxygen composition.
  • the inorganic peroxygen composition may either be in a solid or anhydrous form, or be an aqueous dispersion.
  • An organic peroxygen compound or dispersion may be added to the inorganic peroxygen composition to form the initiator.
  • the organic peroxygen composition may be in a solid, or anhydrous form, or be an aqueous dispersion.
  • inorganic peroxygen compositions such as the peroxy disulfates, the perborates, the percarbonates, the perphosphates and other inorganic peroxides such as zinc and calcium peroxides may be 5 added alone or in the presence of other components, including organic peroxygen compositions, to cure polyester resins.
  • the peroxygen compounds may be added in the presence of a number of further ingredients to permit utilization for particular end uses and to impart certain desirable characteristics thereto. Examples of such ingredients include o defoamers, water soluble inorganic salts, blowing agents, acidic inorganic salts, fire retardants, wetting agents, any of the various promotors previously described or similar thereto, various fillers and piastfcizers.
  • the various inorganic peroxygen initiators of the present invention may be used to initiate cross-finking of any unsaturated polyester resin mixes and may 5 be added thereto according to well-known methods of initiating such cross- linking.
  • Exemplary inorganic peroxygn compositions useful as initiators for curing unsaturated polyester resins according to the present invention include the persulfates, perborates, percarbonates, perphosphates and the o peroxides, and specifically sodium persulfate, ammonium persulfate, potassium sulfate, sodium perborate, sodium percarbonate, zinc peroxide, and calcium peroxide.
  • the inorganic peroxygen initiator is present with respect to said unsaturated polyester resin in an amount of from about 0.1 % weight to 5 about 4.0% weight.
  • Initiators according to the present invention may be employed in a number of different environments, realizing improvement in each due to the nature and characteristics of the composition.
  • inorganic peroxygen compounds are well known as catalysts for emulsion 5 polymerizations but have not been utilized in the free radical polymerication involved in curing unsaturated polyester resin syrups.
  • the organic peroxygen compounds have been the initiator of choice for such systems.
  • inorganic peroxygen compounds as opposed to organic o oxygen compounds have the characteristic of being very stable. Inorganic peroxygn compounds generally do not deteriorate under normal storage conditions over prolonged periods of time if they are kept dry in closed containers. Moreover, inorganic peroxygen compounds are much less costly than the organic peroxygens, sometimes costing as much as two to 5 three times less per pound than the organics.
  • a further advantage over organic oxygen compounds is the ability of inorganic peroxygen compounds to decompose harmlessly over a period of time, unlike organic peroxygen compounds which must be carefully disposed of using hazardous waste disposal techniques.
  • inorganic peroxygen o compounds are generally non-flammable, unlike the normally highly flammable organic peroxygen compounds. Moreover, it is generally thought that organic peroxygens, particularly methylethylketone peroxide and the phthalates are carcinogens.
  • the initiator of the present invention preferably utilizes an admixture of an inorganic peroxygen compound and organic peroxygen compound. Using this combination of inorganic and organic initiators results in the ability to control the curing of unsaturated polyester resins within a precise, predetermined time. Although use of an o inorganic peroxygen compound alone as the initiator for such systems is part of the present invention and will result in the successful curing of unsaturated polyester resins, curing times for such systems are harder to predict..
  • the peroxygen compounds may 5 be dispersed in the polyester resin in the anhydrous form or may alternatively be first formed into an aqueous solution and then dispersed in the resin. Accordingly, dry inorganic and dry organic peroxygen compounds may be utilized in the present invention.
  • dispersion methods disclosed herein are not necessarily critical to the preparation of the initiators of the present invention. However, as explained below, methods utilizing a Kady Mill and/or Eppenbach Mixer are preferred in making the present initiators.
  • the inorganic peroxygen compounds utilized herein are generally soluble in the organic peroxide dispersions. However, when used alone as the initiator, the inorganic peroxygen compounds are generally insoluble in the unsaturated polyester resins. The organic peroxygen compounds used alone are, however, soluble in such resins. When the inorganic peroxygen compounds are dissolved in water and the water solution is dispersed in the unsaturated polyester resin, an aqueous emulsion is formed thereby.
  • the preferred range of inorganic peroxide relative to the amount of polyester resin cured thereby is at least 0.1%, and preferably, between about 0.2% and about 4.0%.
  • inorganic initiator curing of the polyester resins may be incomplete, thus resulting in a rubbery and soupy laminate.
  • the resins will not cure optimally and will result in a rubbery, undesirable laminate.
  • inorganic peroxygen compounds with or without organic peroxygen compounds, other constituents may be added to the initiator systems of the present invention for curing unsaturated polyester resins.
  • a defoamer may be included to reduce foaming.
  • a water soluble inorganic salt may be included to render the suspension or dispersion stable and retain the peroxides in suspension.
  • Such salts which must be stable to the peroxides, may include sodium chloride, potassium chloride, calcium chloride and most other chloride salts except those of the transition metals which may cause the peroxide to decompose.
  • the soluble phosphate and sulfate salts of the group I and II metals are also generally acceptable.
  • Carbonate or bicarbonate salts of the Group I or II metals may also be included in the systems of the present invention so that a variance of the amount of initiator employed will produce a low density foamed or a high density polymer product.
  • the carbonate or bicarbonate salts liberate carbon dioxide which serves as a blowing agent to foam the polyester.
  • Acidic inorganic salts may also be included in the dispersion, attributing a number of beneficial aspects thereto.
  • such salts exemplified by NaH2P ⁇ 4, Na2HP ⁇ 4, NaHS ⁇ 4 and AICI3
  • sodium dihydrogen phosphate and sodium hydrogen phosphate are particularly beneficial for serving as natural buffers for the system and for maintaining pH in a range of from about 3 to about 8.
  • Such inorganic salts act as sequesterants to reduce the likelihood of decomposition of the peroxide due to transition metal ions.
  • fire retardants and fillers may be employed in the initiator systems. Examples of such compounds include alumina trihydrate, gypsum, borax, magnesium sulfate and tri-sodium polyphosphate.
  • Accelerators may generally be divided into three classes- metal compounds (primarily the organic cobalts), amines, and sulfur compounds, with the cobalt compounds and amines being the most widely used.
  • promoters examples include stannous octoate, amines such as dimethylaniline and diethylaniline, mercaptans such as lauroyl percaptan and dodecyl mercaptan, organic cobalts such as cobalt naphthenate and cobalt octoate, manganese octoate, zirconium naphthenate, dimethyl paratoludene and other known promoters.
  • the polyester resin systems may further include inhibitors such as hydroquinone, p-tert-butylcatechol, pyrogallol, chloranil, picric acid, and qu ⁇ nones, to inhibit polymerization and/or reduce the peak exotherm temperatures involved.
  • inhibitors such as hydroquinone, p-tert-butylcatechol, pyrogallol, chloranil, picric acid, and qu ⁇ nones, to inhibit polymerization and/or reduce the peak exotherm temperatures involved.
  • Plasticizers may also be employed to disperse the initiator into a paste-like state.
  • plasticizers include butyl 5 benzolphthalate, dioctyl maleate, isopropyl phenyl phosphate, and other plasticizers.
  • the initiators of the present invention are generally produced according to the teachings U. S. Patent No.4,917,816 ("the '816 patent") which was issued to the inventor of the present subject matter on April 17, 1990. That patent is incorporated herein by reference.
  • the mixture of dispersion constituents including a compound that 5 produces an ionic region about the dispersed peroxygen particles and permits viscosity control, is subjected to a low shear, attrition-type dispersion mill for a predetermined period of time and is then degassed.
  • the dispersion constituents other than the peroxygen compounds are preferably first blended in a low shear mixer after which the o blend is added to a low shear attrition-type dispersion mill.
  • the particular peroxide is then added to the blend in the dispersion mill and the mill is operated for a predetermined time to produce the desired dispersion. Thereafter, the dispersion is removed from the dispersion mill and is preferably degased and filtered.
  • viscosity can be controlled from a very low viscosity, for example, about 100 centiposies to a very high viscosity, for example, 15,000 ce ⁇ tiposies or greater.
  • the initiator is sprayable in conventional spray equipment o without damage or fouling while at the higher viscosities a thick paste results.
  • any of the additional constituents previously mentioned may be added to the dispersions to stabilize same, reduce the flammable and explosive nature of the peroxides, for foaming ofthe polymer, and the 5 like.
  • the dispersions according to the present invention may be provided by blending all of the constituents in a low shear mixer, and subjecting the mixture to a high shear dispersion mill for a predetermined period of time. Thereafter, the dispersion is removed from the dispersion 5 mill and is preferably degased and filtered.
  • Such high shear dispersion mills such as a Cowles Mill or, more preferably, an Eppenbach Mill, yield an acceptable dispersion in accordance with the present invention.
  • the inorganic peroxygen compounds that may be suitably employed according to the present invention include any of the various 0 inorganic peroxides and, particularly, those which have been heretofore used as catalysts for emulsion polymerizations.
  • Exemplary inorganic peroxides include persulfates such as sodium persulfate, ammonium persulfate, and potassium persulfate, the perborates such as sodium perborate, the percarbonates such as sodium percarbonate, and other 5 inorganic peroxides such as zinc peroxide and calcium peroxide.
  • Organic peroxides that may be suitably employed according to teachings of the present invention include solid peroxides dispersible in an aqueous medium as exemplified by benzoyl peroxide, lauroyl peroxide, di- cumyl peroxide, and di-cetyl peroxydicarbonate.
  • Benzoyl peroxide is the o preferred organic peroxide when an organic peroxide is used in the present invention.
  • care must be taken when handling the organic peroxygen, particularly the dry form of benzoyl peroxide.
  • Benzoyl peroxide's highly flammable and explosive nature makes it an extremely dangerous compound which should be used in small amounts.
  • Dispersions or suspensions of the peroxides may range from very low viscosity, sprayable compositions for catalysis of unsaturated polyester resin syrups, to very viscous dispersions in virtually paste form which likewise would be suitable for catalysis but are employed in molding operations, mine bolt securement, repair of structured elements where the o materials are poured or spread by hand or the like. Additionally, present compositions may be provided in which the peroxide is present in very finely divided powder form.
  • Unsaturated polyester resin syrups which may be catalyzed by the inorganic peroxide compositions of the present invention include 5 unsaturated polyester resins having a copolymerizable monomer containing a terminal vinyl group.
  • the unsaturated polyester resin may be derived from the polyesterifrcation of a polycarboxylic acid or a polycarboxylic acid anhydride with a polyol according to techniques well known to those skilled in the art. Because the polyester resin to be produced is unsaturated, the polycarboxylic acid or anhydride, the polyol, or both, must contain at least one ethylenicly unsaturated bond.
  • Exemplary of polycarboxylic acids and anhydrides which are suitable for use in production of the unsaturated polyesters include, without limitation, phthalic acid, isopthalic acid, terephthalic acid, adipic acid, succinic acid, tetrahydrophthalic acid, tetrabromophthalic acid, maleic acid, fumaric acid, the anhydride of any of the aforementioned acids, and combinations thereof.
  • Polyols suitable for use in preparation of the unsaturated polyester resins are exemplified by ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, diethylene glycol, dipropylene gfycol, polyethylene glycol, polypropylene glycol, trimethylol ethane, trfmethylo! propane, pentaerythritol, hydroxy-alkyl esters of polycarboxylic acids and combinations thereof.
  • a slight stoichoimetric excess of polyol is generally employed in preparation of the polyester resin to facilitate reaction between the polycarboxylic acid or anhydride and the polyol and to reduce the viscosity of the formed polyester resin.
  • a copolymerizable monomer is combinable with the unsaturated polyester resins to yield a resin syrup containing a terminable vinyl group.
  • Such monomers are exemplified by styrene, alpha-methyl styrene, o- chlorostyrene t vinyl toluene, acrylic acid, methacrylic acid, alkyl acrylates, alkyl methacrylates, divinyl benzene, diacrylates, dimenthacrylates, triacrylates, trimefhacrylates and combinations thereof.
  • the monomer may be present in an amount of from about 20 to about 40% of the total weight of the polyester resin syrup, that is, the unsaturated polyester resin comprises from about 90 to about 60% of the total weight.
  • copolymerizable monomers for the resin syrup include the reaction products of polyepoxides with acrylic or methacrylic acids for example the reaction products of a polyol such as 2,2-bis (4-hydroxyphe ⁇ yl) propane with a glycidyl acrylate or methacrylate. If employed, this particular type of copolymerizable monomer replaces a portion of the unsaturated polyester resin.
  • Products according to the present invention may be employed without danger of fire or explosive hazard in spray up systems as catalysts 5 for resin syrups, as thickened pastes in curing of resin syrups or pastes in mine bolt-applications, in repair of structured elements or the like, as active ingredients in dermicidal and other pharmaceutical compositions, and the like.
  • ASTM Standard E11-87 is used herein for sieve size description. Such designations shall include mesh size and the equivalent sieve size in o the following format: (mesh size; sieve size).
  • Example 7 thiourea dioxide was used as a promoter; and in Example 8, erythorbic acid was used as a promoter.
  • Example 5-8 a wetting agent obtained from Dow Corning and identified as DC193 was employed. The resin systems were allowed to cure in a paper cup and a one gallon paint 5 can lid. Table 1 shows the amounts of constituents employed in the various initiator systems studied and the gel times therefor. "Gelling" of a resin generally occurs when the liquid resin changes from a liquid to a colloidal semi-solid state indicating that cross-linking of the polyesters is about 5% 5 complete.
  • Example 1 shows that the addition of an inorganic peroxygen compound to an unsaturated polyester resin system decreases the gelling time required o for the resin. Moreover, the addition of a wetting agent in Examples 5-8 indicated that wetting agents also increase the rate of gelling when used with the peroxygen initiators. Furthermore, Table 1 shows the effects of various promotors with respect to the geling time of the resins.
  • the following examples show the effect of several different inorganic peroxygen compounds on the gelling time of polyester resins when the inorganic peroxygen compounds are added in combination with various organic peroxygen compounds.
  • the polyester resin used in o Examples 1-8 was promoted with dimethylaniline and cobalt naphthenate.
  • Example 14 the substantial decrease in gelling time when sodium percarbonate was employed.
  • alumina trihydrate 400 mesh; 38 ⁇ m sieve size (a flame retardant and filler)
  • EXAMPLE 43 In order to determine the gelling time of an inorganic/organic peroxygen initiator in conjunction with a plasticizer, the following system was utilized. One hundred grams of benzoyl peroxide was dispersed in 300 grams butyl benzyl phthalate by the mechanical methods described above wherein the constituents are subjected to a high-shear dispersion mill process utilizing an Eppenbach Mill after being subjected to the low-shear, attrition-type methods used for Examples 1-8. Butyl benzyl phthalate is a known plasticizer often employed in such initiator systems. One hundred grams of spray-dried fine particles of calcium peroxide were blended into the mix.
  • the resulting low viscosity fluid contained 20% benzoyl peroxide, 20% calcium peroxide and 60% butyl benzyl phthalate plasticizer.
  • Two grams of the initiator system was added to a 100 gram sample of the unsaturated polyester resin employed in Examples 1-8. The resin gelled in 15.0 minutes. Further testing was conducted on the system employing ethylene diamine as a promoter which resulted in faster gel times. The utilization of a plasticizer in which the organic and inorganic peroxygen compounds are dispersed does not decrease the performance of the initiator systems.
  • Examples 44-48 describe the use of different unsaturated polyester resin and the effects of promoting same with various inorganic peroxygen initiators without the addition of an organic peroxygen initiator. As can be seen in the Examples, the various inorganic peroxygen compounds affect gel times differently depending on the promotor employed.
  • EXAMPLE 44 A 100 gram sample of a dicyclopentadiene-based resin acquired from Cargil Resin Division was promoted with 0.1 gram of 12% cobalt naphthenate and initiated by dispersing sodium perborate in the resin according to the methods described in Example 43. The gel time was 90 minutes.
  • EXAMPLE 45 A 100 gram sample of the resin used in Example 44 was promoted with 0.1 gram of 12% cobalt naphthenate and initiated with calcium peroxide. The gel time was 45 minutes.
  • EXAMPLES 46-52 The following constituents were added to the dicyclopentadiene- based resin used in Example 44: 0.1% diethyl aniline, 0.1% N-N dimethyl paratoludene, and 0.1 % cobalt naphthenate. One hundred gram samples of the modified resin were initiated with various inorganic peroxygen compounds and the gel time results are shown below.
  • inorganic initiators and inorganic/organic combination initiator systems were tested for their capability to cure unsaturated polyester resins.
  • Each of the systems which employed inorganic peroxygens such as sodium perborate, sodium percarbonate, sodium persulfate, calcium peroxide, and zinc peroxide in combination with various plasticizers including butyl benzoyl phalate plasticizer (also known as Sanitizer 160), Kronitex 50 a dioctylmaleate plasticizer, isopropylphenyl phenyl phosphate plasticizer
  • Kronitex 50 is a registered trademark of FMC Corporation for its , isopropylene plasticizer, in combination with various promoters including diethylaniline, N,N-dimethyl paratoludene, and cobalt napthanate showed effective gelling of various unsaturated polyester resins.
  • the laminates of Examples 53-56 were formed.
  • the results of the various strength, modulus, and elongation tests indicate that the inorganic peroxygen initiator systems of the present invention are comparable to the previously- known organic peroxygen initiator systems when employed to cure particular unsaturated polyester resins.
  • a dicyclopentadiene-based resin having 70% solids was diluted with styrene to 50% solids and filled to 50% by weight with a 80/20 calcium sulfate dihydrate/calcium carbonate blend.
  • n-dimethyl paratoludene is DMPT
  • diethylaniline is DEA
  • triethanolamine is TEA
  • cobalt naphthenate is CN.

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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)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention décrit des initiateurs caractérisés par un composé de peroxyde inorganique servant à durcir des résines de polyesters insaturées. On peut utiliser un composé de peroxygène inorganique, tel qu'un persulfate, un perborate ou un percarbonate, seul ou combiné à des initiateurs de peroxygène organique connus, de façon à effectuer la réticulation de différents polyesters. On peut ajouter d'autres additifs connus auxdits initiateurs.
PCT/US1993/001767 1992-02-26 1993-02-26 Initiateurs de peroxygene inorganique et procedes d'utilisation WO1993017054A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8048965B2 (en) * 2009-07-30 2011-11-01 Swancor Inc. Co., Ltd. Method for extending shelf life of vinyl ester resin or unsaturated polyester resin
WO2022101665A1 (fr) * 2020-11-13 2022-05-19 Iconics Cycle S.A.S. Matériau hautement résistant ayant d'excellentes propriétés physiques obtenu par la récupération totale de polystyrène expansé et de plastique, et procédé d'obtention de celui-ci

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3723573A (en) * 1971-11-11 1973-03-27 Sun Research Development Process for preparing unsaturated polyester
US4351919A (en) * 1975-04-14 1982-09-28 Blount David H Process for the production of polyester silicate resinous products
US4477636A (en) * 1978-02-13 1984-10-16 Soichi Muroi Hot-melt adhesive and method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3723573A (en) * 1971-11-11 1973-03-27 Sun Research Development Process for preparing unsaturated polyester
US4351919A (en) * 1975-04-14 1982-09-28 Blount David H Process for the production of polyester silicate resinous products
US4477636A (en) * 1978-02-13 1984-10-16 Soichi Muroi Hot-melt adhesive and method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8048965B2 (en) * 2009-07-30 2011-11-01 Swancor Inc. Co., Ltd. Method for extending shelf life of vinyl ester resin or unsaturated polyester resin
WO2022101665A1 (fr) * 2020-11-13 2022-05-19 Iconics Cycle S.A.S. Matériau hautement résistant ayant d'excellentes propriétés physiques obtenu par la récupération totale de polystyrène expansé et de plastique, et procédé d'obtention de celui-ci

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