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WO2000023485A1 - Nouvelles matieres polymerisables et nouvelles resines de polyester - Google Patents

Nouvelles matieres polymerisables et nouvelles resines de polyester Download PDF

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Publication number
WO2000023485A1
WO2000023485A1 PCT/IB1999/001667 IB9901667W WO0023485A1 WO 2000023485 A1 WO2000023485 A1 WO 2000023485A1 IB 9901667 W IB9901667 W IB 9901667W WO 0023485 A1 WO0023485 A1 WO 0023485A1
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weight
group
composition
diol
monoaryl
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Boris A. Zaitsev
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Priority claimed from US09/167,827 external-priority patent/US6258909B1/en
Priority claimed from US09/167,923 external-priority patent/US6143922A/en
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Priority to EP99970671A priority Critical patent/EP1129116A1/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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
    • C07C43/285—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings having unsaturation outside the six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
    • C07C43/295—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/007—Esters of unsaturated alcohols having the esterified hydroxy group bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters

Definitions

  • the present invention relates to novel polymerizable compositions, novel resins, novel crosslinked polymers, novel polyester polymers, novel polyester polymers that display improvement over Rolivsan Resins, and to novel methods for obtaining resins, and polymers.
  • the present invention also relates to novel diol compositions, novel unsaturated monomers, novel resins, novel crosslinked polymers, novel polyester polymers, novel polyester polymers that display improvement over Rolivsan Resins, and to novel methods for obtaining the diols, unsaturated monomers, resins, and polymers.
  • Polymers have been able to provide a wide range of properties and capabilities which have found tremendous outlet in the commercial markets. Polymers are used in all forms of technology from medicine, commercial and residential construction, vehicular construction, optics, imaging, protective coatings, film supports and sheeting, data storage and magnetic recording, toys, inks, adhesives, binders, structural housing for appliances and conveniences, and many other commercial areas. Each of these different fields has its own unique requirements for the performance of the polymeric materials. No one polymer can meet all of the requirements for all of the fields of potential use. For this reason, certain polymers have been developed to provide better performance within certain areas of technology.
  • polyesters such as polyethyleneterephthalate and polyethylenenaphthalate
  • films supports for imaging technology as are certain cellulose acetates.
  • Polycarbonates are preferred polymeric materials for use with window construction and lens constmction.
  • Polyacrylates have found general utility for protective coatings, particularly weatherable and UV exposed protective coatings. Epoxy resins and acrylates have found wide acceptance as adhesive materials; silicone resins have found utility as caulking, release compositions, and moisture protective coatings and compositions.
  • Polyamides have found utility as fabric materials, thermal adhesive and biocompatible polymers in the medical field, etc.
  • oligomers 5-88% by weight of : oligomers.
  • the objective of this class of resins was to provide easy processing for high temperature resistant thermosetting resins and advanced composites.
  • the resin reaction mixtures were provided as solvent-free compositions having viscosity ranges of from 600 up to 5,000 cps at room temperature, with melting points between 5 and 50°C for the uncured resins.
  • the resins were to provide excellent chemical resistance to the most aggressive chemical materials (e.g., organic solvents, strong acids, alkalis, hydrazine and solutions of hydrofluoric acid).
  • the resins were also to provide high-temperature (300 ⁇ 50°C) performance properties and advanced composite reinforced plastics (e.g., fiberglass, polyamide and polyimide fiber, graphite, and tungsten- reinforced plastics).
  • the resins were also to have mixing compatibility with conventional reactive resins and oligomers such as epoxy resins, unsaturated polyester resins, vinylester resins, and bts-maleimide resins.
  • the Rolivsan Resins were also expected to exotherm in the presence of phenols, condensing with them quite readily (alkylating phenols by ethylenically unsaturated ingredients of Rolivsan Resins) at room temperature in the presence of acidic catalysts (strong acids).
  • BHEPE bis-[4-(l- hydroxyethyl)phenyl] ether
  • the BHEPE had been obtained by the catalytic hydrogenation of bts-(4-acetyl)pl ⁇ enyl ether (B APE), for example on a Raney-Nickel catalyst at conditions varying from room temperature (at high pressure) to 40 to 50°C with a hydrogen pressure of 100 atmospheres for 0.5 to 1 hour in ethyl alcohol followed by recrystallization from toluene or benzene (mp 86°C).
  • the Rolivsan Resins were formed by heating the BHEPE (which have been found by the present inventors to have comprised uncontrollable amounts ( ⁇ 5 ⁇ 3%) of a phenolic impurity) with unsaturated carboxylic acids (e.g., methacrylic acid) in the presence of the considerable amounts (2.5% of BHEPE weight) of acid catalysts (such as -toluenesulfonic acid monohydrate) in an aromatic solvent at its boiling temperature in the presence of considerable amounts (>1% of BHEPE weight) of hydroquinone. It has been found by heating the BHEPE (which have been found by the present inventors to have comprised uncontrollable amounts ( ⁇ 5 ⁇ 3%) of a phenolic impurity) with unsaturated carboxylic acids (e.g., methacrylic acid) in the presence of the considerable amounts (2.5% of BHEPE weight) of acid catalysts (such as -toluenesulfonic acid monohydrate) in an aromatic solvent at its boiling temperature in the presence of considerable
  • BHEPE bis-[4-(l-hydroxyethyl)phenyl] ether
  • Rolivsan resins have not provided the low range of viscosity and the intended viscosity (less than 300 cps at 25°C, especially less than 200 at 25°C, or about 100 cps at RT) that was very important for some uses, such as polymer coatings, filled polymer compositions, reactive diluents, crosslinking agents, impregnating and sealing compounds, etc.
  • Rolivsan resins and their method of preparation are related to their very low and uncontrollable reactivity in three dimensional free radical (co)polymerizations as the most usable method for the cure of unsaturated monomers and oligomers. It can be seen from technical specifications that their gelation time was very long (0.5 to 1.5 hr at 140-150°C). It implies that only high temperature cure schedules could be applied for preparing polymer materials and composites.
  • the present invention relates to a novel composition of diols, said composition of diols comprising
  • R 4 and R 5 are independently selected from the group consisting of hydrogen and lower alkyl groups (e.g., methyl, ethyl, propyl and butyl, most preferably methyl).
  • the diols will usually be provided as compositions that comprise either: a solution of the diols, with the diols comprising more than 99% by weight of the solids of the solution, and diol which has less than 1% by weight of impurity selected from the group consisting essentially of monoaryl hydroxy (Ar-OH) or sulfhydryl (Ar-SH) compounds, especially monoaryl monohydroxy or monosulfhydryl compounds, and monoaryl dihydroxy or hydroxy-sulfhydryl compounds where only one hydroxy or sulfhydryl group is attached directly to the aryl ring.
  • impurity selected from the group consisting essentially of monoaryl hydroxy (Ar-OH) or sulfhydryl (Ar-SH) compounds, especially monoaryl monohydroxy or monosulfhydryl compounds, and monoaryl dihydroxy or hydroxy-sulfhydryl compounds where only one hydroxy or sulfhydryl group is attached directly to the aryl
  • the present invention also relates to a method of providing the novel composition of diols, said method comprising the processes of: 1) providing a solution comprising at least one diol having the formula HO-(H 3 C)R 4 C-Ar-Z-Ar -CR 5 (CH 3 )-OH, or HO-(H 3 C)R 4 C-Q
  • a simple purification method comprises dissolving the diol with monoaryl phenolic or thiophenolic impurities in a solvent (e.g., low alkyl alcohol such as methanol, ethanol and propanol), adding a basic compound to the mixture to form a salt of the monoaryl phenolic or thiophenolic compound, and then separating a main liquor from a solution or precipitate of the diol, thereby reducing the concentration of monoaryl phenolic or thiophenolic compound in the diol precipitate.
  • the monoaryl, monohydroxy, non-phenolic compound may be separated by recrystallization in solvent, such as toluene.
  • the present invention also relates to novel unsaturated monomers.
  • the monomers may be made from the diols of the present invention.
  • the present invention also relates to novel diols, unsaturated compounds and resin compositions with reduced amounts of monoaryl phenolic or thiophenolic impurities therein , for example, as an adduct with Ml, M2, and oligomer, methods of curing the resins (especially under conditions which were not amenable to curing with resins containing adducts of monoaryl phenolic impurities), and polymeric compositions containing novel classes of copolymerizable monomers with the novel resins.
  • the present invention relates to a novel composition of diols, a novel process for the synthesis of the diols, di ethylenically unsaturated monomers synthesized from the diols, resins containing those diethylenically unsaturated monomers, oligomers, and polymer compositions formed by polymerization of those resin compositions.
  • the novel composition of diols comprises: HO-(H 3 C)R C-Q -CR 5 (CH 3 )-OH wherein Q is a diaryl group comprising two, three, four, five, six and more aryl groups linked directly as in biphenyl, or bridged by oxygen atoms or sulfur atoms, such as Ph(OPh) n Ph, or Ph(SPh) n Ph.
  • R 4 and R 5 are independently selected from the group consisting of hydrogen and lower alkyl groups (e.g., methyl, ethyl, propyl and butyl, most preferably hydrogen, so that the terminal -ol group is
  • the diols comprise either: a solution of the diols, with the diols comprising more than 99% by weight dissolved material or solids of the solution, and any other diol composition which comprises less than 1% by weight of impurity selected from the group consisting essentially of monoaryl hydroxy compounds, especially monoaryl monohydroxy compounds, monoaryl phenolic or thiophenolic compounds, and monoaryl dihydroxy or hydroxy-sulfhydryl compounds where only one hydroxy or sulfhydryl group is attached directly to the aryl ring.
  • the present invention also relates to a method of providing the novel composition of diols, said method comprising the processes of: providing a solution of diol having the formula HO-(H 3 C)R 4 C-Q -CR 5 (CH 3 )-OH, e.g.,
  • R 4 and R 5 are independently selected from the group consisting of hydrogen and lower alkyl groups (e.g., methyl, ethyl, propyl and butyl), most preferably hydrogen, said solution also comprising impurities selected from the group consisting of the monoaryl hydroxy groups;
  • a simple purification method comprises dissolving the diol Or diol with monoaryl phenolic or thiophenolic impurities in a solvent (e.g., low alkyl alcohol such as methanol, ethanol and propanol), adding a base or base-releasing compound to the mixture to form a salt of the monoaryl phenolic or thiophenolic compound (e.g., a phenolate salt), precipitating the diol in water or ethanol (or other convenient differentiating solvent system) and then separating a main liquor from the solution or liquor carrying the precipitate of the diol, thereby reducing the concentration of monoaryl phenolic or thiophenolic compound in the diol precipitate.
  • a solvent e.g., low alkyl alcohol such as methanol, ethanol and propanol
  • the monoaryl, monohydroxy, non-phenolic compound may be separated by recrystallization in solvent, such as toluene, leaving in the case of the most preferred diol, para-HO-(H 3 C)HC-Ph-O-Ph-CH(CH 3 )-OH, a purer diol.
  • solvent such as toluene
  • the invention also describes a process for the synthesis of the diol by hydrogenation of a corresponding diketone under conditions of catalysis, temperature, time and pressure which avoids the substantive formation of monoaryl hydroxy or mercaptan impurities.
  • Q is as defined above
  • into the diol e.g., caused by the splitting or cleaving of BHEPE at the oxygen bridging group between the two aryl groups
  • X-Ar-X type e.g., where each X independently represents H, OH or a group containing an OH moiety
  • the products are the H-Ar-OH or HO-Ar-OH hydrogenolysis product formed after cleavage of the oxide link as in BHEPE.
  • the cleavage produces a compound with an unsatisfied oxygen or sulfur which is hydrogenated to form the phenol or thiophenol group, and an unsatisfied ring carbon atom which is hydrogenated to complete the phenyl ring.
  • These compounds also include the H-Ar-R 3 -OH and HO-Ar-R 3 -OH type compounds such as:
  • R 3 in this circumstance is a branched alkyl linkage, preferably of 2 to ten carbon atoms, more preferably 2 to six carbon atoms, and most preferably 2 to 3 carbon atoms.
  • Ar is generally a monoaryl group, such as phenyl and substituted phenyl, and in certain circumstances may lead to a trifunctional group which will assist in providing a more highly crosslinked product, where Ar is HO-(H 3 C)HC-Ph-, or is HO-(H 3 C)HC-Ar 2 , wherein Ar 2 is also an aryl group such as phenyl, although further presence of additional hydroxyl containing groups on Ar 2 is not likely or desirable from a selection of initial reactants.
  • Monoaryl hydroxy compounds are defined as low molecular weight (less than 300, preferably less than 200, more preferably less than 150) compounds having a single aromatic ring (preferably or usually phenyl) and at least one hydroxy group, attached to the aromatic ring itself (an arylol, such as phenol) or as a terminal substituent on a substituent group (e.g., seoethylol).
  • monaryl phenolic compound includes all phenol or phenolic compounds having a single phenyl group and one or more (especially one) hydroxy groups directly bonded onto the phenyl ring.
  • monoaryl arylol is the generic equivalent for the term monoaryl phenol.
  • BAPE's reduction included methyl benzyl alcohol (H-Ph-CH(CH 3 )-OH) and para-hydroxy methyl benzyl alcohol (para-HO-(H 3 C)HC-Ph-OH), and the like, where Ph is phenyl (-C 6 H 4 -).
  • the solution of diol may also be provided by a synthetic procedural route which differs from the prior art process.
  • the new synthetic procedural route comprises the steps of hydro genating the ketone precursor for the diol with a more efficient catalyst for the heterogeneous catalysis hydrogenation reaction than the Raney-nickel (inclusive of Raney-nickel/titanium) catalysts used in the prior art.
  • This process would include the hydrogenation of the diacetyl (diketone) precursors of the diols, such as bis-(4-acetyl)phenyl ether (BAPE) in the presence of the hydrogenation catalyst, such as, for example, platinum based catalysts (e.g., platinum carried on alumina), palladium based catalysts (e.g., palladium carried on alumina), lithium-aluminum based catalysts (e.g., lithium- aluminum hydride), borohydride catalysts (e.g., sodium borohydride), etc.
  • the hydrogenation catalyst such as, for example, platinum based catalysts (e.g., platinum carried on alumina), palladium based catalysts (e.g., palladium carried on alumina), lithium-aluminum based catalysts (e.g., lithium- aluminum hydride), borohydride catalysts (e.g., sodium borohydride), etc.
  • the room temperature was used with the higher pressures so that there were not believed to be described conditions of room temperature cure at less than 60 atmospheres.
  • use of hydrogenation catalysts other than (or in addition to) the Raney-nickel catalysts also allows the use of room temperature to less than 30°C, at pressures below 40 atmospheres, preferably below 30 atmospheres, and most preferably below 20, below 15 and below 10 atmospheres. Even with these less forceful conditions, the use of alternative catalysts reduces the time of the reaction and the purity of the product with respect to the absence (e.g., less than 1% by weight of diols, preferably less than 0.15% by weight, and more preferably less than 0.5% or less than 0.3% by weight of diols) of monoaryl hydroxy compounds.
  • Novel ethylenically unsaturated monomer-oligomer compositions may be synthesized from these novel diol compositions or the pure diols.
  • the ethylenically unsaturated monomer may be synthesized from the pure diol or novel diol composition obtained by hydrogenation of a diketone at temperatures below 30°C and pressures below 40 atmospheres.
  • novel diols having an absence or reduced amount of monoaryl hydroxy or sulfhydryl substituted compounds
  • novel ethylenically unsaturated monomers having an absence or reduced amount of monoaryl hydroxy substituted compounds alkylated by ethylenically unsaturated resin components
  • novel resin compositions of the invention may be described.
  • composition structure, content (ratio), and molecular weight of the components.
  • the method for obtaining ethylenically unsaturated compositions described in previous inventions have not taken into account that the structure, molecular weight and properties of the oligomers are very sensitive to the nature and concentration of acidic catalyst, and temperature of the process that usually depended on the boiling temperature of the solvent used.
  • this new invention shows that the oligomers with high level of unsaturation and higher molecular weight are formed in the case of application of such an acidic catalyst as p-toluenesulfonic acid (TSA) used in a relatively considerable amount (greater than 2, greater than 3 or greater than 5 mmole/L, preferably 5-20 or 30 mmole/L, and more preferably about 10-15 mmole/L) and in a temperature range of about 30-100°C, preferably 40-90°C, more preferably 50-85°C, and still more preferably about 70-80°C.
  • TSA p-toluenesulfonic acid
  • a general method of synthesizing the polymerizable composition with a wide range of ingredients comprising the steps providing of a series of transformations of the diol of the invention with a carboxylic acid wherein heating the diols (D) with said carboxylic acid, preferably with methacrylic acid (MAA) is performed at mole ratio D:CA (MAA) not less than 1 :0.1, preferably 1:1.5-2.5, or more in the presence of relatively the lowest concentration of an acid catalyst, preferably a sulfonic acid compound, such as p-toluenesulfonic acid (monohydrate) (TSA) (mainly 0.9-14.0 mmole/L), preferably 3.0-7.0 mmole/L) in aromatic solvent, preferably in toluene at the boiling temperature (80-160°C) of the reaction mixture, preferably at 100-120, more preferably ⁇ 103-110°C while removing the reaction water evolving during the resin's synthesis and with successive stirring at 70-80°C
  • sulfo-cationite ion-exchange resin
  • ion-exchange resin e.g., Amberlite IPR-69 ion-exchange resin, sulfonic acid functionality (strongly acidic), capacity 5 meq/g (dry) or Amberlyst XN-1010 ion-exchange resin, strongly acidic, macroreticular, high surface-area suitable for non-aqueous applications (see, e.g., Aldrich Catalog), or "KU-23" (Russian trade name for ion-exchange resin)
  • the unsaturated oligomers of the above type which could be described by formula (I) or (II)
  • the oligomers of another type are formed, which could be described by formula (III): CH 3 CH 3 CH 3 CH 3 CH 3
  • ⁇ -NMR spectrum of the oligomer component of the composition exhibits characteristic signals: two overlapping doublets at ⁇ 1.3 ppm (for methyl groups of the ether unit [-CH(CH 3 )-O-CH(CH 3 )-]) and two overlapping quadruplets at ⁇ 4.2 ppm (for methyne group of this ether unit).
  • compositions of the invention with very wide range of components may be subdivided into four specific compositions with the narrower range of the components and properties, and specific methods for their preparation:
  • a methacrylic acid ester of a vinyl-substituted sec-ethylol-diaryl oxide or its thioether or methine or biphenyl counterpart e.g.,
  • D with carboxylic acids (CA), preferably with methacrylic acid (MAA) (at mole ratio C:CA (MAA) not less than 1 :1.1, preferably 1 : 1.5-2.5, or more) in the presence of relatively the lowest concentration of a sulfonic acid, such as p- toluenesulfonic acid (monohydrate) (TSA) (mainly 0.9-14.0 mmole/L), preferably 3.0-7.0 mmole/L in aromatic solvent, preferably in toluene at the boiling temperature of the reaction mixture, preferably at - 103-111°C with removing the reaction water evolving during the resin's synthesis.
  • a sulfonic acid such as p- toluenesulfonic acid (monohydrate) (TSA) (mainly 0.9-14.0 mmole/L), preferably 3.0-7.0 mmole/L in aromatic solvent, preferably in toluene at the boiling temperature of the reaction mixture, preferably at - 103-111
  • a method for obtaining these compositions comprises heating the diols (D) with carboxylic acids (CA) in the presence of the relatively highest concentration of sulfonic acid, preferably TSA (greater than 2, greater than 3 or greater than 5 mmole/L, preferably 5-20 or 30 mmole/L, and more preferably about 10-15 mmole/L) in aromatic solvent, preferably benzene, or toluene or o- xylene at the boiling temperature of the solvent with removing the reaction water evolving during the condensation process.
  • TSA sulfonic acid
  • aromatic solvent preferably benzene, or toluene or o- xylene
  • reaction mixture In the event of performing the resin's synthesis in toluene, o-xylene or other higher boiling aromatic solvents, after removing released water, the reaction mixture should be kept at 70-80°C or lower for 1 or several hours with or without adding extra amounts of acidic catalyst (for occurrence of oligomerization on styrene-like endgroups of monomers Ml and M2, and ethylenically unsaturated oligomers (mainly dimers and trimers) described by formula (I) or (II)). 3.
  • acidic catalyst for occurrence of oligomerization on styrene-like endgroups of monomers Ml and M2, and ethylenically unsaturated oligomers (mainly dimers and trimers) described by formula (I) or (II)
  • ⁇ -NMR spectrum of the oligomer component composition exhibits characteristic signals: two overlapping doublets at ⁇ 1.3 ppm (for methyl groups of the ether units [-CH-(CH 3 )-O-CH(CH 3 )-] and two overlapping quadruplets at ⁇ 4.2 ppm (for methyne group of this ether unit).
  • a method for obtaining these compositions comprises heating the diols (D) with carboxylic acids (CA), preferably with methacrylic acid (MAA) (at mole ratio D:CA (MAA) 1:0.5-2.5, in the presence of a sulfocationites, such as Amberlite IPR-69 or Amberlyst XN-1010 ion-exchange resin, strongly acidic, macroreticular, high surface-area suitable for non-aqueous applications in aromatic solvent at the boiling temperature of the reaction mixture, with removing the reaction water evolving during the resin's synthesis.
  • a sulfocationites such as Amberlite IPR-69 or Amberlyst XN-1010 ion-exchange resin, strongly acidic, macroreticular, high surface-area suitable for non-aqueous applications in aromatic solvent at the boiling temperature of the reaction mixture, with removing the reaction water evolving during the resin's synthesis.
  • the second class of the novel resins also represents related divinylaromatic compositions with a wide and various ratio of monomers and oligomers of different molecular weight (i.e., with different molecular weight distribution) comprising:
  • novel divinylaromatic compositions may be subdivided into two types comprising different less wide compositions with less wide range of components:
  • Unsaturated divinylaromatic compositions rich with divinylaromatic monomer and a novel method for obtaining the pure divinylaromatic monomer such as
  • X aryl, alkylated aryl, biaryl, tri-aryl, O-aryl, O-alkylated aryl, S-aryl, S-alkylated aryl, CH 2 -aryl, CH 2 -alkylated aryl, etc., with high yield are of great interest for a lot of applications.
  • a method for obtaining these compositions comprises heating the diols in the presence of relatively the lowest concentration of a sulfonic acid, such as p-toluenesulfonic acid (TSA) (monohydrate) (mainly 0.5-10.0 mmole/L), preferably 1.0-3.0 mmole/L) in aromatic solvent, preferably in o-xylene, at the boiling temperature of the reaction mixture in the range of 100-160°C, preferably at ⁇ 144-150°C, finishing the dehydration process after removing the reaction water.
  • a sulfonic acid such as p-toluenesulfonic acid (TSA) (monohydrate) (mainly 0.5-10.0 mmole/L), preferably 1.0-3.0 mmole/L) in aromatic solvent, preferably in o-xylene
  • compositions 1.1.1 A method of obtaining pure divinylaromatic monomer by treatment of the composition described above and obtained according to the separation and purification of the monomer by recrystallization or sublimation of the monomer from the composition by its heating at, for example, 80 to 150°C under vacuum. It can be seen that these compositions have a number of the important distinctions (concerning qualitative and quantitative composition of resin, i.e., content, structure, properties, and molecular weight of divinylaromatic monomer, its dimer, and other components) from the previous unsaturated compositions (prototype) considered in the section "Background of the Art". In comparison with the previous resins, the resins (compositions) of the invention have the higher level of unsaturation.
  • divinylaromatics proposed in this invention can comprise practically pure materials (95-99.5% of purity), provide a lower toxicity divinyl aromatic monomer (as compared to the divinyl benzene) and have only the intended amount (usually small (1-5%) amount) of its dimer and trimer. It should be emphasized that the dimer and trimer are identical or similar (related) compounds with respect to their properties. They should not be substantially considered as impurities.
  • aromatic diols such as BHEPE only after a special (alkali) purification procedure for avoiding phenolic adducts in the claimable compositions, 2.
  • a method for obtaining these compositions comprises in heating the diols in the presence of relatively the highest concentration of sulfonic acid, preferably TSA (mainly 5-15 mmole/L) in aromatic solvent, preferably benzene, or toluene or o-xylene, at their boiling temperature with removing the reaction water evolving during the condensation process of the resin's formation.
  • sulfonic acid preferably TSA (mainly 5-15 mmole/L) in aromatic solvent, preferably benzene, or toluene or o-xylene
  • the reaction mixture should be kept at 70-80°C for a fixed period of time with or without adding of the extra amount of acidic catalyst depending on the intended characteristics of the resin.
  • the novel highly reactive resins of the invention are different from
  • novel resins of the invention may also differ and may also be differentiated from the Rolivsan resins described in the USSR Inventor's certificates by each of the following descriptions:
  • compositions of the present invention comprise at least three monomers and oligomers comprising at least one diaryl compound comprising at least two aryl groups linked together directly or bridged by a linking group, each of said at least two aryl groups having a vinyl group attached thereto, at least one a methacrylic acid ester of a vinyl-substituted sec-ethylol-diaryl oxide or its thioether or methine counte ⁇ art, and at least one dimethacrylic acid esters of bis-[4(l-hydroxyethyl)aryl] ether, thioether or methine, and highly unsaturated oligomers having mainly formulae (I) and/or (II): CH 3 CH 3 CH 3
  • Novel resins are photosensitive and gelated by the UV radiation of weak intensity (exposition (H 0 ) is 0.4 to 0.9 W/cm 2 or (0.4-0.9)* 10 7 erg/cm 2 ).
  • a free radical photoinitiator such as Darocur.
  • Rolivsan resins also cannot be gelated and cured at temperatures 20-120°C thermally and/or in the presence of 1-5 wt-%> and higher a thermal initiator, such as benzoyl or acetyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, and/or dicumyl peroxide, etc.
  • a thermal initiator such as benzoyl or acetyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, and/or dicumyl peroxide, etc.
  • the following new composites and compositions may be prepared and cured on the basis of the novel resins with: different reinforcements, fillers, and porous materials, e.g., fiberglass or fiberglass cloth, carbon or graphite fibers or fiber cloth, polyamide and polyimide fibers or fiber cloth, boron fibers, fine divided alumina, silica, aluminum plates with porous alumina layer (examples 7- 11, 14, 26, 47-49).
  • the novel resins can be used directly for electric insulation with high temperature index (250-320°C), automotive industry, (micro)electronics, etc.
  • a List of Field of Use of Novel (Zaitforrr Resins 1. Electrical insulation polymer compounds with lower viscosity at 20°C and elevated [e.g., up to 315°C (600°F)] working temperature (with the use of the drop-by-drop-impregnating-drying process for one component (package solventless compositions) for bonding (after cure) the winding of the electric motors/generators (for working in the medium of mineral oil (IPM-10), in air, at high level of humidity).
  • Temperature range -60 to +315°C, working time: 200°C/500 hours, or 315 80 hours (in oil), 203°C/5000 hours (in air), 250°C/880 hours, 315°C/82 hours (in air).
  • Other applications sealing compounds for electronics and electro- technics (transformers, windings, condensers).
  • the objective The creation of the impregnating polymer compounds having:
  • Coating prepared from the Zaitform resin provides protection from the electrical breakdown and the leakage currents.
  • Impregnating/priming microcracks of the oxide (Al 2 O 3 ) layer 5. Impregnating/priming microcracks of the oxide (Al 2 O 3 ) layer. 6. Attaining the very low priming surface roughness of primed aluminum plates (as for highest class polishing).
  • the pick-off force was measured by means of the metal rod (with diameter of 1.5 mm) soldered to the spray-coated layer (printed circuit board).
  • Film's pick-off character was adhesionic, i.e., along interface between the spray-coated film layer and the primed aluminum plate.
  • Vibration resistance test Testing with resonant machine (frequency range 5 to 2,000 Hz, amplitude
  • the thickness of the coating was
  • the low-melting formulations of two different types have been developed for reinforcements impregnation: 1.
  • the formulation A i.e., unsaturated polyester modified with novel divinylaromatic composition of the invention (for composites with the working temperature range of 121-204°C [250-400°F]) is a new patentable low-melting formulation (binder A) (with temperature range of melting 60 to 70°C and gelatin time 10 (@ 140°C) to 40 minutes (@ 125°C) which comprises, e.g., ordinary styreneless and solventless unsaturated polyester resin or vinylester resin (as chief ingredient), such as NPS 609-2 IM (Russian trade name for the formulation comprising the solution of polyethyleneglycolemaleatephthalate in dimethacrylate of triethyleneglycol), commercially available modifiers, thermoinitiators, antioxidant, flow control agent, and the novel divinylaromatic composition (high temperature crosslinking agent).
  • bin A with temperature range of melting 60 to 70°C and ge
  • Formulation B (example 41] (for composites with the working temperature range of 232-316°C [450-600°F]) is a new patentable low-melting formulation with temperature range of melting 80 to 90°C and gelation time 50 minutes (@ 140°C comprising: Zaitform vinylester resins, novel divinylaromatic composition, and commercially available modifiers, thermoinitiators, antioxidant, and flow control agent.
  • novel resins of the invention may also differ and may also be differentiated from the Rolivsan resins described in the USSR Inventor's certificates by each of the following descriptions:
  • compositions of the present invention comprise at least three monomers and oligomers comprising at least one diaryl compound comprising at least two aryl groups linked directly or bridged by a linking group, each of said at least two aryl groups having a vinyl group attached thereto, at least one a methacrylic acid ester of a vinyl-substituted .sec-ethylol-diaryl oxide or its thioether or methine counte ⁇ art, and at least one dimethacrylic acid ester of bis- [4-(l-hydroxyethyl)aryl] ether, thioether or methine, which composition may be photoinitated at room temperature.
  • Novel resin compositions also comprise the three monomer systems of ingredients and oligomers comprising at least one diaryl compounds comprising at least two aryl groups linked directly or bridged by a linking group, each of said at least two aryl groups having a vinyl group attached thereto, at least one a methacrylic acid ester of a vinyl-substituted sec-ethylol-diaryl oxide or its thioether or methine counte ⁇ art, at least one dimethacrylic acid ester of bis-[4- (l-hydroxyethyl)aryl] ether, thioether or methine and highly unsaturated oligomers defined by any one of: and/or has less than 1%> by weight of impurity selected from the group consisting essentially of monoaryl hydroxy compounds, especially monoaryl monohydroxy compounds, and monoaryl dihydroxy compounds where only one hydroxy group is attached directly to the aryl ring; and the presence of comonomers selected from the group consisting of ethy
  • Beads of styrene-divinylbenzene resins made by suspension polymerization are known to be used as the basis of ion-exchange resins.
  • the largest use of DVB is in ion-exchange resins for domestic and industrial water softening.
  • Ion-exchange resins are also used as solid acid catalysts for certain reactions, such as esterification.
  • crosslinking agent In synthesis of polymer sorbents, such as styragel or shodex, structure and composition of the crosslinking agent are of great importance. It should be noted that common divinylbenzene comprises -55% mixture comprising: 36.4% of meta-isomer and 18.6% of para-isomer, -38% of ethylvinylbenzene, and small amount of diethylbenzene, (cf. the product made in Germany, Schuchardt Munchen). In principle, the crosslinks resulting from divinylbenzene should stabilize the bead structure and minimize swelling.
  • the beads (grains) obtained with divinylbenzene exhibit low strength, especially, at swelling, and even failure (disintegration) and are not fit for regeneration.
  • the compositions and the pure divinylaromatic monomers of the invention provide much better control of network stracture of the crosslinked polymers, the distribution of crosslinks and pores, improving solvent and chemical resistance of the sorbents, and their mechanical properties.
  • changing color of wash water in the BHEPE purification method of the invention may be considered as a very convenient purification control: the finished mother solution should be colorless.
  • trace amount ( ⁇ 0.15%>) of phenolics may be found by the color control.
  • Using the color reaction of phenolics with the solution of ferric chloride is a more sensitive method for the phenolic impurities' control, i.e., for observation in the visible or UV region (Murray, M J. , ⁇ naL Chem.. 21:941 (1949); Smullin, C. F., Wetteran, F. P., Anal. Chem.. 22:1836 (1955); Korenman, I. M. Fotometric Analysis.
  • the previous Rolivsan Resin compositions variably contained at least 2% (on a mol basis of monoaryl hydroxy impurities), and usually at least 5% and up to at least 15% by mol basis (which is nearly equivalent to the weight basis) of the diol such as the BHEPE (bw-[4-(l-hydroxyethyl)phenyl] ether or 4,4 '-bis- (sec-ethylol)diphenyloxide) used as an intermediate in the formation of products according to the teachings of the prior art was present as an unknown impurity
  • a polymerizable composition, polymer, and method for preparation of a polymer is also described as part of this invention comprising forming a polymerizable composition comprising at least three monomers, said monomers and oligomers comprising: 2-95%o by weight of: diaryl compounds comprising at least two aryl groups linked together directly (as in biphenyl) or bridged by a linking group, each of said at least two aryl groups
  • a methacrylic acid ester of a vinyl-substituted sec-ethylol-diaryl oxide or its thioether or methine or biphenyl counte ⁇ art e.g.,
  • the reactive composition has less than 1%, preferably less than 0.8%), more preferably less than 0.7%, and still more preferably less than 0.5 or less than 0.2%) by mol basis of the monoaryl phenolic impurities, such as described above.
  • the method and compositions may be practiced where the monoaryl phenolic impurities are present as less than 1% by weight of said at least three monomers and oligomers (preferably on a basis comparison to the first monomer only, the 2-95% by weight of diaryl compounds comprising at least two aryl groups bridged by a linking group, each of said at least two aryl groups having a vinyl group attached thereto), less than 0.5% by weight, less than 0.25% by weight, down to 0% by weight of said at least three monomers and oligomers.
  • the polymerizing may be performed at temperatures less than 100°C, less than 80 or 60°C, less than 40°C, less than 30°C, less than 25°C, and even at or less than 20°C (e.g., room temperature or lower), and may be effected by low temperature free radical polymerization and photoinitiation, in large part because of the reduced amount of free radical inhibitor present.
  • phenyl group may or may not have additional substitution (e.g., for pu ⁇ oses of solubility, compatibility with other materials, oleophilic groups, oleophobic groups, hydrophilic groups, hydrophobic groups, ionic groups, etc.),
  • Example 1 (from previous practice) (B. A. Zaitsev, L. L. Dantsig, G. I. Khramova, and G. A. Shtraikhman, J. App. Chem. of the USSR. 5Q(2), 389-392 (1977): A mixture of 20g of skeletal Raney-nickel catalyst (particle size 0.08 and 0.5mm, 250 mL ethyl alcohol and 76.2g of BAPE were placed in an autoclave with a capacity of 0.5 liter and stirred at room temperature (19°C to 40 or 50°C) and with a hydrogen pressure of up to 100 atmospheres (40 to 100 atm.) until abso ⁇ tion of hydrogen ceased (0.5h).
  • Example 2 (from previous practice) (unpublished data) A mixture of 21.2 kg of suspension of skeletal Raney-nickel-titanium catalyst (consisting of 8.86 wt % of Ni, 0.57 wt % of Ti, and 90.57 wt % of ethyl alcohol, particle size about 0.25mm), 37.4 kg of ethyl alcohol, and 14.92 kg of BAPE were placed in an autoclave with a capacity of 100 liters and stirred (at 150 revolutions/min) at heating up to 40-45°C and with a hydrogen pressure of 2.0- 2.5 MPa until abso ⁇ tion of hydrogen ceased (3-5 h).
  • skeletal Raney-nickel-titanium catalyst consisting of 8.86 wt % of Ni, 0.57 wt % of Ti, and 90.57 wt % of ethyl alcohol, particle size about 0.25mm
  • 37.4 kg of ethyl alcohol and 14.92 kg of BAPE were placed in an autoclave with
  • the reaction mixture was cooled to the room temperature, and the upper layer (the solution of the diol) was separated from the suspension of catalyst (the lower layer).
  • the alcohol was first distilled under normal pressure at 80-84°C, and at the end of the process (when the content of the alcohol decreased to 5- 10%)) under reduced pressure (10-15 mm Hg) and at 30-35°C.
  • the raw BHEPE (14.0 kg) was dissolved in 13.27 kg of benzene at 70 ⁇ 5 oC , and then, after hot filtration decreasing temperature of the benzene solution of raw BHEPE first to 30 ⁇ 5°C, then, to 2 ⁇ 2°C for 3 hours and recrystallization, 12.4 kg (81.8 % of theoretical) of BHEPE was obtained, mp 83-86°C.
  • a high level of a phenolic compound chemically attached to unsaturated components of a resin (which acts as an inhibitor of radical polymerization, e.g., possibly acting as free radical polymerization inhibitors or free radical scavengers), these resins could not be cured at low temperature, e.g., by photo(UV)-crosslinking, etc.
  • the impurities also increased the viscosity of the resin, making it more difficult to coat.
  • the impurities also caused brown coloration in the resin and the resulting polymer which reduced the range of utility for the resin where transparency or color purity was desired.
  • 622258 (R. G. Luchko, I. V. Sytova, B. A. Zaitsev, and G. A. Shtraikhman, Inventor's Certificate No. 622258 (Appl. 1,537,571/23- 04, 15 Jul 1971, Cl. C07C69/54, UDC 547.391.3, 562.4.07 (088.8), Applicant: Institute of Macromolecular Compounds of the USSR Academy of Sciences.
  • the method of obtaining methacrylic ester of 4-vinyl-4'-(sec-ethylol)- diphenyloxyde) is related to obtaining a new compound, the methacrylic ester of 4-vinyl-4'-(sec-ethylol)diphenyloxide which can be used as a binder for the preparation of glass fiber laminates and adhesives based on polymerizable oligomers. These materials yielded products with high temperature resistance and high thermal stability after curing of the oligomer.
  • binders based on oligoglycolacrylates and oligoglycolmaleates obtained by esterifying glycols by unsaturated acids have not met the increasing requirements (concerning, first of all, heat resistance which does not reach 90 to 160°C according to the Vicat softening point of plastics [ASTM D1525-85T]) for such materials. These tests are required by aircraft, aerospace industries, radio- electronics and other rapidly developing industries and engineering fields.
  • the method of esterifying methacrylic acid by 4,4'-bis(sec-ethylol) diphenyloxide had been proposed, with an aim at obtaining a new polymerizable compound which could be used as a binder for the preparation of glass fiber laminates with high temperature resistance and high thermal stability.
  • This process has been carried out in the presence of the acidic catalyst and an inhibitor of polymerization in the medium of organic solvent, such as benzene, at temperatures not higher than the boiling temperature of the reaction mixture.
  • the glycol has undergone partial (incomplete) dehydration, yielding the monoester of methacrylic acid.
  • the monoester obtained had vinyl end groups.
  • the product obtained has provided a network (crosslinked) polymer with high thermal degradation resistant properties after its curing.
  • D1525-85T ASTM Standards on Plastics, Philadelphia, Pa., American Society for Testing Materials, 1959; Frazer A. N., High Temperature Resistant Polymers, Interscience Publ., N.Y., etc. 1968, p. 24) uses samples of a minimum width of 3/4 in., and a thickness of 1/8 in. These samples are subjected to a load of 1000 g by a flat ended needle of 1 mm 2 cross-sectional area. The sample is heated in an immersion bath at a rate of 50°C/hr. The temperature is recorded when the indicator reads 1 mm penetration. This type of device has been slightly modified by the IPhP (the Institute of
  • the objective of this class of resins was to increase the level of strength for heat stable polymer materials based on them and decrease their shrinkage during the preparation (processing).
  • the method for obtaining the resins was in heating bis-[4-(l- hydroxyethyl)phenyl] ether (BHEPE) in unpolar aromatic solvent at the temperature of boiling reaction mixture in the presence of a considerable amount of acidic catalyst, hydroquinone, cuprous chloride, and thiophene. According to the published method: Example 3
  • the benzene solution was dried, passed through a layer of alumina, and benzene removed by distillation under vacuum in the presence of 0.01-0.1%) hydroquinone.
  • the yield of the composition was 7.5 g, T softening was 54-67°C, and its elemental analysis: Found, %: C 79.38, H 6.90, O 13.72.
  • the separation of the composition was carried out as described in the above Example 3.
  • the yield of the composition was 8.2 g
  • T softenmg was 55-65°C
  • the composition's unsaturation was 0.00708 mol of double bonds per 1 g.
  • the composition had comprised: 49% wt-% bis (4- vinylphenyl) ether (BVPE), and 21 wt-% unsaturated oligomers having the formula:
  • Ar C 6 H 4 -O- C 6 H 4
  • Example 5 (from previous practice) (B. A. Zaitsev, L. L. Dantsig and L. G. Feoktistova. USSR Inventor's Certificate No. 927,835, Appl. 2,663,397/23-04, 11 Sep 1978, Cl. C08L 67/06, C08G 63/64, UDC 678.674 (088.8))
  • Photometric method of the determination of phenols was used and tailored for quantitative analysis of phenolic impurities in several batches of bis-[4-(l- hydroxyethly)phenyl] ether (BHEPE) produced on a pilot plant.
  • the method was based on the formation of the color azo coupling of phenols with deazotized p-nitoraniline (Korenmen I.M. Photometric Analysis. Methods for the Determination of Organic Compounds. Moscow, Chemistry Publ., 1970, p. 43 (in Russian); Smith G., King D. Analyst 1964, 89, 305,312; 1965, 90, 55).
  • the analysis was performed with photoelectrical colorimeter "PhEK-56M" for 35 minutes.
  • the present invention increases the yield of the target product and simplifies the process as compared to these alternative methods.
  • Part of this benefit was realized due to divinylaromatic compositions riched with divinylaromatic monomer (75-99 wt-%) comprising at least the following components [examples 37-44]: 75-99% by weight of: aryl compounds comprising at least one non-alkylated or alkylated aryl group and two vinyl groups attached directly to aromatic ring, such as diaryl compounds comprising at least two aryl groups linked together directly as in biphenyl or bridged by a linking group, each of said at least two aryl groups having a vinyl group attached thereto, such as
  • unsaturated trimer of said divinylaromatic monomer such as
  • a novel method for obtaining these compositions compromises heating the diols in the presence of relatively the lowest concentration of a sulfonic acid, such as p-toluenesulfonic acid (TSA) (monohydrate) (mainly 0.5-10.0 mmole/L), preferably 1.0-3.0 mmole/L) in aromatic solvent, preferably in o-xylene at the boiling temperature of the reaction mixture in the range of 100-160°C, preferably at - 144-150°C with finishing the dehydration process after removing the reaction water, (examples, 37-44)
  • TSA p-toluenesulfonic acid
  • a novel method of obtaining pure divinylaromatic monomer is effected by treatment of the composition described herein and in 1.1 with separation and purification of the monomer by recrystallization or sublimation of the monomer from the composition by its heating at 80 to 150°C under vacuum.
  • TSA p-toluenesulfonic acid
  • the polymers, compositions and processes of the present invention have a wide range of utility in the coating art (for insulation, electrical resistance, solvent, chemical and corrosion resistance, thermal stabilization, binder application, and the like).
  • the coating compositions may contain a wide range of conventional additives to improve specific objectives in the use of the polymers of the present invention.
  • conventional additives include, but are not limited to such materials as dyes, pigments, UV absorbers, UV stabilizers, antistatic agents, lubricants, surfactants, fillers, coating aids, coupling agents (e.g., ambifunctional silanes and titanates), antioxidants, reducing agents, and the like.
  • This invention is also related to obtaining unsaturated oligomers suited for the preparation of polymer materials - binders for making laminates, molding materials, potting, sealing and impregnating compounds, lacquers, coatings, and films.
  • Proposed compositions had considerable advantages over common oligomers and resins. They exceeded them for the set of the essential properties, including thermostability, strength of the products of their cure, and ease of their processing into polymer due to liquid viscous state of oligomer.
  • the polymers and glass-cloth laminates obtained on the basis on proposed methods have shown that the polymers obtained from the proposed compositions considerably exceeded for thermal stability and heat resistance the cured products obtained from conventional oligomers and resins having similar processing properties.
  • Zaitform (vinylester ⁇ resins rich with ester compounds, i.e., comprising M2+M3 ⁇ 45 wt-% or ester number ⁇ 120-140 (preferably 170- 1 Q) mg K H/l g of resin
  • Zaitform vinylester ⁇ resins rich with ester compounds, i.e., comprising M2+M3 ⁇ 45 wt-% or ester number ⁇ 120-140 (preferably 170- 1 Q) mg K H/l g of resin
  • the mole ratio Diol (D) : methacrylic acid (MAA) 1 :3.05.
  • BHEPE purified bis-[4-(l-hydroxyethyl)phenyl] ether
  • TSA purified bis-[4-(l-hydroxyethyl)phenyl] ether
  • 200 mL of toluene was heated at the boiling temperature for 50 minutes. Water released during the dehydration was azeotroped from the system (5.5 mL).
  • the solution of the product in toluene was dried over CaCl 2 , passed through a layer of alumina, and the solvent removed by distillation under the reduced pressure at 40°C in the presence of about 0.040 g (0.1 %>) tert-butyl catechol.
  • the yield was 36 g, n D 21 1.5680.
  • the content of components according to Size Exclusion liquid Chromatography was as follows, wt-%: Monomer Ml, i.e., bis-(4- vinylphenyl) ether (BVPE) 9, Monomer 2 (methacrylic ester of 4-vinyl-4'-(l- hydroxyethyl)-diphenyloxide, or monoester) 38, Monomer 3 (dimethacrylic ester of bis-[4-(l-hydroxyethyl)phenyl] ether, or diester) 28, unsaturated oligomers (mixture of homologs) 25 which could be described by formula (I): CH 3
  • Ar Ph-O-Ph
  • R CH 3
  • n 0-3.
  • fiberglass cloth laminates have been prepared with commercially available alkali-free alumoborosilicate fiberglass satin (8/3) weave cloth under Russian trade name "T-10-80" with the following characteristics: thickness 0.23 mm, weight 0.233 kg/m 2 , diameter of elemental filament 6 microns, a number of fibers/cm 36+1 (wa ⁇ ), 20+1 (weft), breaking load (N) of fabric strip (25 mm 100 mm) is not less than 2700 (wa ⁇ ) and 1500 (weft).
  • Five plies of the prepreg were stacked and heated in the temperature range 80-300°C during several hours under the initial specific pressure about 1.0 kgf/cm 2 .
  • the laminates exhibited the following flexural strength values (after final cure temperature 300°C), kgf, cm 2 : 5170 @ 20°C, 3370 @ 250°C.
  • the samples of the fiberglass cloth laminates have been prepared as described above. Six plies of the prepreg were stacked and heated in the temperature range 80-250°C during several hours under the initial specific pressure about 0.4 kgf/cm 2 . The laminates exhibited the following flexural strength values (after final cure temperature 250°C), kgf cm 2 : 6400 @ 20°C, 4100 @ 250°C, and 1650 @ 320°C.
  • the unidirectional carbon fiber composites have been prepared with
  • the mole ratio Diol (D) : methacrylic acid (MAA) 1 :1 .
  • the samples of the fiberglass cloth laminates have been prepared as described above.
  • Five plies of the prepreg were stacked and heated in the temperature range 80-300°C during several hours under the initial specific pressure about 1.0 kgf/cm 2 .
  • the laminates exhibited the following flexural strength values (after final cure temperature 300°C), kgf cm 2 : 5700 @ 20°C, 3500 @ 250°C, and 2900 @ 250°C (after aging in air at 320°C for 10 hours).
  • the mole ratio Diol (D) : methacrylic acid (MAA) 1 • ?.
  • the mole ratio Diol (D) : methacrylic acid (MAA) 1 :1.5.
  • the samples of the fiberglass cloth laminates have been prepared as described above. Five plies of the prepreg were stacked and heated in the temperature range 80-300°C during several hours under the initial specific pressure about 1.0 kgf cm 2 . The laminates exhibited the following flexural strength values (after final cure temperature 300°C), kgf cm 2 : 5200 @ 20°C, 3000 @ 250°C.
  • the unidirectional carbon fiber composites have been prepared with Russian unidirectional carbon fiber tape (commercially available under trade name "LUP-01": density 1.7 g/cm 3 , weight 35 g/m 2 , number of fibers/10 cm 400 (wa ⁇ ), diameter of fiber 10-11 micron, porosity 3.5%, strength of 10 mm fiber 2.5 Gpa).
  • LUP-01 Russian unidirectional carbon fiber tape
  • Nine plies of the prepreg were stacked and heated in the temperature range 80-260°C during several hours under specific pressure about 15 kgf cm 2 .
  • the composites had the following flexural strength values, kgf/cm 2 : (after final cure temperature 260°C/1 hour): 12,000 @ 20°C, 5700 @ 250°C and 5,000 @ 320°C; (after additional heating @ 320°C/2 hours): 4900 @ 320°C, 4300 @ 370°C, 1800 @ 400°C.
  • the resin's gelation time at 140°C was 18-20 minutes; gelation time (photo-crosslinking) at room temperature (19°C) in the presence of 1 wt-% of Darocur (Merck photoinitiator for UV curing) was 1 minute, 40 seconds (the irradiation of luminescent lamp, 40 w).
  • the samples of the fiberglass cloth laminates have been prepared as described above.
  • Five plies of the prepreg were stacked and heated in the temperature range 80-300°C during several hours under the initial specific pressure about 1.0 kgf cm 2 .
  • the laminates exhibited the following flexural strength values (after final cure temperature 300°C), kgf cm 2 : 5500 @ 20°C, 3800 @ 250°C, and 3500 @ 250°C (after aging in air at 320°C for 10 hours).
  • the mole ratio Diol (D) : methacrylic acid (MAA) 1 :2.5.
  • the content of components according to SEC was as follows, wt-%:
  • the solution of the resin in toluene was dried over CaCl 2 passed through a layer of alumina, and toluene removed by distillation under vacuum in the presence of about 0.1 %> 4-tert- butyl catechol.
  • the yield of the resin was 9.5 g, n D 20 1.5748.
  • According to the reversed phase chromatography (column Separon Si C18, toluene was used as eluate, the elution rate was 0.1 mL/minute, a refractometric detector was used).
  • the mole ratio Diol (D : methacrylic acid (MAA 1 :1 .47. Synthesis of the resin based on the diol with diphenyl methane unit was conducted in a four- neck, 250 mL round-bottom flask equipped with a mechanical stirrer, gas inlet, thermometer, Dean Stark trap, and condenser.
  • the flask was charged with 10.001 g (0.0413 mole) of the purified bis- [4-(l-hydroxyethyl)phenyl] -methane (BHEPM), 0.205 g (0.21%) of 4-tert-butyl catechol (inhibitor of free-radical polymerization), 100 mL of toluene (solvent and azeotroping agent), 4.96 mL (5.0344 g, or 0.05848 mole) of the freshly distilled methacrylic acid and, at stirring, 0.1602 (1.60% the BHEPM weight of 7.32 mmole/L) of TSN This reaction mixture was, then, heated until the toluene began to reflux (at boiling point) about 102-111°C for 3 hours, 45 minutes.
  • BHEPM purified bis- [4-(l-hydroxyethyl)phenyl] -methane
  • 4-tert-butyl catechol inhibitor of free-radical polymerization
  • 100 mL
  • BHEPM weight of 4-tert-butyl catechol, 0.3014 g (3.01% of BHEPM weight or
  • n D 20 was 1.5750 and 1.5965 for the first sampling and the residue, respectively.
  • the mole ratio Diol (D) : methacrylic acid (MAA) 1 :2.55.
  • reaction temperature was decreased to 70°C; it was kept at 70°C for 1 hour, 10 minutes.
  • the content of components according to SEC was as follows, wt-%>: Monomer Ml (BVPE) 23, Monomer 2 (monoester) 14, Monomer 3 (diester) ⁇ 2, unsaturated oligomers (mixture) which could be described by the formula (I) 61.
  • the resin's gelation time at 140°C was 14-18 minutes.
  • the samples of the fiberglass cloth laminates have been prepared as described above.
  • Five plies of the prepreg were stacked and heated in the temperature range 80-300°C during several hours under the initial specific pressure about 1.0 kgf/cm 2 .
  • the laminates exhibited the following flexural strength values (after final cure temperature 300°C), kgf/cm 2 : 6000 @ 20°C, 3600 @ 250°C, and 3000 @ 250°C (after aging in air at 320°C for 10 hours).
  • the mole ratio Diol (D) : methacrylic acid (MAA) 1 :1 .57
  • the mole ratio Diol (D) : methacrylic acid (MAA) 1 :7.55.
  • reaction temperature was decreased to 70°C; it was kept at 70°C for 1 hour, 10 minutes.
  • yield was 81.4 g, mp 35-40°C, n D 40 1.6050.
  • the content of components according to SEC was as follows, wt-%: Monomer Ml (BVPE) 26, Monomer 2 (monoester) 16, Monomer 3 (diester) 3, unsaturated oligomers (mixture) which could be described by the formula (I) 53.
  • the mole ratio Diol (D) : methacrylic acid (MAA) 1 :2.50.
  • the mole ratio Diol (D) : methacrylic acid (MAA) 1 :1.
  • the mixture of 10.00 g (0.0387 mole) of the purified BHEPE, 0.0106 g (0.10% of BHEPE weight) of 4-tert-butyl catechol, 3.25 mL (3.30 g, or 0.0383 mole) of the freshly distilled methacrylic acid, and 50 mL of toluene was heated with 3.0 g of the "KU-23" resin at the boiling temperature for 2 hours. Then, additional portion (1.0 g) of the "KU-23" resin was added to the reaction mixture and heating was prolonged for 10 hours.
  • Example 37 The mixture of 120.00 g (0.4645 mole) of bis- [4-(l -hydroxy ethyl)phenyl] ether (BHEPE), 0.12 g (0.1% of BHEPE weight) of 4-tert-butyl catechol, 0.3002 g (0.25% of BHEPE weight or 1.0114 mmol/L) of TSN and 1.440 L of o-xylene was heated at the boiling temperature for 80 minutes. Water released during the dehydration was azeotroped from the system. Then, the reaction mixture was treated as described in Example 7.
  • BHEPE bis- [4-(l -hydroxy ethyl)phenyl] ether
  • 4-tert-butyl catechol 0.3002 g (0.25% of BHEPE weight or 1.0114 mmol/L) of TSN
  • 1.440 L of o-xylene was heated at the boiling temperature for 80 minutes. Water released during the dehydration was azeotroped from the system. Then, the reaction mixture
  • the yield of the unsaturated composition riched with bis-(4-vinylphenyl) ether (BVPE) was 100.5 g (97.3% of theor.), mp 85-87°C, gelation time for the composition stab, with 0.3 wt-% of 4-tert-butyl catechol: 1-3 minutes at 120°C, 5-6 minutes at 100°C, 90 minutes at 90°C.
  • wt-% Monomer Ml (BVPE) 95 ⁇ 3, its unsaturated dimer 5 ⁇ 3, its insaturated trimer and tetramers ⁇ 0.5%>. Recrystallized from ethyl alcohol, BVPE had purity of higher than 99.5% and mp 87-89°C.
  • Example 38 The mixture of 30.03 g (0.1163 mole or 0.2981 mole/L) of BHEPE, 0.030 g (0.1% of BHEPE weight) of 4-tert-butyl catechol, 0.1470 g (0.49% of BHEPE weight or 1.981 mmol/L) of TSA, and 360 mL of toluene was heated at the boiling temperature for 2 hours, 20 minutes. Water released during the dehydration was azeotroped from the system. Then, the reaction mixture was treated as described in Example 1. The yield of the unsaturated composition riched with bis-(4-vinylphenyl) ether (BVPE) was 25.0 g (96.7% of theor.), mp 84-86°C.
  • BVPE bis-(4-vinylphenyl) ether
  • BVPE Monomer Ml
  • Example 40 The mixture of 10.02 g (0.0391 mole) of bis- [4-(l -hydroxy ethyl)phenyl]- methane (BHEPM) 0.010 g of 4-tert-butyl catechol, 0.125 g (1.248% of BHEPM weight or 5.050 mmole/L) p-toluenesulfonic acid (monohydrate) (TSA), and 120 mL of o-xylene was heated at the boiling temperature for 1.5 hours. Water released during the dehydration was azeotroped from the system.
  • BHEPM bis- [4-(l -hydroxy ethyl)phenyl]- methane
  • TSA p-toluenesulfonic acid
  • the solution of the product in o-xylene was dried over CaCl 2 passed through a layer of alumina, and the solvent removed by distillation under the reduced (1-2 mm Hg) pressure at 40°C in the presence of about 0.00168 g tert-butyl catechol.
  • the yield of the unsaturated composition riched with bis-(4-vinylphenyl) methane (BVPM) was 7.59 g (88% of theor.), mp 30-33°C, n D 40 1.603.
  • Example 41 The mixture of 10.00 g (0.03901 mole) of BHEPM, 0.0093 g (0.093% of BHEPM weight) of 4-tert-butyl catechol, 0.1022 g (1.022% of BHEPM weight or 4.13 mmole/L) of TSA, and 120 mL of o-xylene was heated at the boiling temperature for 2 hours. Water released during the dehydration was azeotroped from the system. Then, the reaction mixture was treated as described in Example 1. The yield of the unsaturated composition riched with BVPM was 7.9 g (91.9%) of theor.), mp 31-34°C, n D 40 1.604.
  • BVPM Monomer Ml
  • mp 36- 38°C was obtained by sublimation of the monomer at 130°C for 1 hour under vacuum (0.5 mm Hg).
  • Example 42 The mixture of 5.0020 g (0.02064 mole) of 4,4'-di-(l- hydroxyethyl)biphenyl (DHEBP), 0.0050 g (0.1% of DHEBP weight) of 4-tert- butyl catechol, 00742 g (1.483% of DHEBP weight or 4.11 mmol/L) of TSN and 90 mL of o-xylene was heated at the boiling temperature for 40 minutes. Water released during the dehydration was azeotroped from the system. Then, the reaction mixture was treated as described in Example 1.
  • DHEBP 4,4'-di-(l- hydroxyethyl)biphenyl
  • the yield of the unsaturated composition riched with 4, 4 -divinylbiphenyl (DVBP) was 3.8 g (89.3%o of theor.).
  • the content of components was as follows, wt-%: Monomer Ml (DVBP) 77, its unsaturated dimer 17, its insaturated trimer 5%, tetramers and higher oligomers ⁇ 1%.
  • Example 43 The mixture of 5.00 g (0.0206 mole) of 4,4'-di-(l-hydroxyethyl)bi ⁇ henyl (DHEBP), 0.0050 g (0.1% of DHEBP weight) of 4-tert-butyl catechol, 00542 g (1.08% of DHEBP weight or 3.00 mmol/L) of TSN and 90 mL of o-xylene was heated at the boiling temperature for 1 hour. Water released during the dehydration was azeotroped from the system. Then, the reaction mixture was treated as described in Example 1. The yield of the unsaturated composition riched with 4,4 -divinylbiphenyl (DVBP) was 4.10 g (96.5% of theor.).
  • DHEBP 4,4'-di-(l-hydroxyethyl)bi ⁇ henyl
  • DVBP 4,4 -divinylbiphenyl
  • the yield of the unsaturated composition riched with 4,4 '-divinylbiphenyl (DVBP) was 3.9 g (91.8% of theor.), mp 135- 151°C.
  • the content of components was as follows, wt-%: Monomer Ml (DVBP) 75, its unsaturated dimer 19, its insaturated trimer 5%, tetramers and higher oligomers 1%. Elemental analysis of the composition: Found, %: C 91.70, H 7.00.
  • M n was 300 (number-average molecular weight of the composition was determined by measuring the thermal effects of condensation with a Hitachi-Perkin-Elmer osmometer, model 115).
  • Example 45 The mixture of 10.0030 g (0.03883 mole) of BHEPE, 0.010 g (0.1% of BHEPE weight) of 4-tert-butyl catechol, 0.1236 g (1.236% of BHEPE weight of 4.994 mmol/L) of TSA, and 120 mL of toluene was heated at the boiling temperature for 1 hour, 20 minutes. Water released during the dehydration was azeotroped from the system ( ⁇ 1.4 mL). Then, temperature was decreased down to 80°C and the reaction mixture was kept at 80°C additionally for 20 minutes. After treatment as described above, the product had high viscosity even at
  • Example 46 The mixture of 10.000 g (0.03871 mole) of BHEPE, 0.010 g (0.1% of
  • BHEPE weight of 4-tert-butyl catechol, 0.0685 g (0.69% of BHEPE weight or 4.0 mmol/L) of TSA, and 90 mL of toluene was heated at the boiling temperature for 1 hour, 30 minutes. Water released during the dehydration was azeotroped from the system (- 1.3 mL). Then, temperature was decreased down to 80°C and the reaction mixture was kept at 80°C additionally for 15 (the first sampling), 30 (the second sampling), 45 (the third sampling), 85 (the fourth sampling) minutes. After treatment as described above, the content of components in the composition was as follows, wt-%:
  • the yield of the composition was 149 g, mp 35-45°C, n D 60 1.628, n D 50 1.634, n D 40 1.637, n D 30 1.640, n D 25 1.643, number- average molecular weight (M n ) 900 g/mole; the content of components in the composition was as follows, wt-%>: Ml (BVPE) 20 and unsaturated oligomers described by formula (I) 80 (including its unsaturated dimer 15, unsaturated trimer 13, unsaturated tetramer 12, unsaturated pentamer 10, unsaturated hexamer 8, and higher homologues 22). Unsaturation of the composition was 0.53 mole double bonds/100 g of product.
  • unidirectional carbon fiber composites have been prepared with Russian unidirectional carbon fiber tape (commercially available under Russian trade name "LUP-01": density 1.7 g/cm 3 , weight 35 g/m 2 , number of fibers/10 cm 400 (wa ⁇ ), diameter of fiber 10-11 microns, porosity 3.5%, strength of 10 mm fiber 2.5 Gpa).
  • LUP-01 Russian unidirectional carbon fiber tape
  • the carbon fiber composites had the following flexural strength values, kgf cm 2 : (after final cure temperature 260°C/1 hour): 11,900-13,500 @ 20°C, 5,000-7,000 @ 250°C and 4,800-5,000 @ 320°C; (after additional heating in air @ 320°C/2 hours): 4,900 @ 320°C, 4,300 @ 370°C, 1,800 @ 400°C.
  • binder A is based on the Russian vinyl ester resin modified with divinylaromatic unsaturated composition obtained according to Example 39 (mp 82-86°C) and the targeted additives.
  • a formulation (binder A) comprising 58.54 g of unsaturated polyester resin "NPS 609-2 IM" (Russian trade name for the resin comprising the product of condensation of ethylene glycol with maleic and phthalic anhydrides mixed with dimethacrylate of triethylene glycol (as a reactive diluent), 2.95 g of epoxy resin ED-20 (Russian trade name for the epoxy resin derived from bisphenol A [DGEBA with 22 wt-% of epoxy groups]), 7.14 g of acrylamide, 30 g of divinylaromatic composition comprising 20 wt-% of BVPE (bis-(4- vinylphenyl)ether) and 80 wt-%> of its unsaturated oligomers) (crosslinking agent), 0.14 g of benzoyl peroxide, 0.60 g of dicumyl peroxide, 0.050 g of Santoflex 13 (N-(l,3-dimethyl-butyl)-N'-phenylphenylene
  • prepreg For preparation of a unidirectional, resin-impregnated tape and fiberglass cloth commonly referred to as prepreg, a single ply of the carbon (glass) fabric was placed on a propylene film and then impregnation tape (cloth) with the binder- A (mp 45-60°C) was performed at 70-90°C using hot melt electric platen (0.7x0.52 m) made from carbon felt-fiber glass cloth laminate (prepregger). The binder's content in the prepreg was approximately 50% by weight.
  • the fiberglass cloth laminates and carbon fiber composites had the following characteristics: thickness 1.40 and 0.95 mm, resin's content 30 and 30%, flexural strength (MPa): 600 and 900 at 20°C, 350 and 600 at 120°C, 250 and 500 at 150°C, 180 and 400 at 200°C, and very low value and 280 at 250°C, respectively.
  • MPa flexural strength
  • Example 49 The binder of the type B (formulation B) is based on Zaitform resin modified with the divinylaromatic composition obtained according to Example 39 (mp 82-86°C, and the targeted additives.
  • This formulation comprises the following ingredients: 30.0 g of the composition, 59.35 g of the Zaitform resin obtained according to Example 9, 3.00 g of epoxy resin (Russian trade name "ED-20” derived from bisphenol A, with 22.0 wt-%> of epoxy groups and viscosity of 16 Pas), 7.00 g of methacrylamide, and 0.60 g of dicumyl peroxide, 0.05 g of Santoflex 13.
  • the prepregs prepared from formulation B, fiberglass cloth, or carbon fiber tape have been used at similar values of pressure (2 kgf cm 2 for glass cloth laminates and 10 kgf cm 2 for carbon fiber composites), the cure schedules include the increase in temperature from 100 to 300°C for 8 to 11 hours.
  • the fiberglass cloth laminates and carbon fiber composites based on the binder B have the following characteristics: thickness 1.00 and 0.90 mm, flexural strength (MPa): 600 and 1200 at 20°C, 240 and 620 at 320°C, respectively, and additionally for carbon fiber composites: 520 at 350°C, and 250 at 400°C.
  • Example 50 According to the technical specification (TU 6-36-57-0-91) on Rolivsan MV-1, warranty concerning storage (shelf) time was 12 months of the date of preparation. For the pu ⁇ ose of increasing gelation time at RT, 0.0126 (0.5 wt-% > of the resin weight) and 0.0125 g of dimethylformamide were added to 2.501 g of Rolivsan and 2.495 g of Zaitform resins, respectively, and two series of 10 samples of each modified resin were stored for a long time. Gelation time has been determined at 20, 80 and 150°C in a month, a quarter, a year. The observation and the samples' testing for a long time (over 5 years) shows a slight increasing (approximately 10%) in viscosity of these samples and decreasing approximately 5-15%) in gelation time at 150°C after storing for 3 years.
  • Example 51 Example 51
  • Beads (grains) of styrene-BVPE resins of 5-10 microns' size) were obtained by bead (suspension) copolymerization of styrene with BVPE (10 wt- % > ) (crosslinking agent) in the system: styrene/water (1/20, in vol.), starch (0.5 wt-%>) (stabilizer), isooctane (6 wt-%) (porogen), benzoyl peroxide (5 wt-%>) (thermoinitiator) at stirring 9,000 revol./minute.
  • Figures 1 and 2 show SEC for a sample comprising a mixture of oligostyrene with the average molecular weight of 480 with benzene (microcolumn (0.5 ⁇ 300 mm), eluent was methylethylketone, the flow rate was 3 microliters/minute, the inlet pressure was 34 atm).
  • the polymerizable oligomers and resins of the present invention are shown in the examples to be available in different molecular weight ranges, generally referred to as middle or mid-range molecular weights (e.g., defined herein as about 200 to 500, preferably about 250 to 450), and middle or mid-range viscosity (e.g., defined herein as about 550 to 1050, preferably 600 to 1000 cps at 25°C).
  • the molecular weights referred to are number average molecular weights determined by measuring the thermal effects of condensation with a Hitachi-Perkin-Elmer osmometer (Model 115) with methodology was as published in Zaitsev, B. A. And Kiseleva, R.
  • SEC Size Exclusion Liquid Chromatography
  • Photometric method of the determination of phenols was used and tailored for quantitative analysis of phenolic impurities in several batches of bis-[4-(l- hydroxyethyl)phenyl] ether (BHEPE) produced on a pilot plant.
  • the method was based on the formation of the color azo compounds as a result of azo coupling of phenols with diazotized p-nitroaniline (Korenman I.M. Photometric Analysis. Methods for the Determination of Organic Compounds. Moscow, Chemistry Publ., 1970, p. 43 (in Russian); Smith G., King D. Analyst 1964, 89, 305,312; 1965, 90, 55).
  • the analysis was performed with photoelectrical colorimeter "PhEK-56M" for 35 minutes.
  • the mole ratio Diol (D) : methacrylic acid ( MAA ) 1 :1 .5
  • the temperature was decreased to 70°C, 0.3012 g of the extra-amount of TSA was added to the reaction mixture, and the reaction mixture was maintained and stirred at 70°C for 0.5 hour. After treatment as described above, the yield was 106 g, n D 20 1.587.
  • the content of components according SEC was as follows, wt %: Monomer Ml (BVPE) 14, Monomer 2 (monoester) 32, Monomer 3 (diester) 26, unsaturated oligomers (mixture) which could be described by the formula (I) 28.
  • the specimens of glass cloth laminates have been prepared on the basis of the glass fabric ( Russian trade name "T- 10-80" (unannealed). Five plies, size 5x2.5 cm were stacked, heated, and pressed under specific pressure of about 1.0 kgf/cm 2 .
  • the cure schedule was °C/hrs: 150/1, (150-160/15 min, 160/1, 160- 180/30 min, 180/2, 180-200/30 min, 200/1, 200-220/30 min, 220/1, 220-250/30 min, 250/1, 250-260/15 min, 260/1.
  • the thickness of the laminates' specimens was 0.90 to 1.00 mm.
  • Zaitform resins are capable of exerting revolutionary influence on the advancement of high technology to printing industries It has been established by experimentation that the polymer network of the both the cured Rolivsan and the cured Zaitform resins is capable of pyrolytic splitting resulting in the formation of fusible, soluble and curable oligomers at comparatively moderate temperature (320-340°C) of the pyro lysis. This network can be fully and rapidly broken-down to gaseous and volatile substances at a higher temperature of pyrolysis (>350°C) and especially under reduced pressures 0.01 to 600 mm Hg.
  • cooking values for the cured Rolivsan and Zaitform resins which have highly crosslinked polymer networks are extremely low (5- 15%) as compared to phenol-formaldehyde, aromatic polyimide, and other thermostable resins.
  • Another unusual level of performance of the crosslinked polymers formed by curing Zaitform resins is their ability of transition to the gaseous state without melting.
  • LaserGraver machines utilize an advanced engraving imaging technology that enables to produce both master films and offset plates with 2540 dpi resolution in single-stage, no- chemical process.
  • Direct dry image setting master films are engraved on inexpensive silverless film coated with thin black resin layer.
  • the image is formed by ablation of the coating while transparent film base remains untouched.
  • the coating has a high optical density of 4.5Dlog, thus providing high contrast for the film.
  • a small size of laser spot (up to 10 mm) provides true 2540 dpi resolution up to 180 lpi screen ruling for color separation.
  • laser engraving in its essence is a waterless and single-stage process.
  • LaserGraver is controlled by PC-based Level 2 software RIP and supports all features commonly found in imagesetters, as in Direct Imaging Computer-to- Plate systems.
  • the most important advantage of engraving technology is in realization of direct single-stage dry Computer-to-Plate processing.
  • the same ablation principle is used to make different types of offset plates: aluminum- based plates for large runs and color printing, polyester plates for medium runs and black-and-white printing and resin-coated paper plates for small orders.
  • LaserGraver actually substitutes a whole equipment set for traditional offset prepress: and imagesetter, film processing equipment, UV plate copying unit and a plate processor, and does it with no sacrifice of quality. With LaserGraver machines, it is asserted that one can use any desktop publishing software for Windows and Apple. The LaserGraver may be serviced by one operator.
  • LaserGraver may be used with asserted new standards of quality in rubber stamp manufacturing.
  • This high power laser machine engraves rubber sheet with the finest yet powerful light beam directly, producing deep gravure with extremely small and accurate elements.
  • the rubber needs no processing after engraving and can be cut in individual pieces, pasted to the stamp and delivered to customer immediately.
  • LaserGraver opens a new possibilities in rubber stamp layout design. Now you can use halftoned photos, extremely fine type (1-2 points), complicated pattern like those found in bank notes. It is possible to define a slope angle of printing elements profile in order to increase stamp lifetime and to avoid image distortion in case of inaccurate stamping. The quality and precision of manufacturing process makes faking of the stamps almost impossible. With its 2032 dpi resolution (2540 dpi resolution optional), LaserGraver provides the quality of imaging close to that of imagesetter. LaserGraver is a desktop unit completely controlled via software. It makes about 12 rubber stamps per hour. From the viewpoint of software, it behave like PostScript printer or imagesetter. The soft ware PC-based RIP gives access to all features of both PC and Macintosh desktop publishing software.
  • LaserGraver could also be used in so called imagesetter mode. In this mode, it engraves special black resin coated film directly producing master films of imagesetter quality. The film needs no developing and costs much less than ordinary photosensitive film. Its optical density is as high as 4.5 Dlog.
  • the quality is sufficient for color separations with up to 133 lpi screen ruling. In fact it is enough for many pu ⁇ oses such as business card manufacturing, low-run offset printing, silk screen printing photopolymer platemaking, etc. With LaserGraver, quality films could be made in-house. Actually, the machine is ideal "all-in-one solution for small ente ⁇ rises, eliminating all wet and darkroom process.
  • ZAITFORM COATING on PHENOL-FORMALDEHYDE RESINS ARTICLES provide a RESOLUTION of 320 lpi. This implies that the resins can be used for obtaining the printing materials of the most high quality.
  • Example 54 The formulation comprising 0.900 g of Zaitform resin (obtained according to Example 52), or Rolivsan MV-1 resin, 0.01 g dicumyl peroxide, and 0.05-0.09 g of carbon black was prepared at 50-120 °C and stirring. The formulation was heated to 100-140 °C and was applied on a hot polymer roller made from phenol-formaldehyde molding powder. The thickness of the Zaitform layer (cover) was 30-500 microns. The following cure schedule was used (°C/hours): 140/1,
  • Imaging time for 2540 resolution: A4 15 min Laser type (wavelength): solid-state YAG: Nd (1.06 microm)
  • Input data format PostScript, PCX Operation environment : daylight, prepress area
  • top value 320 lpi
  • Zaitform resins for evaluating Zaitform resins as binders in reinforcing rods (bars) for use as alkali resistant materials, accelerated aging test have been carried out. For this pu ⁇ ose, the investigation of the dependence of the flexure strength of cured Zaitform resins, (specimens of glass cloth laminates and clear castings) on exposure to alkali buffer solution both at room temperature (RT) and boiling temperature has been performed.
  • the present invention relates to additional and even more versatile precursors of great structural variety for zaitform resins.
  • these precursors for Zaitforms resins include aromatic compounds/hydrocarbons with different numbers of secondary alcoholic groups, i.e. 1-hydroxyethyl (HO(H 3 C)HC-) groups.
  • the extended precursors may include now polyfunctional bridged and non-bridged aromatic compounds, namely mono-, di-, tri-, tetra, ...and poly secondary aromatic di-, tri-, tetra, ... and polyols, the aromatic cycles of which can contain also ethyl groups and other substituents, such as alkyl (e.g.
  • methyl and alkoxy groups.
  • These more extended precursors may include not only the individual 1-hydroxyethyl (HO(H 3 C)HC-) containing compounds, but also their mixtures/compositions.
  • These aromatic compounds may comprise different numbers of 1 -hydroxyethyl groups (preferably 2 or more, y>2), and may comprise few number of ethyl (preferably 0-1, n ⁇ 2), and even acetyl groups (preferably 0-1, x ⁇ 2), and other substituent, such as methyl groups, e.g.:
  • Ar is phenylene, arylene and bridged arylene groups which may also comprise alkyl(preferably methyl) and alkoxy/(preferably methoxy) groups.
  • compositions of 1-hydroxyethyl containing compounds may comprise mainly di-( 1-hydroxyethyl) containing compounds, i.e., the previously described disecondary aromatic diols, and also a small amount of mono-, tri- and tetra-(l- hydroxyethyl) containing compounds.
  • the structure and composition of the extended circle of Zaitform precursors are due to the methods/routes for their production.
  • the initial (raw) materials for obtaining these type of precursor my include different aromatic hydrocarbons (Ar), where Ar is aromatics (unsubstituted or alkyl/alkoxy substituted), such as benzene, toluene, xylene, mesitylene, biphenyl, methylated biphenyl, diphenylmethane, diphenyloxide, naphthalene and their methylated products, and polynuclear aromatic hydrocarbons.
  • Ar aromatic hydrocarbons
  • Ar is the aromatic remainder (e.g., the remainder -AR is formed by removal of an atom, such as hydrigen or halogen from a compound such as H-Ar) of a molecule that may comprise also alkyl (methyl), alkoxy (methoxy) substituent(s), or bridging group(s) between aromatic rings, such as alkylene (methylene), -O-, -S-, and even -CO- (as sequence of the oxidation of methylene group, e.g., in the particular case of using diphenylmethane as an initial (raw) aromatic hydrocarbon.
  • the initial (raw) materials for obtaining this type of precursors encompass different aromatic hydrocarbons (H n - Ar), where Ar is an aromatic remainder of unsubstituted or alkyl/alkoxy substituted aromatic compound, such as benzene, toluene, xylene, mesitylene, biphenyl, methylated biphenyl, diphenylmethane, diphenyloxide, naphthalene and their methylated products, and polynuclear aromatic hydrocarbons.
  • Ar is an aromatic remainder of unsubstituted or alkyl/alkoxy substituted aromatic compound, such as benzene, toluene, xylene, mesitylene, biphenyl, methylated biphenyl, diphenylmethane, diphenyloxide, naphthalene and their methylated products, and polynuclear aromatic hydrocarbons.
  • New routes for the production of the extended precursors include the following reactions:
  • the degree of alkylation can be controlled by changing the alkylation conditions and involving the reactions of transalkylation with benzene, ethylbenzene, etc.
  • Catalyst of alkylation may be H-zeolites, such as ZSM-5, Y, beta, H-mordenite, etc., Friedel-Crafts catalyst, such as A1C1 3 . Chlorinated hydrocarbons or excess of aromatic hydrocarbons may be used as solvents.
  • ethylaromatics with air/O 2 to (a) acetyl/ 1-hydroxyethyl or (b) mainly acetyl containing aromatics, e.g.:
  • main amount and "small amount” are merely relative terms with respect to these groups.
  • One group may comprise a lower or greater weight percent of that particular component as compared to the other component, or may be approximately the same. The indication is merely that the two components do not have to be stoichiometrically equivalent.
  • Chlorinated hydrocarbons can be used as solvents.
  • Hydrogen peroxide (H 2 O 2 ) over titanium silicalites may be applied as another catalyst of the liquid phase oxidation of ethylaromatic hydrocarbons directly to I-hydroxyethyl containing compounds.
  • Acidic impurities such as benzoic acid or similar products
  • Acidic impurities such as benzoic acid or similar products
  • Alkali treatment may be applied for their removing. The degree of oxidation also can be controlled. 3.
  • Example 3 Synthesis of di(l '-hydroxy 'ethyl) benzene by the hydrogenation of p-diacetylhenzene p-Diacetylhenzene was obtained by the oxidation of p-diethylbenzene with air (see scheme), and/? ⁇ r ⁇ -diethylbenzene was one of the industrial products of Zeolite-based alkylation of benzene with ethylene.
  • a mixture of 7.0 g of skeletal Raney-Nickel catalyst, 250 ml ethyl alcohol and 40.0 g of p-diac.p.tylhenzene was placed in autoclave with a capacity of 0.6 L and stirred at 95-100°C and under the initial hydrogen pressure of 106 atm. until abso ⁇ tion of hydrogen cease (50 min); final pressure was 49 atm.
  • the catalyst was then separated by centrifuging, the alcohol was removed under reduced pressure, and the residue was recrystallized from toluene, melting point of the recrystallized product was 87-89°C, and the yield was 95% of theoretical one.
  • DHEB purified l,4-di-( ⁇ - hydroxyethyl)benzene
  • the mole ratio DHEB : methacrylic acid (MA A) 1 2.41 .
  • the solutions of the product in benzene were dried over CaCl 2 passed through a layer of alumina, and the solvent removed by distillation under the reduced pressure at 40°C in the presence the trace amounts (0.1%) hydroquinone.
  • Example 8 The mixture of 3.0003 g (0.0181 mole) of l,4-di-( ⁇ - hydroxyethyl)benzene (DHEB), 0.0032 g (0.11% of DHEB weight) of 4-tert- butyl catechol, 0.0362 g (1.207% of DHEB weight or 3.019 mmol/L) of TSA, and 60 mL of toluene was heated at the boiling temperature for 15 min. Because of the absence of the reaction water evolution, extra portion of TSA (0.0365 g, i.e. total concentration increased up to 6.063 mmole/L) was added and refluxing was continued for 2 hr 30 min (the first sampling).
  • TSA 0.0365 g, i.e. total concentration increased up to 6.063 mmole/L
  • the resin of the first sampling comprised approximately 65% > of/>-divinylbenzene, 30%> of its unsaturated dimer and 5%> higher oligomers.
  • Example 10 The mixture of 1.40 g (0.0084 mole) of l,4-di-( ⁇ - hydroxyethyl)benzene (DHEB), 0.014 g (1% of DHEB weight) of hydroquinone, 0.0350 g of CuCl, two drops of thiophene, 0.0350 g (2.5% of DHEB weight or 3.57 mmol/L) of TSA, and 50 mL of toluene was heated at the boiling temperature for 2 hrs. The reaction mixture was treated as noted above. The product had n D 19 1.5570, n D 50 1.545. Elemental analysis. Found: C 79.8%, H 7.9%.
  • the earlier proposed route to producing of zaitform resins can be cardinally changed and improved by means of replacing the Friedel-Crafts acetylation of aromatic hydrocarbons (with corrosive reagents (A1C1 3 , AcCl, HCl) generating a lot of waste) by the alkylation of the same aromatics with ethylene and/or di-, tri-, tetra- or polyalkylbenzenes (or their mixtures, compositions) and the sequential oxidation of ethylated aromatic hydrocarbons to acetylated or even directly to hydroxyethylated aromatic hydrocarbons based on advanced zeolite technology or the adso ⁇ tion of catalysts, e.g. oxidants onto solid supports.
  • precursors for zaitform and Rolivsan resins synthesis are very important result and sequence of applying the new approach; the precursor concept is extended from disecondary aromatic diols to mono-,di- tri- or polyalkylated aromatic hydrocarbons with alkyl (ethyl) groups oxidized partly or fully to hydroxyethylgroups both in the form of individual compounds and their compositions/mixtures.
  • This new route to a cost-effective producing of zaitform resins on a large scale can straight blend in with the newest styrene's technology line as an additional compatible branch.
  • a new route to zaitform resins (ZR) envisages their manufacturing as a coproduction with styrene and related monomers, such as divinylbenzenes and propylene oxide, i.e., the ZR production could be as one of the related processing branch of the styrene (petrochemical) industries.
  • the proposed pathways extend greatly the precursors' basis from di- secondary aromatic diols to aromatics or aromatic compositions comprising different number of sec.
  • alcoholic (1-hydroxyethyl) groups such as mono-, di-, tri, and poly-secondary mono-,di-, tri, etc., up to poly-ols, and, thereby, result in additional variety of zaitform resins.
  • the process invention also thereby includes a process for preparation of polymerizable resins comprising the alkylation of aromatic hydrocarbons with at least one organic compound selected from the group consisting of ethylene monoethyl-benzene, di-ethylbenzene, tri-ethylbenzene, tetra-ethylbenzene, polyethylbenzenes, mono-, di-, tri, tetra, etc.

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Abstract

Cette composition à base d'ester vinylique contenant au moins trois monomères et oligomères est constituée, (a), de 2 à 95 % en poids de composés diaryles renfermant au moins deux groupes aryle liés directement ensemble ou pontés par un groupe de liaison, chacun de ces groupes aryle possédant un groupe vinyle rattaché, (b), de 2 à 65 % en poids d'un ester d'acide méthacrylique d'un oxyde sec-éthylol-diaryl à substitution vinyl ou sa contrepartie thioéther ou méthine ou biphényle, (c), de 1 à 35 % en poids d'esters d'acide diméthacrylique de bis-[4-(1-hydroxyéthyl)aryl] éther, de thioéther ou de méthine ou leurs contreparties dans lesquelles les noyaux aromatiques sont directement liés ensemble et, (d), de 2 à 95 % d'oligomères insaturés. Cette composition réactive comporte moins de 1 %, en pourcentage molaire, de composés monaryl-phénoliques.
PCT/IB1999/001667 1998-10-07 1999-10-07 Nouvelles matieres polymerisables et nouvelles resines de polyester Ceased WO2000023485A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112469740A (zh) * 2018-07-26 2021-03-09 迪睿合株式会社 树脂颗粒和树脂颗粒的制造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5763688A (en) * 1994-12-07 1998-06-09 Research Development Corporation Of Japan Method for producing an alcohol
EP0849246A2 (fr) * 1996-12-20 1998-06-24 Ciba SC Holding AG Dérivés de 4-vinyl-4'-alpha-hydroxyethyl-biphenyl

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5763688A (en) * 1994-12-07 1998-06-09 Research Development Corporation Of Japan Method for producing an alcohol
EP0849246A2 (fr) * 1996-12-20 1998-06-24 Ciba SC Holding AG Dérivés de 4-vinyl-4'-alpha-hydroxyethyl-biphenyl

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199701, Derwent World Patents Index; Class A12, AN 1997-010359, XP002132836 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112469740A (zh) * 2018-07-26 2021-03-09 迪睿合株式会社 树脂颗粒和树脂颗粒的制造方法

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