RU2566756C2 - Modified polyester composition and method for obtaining thereof - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to modified polyester compositions comprising polyester resin modifiers on the basis of nano oxides. Disclosed polyester composition is used as a binder, comprising polyester resin with a modifier based on nano particles of the oxides selected from SiO₂, Al₂O₃, MgO, ZrO₂, CeO₂, TiO₂, ZnO, FeO, Fe₂O₃, Fe₃O₄ and SnO, and containing a C₂-C₁₆ fragment with at least one hydroxyl group, and covalently bonded by the said hydrocarbon C₂-C₁₆ fragment with the said polyester resin; and a polyester resin modifier based on nano particles of the oxides selected from SiO₂, Al₂O₃, MgO, ZrO₂, CeO₂, TiO₂, ZnO, FeO, Fe₂O₃, Fe₃O₄ and SnO, comprising unsaturated C₂-C₂₀ groups, selected from the C₂-C₂₀ alkene, C₂-C₂₀ alkine or C₂-C₂₀ cycloalkene, covalently bonded by oxygen with the surface of the said nano particles. Disclosed method for polyester composition is used as a binder, comprising a) providing a polyester resin with a modifier based on nano particles of the oxides selected from SiO₂, Al₂O₃, MgO, ZrO₂, CeO₂, TiO₂, ZnO, FeO, Fe₂O₃, Fe₃O₄ and SnO, and containing a C₂-C₁₆ fragment with at least one hydroxyl group, and covalently bonded by the said hydrocarbon C₂-C₁₆ fragment with the said polyester resin; b) combining the said polyester resin with the modifier based on nano particles of the oxides selected from SiO₂, Al₂O₃, MgO, ZrO₂, CeO₂, TiO₂, ZnO, FeO, Fe₂O₃, Fe₃O₄ and SnO, comprising unsaturated C₂-C₂₀ groups, selected from the C₂-C₂₀ alkene, C₂-C₂₀ alkine or C₂-C₂₀ cycloalkene, covalently bonded by oxygen with the surface of the said nano particles. Disclosed modified polyester resin, comprising a modifier is based on nano particles of the oxides selected from SiO₂, Al₂O₃, MgO, ZrO₂, CeO₂, TiO₂, ZnO, FeO, Fe₂O₃, Fe₃O₄ and SnO, comprising C₂-C₁₆ fragment with at least one hydroxyl group, and covalently bonded by the said hydrocarbon C2-C16 fragment with the said polyester resin; and method for obtaining thereof. Disclosed a polyester resin modifier based on nano particles of the oxides selected from SiO₂, Al₂O₃, MgO, ZrO₂, CeO₂, TiO₂, ZnO, FeO, Fe₂O₃, Fe₃O₄ and SnO, comprising unsaturated C₂-C₂₀ groups, selected from the C₂-C₂₀ alkene, C₂-C₂₀ alkine or C₂-C₂₀ cycloalkene, covalently bonded by oxygen with the surface of the said nano particles; and method of obtaining thereof. Also described a product resulting from curing of the said polyester composition, and described use of the said polyester composition for the production of a composite material.

EFFECT: improved physical and chemical characteristics of the end product.

28 cl, 3 tbl

Description

FIELD OF TECHNOLOGY

The present invention relates to the field of creating new materials, in particular, relates to new modified polyester compositions containing modifiers of a polyester resin based on nanoparticles of oxides, which can improve the physicomechanical characteristics of the final product. The invention also relates to new modifiers of a polyester resin based on nanoparticles of oxides, methods for their preparation and use for modifying a polyester composition. In addition, the present invention provides the use of a modified polyester composition to produce an article, in particular composite materials in which the modified polyester composition acts as a binder.

BACKGROUND

Currently, materials based on polyester resins are finding wider application in various branches of technology and industry. In particular, due to its excellent physicomechanical and chemical characteristics, polyester resins are used in such high-tech industries as aircraft and shipbuilding, construction, electronics, and mechanical engineering. Polyester resins are often used to produce composite materials, in particular to produce fibrous, filled or layered reinforced composites. The requirements for polyester resins are constantly being tightened by both consumers and environmental organizations. So, when using a polyester resin to obtain a structural material that experiences mechanical stress during operation, special requirements are imposed on the physicomechanical properties of such a material, such as hardness, rigidity, tensile / compression strength. From a safety point of view, polyester resins should preferably not support combustion and also contain toxic readily volatile substances such as styrene.

In general, polyester resins are a polycondensation product of polyols and dibasic or polybasic organic acids or anhydrides of dibasic or polybasic organic acids. The most common ingredients for the preparation are ethylene glycol and maleic and phthalic acids and anhydrides. Also in their composition polyester resins, as a rule, additionally contain agents for regulating the viscosity, premature curing inhibitors, accelerators, etc. Initially, the liquid polyester resin is cured by crosslinking the polymer chains with substances that readily disintegrate into free radicals, for example, with peroxides such as benzoyl peroxide and methyl ethyl ketone peroxide, to give a cured to the final product.

To date, various attempts have been made to modify the polyester resin with oxide nanoparticles. In general, most of these modifications were aimed at improving the thixotropic behavior and viscosity, and in the general sense of the rheological characteristics of the resin. So, one of the options for modifying the resin was the use of nanoparticles of oxides, for example silicon oxide, as a filler.

For example, from the technical bulletin of Evonik Degussa (DE) (http://www.aerosil.com, AEROSIL fumed silica in unsaturated polyester resins and vinyl ester resins, TB 54), it is known to use nanosized silica (trade name Aerosil) in unsaturated polyester and vinyl ester resins. This bulletin discusses the reinforcing, thickening and thixotropic effects of various surface-modified aerosils in standard polyester and vinyl ester resins. As you know, the polyester resin has pronounced hydrophobic properties, despite the fact that silicon dioxide nanoparticles are hydrophilic, due to the presence of silanol groups on the surface. Thus, when mixing a polyester resin with a conventional unmodified hydrophilic aerosil, silicon nanoparticles are unevenly distributed over the volume of the resin and form agglomerates, which can lead to a significant decrease in the properties of the product obtained by curing. Reducing the number of agglomerates, improving the rheological properties and a more uniform distribution of particles in the volume can be achieved by attaching silane groups containing hydrophobic fragments, for example alkanes, to the surface of the particles. The main disadvantage of this approach is that the addition of silicon oxide nanoparticles as a filler, essentially does not contribute to the improvement of strength, stiffness and other characteristics associated with mechanical stresses arising from the operation of the final product.

Similar problems of combining nanoparticles based on oxides and curable resins, in particular polyester and vinyl ester resins, are discussed in US patent 8448885. Thus, using the invention according to US patent 8448885, modified silicon oxide nanoparticles are proposed to be introduced without using a traditional solvent.

WO 2006125736 describes the use of functionalized nanoparticles of various oxides, for example, silicon and aluminum, as a filler having coloring properties in various types of polymer resins, including unsaturated polyester resins. The present invention proposes to functionalize the surface of nanoparticles through a silane fraction. The publication also mentions the possible effect of a filler based on nanoparticles functionalized with a silane moiety as a stabilizer, inhibitor and compatibilizer of a polyester resin.

In WO2008043634, silica particles are proposed that are surface modified with organosilicon nitrogen-containing compounds. Also proposed is their use in resins, including polyester, which are used to produce adhesives. The objective of the invention was to increase the crack resistance, scratch and abrasion resistance and thermal stability of the polymer, as well as the ability to use large concentrations of filler from silicon oxide nanoparticles.

Thus, in the prior art there is no information on how to improve the physicomechanical characteristics of polyester resins, the increase of which is especially necessary for resins, the products of which are used as structural materials and experience strong operational mechanical stresses.

Therefore, at present, there is still a need for new modified polyester compositions which, as a result of curing, make it possible to obtain products and products having improved physical and mechanical properties, such as shear / tensile strength, hardness, stiffness, and improved chemical properties, such as fire resistance, corrosion and moisture resistance, low emission of volatile substances (for example, volatile solvents such as styrene). Furthermore, it was an object of the present invention to provide convenient and simple processes for the preparation of such modified polyester compositions. Another objective was the provision of new polyester compositions, allowing to obtain products with the best physico-chemical characteristics at a price comparable to unmodified analogues.

Furthermore, it was an object of the present invention to provide a new polyester composition exhibiting improved binding ability in the preparation of composite materials.

In the present invention, these problems are solved using the proposed polyester composition containing a polyester resin and at least one polyester resin modifier based on oxide nanoparticles.

SUMMARY OF THE INVENTION

The present invention provides a polyester composition comprising a polyester resin and an oxide nanoparticle polyester resin modifier containing unsaturated C ₂ -C ₂₀ hydrocarbon groups covalently bonded to the particle surface through oxygen.

The present invention also relates to a method for producing a polyester composition comprising providing a polyester resin and combining said polyester resin with an oxide nanoparticle polyester resin modifier containing unsaturated C ₂ -C ₂₀ hydrocarbon groups covalently bonded to the particle surface.

In addition, the invention provides a modified polyester resin comprising an oxide nanoparticle polyester resin modifier bonded to said polyester resin via a covalent bond through a C ₂ -C ₁₆ hydrocarbon moiety containing at least one free hydroxyl group, and a method for producing such a modified a polyester resin, comprising a) providing a modifier of a polyester resin based on nanoparticles of oxides containing a C ₂ -C ₁₆ hydrocarbon fragment containing at least one well, a hydroxyl group; b) condensation of a C ₂ -C ₁₆ dihydric or polyhydric alcohol and a C ₂ -C ₂₀ dihydric or polybasic organic acid or its anhydride to obtain an oligoester; c) polycondensation of the obtained oligoester with a modifier from stage a)

Accordingly, the invention also provides a polyester resin modifier based on nanoparticles of oxides selected from the group consisting of SiO ₂ , TiO ₂ ; Al ₂ O ₃ , MgO; ZrO ₂ , CeO ₂ , ZnO; FeO, Fe ₂ O ₃ , Fe ₃ O ₄ ; SnO containing unsaturated C ₂ -C ₂₀ hydrocarbon groups covalently bonded to the particle surface through oxygen, and a method for producing it, comprising reacting oxide nanoparticles with an unsaturated C ₂ -C ₂₀ halogen-containing hydrocarbon.

In addition, the present invention relates to articles such as composites containing a cured polyester composition, a modified polyester resin or oxide nanoparticle polyester resin modifiers according to the invention, and also to the use of said polyester compositions, modified polyester resins and oxide nanoparticle modifiers to obtain such products.

DETAILED DESCRIPTION OF THE INVENTION

In General, the present invention relates to a new polyester composition containing a polyester resin and a modifier of a polyester resin based on nanoparticles of oxides, which can be used to obtain products, including composite materials with improved physico-mechanical and chemical characteristics. In particular, products obtained on the basis of the proposed polyester composition have increased hardness, tensile / compression / bending strength. In addition, products obtained on the basis of the proposed polyester composition do not support combustion, and also do not contain easily volatile toxic ingredients.

In the present description, the polyester resin refers to the condensation product of one or more carboxylic acids or their derivatives, such as anhydrides and esters with one or more alcohol, for example a di- or polyhydric alcohol.

In one embodiment, the di- or polyhydric alcohols include diethylene glycol and ethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-butropylene, 1,3-butrene, tetra butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1, 3-propanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedi methanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 4,4'-dihydroxybiphenol, 4,4'-methylenediphenol, 4,4'-isopropylindenediphenol, 1,5-dihydroxynaphthalene, 2,5-dihydroxynaphthalene , 2,2-bis- (4-hydroxyphenyl) propane (bisphenol A), bisphenol S, oligo- and polymers of these di- or polyhydric alcohols, and combinations thereof.

In one embodiment, the carboxylic acid may be an unsaturated or saturated carboxylic acid. In some embodiments, unsaturated carboxylic acids include acrylic acid, chloromaleic acid, citraconic acid, fumaric acid, itaconic acid, maleic acid, mesaconic acid, methacrylic acid; saturated or aromatic carboxylic acids include adipic acid, benzoic acid, dihydrophthalic acid, dimethyl-2,6-dicarboxylic acid, d-methyl-glutaric acid, dodecandicarboxylic acid, ethylhexanoic acid, glutaric acid, hexahydrophthalic acid, isohydrophthalic acid, isohydrophthalic acid, isohydrophthalic acid, isohydrophthalic acid, , phthalic acid, pimelic acid, propionic acid, sebacic acid, succinic acid, terephthalic acid, tetrachlorophthalic acid, tetrahydrophthalic acid, trimellitic acid, 1,2,4,5-benzene carboxylic acid, 1,2,4-benzene-tricarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, dicyclopentadiene maleic acid, as well as their anhydrides and derivatives.

In preferred embodiments, the carboxylic acid or anhydride is selected from phthalic acid, isophthalic acid, maleic acid, phthalic anhydride, and maleic anhydride.

In some embodiments, the polyester resin is a non-combustible polyester resin based on a halogen-substituted anhydride, such as flame retardant tetrabromophthalic anhydride.

In preferred embodiments, the di- or polyhydric alcohol is selected from ethylene glycol and propylene glycol, 1,3-propanediol and 1,4-butanediol.

In one embodiment, the polyester resin contains a solvent, for example, alpha-methyl styrene, vinyl toluene, divinylbenzene, methyl methacrylate, diallyl phthalate, styrene, triethylene glycol dimethacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate and triallyl cyanurate. According to a preferred embodiment, the polyester resin does not contain styrene and other volatile and toxic solvents.

In one embodiment, the polyester resin comprises a polymerization inhibitor, for example, hydroquinone, toluhydroquinone, mono-tert-butylhydroquinone, 2, -5-di-tert-butylhydroquinone, and the like.

According to one implementation options, the polyester resin further comprises an epoxy resin or a vinyl ester resin.

Conventional polymerization accelerators and initiators such as organic peroxides such as benzoyl peroxide and methyl ethyl ketone peroxide can be used to cure the polyester resin.

According to one embodiment, the oxide nanoparticles are inorganic oxide particles containing free hydroxyl groups on the surface, including SiO ₂ , Al ₂ O ₃ , MgO; ZrO ₂ ; CeO ₂ , TiO ₂ ; ZnO; FeO, Fe ₂ O ₃ , Fe ₃ O ₄ ; SnO.

According to a preferred embodiment, the oxide nanoparticles are selected from silica (SiO ₂ ) and alumina (Al ₂ O ₃ ).

In some embodiments, the nanoparticle size is from about 1 nm to about 1000 nm, in some embodiments from about 1 nm to about 500 nm, and in some embodiments from about 1 nm to about 250 nm, and preferably from about 1 nanometers to approximately 100 nanometers.

In some embodiments, the polyester composition may contain additional agents conventionally used to impart desired properties to the polyester resin, such as fillers, reinforcing materials, flame retardants, as well as additional curing agents, such as accelerators, moderators and thickeners. Non-limiting examples of accelerators include cobalt naphthanate, zinc octoate, cobalt octoate, and the like.

Oxide Nanoparticle Polyester Resin Modifiers

The present invention provides novel modifiers of polyester resins based on oxide nanoparticles.

In one aspect, the present invention provides an oxide nanoparticle polyester resin modifier comprising unsaturated C ₂ -C ₂₀ hydrocarbon groups covalently bonded to the surface of particles through oxygen.

In one embodiment, unsaturated C ₂ -C ₂₀ hydrocarbon groups are residues of C ₂ -C ₂₀ unsaturated aliphatic hydrocarbons.

According to a more specific embodiment, the C ₂ -C ₂₀ residue of the unsaturated aliphatic hydrocarbon is C ₂ -C ₂₀ alkene, C ₂ -C ₂₀ alkine or C ₂ -C ₂₀ cycloalkene. In general, said unsaturated C ₂ -C ₂₀ hydrocarbon groups can be any hydrocarbon groups containing at least one unsaturated bond. Non-limiting examples of C ₂ -C ₂₀ unsaturated hydrocarbons include ethylene, propylene (allyl), butene, butadiene, pentene, 2-pentene, hexene, heptene, octene, nonene, decene, 1-undecene 1-dodecene, 1-tridecene, 1 -tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosen, 1-docosen, 4-methyl-1-pentene, 3-methyl-1-butene, 3-methyl -1-pentene, 2,3-dimethyl-2-butene, 5-methyl-1-nonene, 3,5,5-trimethyl-1-hexene and vinylcyclohexane. Non-limiting examples of cyclic C ₂ -C ₂₀ unsaturated hydrocarbons include cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, 2-methylcyclopentene, 4-methylcyclopentene, vinylcyclohexane, norbornadiene, dicyclopentadiene, vinylcyclohexene-2, 5 1,3-divinylcyclopentane, 1,2-divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-divinylcyclohexane, 1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane, 1-allyl-5- vinylcyclooctane and 1,5-diallylcyclooctane. Non-limiting examples of C ₂ -C ₂₀ triple bond unsaturated hydrocarbons include propine, 1-butyn, 2-butyn, 1-pentin, 2-pentin, 3-methyl-1-butene, 1-hexine, 1-heptin, 1-octin , 1-nonin, 1-decin, as well as their derivatives.

The use of this modifier in the composition of the polyester composition can significantly improve the physico-chemical characteristics of the final product made from such a composition, in particular, to increase the bending strength, tensile strength, compressive strength and Brinell hardness. In General, it is believed that the action of the specified modifier can be based on the interaction of unsaturated groups with a polyester resin during curing. In particular, it is believed that due to the presence of free multiple C — C bonds, the modifier can participate in the polymerization reaction, in particular, radical or ionic polymerization, which occurs when the polyester is crosslinked with a solvent also playing the role of a crosslinking agent, with the participation of the polymerization initiator, which is a donor of free radicals, thereby chemically integrating into the structure of the cured polymer, ensuring the achievement of these advantages of the cured product.

In yet another aspect, the present invention provides an oxide nanoparticle polyester resin modifier comprising a C ₂ -C ₁₆ hydrocarbon moiety containing at least one free reactive, preferably terminal, hydroxyl group that is coupled to the polyester resin via a covalent bond during the condensation reaction.

In one embodiment, the C ₂ -C ₁₆ hydrocarbon moiety containing at least one hydroxyl group is a C ₂ -C ₁₆ residue of a di- or polyhydric alcohol. In general, a C ₂ -C ₁₆ hydrocarbon fragment containing at least one hydroxyl group may be any C ₂ -C ₁₆ hydrocarbon fragment containing at least one free reactive, preferably terminal, hydroxyl group capable of joining condensation reaction (esterification) with mono - and polyester compounds. Non-limiting examples of C ₂ -C ₁₆ dihydric or polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,3-propylene glycol, tetrapropylene glycol, tetrapylene glycol, 1 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl- 1,3-propanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2 2,4,4-tetramethyl-1,3-cyclobutanediol, 4,4'-dihydroxybiphenol, 4,4'-methylenediphenol, 4,4'-isopropylindenediphenol, 1,5-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2 2-bis- (4-hydroxyphenyl) propane (bisphenol A), bisphenol S, oligo- and polymers of these di- or polyhydric alcohols, and combinations thereof.

The use of this modifier in the composition of the polyester resin can significantly improve the physico-chemical characteristics of the final product made of such a resin, in particular, to increase the bending strength, tensile strength, compressive strength and Brinell hardness. This modifier is included in the structure of the polyester during the direct preparation of the specified polyester, through a condensation reaction through a free hydroxyl group, with previously obtained oligoesters of alcohol and dibasic or polybasic carboxylic acid. Thus, even before polymerization (curing), the modifier is present in the structure of the polyester resin, that is, it is essentially a structural element of the polyester, which, as mentioned above, ensures the achievement of unexpectedly high physical and mechanical properties of the final product. In addition, it was found that the use of a polyester resin modifier with a longer hydrocarbon chain between the hydroxyl group and the surface of the nanoparticle leads to greater elasticity of the final resin. In addition, the use of the inclusion of a modifier based on nanoparticles of oxides in the structure of the polyester resin gives it increased fire resistance properties.

According to one embodiment, the polyester composition comprises a polyester resin comprising an oxide nanoparticle polyester resin modifier coupled to said polyester resin via a C ₂ -C ₁₆ hydrocarbon moiety containing at least one hydroxyl group.

Polymer composition

According to another embodiment, the polymer composition comprises

a polyester resin containing an oxide nanoparticle polyester resin modifier bonded by covalent bonding to said polyester resin via a C ₂ -C ₁₆ hydrocarbon moiety containing at least one hydroxyl group;

- a modifier of a polyester resin based on oxide nanoparticles containing unsaturated C ₂ -C ₂₀ hydrocarbon groups covalently bonded to the surface of the particles through oxygen.

According to one embodiment, the polyester composition contains from 0.01 to 15%, preferably from 0.01 to 2%, a polyester resin modifier containing unsaturated C ₂ -C ₂₀ hydrocarbon groups.

It was also unexpectedly discovered that the use of more than two types of modifiers of a polyester resin based on nanoparticles of oxides in a polyester composition at the same time, for example, at the same time a modifier of a polyester resin based on nanoparticles of oxides covalently incorporated into the structure of a polyester molecule through ether bonds, and a modifier of a polyester resin based on oxide nanoparticles embedded in the polymer matrix during the polymerization reaction during curing, leads to a synergistic improvement in physicochemical iCal properties of the cured product of said polyester composition, as well as improved heat and corrosion resistance, compared to both the conventional unmodified polyester resin and a polyester resin filled with nanoparticles nemodifitsirovaynymi oxides such silicon oxide.

Methods for obtaining modifiers

In yet another aspect, the present invention provides a method for producing a nanoparticle oxide polyester resin modifier comprising a C ₂ -C ₁₆ hydrocarbon moiety containing at least one free reactive, preferably terminal, hydroxyl group.

In general, such a modifier can be obtained by any suitable method allowing the chemical addition of a hydrocarbon substituent containing at least one free reactive, preferably terminal, hydroxyl group, via surface hydroxyl groups.

According to one embodiment, such a nanoparticle oxide polyester resin modifier containing a C ₂ -C ₁₆ hydrocarbon moiety containing at least one free reactive, preferably terminal, hydroxyl group, can be obtained by grafting (chemical interaction) to oxide particles through the surface hydroxyl groups of a C ₂ -C ₁₆ hydrocarbon, preferably a C ₂ -C ₁₆ dihydric or polyhydric alcohol. The specified grafting can be carried out in several stages.

In particular, in the first production step, surface preparation is optionally carried out, for example by means of a surface standardization technique, in order to remove adsorbed water and “open” surface hydroxyl groups. This method involves the processing of oxide nanoparticles by exposure to elevated temperature in the atmosphere (stream) of an inert gas, or at reduced pressure.

Further, the oxide nanoparticles surface are halogenated, preferably chlorinated, to obtain a halogen-substituted surface. Halogenation is carried out using any suitable halogenating reagent to replace surface hydroxyl groups to produce active chlorine atoms on the surface. Examples of such halogenating agents are HCl, HBr, SOCl ₂ , PCl ₃ , CCl _4, and the like. According to another embodiment, halogenation is carried out using a linker. In particular, halogenation using a linker is carried out using a dihalogenated branched or unbranched C ₁ -C ₁₆ alkane or an organosilicon compound. Non-limiting examples of such dihalogenated C ₁ -C ₁₆ alkanes include 1,2-dichloroethane, 1,3-dichloropropane and 1,4-dichlorobutane, etc. Halogenation can be carried out both in the gas phase and in solution.

At the next stage, oxide nanoparticles are modified with di- or polyhydric alcohols, in particular by adding to the halogen-substituted particles of oxides of a suitable hydrocarbon reagent containing hydroxyl groups, preferably a di- or polyhydric alcohol, more preferably di- or the polyhydric alcohol described in this application. As a result, the surface halogen is replaced by the indicated hydrocarbon reagent to form a polyester resin modifier based on oxide nanoparticles containing on the surface a hydrocarbon fragment containing at least one hydroxyl group capable of entering into a condensation reaction. Moreover, said hydrocarbon fragment containing at least one hydroxyl group is bonded to the surface of oxide nanoparticles via a covalent bond.

Alternatively, said polyester resin modifier is prepared by reacting the hydroxyl groups of the oxide nanoparticles with a dihalogenated C ₂ -C ₁₆ hydrocarbon, preferably a dihalogenated C ₁ -C ₁₆ alkane, followed by hydrolysis of the residual (free) halogen to a hydroxyl group. According to one embodiment, the hydrolysis is carried out by treatment with water vapor (in a flow reactor, in the gas phase) or with bases in solution (in the liquid phase).

In yet another aspect, the present invention provides a method for producing a nanoparticle oxide polyester resin modifier containing unsaturated C ₂ -C ₂₀ hydrocarbon groups.

In general, such a polyester resin modifier can be obtained by any suitable method allowing the chemical addition of a hydrocarbon substituent containing free unsaturated (multiple) bonds to the surface of oxide nanoparticles, for example via surface hydroxyl groups.

According to one implementation option, such a nanoparticle oxide polyester resin modifier containing free unsaturated C ₂ -C ₂₀ hydrocarbon groups can be obtained by grafting (chemical interaction) to the oxide particles through surface hydroxyl groups of a halogen-substituted C ₂ -C ₂₀ unsaturated aliphatic hydrocarbon, which is a halogen-substituted C ₂ -C ₂₀ alkene, a halogen-substituted C ₂ -C ₂₀ alkine or a halogen-substituted C ₂ -C ₂₀ cycloalkene. The specified grafting can be carried out in several stages. In particular, it is possible to first prepare the surface of oxide nanoparticles, for example, by exposure to an inert gas at elevated temperature in the atmosphere (flow), or at reduced pressure.

Further, said halogen-substituted C ₂ -C ₂₀ unsaturated aliphatic hydrocarbon is attached to the surface of the oxide nanoparticles by a substitution reaction of surface hydroxyl groups for the corresponding halogen-substituted C ₂ -C ₂₀ unsaturated aliphatic hydrocarbon. The result is a modifier of a polyester resin based on nanoparticles of oxides containing unsaturated C ₂ -C ₂₀ hydrocarbon groups capable of entering into polymerization reactions.

A method of obtaining a polyester resin

In yet another aspect, the present invention provides a method for producing a polyester resin comprising an oxide nanoparticle polyester resin modifier coupled to said polyester resin via a C ₂ -C ₁₆ hydrocarbon moiety containing at least one hydroxyl group.

In General, a polyester resin with the specified modifier can be obtained by any suitable method that allows you to chemically embed the modifier in the chain of the polyester.

According to one implementation options, a method for producing a polyester resin comprises the following steps:

a) providing a modifier of a polyester resin based on oxide nanoparticles containing a C ₂ -C ₁₆ hydrocarbon fragment containing at least one hydroxyl group;

b) condensation of a C ₂ -C ₁₆ dihydric or polyhydric alcohol and a C ₂ -C ₂₀ dihydric or polybasic organic acid or its anhydride to obtain an oligoester;

c) polycondensation of the obtained oligoester with a modifier from stage a)

Although, in general, stages b) -c) can be carried out simultaneously, that is, polycondensation of a di- or polyhydric alcohol, dibasic or polybasic acid and a modifier can be carried out simultaneously to obtain a modified polyester resin, it is preferable to carry out the stages sequentially, i.e., condensation is carried out first a di- or polyhydric alcohol and a di- or polybasic organic acid or its anhydride to obtain oligoesters and then polycondensation of the oligoesters and a modifier to obtain modifications constant polyester resin. This approach avoids some undesirable reactions, in particular undesired transesterification.

According to one implementation options, the content of the modifier of the polyester resin based on nanoparticles of oxides containing a C ₂ -C ₁₆ hydrocarbon fragment containing at least one hydroxyl group is from 0.01 to 15% by weight, preferably from 0.01 to 2% mass

A method of obtaining a polyester composition

In yet another aspect, the present invention provides a method for producing a polyester composition, comprising

a) providing a polyester resin;

b) combining said polyester resin with a polyester resin-based polyester resin modifier containing unsaturated C ₂ -C ₂₀ hydrocarbon groups covalently bonded to the surface of the particles.

For the purposes of the present invention, any polyester resin capable of reacting with a graft copolymerization reaction to produce a cured polyester resin is suitable. The combination of the polyester resin can be carried out by any suitable method, for example by mixing, preferably with continuous stirring in an inert medium.

Application and Products

In yet another aspect, the present invention provides the use of a polyester composition according to the invention, a modified polyester resin, and oxide nanoparticle based polyester resin modifiers for the manufacture of articles.

In general, the preparation of products is carried out by curing the polyester composition or the polyester resin with a polymerization initiator suitable for a particular type of polyester.

According to one implementation options, the product is a composite material.

According to a more specific embodiment, said composite material may be a fiber reinforced composite material, a filled composite material, a layered composite material. Moreover, the polyester composition or polyester resin according to the present invention plays the role of a binder in the specified composite material.

In the present description, the reinforcing material for the composite material may be fiberglass, for example, fiberglass and glass fiber, carbon fiber, for example carbon fabric, polyamide fabric, polyimide fabric and hybrid reinforcing materials.

The range of applications of products from polyester compositions and polyester resins is very wide and includes, but is not limited to, the use of construction as structural materials for walls, interior and exterior decoration, roofs, floors, etc., use in shipbuilding, as elements ship hulls of various classes, as well as coatings for protecting ship linings and decorative finishes, applications in the automotive industry, carriage building, mechanical engineering and aircraft construction, as structural elements of hulls. In addition, the polyester composition or polyester resin according to the invention can be used in the chemical industry for the manufacture of pipes, containers, apparatuses and other devices exposed to aggressive environments. It is also possible to use transformers, electric motor windings, generators, cables, electronic boards, ballasts, power line elements as electrical insulation in the electrical industry.

EXPERIMENTAL PART

Characterization of the feedstock for the synthesis of resin

The list of starting components (raw materials) for the synthesis of the composition and resin are presented in Table 1.

Before the process of obtaining, the initial components should be checked according to the main indicators for compliance with the requirements of current standards or specifications. A list of such indicators is presented in Table 1.

Table 1 No. Name of feedstock Corresponding to GOST / STO / TU component Mandatory metrics one Ethylene glycol GOST 19710-74 Specific gravity
Appearance
The content of the main substance 2 Maleic Anhydride GOST 11153-75 Melting temperature
The content of the main substance 3 Phthalic anhydride GOST 7119-77 Melting temperature
The content of the main substance

four Triethylene glycol dimethacrylate (TGM-3) STO 81270164-2-2007 Specific gravity
The content of the main substance
Polymerization rate 5 Epoxy resin ED-20 or ED-22 GOST 10587-84 Appearance
Epoxy Content 6 Hydroquinone GOST 19627-74 Appearance

General description of the process for the synthesis of polyester resin and polyester composition

The technological process, as a whole, consisted of the following stages:

1) Preparation and loading of feedstock;

2) Providing polyester resin modifiers;

3) Condensation of ethylene glycol with maleic and phthalic anhydrides to obtain oligoesters and polycondensation of the obtained oligoesters with a modifier based on nanoparticles of oxides containing a C ₂ -C ₁₆ hydrocarbon fragment containing at least one hydroxyl group;

4) Combining the polyester resin from step 3) with TGM-3 and a polyester resin modifier based on nanoparticles of oxides containing unsaturated C ₂ -C ₂₀ hydrocarbon groups;

5) Drain the finished polyester composition in a container.

1) Preparation and loading of raw materials

Before loading the raw materials into the cooking apparatus, they were washed with a hot alkaline solution, then dried. The raw materials were checked for compliance with the norms listed in the relevant standards.

2) Providing modifiers

OBTAINING MODIFIER 1 (oxide nanoparticle based polyester resin modifier containing a C ₂ -C ₁₆ hydrocarbon fragment containing at least one hydroxyl group capable of entering into a condensation (esterification) reaction).

The synthesis of modifier 1 was carried out in 3 stages. Silicon oxide (Aerosil A300 from Evonik) was used as oxide nanoparticles.

The Aerosil surface was prepared by heat treatment at a temperature of 120 ° C-250 ° C to remove physically sorbed water. The absence of physically sorbed water was monitored by IR and NMR (solid state). Further, in a gas flow reactor, chlorination was carried out using hydrogen chloride (HCl). After the end of chlorination, the regime of removal of unreacted low molecular weight reagents and volatile reaction products from the surface was switched on. The time for applying the regime, in this case, was 4 hours.

Then, the active surface halogen was replaced by a residue containing a free hydroxyl group. Ethylene glycol was fed in portions into the reaction chamber. The reaction temperature was maintained not lower than the boiling point of ethylene glycol to obtain a concentration in the reactor sufficient to shift the equilibrium of the process towards the reaction products. As a result, a modifier was obtained in the form of an aerosil oligoester and ethylene glycol containing at the end a hydroxyl group available for further condensation.

OBTAINING MODIFIER 2 (a modifier of a polyester resin based on oxide nanoparticles containing unsaturated C ₂ -C ₂₀ hydrocarbon groups)

Silicon oxide (Aerosil A300 from Evonik) was used as oxide nanoparticles.

The Aerosil surface was prepared by heat treatment at a temperature of 120 ° C-250 ° C to remove physically sorbed water. The absence of physically sorbed water was monitored by IR and NMR (solid state). Further, allyl chloride was introduced into the reactor at 50 ° C. The reaction was carried out for 30 minutes, after which the pressure in the system was reduced to remove liquid allyl chloride. As a result, a modifier was obtained in the form of an aerosil containing an unsaturated bond allyl substituent on the surface, available for further polymerization reactions during resin curing.

To obtain the polyester composition used reagents in the following quantities:

table 2 name of raw materials The content of the main substance,% Ratio in moles Weight kg Ethylene glycol one hundred 1.05 347 Maleic Anhydride 99.5 0.67 318.4 Phthalic anhydride 99.5 0.33 259 Hydroquinone - 0.005 0.02-0.1 Modifier 1 0.43% (mass) - four

3) Condensation of ethylene glycol with maleic and phthalic anhydrides to obtain oligoesters and polycondensation of the obtained oligoesters with a modifier based on nanoparticles of oxides containing a C ₂ -C ₁₆ hydrocarbon fragment containing at least one hydroxyl group.

The synthesis of polyester was carried out in a cooking apparatus (reactor) made of stainless steel. The rector is equipped with a combined stainless steel mixer with a speed of 40-50 rpm and a jacket.

Upon completion of the loading of ethylene glycol, maleic and phthalic anhydrides, the temperature of the reaction mixture was raised to 140-145 ° C and a vacuum of 5-10 mm Hg was created. The first acid value sample was taken at a temperature of 145-150 ° C, and then every 1-1.5 hours. After the first sampling, the required amount of modifier 1 was loaded into the reactor.

Then, continuously for 2-3 hours, the temperature in the apparatus was raised to 180-190 ° C, at a vacuum of 5-10 mm Hg. Control during the synthesis was controlled by acid number. At an acid number of 44-47 mg KOH / gpe, the reaction mixture was cooled to 160 ° C and hydroquinone was charged. Then it was still cooled and the epoxy resin ED-20 was added in an amount of 0.3-0.6% of the calculated amount of TGM-3. TGM-3 was added at the rate of 55 parts by weight of TGM-3 at 45 parts by weight of the obtained polyester and modifier 2 at the rate of 0.5% (mass). The combination was carried out with continuous stirring of the reaction mixture and in nitrogen atmosphere.

4) Poured the finished polyester composition into containers.

Physical and mechanical characteristics

Physico-mechanical characteristics were measured according to GOST 4647-80 “Plastics. Method for determining Charpy impact strength ”, GOST 11262-80“ Plastics. Tensile test method. Elongation at break ”, GOST 4670-91“ Plastics. Hardness test. Ball indentation method ”, GOST 11262-80“ Plastics. Tensile test method. Tensile strength ”GOST 4648-71“ Plastics. Static bending test method. Bending stress at failure, relative to unmodified resin PN-609-21 m "(GOST 27952-88). The results of physical and mechanical tests are shown in Table 3.

Table 3 Parameter Nemodif. resin PN-609-21 m (control) Polyester resin with modifier 1 Polyester composition with modifiers 1 and 2

Impact strength, kgf * cm / cm ² 3-7 8 eleven Elongation at break,% 1.8-3.3 1.9 1.1 Brinell hardness, kgf / cm ² 15-20 25 32 Tensile strength, MPa 39.2-58.8 62.5 72.0 Bending stress at failure, MPa 53.9-58.8 61.1 78.0

As can be seen from the test data shown in Table 3, the characteristics of the modified polyester resin containing modifier 1, as well as the polyester composition containing a polyester resin with modifier 1 and modifier 2, significantly exceed the characteristics of a traditional polyester resin. Thus, the use of modifiers according to the present invention allows to obtain products with significantly superior characteristics, while maintaining a comparable product weight and cost.

Claims (28)

1. The polyester composition used as a binder, containing a polyester resin containing a modifier based on nanoparticles of oxides selected from SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , CeO ₂ , TiO ₂ , ZnO, FeO, Fe ₂ O ₃ , Fe ₃ O ₄ and SnO containing a C ₂ -C ₁₆ hydrocarbon fragment having at least one hydroxyl group and bonded via said C ₂ -C ₁₆ hydrocarbon fragment to a polyester resin; and
a modifier of a polyester resin based on nanoparticles of oxides selected from SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , CeO ₂ , TiO ₂ , ZnO, FeO, Fe ₂ O ₃ , Fe ₃ O ₄ and SnO containing unsaturated C ₂ - C ₂₀ hydrocarbon groups selected from the residue C ₂ -C ₂₀ alkene, C ₂ -C ₂₀ alkyn or C ₂ -C ₂₀ cycloalkene covalently bonded to the surface of said nanoparticles via oxygen. 2. The polyester composition according to claim 1, characterized in that said polymer resin is a saturated or unsaturated polyester resin. 3. The polyester composition of claim 1, wherein said polymer composition further comprises a solvent, such as triethylene glycol dimethacrylate, ethylene glycol dimethacrylate; and / or a polymerization inhibitor, such as hydroquinone, and / or an epoxy resin. 4. The polyester composition according to claim 1, characterized in that the size of said oxide nanoparticles is from about 1 to about 100 nm. 5. The polyester composition according to claim 1, characterized in that said C ₂ -C ₁₆ hydrocarbon fragment containing at least one hydroxyl group is a C ₂ -C ₁₆ residue of a di- or polyhydric alcohol. 6. The polyester composition according to claim 5, characterized in that between the oxide nanoparticle and the C ₂ -C ₁₆ hydrocarbon moiety containing a hydroxyl group, a linker is present, for example, a residue of an organosilicon compound or a C ₁ -C ₁₆ alkane. 7. The polyester composition according to claim 1, containing from 0.01 to 15 wt.% A polyester resin modifier based on oxide nanoparticles containing unsaturated C ₂ -C ₂₀ hydrocarbon groups covalently bonded to the surface of said nanoparticles. 8. A method of obtaining a polyester composition comprising
a) providing a polyester resin containing a modifier based on nanoparticles of oxides selected from SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , CeO ₂ , TiO ₂ , ZnO, FeO, Fe ₂ O ₃ , Fe ₃ O ₄ and SnO, containing a C ₂ -C ₁₆ hydrocarbon moiety having at least one hydroxyl group and bonded by said C ₂ -C ₁₆ hydrocarbon moiety to said polyester resin;
b) combining said polyester resin with a polyester resin modifier based on nanoparticles of oxides selected from SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , CeO ₂ , TiO ₂ , ZnO, FeO, Fe ₂ O ₃ , Fe ₃ O ₄ and SnO containing unsaturated C ₂ -C ₂₀ hydrocarbon groups selected from the residue C ₂ -C ₂₀ alkene, C ₂ -C ₂₀ alkyn or C ₂ -C ₂₀ cycloalkene, covalently bonded to the surface of said nanoparticles via oxygen. 9. The method of claim 8, further comprising adding to the polyester composition a solvent, such as triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, and / or a polymerization inhibitor, such as hydroquinone, and / or epoxy. 10. The method according to p. 8, characterized in that said modifier based on oxide nanoparticles containing a C ₂ -C ₁₆ hydrocarbon fragment having at least one hydroxyl group is obtained a) by halogenation of the surface hydroxyl groups of oxide nanoparticles with subsequent substitution of halogen C ₂ -C ₁₆ dihydric or polyhydric alcohol, b) by reacting the hydroxyl groups of the oxide nanoparticles with a dihalogenated C ₂ -C ₁₆ hydrocarbon, followed by hydrolysis of the residual halogen to a hydroxyl group. 11. A modified polyester resin containing a modifier based on nanoparticles of oxides selected from SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , CeO ₂ , TiO ₂ , ZnO, FeO, Fe ₂ O ₃ , Fe ₃ O ₄ and SnO, containing a C ₂ -C ₁₆ hydrocarbon moiety having at least one hydroxyl group, and bonded via said C ₂ -C ₁₆ hydrocarbon moiety to a covalent bond with said polyester resin. 12. The polyester resin according to claim 11, characterized in that said C ₂ -C ₁₆ hydrocarbon fragment containing at least one hydroxyl group is a C ₂ -C ₁₆ residue of a di- or polyhydric alcohol. 13. The polyester resin according to p. 12, characterized in that between the oxide nanoparticle and the C ₂ -C ₁₆ hydrocarbon fragment containing a hydroxyl group, a linker is present, for example, the remainder of the organosilicon compound or C ₁ -C ₁₆ alkane. 14. A method of obtaining a modified polyester resin, comprising
a) providing a polyester resin modifier based on oxide nanoparticles selected from SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , CeO ₂ , TiO ₂ , ZnO, FeO, Fe ₂ O ₃ , Fe ₃ O ₄ and SnO containing C ₂ -C ₁₆ hydrocarbon fragment having at least one hydroxyl group;
b) condensation of a C ₂ -C ₁₆ dihydric or polyhydric alcohol and a C ₂ -C ₂₀ dihydric or polybasic organic acid or its anhydride to obtain an oligoester;
c) polycondensation of the obtained oligoester with the modifier from stage a). 15. The method of claim 14, further comprising adding to the modified polyester resin a solvent, such as triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, and / or a polymerization inhibitor, such as hydroquinone, and / or an epoxy resin. 16. The method according to p. 14, characterized in that the specified modifier based on nanoparticles of oxides containing a C ₂ -C ₁₆ hydrocarbon fragment containing at least one hydroxyl group, obtained a) by halogenation of the surface hydroxyl groups of the nanoparticles of oxides followed by halogen substitution With ₂ -C ₁₆ dihydric or polyhydric alcohol, or b) by reacting the hydroxyl groups of the oxide nanoparticles with a dihalogenated C ₂ -C ₁₆ hydrocarbon, followed by hydrolysis of the residual halogen to a hydroxyl group. 17. The method according to p. 14, characterized in that the di- or polyhydric alcohol is a C ₁ -C ₁₆ alkanediol, and the C ₂ -C ₂₀ dibasic or polybasic organic acid or anhydride is a C ₂ -C ₂₀ dicarboxylic or polybasic acid or its anhydride. 18. The modifier of the polyester resin based on nanoparticles of oxides selected from SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , CeO ₂ , TiO ₂ , ZnO, FeO, Fe ₂ O ₃ , Fe ₃ O ₄ and SnO containing unsaturated C ₂ -C ₂₀ hydrocarbon groups selected from the residue C ₂ -C ₂₀ alkene, C ₂ -C ₂₀ alkyn or C ₂ -C ₂₀ cycloalkene covalently bonded to the surface of said nanoparticles via oxygen. 19. The modifier according to claim 18, characterized in that the size of said oxide nanoparticles is from about 1 to about 100 nm. 20. The modifier according to claim 18, obtained by replacing the hydroxyl groups on the oxide nanoparticle with a hydrocarbon containing an unsaturated bond and a reactive, preferably terminal, halogen group. 21. The modifier according to claim 18, characterized in that between the oxide nanoparticle and unsaturated C ₂ -C ₂₀ hydrocarbon groups there is a linker, for example, the remainder of an organosilicon compound or C ₁ -C ₁₆ alkane. 22. A method of obtaining a polyester resin modifier, comprising reacting oxide nanoparticles selected from SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , CeO ₂ , TiO ₂ , ZnO, FeO, Fe ₂ O ₃ , Fe ₃ O ₄ and SnO, with an unsaturated C ₂ -C ₂₀ hydrocarbon selected from the residue C ₂ -C ₂₀ alkene, C ₂ -C ₂₀ alkyn or C ₂ -C ₂₀ cycloalkene containing a halogen group. 23. The method according to p. 22, characterized in that the method further comprises the step of preparing the surface of the oxide nanoparticles at a temperature of 120-200 ° C. 24. The method according to p. 22, characterized in that the interaction of the oxide nanoparticles with a unsaturated hydrocarbon containing a halogen group is carried out at a temperature of from 100 to 250 C. 25. The method according to p. 22, characterized in that the size of these nanoparticles of oxides is from about 1 to about 100 nm. 26. The product obtained by curing the polyester composition according to any one of paragraphs. 1-7. 27. The product according to p. 26, which is a composite material, such as a fibrous composite material, a filled composite material or a layered composite material. 28. The use of the polyester composition according to p. 1 to obtain a composite material.