Ethylenically unsaturated polyester resin composition

Abstract

An ethylenically unsaturated polyester resin composition comprising: (i) (ia) an ethylenically unsaturated polyester resin obtainable by reacting at least one unsaturated dicarboxylic acid, including at least one ethylenically unsaturated dicarboxylic acid, or an ester or anhydride thereof, with (ib) at least one polyol; and (ii) a reactive diluent, wherein the reactive diluent (ii) is an N-vinyloxazolidinone of formula (I), wherein R 1 , R 2 , R 3 and R 4 are each independently selected from a hydrogen atom and an organic moiety containing 1 to 10 carbon atoms. The ethylenically unsaturated polyester resin (i) has a viscosity of at least 5.5 MPa 1 / 2 Hansen solubility parameter δ p The ethylenically unsaturated polyester resin composition can be used for thermosetting resins. The N-vinyloxazolidinone of formula (I) is particularly suitable for solubilizing the ethylenically unsaturated polyester resin (i), and generally exhibits low toxicity and is substantially odorless.

Description

[Technical Field]

[0001] FIELD OF THE INVENTION The present invention relates to ethylenically unsaturated polyester resin compositions and the use of the compositions in particular applications. [Background technology]

[0002] Unsaturated polyester resins (UPRs) are thermosetting polymers that are used in a wide variety of applications, including as matrix materials in composites. Unsaturated polyesters are obtained by the condensation reaction of polyols (polyhydric alcohols) with unsaturated dibasic acids.

[0003] EP 3626759 A1 describes high temperature unsaturated polyester (UP) resins based on cyclic and acyclic raw materials and details the use of such resins in various fields.

[0004] The unsaturated polyester resin is preferably provided in a malleable or liquid form. To optimize the rheology and thereby improve the processability of the resin, at least one reactive diluent (thinner) is usually added to the resin. During the curing of the resin, the reactive diluent copolymerizes with the resin.

[0005] Reactive diluents are typically low-viscosity mono-, di- or polyfunctional monomers or oligomers. Examples of frequently used reactive diluents include styrene and styrene derivatives, vinyl ethers, acrylates and methacrylates. Most commonly, styrene is used as a reactive diluent for unsaturated polyester resins.

[0006] However, the use of common reactive diluents has several drawbacks. For example, styrene derivatives can result in large amounts of residual monomer, vinyl ethers are susceptible to hydrolysis, methacrylates exhibit relatively low reactivity, and acrylates can induce tack in the resulting polymer. Furthermore, the use of styrene in particular is considered problematic due to odor issues and concerns regarding its toxicity. Summary of the Invention [Problem to be solved by the invention]

[0007] There is a need for additional unsaturated polyester resin compositions derived from reactive diluents that address at least some of the above-mentioned drawbacks. The amount of reactive thinner should be minimized. Furthermore, it would be desirable to provide unsaturated polyesters based on biosourced materials. [Means for solving the problem]

[0008] The present invention provides (i) (ia) at least one unsaturated dicarboxylic acid, including at least one ethylenically unsaturated dicarboxylic acid, or an ester or anhydride thereof; (ib) at least one polyol; an ethylenically unsaturated polyester resin obtainable by reacting (ii) a reactive diluent which is an N-vinyloxazolidinone of formula (I) [ka] (In the formula, R 1 , R 2 , R 3 and R 4 are each independently selected from a hydrogen atom and an organic moiety containing 1 to 10 carbon atoms, The ethylenically unsaturated polyester resin (i) has a compressive strength of at least 5.5 MPa 1 / 2Hansen solubility parameter δ p The present invention provides an ethylenically unsaturated polyester resin composition characterized by:

[0009] The N-vinyloxazolidinone of formula (I) has a viscosity of at least 5.5 MPa 1 / 2 Hansen solubility parameter δ p It has been found that the ethylenically unsaturated polyester resin (i) is particularly suitable for solubilizing the ethylenically unsaturated polyester resin (i) having a Hansen solubility parameter δ p denotes the energy due to dipole-dipole intermolecular forces between molecules. Furthermore, unlike, for example, styrene, N-vinyloxazolidinones of formula (I), particularly 5-methyl-3-vinyl-oxazolidin-2-one, generally exhibit low toxicity and are substantially odorless. DETAILED DESCRIPTION OF THE INVENTION

[0010] Without being bound by theory, it is believed that the high polarity of the N-vinyloxazolidinones of formula (I) makes these compounds highly compatible with the relatively polar unsaturated polyester resins, which is explained by the relatively high Hansen solubility parameters δ of these unsaturated polyester resins. p is reflected in.

[0011] The definition and calculation of the solubility parameter in the three-dimensional Hansen solubility space is described in C. M. Hansen: "The Three Dimensional Solubility Parameter and Solvent Diffusion Coefficient - Their Importance in Surface Coating Formulation", Danish Technical Press, Copenhagen, 1967.

[0012] As mentioned above, δ p represents the energy due to the dipole-dipole intermolecular forces between molecules, and δ d represents the energy due to the dispersion force between molecules, and δ hindicates the energy due to intermolecular hydrogen bonds. The unit of the Hansen solubility parameter is MPa. 1 / 2 is.

[0013] Hansen solubility parameters for many compounds are tabulated in standard works such as "Hansen Solubility Parameters: A User's Handbook", C.M. Hansen, 2007, 2nd Edition, CRC. Well-known modeling software such as HSPIP3.1.25 (3rd Edition) or COSMOquick2021, developed and sold by C.M. Hansen, can also be used to calculate Hansen solubility parameters based on the chemical structure of a compound. Hansen solubility parameters are calculated assuming room temperature, approximately 25°C. Herein, Hansen solubility parameters, particularly δ p is calculated according to the method described for the Examples below.

[0014] Hansen solubility parameter δ p If the value is less than the claimed value, the solubility of the ethylenically unsaturated polyester resin (i) in the N-vinyloxazolidinone of formula (I) may be insufficient, and the advantageous properties of the reactive diluent (ii) may not be very pronounced. Furthermore, styrene, a known reactive thinner, has a solubility of at least 5.5 MPa. 1 / 2 Hansen solubility parameter δ p It has been found that the above-mentioned ethylenically unsaturated polyester resins do not reliably provide sufficient solubility for the ethylenically unsaturated polyester resin (i) having the formula:

[0015] In a preferred embodiment, the ethylenically unsaturated polyester resin (i) has a viscosity of at least 5.7 MPa 1 / 2 , for example at least 6.0 MPa 1 / 2 , or at least 6.3 MPa 1 / 2 , more preferably 6.5 MPa 1 / 2 , specifically at least 7.0 MPa 1 / 2 , most preferably at least 8.0 MPa 1 / 2 Hansen solubility parameter δ pIt is characterized by the Hansen solubility parameter δ p is preferably up to 16 MPa 1 / 2 , more preferably up to 12 MPa 1 / 2 , most preferably up to 8.5 MPa 1 / 2 is.

[0016] In a further embodiment, the ethylenically unsaturated polyester resin (i) has a viscosity of at least 15.0 MPa 1 / 2 , preferably at least 17.0 MPa 1 / 2 , more preferably at least 17.5 MPa 1 / 2 , most preferably at least 18.0 MPa 1 / 2 , e.g., at least 18.5 MPa 1 / 2 Hansen solubility parameter δ d It is characterized by the Hansen solubility parameter δ d is preferably up to 22.0 MPa 1 / 2 , more preferably up to 20.5 MPa 1 / 2 , most preferably up to 19.5 MPa 1 / 2 is.

[0017] In a further embodiment, the ethylenically unsaturated polyester resin (i) has a viscosity of at least 15.0 MPa 1 / 2 , preferably at least 15.5 MPa 1 / 2 , more preferably at least 16.0 MPa 1 / 2 , most preferably at least 17.0 MPa 1 / 2 Hansen solubility parameter δ h It is characterized by the Hansen solubility parameter δ h is preferably at most 30.0 MPa 1 / 2 , more preferably at most 24.0 MPa 1 / 2 , and most preferably at most 18.0 MPa 1 / 2 is.

[0018] In one embodiment, the ethylenically unsaturated polyester resin (i) is characterized by: -At least 5.5MPa 1 / 2 , preferably at least 5.7 MPa1 / 2 For example, at least 6.0 MPa 1 / 2 , or at least 6.3 MPa 1 / 2 , more preferably at least 6.5 MPa 1 / 2 , especially at least 7.0 MPa 1 / 2 , most preferably at least 8.0 MPa 1 / 2 Hansen solubility parameter δ p , and -At least 15.0MPa 1 / 2 , preferably at least 17.0 MPa 1 / 2 , more preferably at least 17.5 MPa 1 / 2 , most preferably at least 18.0 MPa 1 / 2 , e.g., at least 18.5 MPa 1 / 2 Hansen solubility parameter δ d .

[0019] The upper limits stated above are preferred.

[0020] In a further embodiment, the ethylenically unsaturated polyester resin (i) is characterized by: -At least 5.5MPa 1 / 2 , preferably at least 5.7 MPa 1 / 2 For example, at least 6.0 MPa 1 / 2 , or at least 6.3 MPa 1 / 2 , more preferably at least 6.5 MPa 1 / 2 , especially at least 7.0 MPa 1 / 2 , most preferably at least 8.0 MPa 1 / 2 Hansen solubility parameter δ p ; -At least 15.0MPa 1 / 2 , preferably at least 17.0 MPa 1 / 2 , more preferably at least 17.5 MPa 1 / 2 , most preferably at least 18.0 MPa 1 / 2 , e.g., at least 18.5 MPa 1 / 2 Hansen solubility parameter δ d and -At least 15.0MPa 1 / 2 , preferably at least 15.5 MPa 1 / 2 , more preferably at least 16.0 MPa 1 / 2 , most preferably at least 17.0 MPa 1 / 2 Hansen solubility parameter δ h .

[0021] The upper limits stated above are preferred.

[0022] Parameter δ p , δ d and δ h can be thought of as the coordinates of a point in three dimensions, also known as Hansen space. The closer two molecules are in Hansen space, the more likely they are to dissolve in each other. To determine whether the parameters of two molecules, typically a solvent and a polymer, are within range, an interaction radius (or R0 value) is generally assigned to the substances to be dissolved. The R0 value determines the radius of a sphere in Hansen space. All suitable solvents lie within the sphere, while unsuitable solvents lie outside the sphere.

[0023] The interaction radius R0 is the maximum distance R at which a substance becomes solubilized. a The distance R is defined by the value a is calculated from the Hansen solubility parameters of the substance under consideration. Subsequently, experimental solubility tests are carried out. The results are expressed as R a The parameters are correlated with theoretical calculations. a The value of can be calculated by the following formula:

number

[0024] R a A detailed discussion of how to determine R values ​​can be found in "Hansen Solubility Parameters: A User's Handbook," C.M. Hansen, 2007, 2nd Edition, CRC.

[0025] R a From the R0 value, the relative energy density (RED) is RED = R a / R0. If the RED value is less than 1, the substance is soluble. If the RED value is 1, the substance is partially soluble. If the RED value is greater than 1, the substance is not soluble.

[0026] For example, styrene has an experimentally determined R value of 12.65, which is the R calculated from the Hansen parameters for styrene and, for example, a particular polyester resin. a If the value is above 12.65, the RED value is above 1, meaning the material is insoluble in styrene.

[0027] In one embodiment, the ethylenically unsaturated polyester resin (i) has an R of greater than 12.65, preferably greater than 12.70 or 12.80, relative to styrene. a It is characterized by a value.

[0028] If the Hansen solubility parameter values ​​of the individual substances are known, the Hansen solubility parameter values ​​of the mixture can be calculated. Each parameter is calculated in the volume ratio: δ M =φ1*δ1+φ2*δ2 (where φ1 is the volume fraction of substance 1, φ2 is the volume fraction of substance 2, and δ1 is the Hansen solubility parameter (δ d , δ p or δ h ) and δ2 is the Hansen solubility parameter of substance 2 (δ d , δ p or δ h )). The optimum ratio of solvents for a given substance (minimum distance R a Even two (or more) substances that are typically unsuitable for dissolving a compound may be suitable solvents in certain ratios because their mixture may lie within the solubility sphere R0.

[0029] In the N-vinyloxazolidinone of formula (I), R 1 , R 2, R 3 and R 4 The moieties are independently selected from hydrogen atoms and organic moieties containing 1 to 10 carbon atoms. The organic moieties preferably contain 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, most preferably 1 to 4 carbon atoms, for example 1 to 3 carbon atoms. The organic moieties may contain heteroatoms such as oxygen, nitrogen and / or sulfur, especially oxygen and / or nitrogen.

[0030] The organic moiety is preferably C1-C 10 Alkyl groups and C1-C 10 Preferably, the organic moiety is selected from methyl, ethyl and propyl, more preferably from methyl and ethyl, most preferably from methyl.

[0031] In a preferred embodiment, the N-vinyloxazolidinone of formula (I) is characterized in that: -R 1 , R 2 , R 3 and R 4 At least two of R are hydrogen atoms, for example, 1 , R 2 , R 3 and R 4 each of is a hydrogen atom; or -R 1 is a C1-C4 alkyl group, preferably methyl, and R 2 , R 3 and R 4 is a hydrogen atom; or -R 4 is a C1-C4 alkyl group, preferably methyl, and R 1 , R 2 and R 3 is a hydrogen atom; or -R 1 and R 2 is a hydrogen atom, and R 3 and R 4 is a C1 to C4 alkyl group, preferably methyl.

[0032] The synthesis of N-vinyl oxazolidinone compound of formula (I) is well known in the art.For example, N-vinyl oxazolidinone compound can be prepared by pyrolysis of N-(1-hydroxyalkyl)-2-oxazolidinone according to US Patent No. 4,831,153.In particular, N-vinyl oxazolidinone compound can be synthesized by reacting acetylene with oxazolidinone compound (so-called "Reppe chemistry").

[0033] Preferred N-vinyloxazolidinones of formula (I) include 3-vinyloxazolidin-2-one (NVO) and vinylmethyloxazolidinones, such as 4-methyl-3-vinyl-oxazolidin-2-one (4-NVMO) and 5-methyl-3-vinyl-oxazolidin-2-one (5-NVMO), especially 5-methyl-3-vinyl-oxazolidin-2-one.

[0034] Vinylmethyloxazolidinone is commercially available. For example, BASF SE's VMOX® mainly contains 5-methyl-3-vinyl-oxazolidin-2-one and also 4-methyl-3-vinyl-oxazolidin-2-one. In one embodiment, the vinylmethyloxazolidinone contains 5-methyl-3-vinyl-oxazolidin-2-one and up to 20% by weight, preferably up to 10% by weight, more preferably up to 5% by weight, of 4-methyl-3-vinyl-oxazolidin-2-one, such as up to 1% by weight or up to 0.05% by weight of 4-methyl-3-vinyl-oxazolidin-2-one, based on the total amount of vinylmethyloxazolidinone.

[0035] Preferably, reactive diluent (ii) comprises 3-vinyloxazolidin-2-one, 5-methyl-3-vinyl-oxazolidin-2-one, and 4-methyl-3-vinyl-oxazolidin-2-one in a total amount of at least 90 mol%, more preferably at least 95 mol%, and most preferably at least 98 mol%, based on the total amount of reactive diluent (ii). In a particularly preferred embodiment, reactive diluent (ii) comprises 5-methyl-3-vinyl-oxazolidin-2-one and 4-methyl-3-vinyl-oxazolidin-2-one in an amount of at least 90 mol%, more preferably at least 95 mol%, and most preferably at least 98 mol%, based on the total amount of reactive diluent (ii).

[0036] The ethylenically unsaturated polyester resin has, in its main chain, an ethylenically unsaturated double bond derived from the polymerized ethylenically unsaturated dicarboxylic acid of component (ia).

[0037] In this context, the term "ethylenically unsaturated" refers to a moiety having an olefinic C=C double bond that is not part of an aromatic ring and is therefore susceptible to radical polymerization. Typically, the ethylenically unsaturated double bond is present as a vinyl (-CH=CH-) double bond or a vinylidene (>C=CH2) double bond.

[0038] The ethylenically unsaturated polyester resin can be obtained by reacting (ia) at least one unsaturated dicarboxylic acid, including at least one ethylenically unsaturated dicarboxylic acid, or an ester or anhydride thereof, with (ib) at least one polyol. Optionally, the monomers for forming the ethylenically unsaturated polyester resin can include a saturated dicarboxylic acid or ester thereof.

[0039] The term "ester" in the context of unsaturated and saturated dicarboxylic acids can be any ester suitable for polyester-forming reactions. Typically, the term "ester" refers to an alkyl ester, particularly a C1-C4 alkyl ester, especially a methyl or ethyl ester.

[0040] The unsaturated dicarboxylic acid comprises at least one ethylenically unsaturated dicarboxylic acid, which means that it has at least one ethylenically unsaturated double bond as described herein.The unsaturated dicarboxylic acid can also be a combination of at least one ethylenically unsaturated dicarboxylic acid and one or more aromatic dicarboxylic acids.The unsaturated dicarboxylic acid preferably comprises at least 50 mol%, particularly at least 80 mol%, of at least one ethylenically unsaturated dicarboxylic acid based on the total amount of unsaturated dicarboxylic acids.

[0041] Those skilled in the art will readily appreciate that any dicarboxylic acid may be used in the form of its ester or anhydride in forming the ethylenically unsaturated polyester.

[0042] Ethylenically unsaturated dicarboxylic acids contain two carboxyl groups and at least one ethylenically unsaturated moiety, i.e., a moiety having an olefinic double bond that is not part of an aromatic ring and is therefore susceptible to radical polymerization. Typically, the ethylenically unsaturated double bond of an ethylenically unsaturated dicarboxylic acid is present as a vinyl (-CH=CH-) double bond or a vinylidene (>C=CH2) double bond. Ethylenically unsaturated dicarboxylic acids may be linear or branched. Ethylenically unsaturated dicarboxylic acids preferably contain 4 to 8 carbon atoms, more preferably 4 to 7 carbon atoms, and most preferably 4 to 5 carbon atoms.

[0043] Aromatic dicarboxylic acids suitable for combination with the at least one ethylenically unsaturated dicarboxylic acid preferably contain 6 to 9 carbon atoms, more preferably 6 to 8, and most preferably 8. Suitable aromatic dicarboxylic acids include phthalic acid, isophthalic acid, and terephthalic acid.

[0044] Compound (ia) is preferably maleic acid, maleic anhydride, fumaric acid, fumaric acid dimethyl ester, itaconic acid, itaconic acid dimethyl ester, mesaconic acid, citraconic acid, or tetrahydrophthalic anhydride, or a combination of at least one of the foregoing compounds with at least one compound selected from phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, dimethyl terephthalate, 2,5-furandicarboxylic acid, and 2,5-furandicarboxylic acid dimethyl ester. Compound (ia) is more preferably selected from maleic acid, maleic anhydride, fumaric acid, itaconic acid, and tetrahydrophthalic anhydride, and most preferably from fumaric acid and maleic anhydride.

[0045] Suitable saturated dicarboxylic acids are, in particular, aliphatic dicarboxylic acids typically having 4 to 14 carbon atoms, such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacinic acid, and brassylic acid. Suitable saturated dicarboxylic acids also include alicyclic dicarboxylic acids typically having 6 to 14 carbon atoms, such as 1,2-, 1,3-, or 1,4-cyclohexanedicarboxylic acid. The amount of saturated dicarboxylic acid typically does not exceed 50 mol %, preferably 20 mol %, of the total amount of dicarboxylic acid used in the reaction to form the ethylenically unsaturated polyester.

[0046] The polyol (ib) is an organic compound containing multiple hydroxyl groups. Preferably, the polyol (ib) contains 2 to 5 hydroxyl groups, more preferably 2 or 3 hydroxyl groups, and most preferably 2 hydroxyl groups. The polyol (ib) may be linear or branched, preferably branched. The polyol (ib) may be saturated or unsaturated.

[0047] Suitable polyols include aliphatic polyols, such as glycols, i.e., aliphatic diols such as ethylene glycol, propylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,3-propanediol, dipropylene glycol, and neopentyl glycol; triols such as glycerin; and aliphatic sugar alcohols such as sorbitol, xylitol, and erythritol; and heterocyclic polyols, particularly heterocyclic polyols containing at least one ring oxygen atom, such as maltitol or isosorbide. Glycols and heterocyclic polyols are particularly preferred.

[0048] A particularly preferred polyol is isosorbide. Preferably, polyol (ib) comprises a total amount of isosorbide of at least 30 mol%, more preferably at least 40 mol%, most preferably at least 70 mol%, for example at least 90 mol% or at least 99 mol%, relative to the total amount of polyol (ib).

[0049] The ethylenically unsaturated polyester resin (i) can be obtained by reacting the compounds (Ia) and (Ib) preferably in a molar ratio of 1.2:1 to 1:1.2, more preferably 1.1:1 to 1:1.1, and most preferably 1.05:1 to 1:1.05.

[0050] The ethylenically unsaturated polyester resin (i) preferably has a number average molecular weight, as determined by gel permeation chromatography, in the range of 500 to 10,000 g / mol, more preferably 800 to 8,000 g / mol, and most preferably 1,000 to 5,000 g / mol.

[0051] The ethylenically unsaturated polyester resin (i) preferably has an acid value in the range of 5 to 80 mgKOH / g, more preferably 10 to 65 mgKOH / g, and most preferably 15 to 55 mgKOH / g.

[0052] The acid number (neutralization number) is the mass of potassium hydroxide (KOH) in milligrams required to neutralize one gram of ethylenically unsaturated resin. The acid number indicates the number of carboxylic acid groups per gram of compound and can be determined according to DIN EN ISO 2114.

[0053] In a further embodiment, the ethylenically unsaturated resin (i) has an ethylene group density in the range of 1.0 to 7.5 mol / kg, particularly 2.0 to 7.0 mol / kg, for example 2.5 to 6.0 mol / kg. The ethylene group density refers to the molar ratio of ethylene groups per kg of resin. The ethylene group density can be determined by nuclear magnetic resonance (NMR) spectroscopy.

[0054] Preferably, the weight ratio of ethylenically unsaturated resin (i) to reactive diluent (ii) in the curable resin composition is in the range of from 15:85 to 85:15, more preferably from 25:75 to 75:25, especially from 30:70 to 60:40.

[0055] The ethylenically unsaturated polyester resin composition of the present invention preferably contains the ethylenically unsaturated polyester resin (i) in an amount of 15 to 85% by weight, more preferably 15 to 75% by weight, and most preferably 20 to 60% by weight, based on the total weight of the ethylenically unsaturated polyester resin composition.

[0056] The ethylenically unsaturated polyester resin composition of the present invention preferably contains the reactive diluent (ii) in an amount of 0.5 to 85% by weight, for example, 3 to 85% by weight or 5 to 85% by weight, preferably 10 to 80% by weight, more preferably 15 to 80% by weight, for example, 20 to 80% by weight, even more preferably 25 to 80% by weight, and most preferably 40 to 80% by weight, for example, 50 to 75% by weight, based on the total weight of the ethylenically unsaturated polyester resin composition.

[0057] The ethylenically unsaturated polyester resin composition of the present invention preferably contains the ethylenically unsaturated polyester resin (i) and the reactive diluent (ii) in a total amount of 15 to 100% by weight, more preferably 20 to 100% by weight, and most preferably 20 to 99% by weight, based on the total weight of the ethylenically unsaturated polyester resin composition.

[0058] In addition to the reactive diluent (ii), the ethylenically unsaturated polyester resin composition of the present invention may contain one or more additional reactive diluents selected from styrene and styrene derivatives, epoxides, vinyl ethers, acrylates, and methacrylates. In this case, the reactive diluent (ii) acts as a solubility enhancer. Styrene derivatives include 3-methylstyrene, 4-methylstyrene, 4-tert-butylstyrene, and alpha-methylstyrene. Suitable acrylates include methyl methacrylate, tert-butyl acrylate, cyclohexyl acrylate, 4-tert-butyl-cyclohexyl acrylate, dimethyl itaconate, methyl cinnamate, ethyl cinnamate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, isobornyl acrylate, isobornyl methacrylate, 1,4-butanediol dimethacrylate, triethylene glycol dimethyl acrylate, and trimethylolpropane trimethacrylate. Suitable vinyl ethers include cyclohexyl vinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, cyclohexane-1,4-dimethanol divinyl ether, and 1,4-butanediol divinyl ether. Suitable epoxides include 2,2-bis[4-(glycidyloxy)phenyl]propane, bis-[4-(glycidyloxy)phenyl]methane, and 1,4-bis(2,3-epoxypropyloxy)butane.

[0059] In order to achieve high solubilization of the ethylenically unsaturated polyester resin (i), it is preferred that the reactive diluent (ii) is present in an amount of at least 0.5 wt.%, more preferably at least 5 wt.%, most preferably at least 10 wt.%, for example at least 25 wt.%, at least 40 wt.%, at least 50 wt.%, at least 60 wt.% or at least 75 wt.%, based on the total amount of the reactive diluent (ii) and any further reactive diluents.

[0060] Preferably, the weight ratio of the ethylenically unsaturated resin (i) to the total amount of reactive diluents in the curable resin composition is in the range of 15:85 to 85:15, more preferably 25:75 to 75:25, and especially 30:70 to 70:30.

[0061] In one embodiment, the ethylenically unsaturated polyester resin composition does not include any additional reactive diluents.

[0062] The composition may contain additional ingredients including stabilizers; inhibitors; additional curing compounds different from the ethylenically unsaturated polyester resin (i); pigments and dyes; fillers; thickeners; fibers; flame retardants; biocides; thermoplastic shrinkage control agents; toughening agents; curing agents; waxes and other film formers; lubricants; mold release agents; wetting agents; degassing agents; and / or coupling agents.

[0063] In particular, the composition may contain at least one stabilizer or a mixture of stabilizers. Suitable stabilizers include nitroxyl compounds such as 1-oxyl-2,2,6,6-tetramethylpiperidine or 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine. Furthermore, phenol derivatives having at least one substituent at the α-position of the phenol group, such as 2,6-di-tert-butyl-4-methylphenol, Irganox® 1330 or Irganox® 3114, and tocopherol, are suitable. Further suitable stabilizers include aromatic amines and phenylenediamines, hindered amines such as Tinuvin NOR356, Tinuvin 765, and Tinuvin 770, imines, sulfonamides, oximes, hydroxylamines, urea derivatives, phosphorus-containing compounds, sulfur-containing compounds such as phenothiazine, tetraazaannulene (TAA)-based complexing agents, and / or metal salts. Phosphorus-containing compounds are, for example, triphenylphosphine, triphenyl phosphite, hypophosphorous acid, phosphorous acid, trinonyl phosphite, triethyl phosphite, and diphenylisopropylphosphine.

[0064] Suitably, the ethylenically unsaturated polyester resin composition contains a total amount of stabilizer in the range of 0.01 to 5% by weight, preferably 0.02 to 3% by weight, more preferably 0.025 to 2.5% by weight, based on the total amount of the ethylenically unsaturated polyester resin composition.

[0065] Suitable inhibitors include hydroquinone, 2-methylhydroquinone, 2-tertbutyl-hydroquinone, p-benzoquinone, 2-methyl-p-benzoquinone, 2-tert-butyl-p-benzoquinone, 1,4-naphthoquinone, 4-tert-butyl-catechin (TBC), 1,2-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, N-nitroso-N-phenylhydroxylamine ammonium salt, and tris(N-nitroso-N-phenylhydroxyl-aminato)aluminum.

[0066] The additional curing compound different from the ethylenically unsaturated polyester resin (i) can be a compound having a polymerizable ethylenically unsaturated group, such as a vinyl group, such as a vinyl ether, a vinyl ester, or an N-vinyl group, an allyl group, or a (meth)acryloyl group. The expression "(meth)acryloyl group" is understood to refer to an acryloyl group or a methacryloyl group, preferably an acryloyl group. A compound having at least one (meth)acryloyl group is referred to as a (meth)acryloyl compound. The additional curing compound can be selected from ethylenically unsaturated resins, including ethylenically unsaturated polyester resins, vinyl ester resins, and urethane (meth)acrylate resins.

[0067] Suitable pigments and dyes are materials that change the color of reflected or transmitted light as a result of wavelength-selective absorption. An example of a pigment is titanium dioxide.

[0068] The filler is an inert compound that increases the volume of the unsaturated polyester resin composition. For every 100 parts by weight of the mixture of the unsaturated polyester resin (i) and the reactive diluent (ii), preferably 20 to 280 parts by weight of the filler is present in the unsaturated polyester resin composition. An example of the filler is calcium carbonate.

[0069] Thickeners increase the viscosity of the unsaturated polyester resin composition, reducing its tackiness and thus improving the handling of the composition. Examples of thickeners are isocyanates such as 4,4'-methylene-diphenyl-diisocyanate, magnesium oxide (MgO), calcium hydroxide (Ca(OH)2), and calcium oxide (CaO).

[0070] The fibers improve the mechanical properties and mechanical stability of the cured unsaturated polyester resin composition. For every 100 parts by weight of the unsaturated polyester resin (i) and the reactive diluent (ii), preferably 10 to 200 parts by weight of fibers, more preferably 15 to 200 parts by weight of fibers, and most preferably 25 to 180 parts by weight of fibers, such as glass fibers, carbon fibers, ceramic fibers, aramid fibers, boron fibers, basalt fibers, steel fibers, natural fibers, and / or nylon fibers. Glass fibers are preferred.

[0071] Glass fiber is a material consisting of many ultrafine glass fibers, formed by extruding thin strands of glass, such as silica-based glass. It has been found that the use of N-vinyloxazolidinone of formula (I) as a reactive diluent to obtain hardened glass fiber materials increases the impact strength of these materials compared to known reactive diluents such as styrene.

[0072] Glass fibers, and the optional further fibers discussed above, can be characterized by their length-to-diameter ratio (aspect ratio). Fibers are understood to be materials having a length-to-diameter ratio of at least 10, particularly at least 20, more particularly at least 50 or at least 100, including fibers modified, for example, by spinning. In a preferred embodiment, the fibers have a length-to-diameter ratio in the range of 20 to 100,000, preferably 50 to 100,000, and most preferably 100 to 100,000. The length and diameter of the fibers can be determined by a suitable microscope.

[0073] The length of suitable glass fibers is typically in the range of 1 mm to 1 m, preferably 2 mm to 1 m, and most preferably 3 mm to 1 m. The diameter of suitable glass fibers is typically in the range of 6 to 25 μm, preferably 10 to 25 μm, and most preferably 12 to 25 μm.

[0074] The glass fibers may be present in the material as individual glass fibers, mesh, fabrics including knitted and woven fabrics, non-crimp woven scrims, rovings, and the like.

[0075] Flame retardants are substances that prevent or delay the onset of ignition. Suitable flame retardants include solid flame retardants such as alumina trihydrate (ATH), magnesium hydroxide (Mg(OH)2), and ammonium polyphosphate (APP). Other suitable flame retardants include triphenyl phosphate, resorcinol tetraphenyl diphosphate, bisphenol A tetraphenyl diphosphate, decabromodiphenylethane, ethylene-bis-(tetra-bromophthalimide), tris(tribromophenyl) cyanurate, and / or dodecachloropentacyclo-octadecadiene (Dechlorane Plus®). Additionally, halogenated flame retardants may be used in combination with synergists such as antimony trioxide (Sb2O3) or 2,3-dimethyl-2,3-diphenyl-butane (Dicumene®).

[0076] Biocides are substances that destroy, deter, render harmless, or exert a control effect against any harmful organisms by chemical or biological means. Suitable biocides include silver, copper, or zinc-based substances, provided as salts (zinc pyrithione) or oxides, or by supported zeolites, or by nanoparticles. Further suitable biocides include chitosan, 10,10'-oxybisdphenoxarsine (OBPA), isothiazolinone, 2,4,4'-trichloro-2'-hydroxy-diphenyl ether (triclosan), N-(fluorodichloro-methylthio)phthalimide, thiabendazole (TBZ), or methylthio-cyclopropylamino-tert-butylamino-sym-triazine, and synthetic polymers poly(tert-butylaminoethyl methacrylate), poly(tert-butylaminomethylstyrene), and their active copolymers.

[0077] Thermoplastic shrinkage reducing agents are materials that can be used in sheet molding compound (SMC) and bulk molding compound (BMC) techniques to compensate for shrinkage by forming microvoids in the thermoplastic phase during cure. Suitable thermoplastic shrinkage control agents include solid polymers such as powdered polyethylene, and solutions in styrene made from thermoplastic polymers such as polystyrene and styrene copolymers, polymethyl methacrylate (PMMA), polyvinyl acetate (PVAc) and functionalized PVAc, saturated (non-curable) polyesters, and rubbers.

[0078] Toughening agents are used to improve the damage tolerance of cured ethylenically unsaturated polyester resin compositions. In particular, they can reduce crack formation under long-term static and dynamic loads while improving elongation at break and impact strength. Suitable toughening agents include rubber, nanoparticles, i.e., particles with an average diameter of less than 1 μm or precursors for forming such nanoparticles, thermoplastic polymers other than the ethylenically unsaturated polyester resin (i), and block copolymers other than the ethylenically unsaturated polyester resin (i). The toughening agent may be present in the resin composition in an amount of 2 to 40% by weight, preferably 3 to 30% by weight, and more preferably 5 to 25% by weight, based on the total amount of the ethylenically unsaturated polyester resin composition.

[0079] Suitable rubbers include acrylonitrile-butadiene rubber (NBR), hydrogenated NBR (H-NBR), polychloroprene (CR), styrene-butadiene rubber (SBR), natural rubber (NR), polyisobutylene (PIB), ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), as well as rubbers based on polyacrylate, acrylate rubber (AM) and fluororubber, and functionalized rubbers such as carboxy-terminated NBR (CTBN) or epoxy-terminated NBR (ETBN).

[0080] Suitable nanoparticles include soot, carbon black (high abrasion furnace, ultra-high abrasion furnace), pyrogenic silicic acid, surface-modified pyrogenic silicic acid, fumed silica, precipitated silica, rigid phase materials from polyurethane recycle, silica particles modified by hydrolysis of functionalized silanes, montmorillonite, bentonite, and exfoliated montmorillonite.

[0081] Suitable thermoplastic polymers other than the ethylenically unsaturated polyester resin (i) include polysulfone (PSU), polyethersulfone (PES), polyphenylenesulfone (PPSU), polyoxy-2,6-dimethyl-1,4-phenylene (PPE), polycarbonates based on bisphenol A and bisphenol TMC (APEC HT®), copolymers of styrene and maleic anhydride (XIRAN®), copolymers of maleic anhydride and N-phenylmaleimide (XIRAN®), copolymers of styrene and glycidyl methacrylate, copolymers of styrene and acrylonitrile (SAN), copolymers of styrene, butadiene and acrylonitrile (ABS), copolymers of styrene, acrylate monomers and acrylonitrile (ASA), copolymers of acrylonitrile and α-methyl-styrene (AMSAN), amorphous polyamides, polymethacrylimides, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), ethylene-tetrafluoroethylene-copolymer (ETFE), and copolymers of tetrafluoroethylene and hexafluoropropylene.

[0082] Suitable block copolymers other than the ethylenically unsaturated polyester resin (i) include styrene-butadiene-styrene block copolymers (SBS), polyetheramide block copolymers, polyetherester block copolymers, thermoplastic polyurethanes (TPU) based on polyesters, polyethers and polycarbonates.

[0083] A hardener is a compound or mixture of compounds that accelerates the hardening process.

[0084] If the cure is carried out at a temperature between 5 and 45° C., it may be called a “low temperature cure.” Low temperature cures may be carried out via benzoyl peroxide in combination with an amine accelerator or via hydroperoxides in combination with metal accelerators.

[0085] Suitable benzoyl peroxides include dibenzoyl peroxide and 4,4'-dichloro-dibenzoyl peroxide. Suitable amine accelerators include N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyltolidine, N,N-diethyltolidine, N,N-bis(2-hydroxyethyl)aniline, N,N-bis(2-hydroxyethyl)tolidine, N,N-bis(2-hydroxypropyl)aniline, and / or N,N-bis(2-hydroxypropyl)toluidine.

[0086] Suitable hydroperoxides include hydrogen peroxide, tert-butyl hydroperoxide, tert-amyl hydroperoxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, acetylacetone peroxide, trimethylcyclohexanone peroxide, iso-butyl methyl ketone peroxide. Suitable metal promoters include organic salts of Co(II), Mn(II), Cu(I), Cu(II) or Fe(II), such as metal salts of ethylhexanoate or naphthenate.

[0087] When curing is carried out at temperatures above 45°C to 120°C, it may be referred to as "thermal curing." Thermal curing can be carried out using one or more thermal initiators as the curing agent. Suitable thermal initiators include peroxides, azo compounds, and CC labile compounds.

[0088] Suitable peroxides include methyl ethyl ketone peroxide, 2,4-pentanedione peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxyneodecanoate, 2,5-dimethyl-2,5-di-(2-ethyl-hexanoylperoxy)hexane, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-Butyl peroxy-2-methylbenzoate, tert-butylperoxy-2-ethylhexyl carbonate, tert-butylperoxyisopropyl carbonate, tert-amylperoxybenzoate, tert-butylperoxybenzoate, 1,1-di-(tert-amylperoxy)cyclohexane, 1,1-di-(tert-butylperoxy)-3,3,5-trimethyl-cyclohexane, 1,1-di-(tert-butylperoxy)-cyclohexane, 2,2-di-(tert -amylperoxy)butane, 4,4-di-(tert-butylperoxy)n-butyl valerate, dilauroyl peroxide, di-(2-tert-butylperoxyisopropyl)benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, di-tert-butyl peroxide, di-tert-amyl peroxide, dicumyl peroxide, di(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(tert-amyl-peroxy)hexane, tert-butyl Examples of peroxycarbonyl compounds include cumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxocyclononane, di-(4-tert-butylcyclohexyl)peroxydicarbonate, di-(2-ethylhexyl)peroxycarbonate, tert-butyl hydroperoxide, cumyl hydroperoxide, isopropyl cumyl hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide.

[0089] Suitable azo compounds include 2,2'-azobis(2-isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), and 1,1'-azobis(hexahydrobenzo-nitrile).

[0090] Suitable CC labile compounds include 2,3-dimethyl-2,3-diphenylbutane and 3,4-dimethyl-3,4-diphenylhexane.

[0091] Further suitable curing agents include compounds that generate radicals when irradiated with UV-A light, i.e., light with a wavelength of 315 to 380 nm. Such curing agents may be referred to as photoinitiators. Suitable photoinitiators include benzoin, benzil, α-hydroxyketones, α-aminoketones, acylphosphine oxides, bisacylphosphine oxides, or combinations thereof. Preferred photoinitiators include Irgacure® 369, Irgacure® 651, Irgacure® 184, Irgacure® 819, Irgacure® 907, and Lucirin® TPO.

[0092] In one embodiment, the ethylenically unsaturated polyester resin composition does not include a curing agent.

[0093] The present invention provides the use of the above-mentioned ethylenically unsaturated polyester resin composition as a matrix polymer for reinforced and non-reinforced thermosetting resins in the SMC technology (sheet molding compound technology), BMC technology (bulk molding technology), resin transfer molding (RTM), compression molding, thermoforming, FCS technology (fiber composite spraying technology), injection molding, vacuum assisted resin infusion, continuous sheet production, filament winding, rotational molding, lamination, vacuum pressure impregnation (VPI process), pultrusion, casting, bundling, bonding, coating such as gel coating, top coating, spray coating, filling, in-mold coating, knife coating, dipping, dripping, painting, wire coating (enamel coating), fiber spinning, foaming.

[0094] The present invention further provides a thermoset resin obtainable by curing the ethylenically unsaturated polyester resin composition of the present invention. It is understood that the above discussion and embodiments relating to the composition of the present invention apply equally to the thermoset resin of the present invention.

[0095] In a preferred embodiment, curing is carried out by radical polymerization with a curing agent. Suitable curing agents are described above. Alternatively, curing can be carried out in the absence of a curing agent.

[0096] Curing can be carried out by high-energy radiation. Examples of high-energy radiation suitable for curing are electron beam radiation or α-, β- or γ-radiation, preferably γ-radiation.

[0097] Curing of the unsaturated ethylenically unsaturated polyester resin composition is preferably carried out at elevated temperatures, preferably in the range of 120 to 250° C. The temperature may be increased in steps during the curing process.

[0098] In a preferred embodiment, the unsaturated polyester resin composition is cured at a temperature in the range of 15 to 50°C for 2 to 200 hours, and then at 80 to 120°C for 2 to 24 hours.

[0099] In one embodiment, the cured unsaturated polyester resin composition is further subjected to a post-curing process. The duration of the post-curing is preferably 1 to 12 hours. The post-curing is preferably carried out at a temperature of 80 to 200°C, particularly 80 to 150°C.

[0100] The thermosetting resins according to the present invention may be used in the manufacture of tanks, polymer concrete, artificial marble, equipment structures, medical devices, railway equipment, oil and gas field equipment, automobile body parts, truck body parts, headlight reflectors, gel coats, top coats, protective layers and other coating applications such as spray coating, in-mold coating and painting, putty, cast products, buttons, porous materials (e.g., foams, membranes, etc.), fiber manufacturing, tool manufacturing, electronic devices, flame retardant thermosetting resins, profiles, containers, molded articles, polymer parts, long field lamp carriers, oil sinks, sheets / plates, railway interior parts, bonding, and pipes.

[0101] The present invention is further illustrated in the examples that follow. [Example]

[0102] The unsaturated polyester resin was obtained as described below.

[0103] The following table provides a summary of the reactants, stabilizers and initiators used in the examples.

[0104] [Table 1]

[0105] [Table 2]

[0106] A. Manufacturing of unsaturated polyester resin The unsaturated polyester resins were obtained by reacting (ia) at least one ethylenically unsaturated dicarboxylic acid, or ester or anhydride thereof, with (ib) at least one polyol in the molar ratios specified in the table below: The unsaturated polyester resins were prepared by melt polycondensation.

[0107] A four-neck flask (2 L) was prepared. A single-blade stirrer was attached to the center neck. The stirrer bearing casing was continuously cooled with water. The other three necks were equipped with a thermocouple, an insulated packed column, and plugs. A distillation bridge equipped with a ground thermometer was attached to the column to monitor the head temperature of the system during polycondensation. A measuring cylinder (250 mL) was attached to the distillation bridge to collect and measure the amount of condensed water. The thermocouple was connected to a Julabo laboratory controller (PID), and the reactor temperature was controlled via a computer program (JULABO EasyTemp Professional). A heating mantle, also controlled by the Julabo laboratory controller, served as the heat source.

[0108] At the beginning of the reaction, 500 ppmw of hydroquinone was added to the entire reaction mixture as a free radical scavenger. 400 ppmw of Fascat 4100 (butyltinic acid) was added to the entire reaction mixture as an esterification catalyst at 140°C. The reaction was carried out in a four-neck flask (2 L) equipped with a stirrer and a thermometer under a nitrogen atmosphere (99.999% nitrogen).

[0109] Heating from room temperature to 135°C was performed program-controlled as quickly as possible while avoiding overheating. The first water formation was observed between 135°C and 145°C. The reaction temperature was increased by 10°C per hour in the range of 135°C to 185°C. The reaction was stopped when the unsaturated polyester melt reached 185°C. The polymer was cooled and then left overnight in solid form.

[0110] The polymer was then remelted by heating to 185°C. 400 ppmw of Fascat 4100 was added to the total reaction mixture at 140°C. The reaction was carried out until the viscosity of the unsaturated polyester increased significantly and the torque of the stirrer motor reached 2 Ncm, or until the required acid number was achieved, as checked periodically. The unsaturated polyester was then poured into shallow rectangular molds where it was allowed to cool and solidify.

[0111] The acid number (neutralization number) is the mass of potassium hydroxide (KOH) in milligrams required to neutralize one gram of ethylenically unsaturated resin. The acid number indicates the number of carboxylic acid groups per gram of compound and was determined by titration according to DIN EN ISO 2114.

[0112] Glass transition temperature T of ethylenically unsaturated polyester resin g was determined by differential scanning calorimetry (DSC). DSC measurements were performed using a DSC instrument Sirius 3500 manufactured by Netzsch. A sealable Tzero aluminum pan was used. For the DSC measurement, approximately 15 mg of unsaturated polyester resin was added to the Tzero pan. A Tzero lid was then placed on the pan and sealed using a press, the pan was inserted into the DSC, and the measurement was started.

[0113] For the measurement, the pan was first cooled to 0°C, then the pan was heated at 10 K / min to 100°C. The above steps were then repeated a second time so that two cycles were measured. g was determined from the second cycle.

[0114] Mass average molecular weight M w and number average molecular weight M n was determined by gel permeation chromatography using specifically styrene-divinylbenzene copolymer as the stationary phase and tetrahydrofuran (THF) as the eluent, with calibration using polystyrene of defined molecular weight. Gel permeation chromatography can be performed using a SECcurity GPC Systems instrument manufactured by PSS Polymer Standard Solution. The polydispersity index Q is determined by the M w / M n It was calculated as:

[0115] Specifically, a PSS Polymer Standard Solution analytical column was used as the separation column. The stationary phase consisted of styrene-divinylbenzene copolymer (SDV) with a particle size of 3 μm and a nominal pore size of 100 Å. The eluent was tetrahydrofuran (THF). The separation column was adjusted to 35 °C in a column oven. The injected sample volume was 50 μL at a sample concentration of 4.94 g / L, corresponding to 50 mg of sample per 9 g of eluent in sample preparation. The eluent flow rate was 0.5 mL / min. Samples were detected using a refractive index detector and a UV-Vis detector, and measurement signals were registered every second. Two GPC measurement series were performed for each polyester. Chromatograms were evaluated using PSS WinGPC UniChrom software. Calibration was performed using appropriate standard kits of styrene oligomers and polymers.

[0116] The melt viscosity was determined at 100°C or 150°C using an ICI-Cone-Plate viscometer manufactured by Epprecht Control & Instrument (FIC) according to the following table. A standard cone C (φ=19.5 mm, cone angle 0.5) was used for the measurement. Approximately 0.5 g of solid unsaturated polyester resin was used for the measurement.

[0117] The following table shows the properties of the unsaturated polyester resin.

[0118] [Table 3]

[0119] [Table 4]

[0120] [Table 5]

[0121] B. Prediction of Hansen Solubility Parameters for Unsaturated Polyester Resins The Hansen parameters of unsaturated polyester resins were predicted based on the corresponding oligomers using COSMOquick2021 software. First, the molecules were drawn as 12-mer oligomers using the included JChemPaint module. Then, the corresponding SMILES strings were generated. Finally, the Hansen solubility parameters were obtained using a quantitative structure-activity relationship (QSPR) model. The QSPR results were fitted to empirical published Hansen values ​​("Hansen Solubility Parameters: A User's Handbook", C.M. Hansen, 2007, 2nd Edition CRC). The results are shown in the table below.

[0122] C1. Production of ethylenically unsaturated polyester resin composition The solidified unsaturated polyester resin obtained according to Section A was crushed using a hammer. If the unsaturated polyester resin did not solidify at room temperature, it was cooled with liquid nitrogen and then crushed at low temperature. The crushed polyester resin was used to prepare an unsaturated polyester resin composition. First, the unsaturated polyester resin particles were weighed into a glass bottle. Then, a reactive diluent was added in an amount of 70% by weight of the total composition, followed by Tinuvin® 765 (BASF, 1,000 ppmw).

[0123] The bottle was placed on a roller mixer. The solubility or progress of the dissolution process of the unsaturated polyester resin particles in the reactive diluent was checked visually at regular intervals. The resin composition was considered ready for use once it was completely dissolved. The results of the solubility test are shown in the table below.

[0124] [Table 6]

[0125] [Table 7]

[0126] The reactive diluent of the present invention has a viscosity of at least 5.5 MPa 1 / 2 Hansen solubility parameter δ p It is clear that while this allows for high solubility of ethylenically unsaturated polyester resins with .gtoreq. 1.0, the same resins are generally insoluble in styrene.

[0127] C2. Preparation of further ethylenically unsaturated polyester resin compositions According to Resin 14 in Section A, fumaric acid and 2-methyl-2-propylpropane-1,3-diol (molar ratio 1.0:1.02; δ = 5.702 MPa) 1 / 2 The polyester obtained from the above process was cooled with liquid nitrogen and then cryogenically crushed. The crushed polyester was used to prepare an unsaturated polyester resin composition. First, the unsaturated polyester particles were weighed into a glass bottle. Then, a mixture of styrene and VMOX, as well as stabilizers, were added according to the following table.

[0128] The bottle was placed on a roller mixer. The solubility of the unsaturated polyester particles in the reactive diluent or the progress of the dissolution process was checked visually at regular intervals. The resin composition was considered ready for use once it was completely dissolved.

[0129] The results of the solubility tests are shown in the table below. To determine the Hansen solubility parameters of the mixtures of styrene and VMOX, the mass fractions were converted to volume fractions by using the following formula:

number

[0130] Using the Hansen solubility parameters of styrene and VMOX mixtures compared to those of unsaturated polyester resins, R was calculated according to the following formula: a The values ​​were determined:

number

[0131] [Table 8]

[0132] [Table 9]

[0133] It is clear that the presence of even small amounts of VMOX improves the solubility of the investigated polyester resins compared to pure styrene.

[0134] D. Manufacturing of composite fiber materials Glass fiber reinforced test specimens were prepared using the resin composition of item C1, which contained 70 wt% VMOX. As a first step, tert-butyl peroxybenzoate (Acros Organics, 98%) was added to the resin in an amount of 1 wt%. Approximately 10 g of resin was then placed in a metal dish (diameter: 10 cm; depth: 1 cm). The resin was uniformly distributed and then coated with a biaxial glass fiber cloth (831 g / m) of the same diameter. 2 A layer of fiberglass fabric (0° / 90°, part number S14EB490-00831-01300-474000, manufactured by Saertex) was placed into the resin. A wooden spatula was used to remove any air bubbles, and then a second layer of resin was added. A second layer of fiberglass fabric was placed at a 90° angle to the first layer and also wetted with resin. This process was repeated once more, so that the metal dish contained three layers of fiberglass fabric at 90° to each other and approximately 30 g of resin composition.

[0135] A weight (approximately 500 grams) wrapped in aluminum foil was placed on the resulting specimen to squeeze out excess resin composition from the mold and obtain a smooth specimen surface. Finally, the specimen and weight were wrapped in aluminum foil. The specimen was heat-cured in a laboratory oven under air at 100°C for 1 hour and 160°C for 1 hour. After cooling, the resulting composite fiber material was torn out of its mold and cut into 10 x 50 mm specimens using a table saw.

[0136] The samples were then subjected to dynamic mechanical analysis (DMA) using a Netzsch DMA242C. A three-point bending specimen holder was used. The samples were measured under a nitrogen flow of 83 mL / min according to the method specified in the table below. The temperature dependence of the storage modulus, loss modulus, and loss factor (tan δ) of the cured ethylenically unsaturated polyester resin compositions was determined. The maximum of the tan δ curve (T) corresponds to the glass transition temperature T G was thought to constitute

[0137] [Table 10]

[0138] The glass transition temperatures of the composite fiber materials are shown in the table below.

[0139] [Table 11]

[0140] [Table 12]

Claims

1. (I) (ia) at least one unsaturated dicarboxylic acid, including at least one ethylenically unsaturated dicarboxylic acid, or an ester or anhydride thereof; (ib) at least one polyol; an ethylenically unsaturated polyester resin obtainable by reacting (ii) a reactive diluent which is an N-vinyloxazolidinone of formula (I) 【Chemical 1】 (In the formula, R １ , R ２ , R ３ and R ４ are each independently selected from a hydrogen atom and an organic moiety containing 1 to 10 carbon atoms. An ethylenically unsaturated polyester resin composition comprising: The ethylenically unsaturated polyester resin (i) has a viscosity of at least 5.5 MPa １／２ Hansen solubility parameter δ ｐ An ethylenically unsaturated polyester resin composition characterized by:

2. -R １ , R ２ , R ３ and R ４ At least two of, for example, R １ , R ２ , R ３ and R ４ each of is a hydrogen atom; or -R １ , R ２ , R ３ and R ４ each of is a hydrogen atom; or -R １ But C １ ~C ４ is an alkyl group, and R ２ , R ３ and R ４ is a hydrogen atom; or -R ４ But C １ ~C ４ is an alkyl group, and R １ , R ２ and R ３ is a hydrogen atom; or -R １ and R ２ is a hydrogen atom, and R ３ and R ４ But C １ ~C ４ The composition of claim 1 , wherein the alkyl group is an alkyl group.

3. 3. The composition according to claim 1, wherein the N-vinyloxazolidinone of formula (I) is 3-vinyloxazolidin-2-one, 4-methyl-3-vinyl-oxazolidin-2-one, or 5-methyl-3-vinyl-oxazolidin-2-one, in particular 5-methyl-3-vinyl-oxazolidin-2-one.

4. The composition according to any one of claims 1 to 3, wherein the ethylenically unsaturated dicarboxylic acid is an aliphatic dicarboxylic acid having an ethylenically unsaturated double bond and having 4 to 8 carbon atoms.

5. The composition according to any one of claims 1 to 4, wherein the compound (ia) is selected from maleic acid, maleic anhydride, fumaric acid, fumaric acid dimethyl ester, itaconic acid, itaconic acid dimethyl ester, mesaconic acid, citraconic acid, and tetrahydrophthalic anhydride.

6. The composition according to any one of claims 1 to 4, wherein the compound (ia) is a combination of at least one compound selected from maleic acid, maleic anhydride, fumaric acid, fumaric acid dimethyl ester, itaconic acid, itaconic acid dimethyl ester, mesaconic acid, citraconic acid, and tetrahydrophthalic anhydride, and at least one compound selected from phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, dimethyl terephthalate, 2,5-furandicarboxylic acid, and 2,5-furandicarboxylic acid dimethyl ester.

7. The composition according to any one of claims 1 to 6, wherein the polyol (ib) is a heterocyclic polyol, in particular isosorbide.

8. The composition according to any one of claims 1 to 7, wherein the ethylenically unsaturated polyester resin (i) is obtainable by reacting compounds (ia) and (ib) in a molar ratio ranging from 1.2:1 to 1:1.

2.

9. 9. The composition of any one of claims 1 to 8, wherein the ethylenically unsaturated polyester resin (i) has a number average molecular weight in the range of 500 to 10,000 g / mol, as determined by gel permeation chromatography.

10. The composition of any one of claims 1 to 9, wherein the ethylenically unsaturated polyester resin (i) has an acid value in the range of 5 to 80 mg KOH / g.

11. 11. The composition of any one of claims 1 to 10, comprising the ethylenically unsaturated polyester resin (i) in an amount of 15 to 85 wt%, preferably 15 to 75 wt%, more preferably 20 to 60 wt%, based on the total weight of the ethylenically unsaturated polyester resin composition.

12. The composition of any one of claims 1 to 11, comprising the reactive diluent (ii) in an amount of 0.5 to 85 wt%, based on the total weight of the ethylenically unsaturated polyester resin composition.

13. The composition of any one of claims 1 to 12, further comprising a stabilizer.

14. 14. Use of the ethylenically unsaturated polyester resin composition according to any one of claims 1 to 13 for reinforced and non-reinforced thermosetting resins in the SMC technology (sheet moulding compound technology), BMC technology (bulk moulding technology), resin transfer moulding (RTM), compression moulding, thermoforming, FCS technology (fiber composite spraying technology), injection moulding, vacuum assisted resin infusion, continuous sheet production, filament winding, rotational moulding, lamination, vacuum pressure impregnation (VPI process), pultrusion, casting, bundling, bonding, coating such as gel coating, top coating, spray coating, filling, in-mold coating, knife coating, dipping, dripping, painting, wire coating (enamel coating), fibre spinning and foaming.

15. A thermosetting resin obtainable by curing the ethylenically unsaturated polyester resin composition according to any one of claims 1 to 13.

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