Ethylenically unsaturated polyester resin composition

Abstract

Disclosed is an ethylenically unsaturated polyester resin composition comprising (i) an ethylenically unsaturated polyester resin obtainable by reacting: (i-a) at least one unsaturated dicarboxylic acid, or an ester or anhydride thereof, where the unsaturated dicarboxylic acid comprises at least one ethylenically unsaturated dicarboxylic acid; and (i-b) at least one polyol; and (ii) a reactive diluent. The reactive diluent (ii) is an N-vinyl oxazolidinone of formula (I) wherein R1, R2, R3 and R4 are independently from each other selected from a hydrogen atom and an organic moiety comprising from 1 to 10 carbon atoms. The ethylenically unsaturated polyester resin (i) is characterized by a Hansen solubility parameter [delta] p of at least 5.5 MPa1 / 2. The ethylenically unsaturated polyester resin composition can be used in thermosetting materials. N-vinyl oxazolidinones of formula (I) are particularly suitable for solubilizing ethylenically unsaturated polyester resins (i) and generally exhibit low toxicity and almost odorless.

Description

[0001] The present invention relates to ethylenically unsaturated polyester resin compositions and the use of such compositions in specific applications.

[0002] Unsaturated polyester resins (UPR) are thermosetting polymers and are used in a wide variety of applications, for example as matrix materials in composite materials. Unsaturated polyesters are obtained by condensation reaction of polyols (polyhydric alcohols) with unsaturated diprotic acids.

[0003] EP 3 626 759 A1 describes high-temperature unsaturated polyester (UP) resins based on cyclic and acyclic raw materials and describes in detail the use of such resins in various fields.

[0004] The unsaturated polyester resin is suitably provided in a ductile or liquid form. In order to optimize the rheology and thereby improve the processability of the resin, at least one reactive diluent (viscosity reducer) 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, monofunctional, difunctional 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 disadvantages. For example, styrene derivatives may produce a large amount of residual monomers, vinyl ethers are easily hydrolyzed, methacrylates exhibit relatively low reactivity, and acrylates may cause stickiness in the obtained polymer. In addition, the use of styrene, in particular, is considered problematic due to odor problems and concerns about its toxicity.

[0007] There is a need for additional unsaturated polyester resin compositions obtained from reactive diluents which address at least some of the above disadvantages. The amount of reactive viscosity reducer should be as low as possible. Furthermore, it is desirable to provide unsaturated polyesters based on bio-sourced raw materials.

[0008] The present invention provides an ethylenically unsaturated polyester resin composition, comprising

[0009] (i) an ethylenically unsaturated polyester resin which can be obtained by reacting:

[0010] (ia) at least one unsaturated dicarboxylic acid, or an ester or anhydride thereof, wherein the unsaturated dicarboxylic acid comprises at least one ethylenically unsaturated dicarboxylic acid; and

[0011] (ib) at least one polyol; and

[0012] (ii) a reactive diluent which is an N-vinyl oxazolidinone having the formula (I)

[0013]

[0014] Where R 1 , R 2 , R 3 and R 4 are independently selected from a hydrogen atom and an organic moiety containing 1 to 10 carbon atoms;

[0015] The ethylenically unsaturated polyester resin (i) is characterized by a Hansen solubility parameter δ p At least 5.5MPa 1 / 2 .

[0016] It was found that N-vinyl oxazolidinones having the formula (I) are particularly suitable for solubilizing the Hansen solubility parameter δ p At least 5.5MPa 1 / 2 The ethylenically unsaturated polyester resin (i) of p indicates the energy from intermolecular dipole intermolecular forces. Furthermore, and unlike, for example, styrene, N-vinyloxazolidinones of formula (I) generally exhibit low toxicity and are virtually odorless, in particular 5-methyl-3-vinyl-oxazolidin-2-one.

[0017] Without wishing to be bound by theory, it is hypothesized that the high polarity of N-vinyl oxazolidinones of formula (I) renders these compounds highly compatible with relatively polar unsaturated polyester resins, as reflected in the relatively high Hansen solubility parameters δ of these unsaturated polyester resins. p superior.

[0018] The definition and calculation of solubility parameters in three-dimensional Hansen solubility space are described in CM Hansen: “The Three Dimensional Solubility parameter and Solvent Diffusion Coefficient–Their Importance in Surface Coating Formulation”, Danish Technical Press, Copenhagen, 1967.

[0019] As mentioned above, δ p represents the energy from the intermolecular dipole intermolecular forces, while δ d represents the energy from the intermolecular dispersion force, and δh It represents the energy from hydrogen bonds between molecules. The unit of the parameter Hansen solubility parameter is MPa 1 / 2 .

[0020] Hansen solubility parameters for many compounds are listed in standard works such as "Hansen Solubility Parameters: A User's Handbook", C.M. Hansen, 2007, 2nd edition, CRC Press. Hansen solubility parameters can also be calculated based on the chemical structure of the compound using well-known modeling software such as HSPIP 3.1.25 (3rd edition) or COSMOquick 2021 developed and distributed by C.M. Hansen. The Hansen solubility parameters are calculated assuming that the room temperature is approximately 25°C. In this article, the Hansen solubility parameters, particularly δ p It is calculated according to the method described in the following working examples.

[0021] If the Hansen solubility parameter δ p Below the required value, the solubility of the ethylenically unsaturated polyester resin (i) in the N-vinyl oxazolidinone of formula (I) may be insufficient and the advantageous properties of the reactive diluent (ii) are less pronounced. In addition, it was found that the known reactive viscosity reducer styrene could not be reliably used for the Hansen solubility parameter δ p At least 5.5MPa 1 / 2 The ethylenically unsaturated polyester resin (i) provides sufficient solubility.

[0022] In a preferred embodiment, the ethylenically unsaturated polyester resin (i) is characterized by a Hansen solubility parameter δ p At least 5.7MPa 1 / 2 , such as at least 6.0MPa 1 / 2 , or at least 6.3MPa 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 Preferably at most 16 MPa 1 / 2 , more preferably at most 12 MPa 1 / 2 , most preferably at most 8.5MPa 1 / 2 .

[0023] In further embodiments, the ethylenically unsaturated polyester resin (i) is characterized by a Hansen solubility parameter δ d 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 , such as at least 18.5MPa 1 / 2 . Hansen solubility parameter δ d Preferably at most 22.0 MPa 1 / 2 , more preferably at most 20.5 MPa 1 / 2 , most preferably at most 19.5 MPa 1 / 2 .

[0024] In further embodiments, the ethylenically unsaturated polyester resin (i) is characterized by a Hansen solubility parameter δ h 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 Preferably at most 30.0 MPa 1 / 2 , more preferably at most 24.0 MPa 1 / 2 , most preferably at most 18.0 MPa 1 / 2 .

[0025] In one embodiment, the ethylenically unsaturated polyester resin (i) is characterized by

[0026] -Hansen solubility parameter δ p At least 5.5MPa 1 / 2 , preferably at least 5.7 MPa 1 / 2 , such as at least 6.0MPa 1 / 2 , or at least 6.3MPa 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 ,as well as

[0027] -Hansen solubility parameter δ d 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 , such as at least 18.5MPa 1 / 2 .

[0028] The above upper limit is preferred.

[0029] In further embodiments, the ethylenically unsaturated polyester resin (i) is characterized by

[0030] -Hansen solubility parameter δ p At least 5.5MPa 1 / 2 , preferably at least 5.7 MPa 1 / 2 , such as at least 6.0MPa 1 / 2 , or at least 6.3MPa 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 ;

[0031] -Hansen solubility parameter δ d 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 , such as at least 18.5MPa 1 / 2 ;as well as

[0032] -Hansen solubility parameter δ h 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 .

[0033] The above upper limit is preferred.

[0034] Parameter δ p , δ d and δ h can be thought of as the coordinates of a point in three-dimensional space (also called Hansen space). The closer two molecules are in Hansen space, the more likely they are to dissolve each other. To determine if the parameters of two molecules (typically a solvent and a polymer) are within range, the interaction radius (or R) is usually calculated. 0 value) is attributed to the substance to be dissolved. 0 The value determines the radius of a sphere in Hansen space. All suitable solvents lie inside the sphere, while unsuitable solvents lie outside it.

[0035] Interaction radius R 0 is the maximum distance R that a substance dissolves a The distance R a is calculated from the Hansen solubility parameters of the substance under consideration. Subsequently, experimental solubility tests were performed. The results are consistent with R a Theoretical calculation of the parameters is related. aThe value of can be calculated by the following formula:

[0036]

[0037] How to determine R a and R 0 A detailed discussion of the values ​​can be found in "Hansen Solubility Parameters: A User's Handbook", CM Hansen, 2007, 2nd edition, CRC Press.

[0038] By R a and R 0 Value, according to RED=R a / R 0 Calculate the relative energy density (RED). If the RED value is less than 1, the substance will dissolve. If the RED value is 1, the substance will partially dissolve. If the RED value is greater than 1, the substance will not dissolve.

[0039] For example, the experimentally determined R 0 The value is 12.65. This means that if the R calculated from the Hansen parameters of styrene and a specific polyester resin, for example a For values ​​above 12.65, the RED value will be above 1 and the material will be insoluble in styrene.

[0040] In one embodiment, the ethylenically unsaturated polyester resin (i) is characterized by R a The value is greater than 12.65, preferably greater than 12.70 or greater than 12.80.

[0041] If the Hansen Solubility Parameter values ​​for the individual substances are known, the Hansen Solubility Parameter values ​​for the mixture can be calculated. Each parameter is calculated individually by adding the parameters for the two substances according to the volume ratio:

[0042]

[0043] in is the volume fraction of substance 1, is the volume fraction of substance 2, δ 1 is the Hansen solubility parameter (δ d , δ p or δ h ) and δ 2 is the Hansen solubility parameter (δ d , δ p or δ h For a given substance, there is an optimal solvent ratio (with the smallest distance R aEven two (or more) substances that are typically not suitable for dissolving a compound can become suitable solvents in certain proportions because the mixture can be located in the solubility sphere R 0 Inside.

[0044] In the N-vinyl oxazolidinone of formula (I), part R 1 , R 2 , R 3 and R 4 Independently of one another, selected from a hydrogen atom and an organic moiety comprising 1 to 10 carbon atoms. The organic moiety preferably comprises 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, most preferably 1 to 4 carbon atoms, such as 1 to 3 carbon atoms. The organic moiety may contain heteroatoms, such as oxygen, nitrogen and / or sulfur, in particular oxygen and / or nitrogen.

[0045] The organic part is preferably selected from C 1 -C 10 Alkyl and C 1 -C 10 Alkoxy, more preferably selected from C 1 -C 4 Alkyl and C 1 -C 4 Alkoxy, most preferably C 1 -C 4 Preferably, the organic moiety is selected from methyl, ethyl and propyl, more preferably from methyl and ethyl, most preferably methyl.

[0046] In a preferred embodiment, the N-vinyl oxazolidinone having formula (I) is characterized in that

[0047] -R 1 , R 2 , R 3 and R 4 At least two of them are hydrogen atoms, such as R 1 , R 2 , R 3 and R 4 each of is a hydrogen atom; or

[0048] -R 1 It is C 1 -C 4 alkyl, preferably methyl, and R 2 , R 3 and R 4 is a hydrogen atom; or

[0049] -R 4 It is C 1 -C 4 alkyl, preferably methyl, and R 1 , R 2 and R3 is a hydrogen atom; or

[0050] -R 1 and R 2 is a hydrogen atom, and R 3 and R 4 It is C 1 -C 4 Alkyl, preferably methyl.

[0051] The synthesis of N-vinyl oxazolidinone compounds with formula (I) is well known in the art. For example, N-vinyl oxazolidinone compounds can be produced by pyrolysis of N-(1-hydroxyalkyl)-2-oxazolidinone according to US 4,831,153. In particular, N-vinyl oxazolidinone compounds can be synthesized by reaction of acetylene with oxazolidinone compounds (so-called "Reppe chemistry").

[0052] 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.

[0053] Vinylmethyloxazolidinone is commercially available. For example, from BASF SE Mainly comprises 5-methyl-3-vinyl-oxazolidin-2-one, and additionally comprises 4-methyl-3-vinyl-oxazolidin-2-one. In one embodiment, vinylmethyloxazolidinone comprises 5-methyl-3-vinyl-oxazolidin-2-one and up to 20 wt.-%, preferably up to 10 wt.-%, more preferably up to 5 wt.-% of 4-methyl-3-vinyl-oxazolidin-2-one, such as up to 1 wt.-%, or up to 0.05 wt.-% of 4-methyl-3-vinyl-oxazolidin-2-one based on the total amount of vinylmethyloxazolidinone.

[0054] Preferably, the reactive diluent (ii) comprises a total amount of 3-vinyloxazolidin-2-one, 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-%, most preferably at least 98 mol-%, relative to the total amount of reactive diluent (ii). In a particularly preferred embodiment, the 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-%, most preferably at least 98 mol-%, relative to the total amount of reactive diluent (ii).

[0055] The ethylenically unsaturated polyester resins carry ethylenically unsaturated double bonds in their backbone, these double bonds originating from the polymerized ethylenically unsaturated dicarboxylic acids of component (ia).

[0056] In this context, the term "ethylenically unsaturated" refers to moieties that carry an olefinic C=C-double bond that is not part of an aromatic ring and is therefore susceptible to free radical polymerization. Typically, the ethylenically unsaturated double bond is a vinyl (-CH=CH-) double bond or a vinylidene (>C=CH-) double bond. 2 ) double bond exists.

[0057] The ethylenically unsaturated polyester resin can be obtained by reacting: (ia) at least one unsaturated dicarboxylic acid, or an ester or anhydride thereof, wherein the unsaturated dicarboxylic acid comprises at least one ethylenically unsaturated dicarboxylic acid; and (ib) at least one polyol. Alternatively, the monomers used to form the ethylenically unsaturated polyester resin may comprise a saturated dicarboxylic acid or an ester thereof.

[0058] In the context of unsaturated dicarboxylic acids and saturated dicarboxylic acids, the term "ester" may be any ester suitable for a polyester-forming reaction. Typically, the term "ester" means an alkyl ester, particularly a C 1 -C 4 - Alkyl esters and especially the methyl or ethyl esters.

[0059] 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-%, in particular at least 80 mol-%, of at least one ethylenically unsaturated dicarboxylic acid, based on the total amount of the unsaturated dicarboxylic acids.

[0060] Those skilled in the art will readily appreciate that in the formation of ethylenically unsaturated polyesters, any dicarboxylic acid may also be used in the form of its ester or its anhydride.

[0061] The ethylenically unsaturated dicarboxylic acids contain two carboxyl groups and at least one ethylenically unsaturated moiety, i.e., a moiety with an olefinic double bond which is not part of an aromatic ring and which is therefore susceptible to free radical polymerization. Typically, the ethylenically unsaturated double bonds of the ethylenically unsaturated dicarboxylic acids are in the form of vinyl (—CH═CH—) double bonds or vinylidene (>C═CH—) double bonds. 2 ) double bonds are present. The ethylenically unsaturated dicarboxylic acids may be linear or branched. The ethylenically unsaturated dicarboxylic acids preferably contain 4 to 8 carbon atoms, more preferably 4 to 7 carbon atoms, most preferably 4 or 5 carbon atoms.

[0062] Aromatic dicarboxylic acids suitable for combination with at least one ethylenically unsaturated dicarboxylic acid preferably contain 6 to 9 carbon atoms, more preferably 6 to 8, most preferably 8. Suitable aromatic dicarboxylic acids include phthalic acid, isophthalic acid and terephthalic acid.

[0063] Compound (ia) is preferably selected from maleic acid, maleic anhydride, fumaric acid, dimethyl fumarate, itaconic acid, dimethyl itaconate, mesaconic acid, citraconic acid, and tetrahydrophthalic anhydride, or a combination of at least one of the compounds and at least one compound selected from the following: phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, dimethyl terephthalate, 2,5-furandicarboxylic acid and dimethyl 2,5-furandicarboxylate. Compound (ia) is more preferably selected from maleic acid, maleic anhydride, fumaric acid, itaconic acid and tetrahydrophthalic anhydride, and most preferably selected from fumaric acid and maleic anhydride.

[0064] 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, sebacic acid and tridecanedioic acid. Suitable saturated dicarboxylic acids also include cycloaliphatic dicarboxylic acids typically having 6 to 14 carbon atoms, such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid or 1,4-cyclohexanedicarboxylic acid. Typically, the amount of saturated dicarboxylic acids will not exceed 50 mol-%, and preferably will not exceed 20 mol-%, of the total amount of dicarboxylic acids used in the reaction to form the ethylenically unsaturated polyester.

[0065] Polyol (ib) is an organic compound containing multiple hydroxyl groups. Preferably, polyol (ib) contains 2 to 5 hydroxyl groups, more preferably 2 or 3 hydroxyl groups, most preferably 2 hydroxyl groups. Polyol (ib) can be straight chain or branched, preferably branched. Polyol (ib) can be saturated or unsaturated.

[0066] Suitable polyols include aliphatic polyols, such as glycols, i.e. aliphatic diols, like ethylene glycol, propylene glycol, diethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,3-propylene glycol, dipropylene glycol and neopentyl glycol; triols, such as glycerol; and aliphatic sugar alcohols, such as sorbitol, xylitol and erythritol; and heterocyclic polyols, in particular heterocyclic polyols containing at least one ring oxygen atom, such as maltitol or isosorbide. Diols and heterocyclic polyols are particularly preferred.

[0067] A particularly preferred polyol is isosorbide. Preferably, polyol (ib) comprises isosorbide in a total amount of at least 30 mol-%, more preferably at least 40 mol-%, most preferably at least 70 mol-%, such as at least 90 mol-% or at least 99 mol-%, relative to the total amount of polyol (ib).

[0068] The ethylenically unsaturated polyester resin (i) is preferably obtainable by reacting compounds (ia) and (ib) in a molar ratio ranging from 1.2:1 to 1:1.2, more preferably 1.1:1 to 1:1.1, most preferably 1.05:1 to 1:1.05.

[0069] The ethylenically unsaturated polyester resin (i) preferably has a number average molecular weight in the range of 500 to 10,000 g / mol as determined by gel permeation chromatography, more preferably 800 to 8,000 g / mol, most preferably 1,000 to 5,000 g / mol.

[0070] The ethylenically unsaturated polyester resin (i) preferably has an acid value in the range of 5 to 80 mg KOH / g, more preferably 10 to 65 mg KOH / g, most preferably 15 to 55 mg KOH / g.

[0071] 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 by DIN EN ISO 2114.

[0072] In a further embodiment, the ethylenically unsaturated resin (i) has a vinyl density in the range of 1.0 to 7.5 mol / kg, in particular in the range of 2.0 to 7.0 mol / kg, such as 2.5 to 6.0 mol / kg. The vinyl density indicates the molar proportion of vinyl groups per kg of resin. The vinyl density can be determined by nuclear magnetic resonance (NMR) spectroscopy.

[0073] Preferably, the weight ratio of the ethylenically unsaturated resin (i) to the reactive diluent (ii) in the curable resin composition is in the range of 15:85 to 85:15, more preferably in the range of 25:75 to 75:25, especially 30:70 to 60:40.

[0074] The ethylenically unsaturated polyester resin composition of the present invention preferably comprises the ethylenically unsaturated polyester resin (i) in an amount of 15 to 85 wt.-%, more preferably 15 to 75 wt.-%, most preferably 20 to 60 wt.-%, based on the total weight of the ethylenically unsaturated polyester resin composition.

[0075] The ethylenically unsaturated polyester resin composition of the present invention preferably comprises the reactive diluent (ii) in an amount of 0.5 to 85 wt.-%, for example 3 to 85 wt.-% or 5 to 85 wt.-%, preferably 10 to 80 wt.-%, more preferably 15 to 80 wt.-%, such as 20 to 80 wt.-%, even more preferably 25 to 80 wt.-%, most preferably 40 to 80 wt.-%, for example 50 to 75 wt.-%, based on the total weight of the ethylenically unsaturated polyester resin composition.

[0076] The ethylenically unsaturated polyester resin composition of the present invention preferably comprises ethylenically unsaturated polyester resin (i) and reactive diluent (ii) in a total amount of 15 wt.-% to 100 wt.-%, more preferably 20 wt.-% to 100 wt.-%, most preferably 20 wt.-% to 99 wt.-%, based on the total weight of the ethylenically unsaturated polyester resin composition.

[0077] In addition to reactive diluent (ii), the olefinic unsaturated polyester resin composition of the present invention may include one or more other reactive diluents selected from the following: styrene and styrene derivatives, epoxides, vinyl ethers, acrylates and methacrylates. In this case, reactive diluent (ii) acts as a solubility enhancer. Styrene derivatives include 3-methylstyrene, 4-methylstyrene, 4-tert-butylstyrene and α-methylstyrene. Suitable acrylates include methyl methacrylate, tert-butyl acrylate, cyclohexyl acrylate, 4-tert-butyl acrylate-cyclohexyl acrylate, dimethyl itaconate, methyl cinnamate, ethyl cinnamate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, isobornyl acrylate, isobornyl methacrylate, 1,4-butanediol dimethacrylate, triethylene glycol dimethacrylate 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-epoxypropoxy)butane.

[0078] In order to achieve high solubility 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.-%, such as at least 25 wt.-%, at least 40 wt.-%, at least 50 wt.-%, at least 60 wt.-% or at least 75 wt.-%, relative to the total amount of reactive diluent (ii) and the further reactive diluent.

[0079] Preferably, the weight ratio of the ethylenically unsaturated resin (i) to the total amount of reactive diluent in the curable resin composition is in the range of 15:85 to 85:15, more preferably in the range of 25:75 to 75:25, especially 30:70 to 70:30.

[0080] In one embodiment, the ethylenically unsaturated polyester resin composition does not include additional reactive diluents.

[0081] The composition may contain additional components including stabilizers; inhibitors; additional curable compounds other than 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.

[0082] 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. In addition, phenol derivatives having at least one substituent in the alpha position of the phenol group are suitable, such as 2,6-di-tert-butyl-4-methylphenol, 1330 or 3114, and tocopherol. Other suitable stabilizers include aromatic amines and phenylenediamines, hindered amines (such as 356. 765, and 770), imines, sulfonamides, oximes, hydroxylamines, urea derivatives, phosphorus-containing compounds, sulfur-containing compounds (such as phenothiazines), complexing agents based on tetraazaannulene (TAA) and / or metal salts. Phosphorus-containing compounds are, for example, triphenylphosphine, triphenyl phosphite, hypophosphorous acid, phosphorous acid, trinonyl phosphite, triethyl phosphite and diphenylisopropylphosphine.

[0083] Suitably, the ethylenically unsaturated polyester resin composition comprises a total amount of stabilizer in the range of 0.01 to 5 wt.-%, preferably 0.02 to 3 wt.-%, more preferably 0.025 to 2.5 wt.-%, relative to the total amount of the ethylenically unsaturated polyester resin composition.

[0084] Suitable inhibitors include hydroquinone, 2-methylhydroquinone, 2-tert-butyl-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.

[0085] Further curable compounds different from the ethylenically unsaturated polyester resin (i) may be compounds having polymerizable ethylenically unsaturated groups, for example vinyl (such as vinyl ether, vinyl ester or N-vinyl), allyl or (meth)acryloyl. The expression "(meth)acryloyl" is understood to mean acryloyl or methacryloyl, preferably acryloyl. Compounds having at least one (meth)acryloyl group are referred to as (meth)acryloyl compounds. These further curable compounds may be selected from ethylenically unsaturated resins, including ethylenically unsaturated polyester resins, vinyl ester resins, and urethane (meth)acrylate resins.

[0086] Suitable pigments and dyes are materials which change the color of reflected or transmitted light due to wavelength-selective absorption. An example of a pigment is titanium dioxide.

[0087] Fillers are inert compounds that increase the volume of the unsaturated polyester resin composition. For every 100 parts by weight of the mixture of unsaturated polyester resin (i) and reactive diluent (ii), preferably 20 to 280 parts by weight of fillers are present in the unsaturated polyester resin composition. An example of a filler is calcium carbonate.

[0088] Thickeners increase the viscosity of the unsaturated polyester resin composition and reduce its tackiness, thereby 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).

[0089] The mechanical properties and mechanical stability of the fiber-reinforced cured unsaturated polyester resin composition. For every 100 parts by weight of unsaturated polyester resin (i) and reactive diluent (ii), preferably 10 to 200 parts by weight of fiber, more preferably 15 to 200 parts by weight of fiber, most preferably 25 to 180 parts by weight of fiber, such as glass fiber, carbon fiber, ceramic fiber, aramid fiber, boron fiber, basalt fiber, steel fiber, natural fiber and / or nylon fiber are present. Glass fiber is preferred.

[0090] Glass fiber is a material composed of many very fine glass fibers and is formed by extruding fine glass filaments (such as silica-based glass). It has been found that the use of N-vinyl oxazolidinones of formula (I) as reactive diluents for obtaining cured glass fiber materials increases the impact strength of these materials compared to known reactive diluents (such as styrene).

[0091] Glass fibers, as well as the optional additional fibers discussed above, can be characterized by their aspect ratio. Fibers are understood to be materials having an aspect ratio of at least 10, particularly at least 20, more particularly at least 50 or at least 100, and also include fibers modified, for example, by spinning. In a preferred embodiment, the fibers have an aspect ratio in the range of 20 to 100,000, preferably 50 to 100,000, most preferably 100 to 100,000. The length and diameter of the fibers can be determined by a suitable microscope.

[0092] The length of suitable glass fibers is typically in the range of 1 mm to 1 m, preferably 2 mm to 1 m, 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, most preferably 12 to 25 μm.

[0093] The glass fibers may be present in the material as individual glass fibers, as a web, a fabric (including knitted and woven fabrics, non-crimped fabrics), a scrim, a roving, and the like.

[0094] Flame retardants are substances that prevent or slow the development of fire. Suitable flame retardants include solid flame retardants such as aluminum 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-(tetrabromophthalimide), tris(tribromophenyl)cyanurate and / or dodecachloropentacyclo-octadecadiene (Dechlorane In addition, halogenated flame retardants can be used with synergists such as antimony trioxide (Sb 2 O 3 ) or 2,3-dimethyl-2,3-diphenyl-butane Use in combination.

[0095] Biocides are materials that destroy, prevent, make harmless or apply control effects to any harmful organisms by chemical or biological means. Suitable biocides include materials based on silver, copper or zinc, which are supplied as salts (zinc pyrithione) or oxides or by the zeolite of load or by nanoparticles. Other suitable biocides include chitosan, 10,10'-oxybisphenoxane (OBPA), isothiazolinone, 2,4,4'-trichloro-2'-hydroxy-diphenyl ether (triclosan), N-(fluorodichloro-methylthio) phthalimide, thiabendazole (TBZ) or methylthio-cyclopropylamino-tert-butylamino-s-triazine and synthetic polymer poly-(tert-butylaminoethyl methacrylate), poly-(tert-butylaminomethylstyrene), and active copolymers thereof.

[0096] Thermoplastic shrinkage control agents are substances that can be used in sheet molding compound (SMC) and bulk molding compound (BMC) technology to compensate for shrinkage by forming microvoids in the thermoplastic phase during curing. Suitable thermoplastic shrinkage control agents include solid polymers (such as powdered polyethylene) and liquid 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.

[0097] Tougheners are used to improve the damage tolerance of cured olefinic unsaturated polyester resin compositions. In particular, elongation at break and impact strength can be enhanced, while crack formation under long-term static and dynamic loads can be reduced. Suitable tougheners include rubber, nanoparticles (i.e., particles with an average diameter less than 1 μm or precursors to form such nanoparticles), thermoplastic polymers different from olefinic unsaturated polyester resin (i), and block copolymers different from olefinic unsaturated polyester resin (i). Tougheners can be present in the resin composition in an amount of 2 wt.% to 40 wt.%, preferably 3 wt.% to 30 wt.%, more preferably 5 wt.% to 25 wt.%, relative to the total amount of the olefinic unsaturated polyester resin composition.

[0098] 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), and rubbers based on polyacrylates, acrylate rubbers (AM) and fluororubbers as well as functionalized rubbers like carboxyl-terminated NBR (CTBN) or epoxy-terminated NBR (ETBN).

[0099] Suitable nanoparticles include soot, carbon black (high wear furnace, ultra high wear furnace), pyrogenic silicic acid, surface modified pyrogenic silicic acid, fumed silica, precipitated silica, rigid phase material from polyurethane recycling, silica particles modified by hydrolysis of functionalized silanes, montmorillonite, bentonite and exfoliated montmorillonite.

[0100] Suitable thermoplastic polymers other than the ethylenically unsaturated polyester resin (i) include polysulfone (PSU), polyethersulfone (PES), polyphenylsulfone (PPSU), polyoxy-2,6-dimethyl-1,4-phenylene (PPE), polycarbonates based on bisphenol A and bisphenol TMC Copolymer of styrene and maleic anhydride Styrene, copolymer with maleic anhydride and N-phenylmaleimide Copolymers of styrene and glycidyl methacrylate, copolymers of styrene and acrylonitrile (SAN), copolymers of styrene, butadiene and acrylonitrile (ABS), copolymers of styrene, acrylate monomer and acrylonitrile (ASA), copolymers of acrylonitrile and α-methyl-styrene (AMSAN), amorphous polyamide, polymethacrylimide, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), ethylene-tetrafluoroethylene copolymer (ETFE), and copolymers of tetrafluoroethylene and hexafluoropropylene.

[0101] 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.

[0102] A curing agent is a compound or mixture of compounds that accelerates the curing process.

[0103] When curing is carried out at a temperature between 5°C and 45°C, it may be referred to as a "cold cure." Cold curing may be carried out via a combination of benzoyl peroxide with an amine accelerator; or via a combination of a hydroperoxide with a metal accelerator.

[0104] Suitable benzoyl peroxides include dibenzoyl peroxide and 4,4'-dichloro-dibenzoyl peroxide. Suitable amine accelerators include N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyltoluidine, N,N-diethyltoluidine, N,N-bis(2-hydroxyethyl)aniline, N,N-bis(2-hydroxyethyl)-toluidine, N,N-bis(2-hydroxypropyl)-aniline, and / or N,N-bis(2-hydroxypropyl)toluidine.

[0105] Suitable hydroperoxides include hydrogen peroxide, tert-butyl hydroperoxide, tert-amyl hydroperoxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, acetylacetone peroxide, trimethylcyclohexanone peroxide, isobutyl 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 ethylhexanoic acid or cyclohexane acid.

[0106] When curing is carried out at a temperature above 45°C and 120°C, it may be referred to as "thermal curing". Thermal curing may be carried out using one or more thermal initiators as curing agents. Suitable thermal initiators include peroxides, azo compounds and CC labile compounds.

[0107] 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 tert-Butyl-2-methylbenzoate, tert-butyl peroxycarbonate 2-ethylhexyl, tert-butyl peroxycarbonate isopropyl, tert-amyl peroxybenzoate, tert-butyl peroxybenzoate, 1,1-di-(tert-amyl peroxy)cyclohexane, 1,1-di-(tert-butyl peroxy)-3,3,5-trimethyl-cyclohexane, 1,1-di-(tert-butyl peroxy)-cyclohexane, 2,2-di-(tert-amyl peroxy)butane, 4,4-di- -Butyl (tert-butyl peroxy) valerate, dilauroyl peroxide, di-(2-tert-butyl peroxyisopropyl)benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di-(tert-butyl peroxy)hexane, di-tert-butyl peroxide, di-tert-amyl peroxide, dicumyl peroxide, di(tert-butyl peroxyisopropyl)benzene, 2,5-dimethyl-2,5-di-(tert-butyl peroxy)hexane, tert-butyl cumyl peroxide The compounds include 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxycyclononane, di-(4-tert-butylcyclohexyl) peroxydicarbonate, di-(2-ethylhexyl) peroxydicarbonate, tert-butyl hydroperoxide, cumyl hydroperoxide, isopropylcumyl hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide.

[0108] Suitable azo compounds include 2,2'-azobis(2-isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile) and 1,1'-azobis(hexahydrobenzonitrile).

[0109] Suitable CC labile compounds include 2,3-dimethyl-2,3-diphenylbutane and 3,4-dimethyl-3,4-diphenylhexane.

[0110] Other suitable curing agents include compounds that generate free 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-hydroxy ketones, α-amino ketones, acylphosphine oxides, bisacylphosphine oxides, or combinations thereof. Preferred photoinitiators include 369, 651, 184. 819, 907 and TPO.

[0111] In one embodiment, the ethylenically unsaturated polyester resin composition does not include a curing agent.

[0112] Furthermore, the present invention provides the use of the ethylenically unsaturated polyester resin composition as described above as a matrix polymer for reinforced and non-reinforced thermosetting materials in the following: SMC technology (sheet molding composite technology), BMC technology (bulk molding technology), resin transfer molding (RTM), compression molding, hot molding, FCS technology (fiber composite spray technology), injection molding, vacuum assisted resin infusion, continuous sheet production, filament winding, rotational molding, lamination, vacuum pressure impregnation (VPI process), pultrusion, casting, bundling, bonding, gel coating, top coating, spraying, filling, in-mold coating, doctor blade coating, dip coating, drip coating, painting, wire painting (enamel coating) and the like coating, fiber spinning and foaming.

[0113] The present invention further provides a thermosetting material obtainable by curing the ethylenically unsaturated polyester resin composition of the present invention. The above discussion and examples concerning the composition of the present invention are to be understood to be equally applicable to the thermosetting material of the present invention.

[0114] In a preferred embodiment, curing is carried out by free radical polymerization via a curing agent. Suitable curing agents are described above. Alternatively, curing can be carried out in the absence of a curing agent.

[0115] Curing can be carried out with the aid of high-energy radiation. Examples of high-energy radiation suitable for curing are electron radiation, or α-, β- or γ-radiation, preferably γ-radiation.

[0116] Curing of the unsaturated ethylenically unsaturated polyester resin composition is preferably carried out at elevated temperatures, preferably in the range of 120° C. to 250° C. The temperature may be increased stepwise during the curing process.

[0117] In a preferred embodiment, the curing of the unsaturated polyester resin composition is performed at a temperature ranging from 15° C. to 50° C. for 2 to 200 hours and thereafter at 80° C. to 120° C. for 2 to 24 hours.

[0118] 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°C to 200°C, in particular 80°C to 150°C.

[0119] The thermosetting materials according to the present invention can be used for the production of storage tanks, polymer concrete, artificial stone, device construction, medical equipment, railway equipment, oil and gas field equipment, automobile body parts, truck body parts, headlight reflectors, gel coatings, topcoats, protective layers and other coating applications (such as spraying, in-mold coating and painting), putties, cast products, buttons, porous materials (such as foams, films, etc.), for the production of fibers, for the production of tools, electronic devices, flame retardant thermosetting materials, profiles, containers, moldings, polymer parts, long field lamp stands, oil tanks, sheets / plates, railway interior components, adhesive parts and pipes.

[0120] The present invention is described in further detail by the following examples.

[0121] Examples

[0122] The unsaturated polyester resin is obtained as described below.

[0123] The following table provides a summary of the reactants, stabilizers, and initiators used in the working examples.

[0124]

[0125]

[0126] A. Production of unsaturated polyester resin

[0127] The unsaturated polyester resin is obtained by reacting (ia) at least one ethylenically unsaturated dicarboxylic acid, or an ester or anhydride thereof and (ib) at least one polyol in the molar ratios specified in the table below. The unsaturated polyester resin is prepared by melt polycondensation.

[0128] A four-necked flask (2L) is provided. In the middle neck, an agitator with a single blade is installed. The bearing housing of the agitator is continuously cooled with water. On the other three necks, a thermocouple, an insulation filling column and a plug are provided. A distillation bridge with a ground joint thermometer is installed on the column to monitor the head temperature of the system during polycondensation. A graduated cylinder (250mL) is attached to the distillation bridge to collect and measure the amount of condensed water. Thermocouple is connected to Julabo laboratory controller (PID) and the reactor temperature is controlled via a computer program (JULABO EasyTemp Professional). A heating jacket (which is also controlled by Julabo laboratory controller) is used as a heating source.

[0129] At the start of the reaction, 500 ppmw of hydroquinone was added as a free radical scavenger relative to the total reaction mixture. 400 ppmw of Fascat 4100 (butyl stannoic acid) was added as an esterification catalyst relative to the total reaction mixture at 140° C. The reaction was carried out in a four-necked flask (2 L) with a stirrer and a thermometer under a nitrogen atmosphere (99.999% nitrogen).

[0130] Heating from room temperature to 135° C. was carried out as quickly as possible by program control while avoiding overheating. At 135° C. to 145° C., the formation of water was first observed. In the range of 135° C. to 185° C., the reaction temperature was increased by 10° C. per hour. As soon as the melt of the unsaturated polyester reached 185° C., the reaction was stopped. The polymer was cooled and then left in its solid form overnight.

[0131] Subsequently, the polymer was melted again by heating to 185°C. 400 ppmw of Fascat 4100 was added at 140°C relative to the total reaction mixture. 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 the desired acid value was reached, which was checked at regular intervals. Subsequently, the unsaturated polyester was poured into a shallow rectangular mold, where it was allowed to cool and solidify.

[0132] 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 is determined in accordance with DIN EN ISO 2114 via titration.

[0133] Glass transition temperature T of ethylenically unsaturated polyester resin g The DSC measurement was performed using a DSC device Sirius 3500 from Netzsch. Hermetically sealed Tzero aluminum pans were used. For the DSC measurement, about 15 mg of unsaturated polyester resin were added to the Tzero pan. The Tzero cover was then placed on the pan and sealed with the help of a press, the pan was inserted into the DSC and the measurement was started.

[0134] For the measurement, the disk is first cooled to 0° C. and then heated to 100° C. at 10 K / min. The above steps are then repeated again, so that two cycles are measured. g is determined from the second loop.

[0135] Mass average molecular weight M w and number average molecular weight M nThe polydispersity index Q is calculated as M w / M n .

[0136] In particular, analytical columns from PSS Polymer Standard Solutions were used as separation columns. The stationary phase consisted of a 3 μm particle size and a nominal pore size of The separation column was composed of styrene-divinylbenzene copolymer (SDV). The eluent was tetrahydrofuran (THF). The separation column was temperature-adjusted to 35°C in a column oven. At a sample concentration of 4.94 g / L, the injected sample volume was 50 μL, which in sample preparation was equivalent to 50 mg sample to 9 g eluent. The flow rate of the eluent was 0.5 mL / min. The samples were detected with a refractive index detector and a UV-vis detector, wherein the measurement signals were recorded once per second. Two GPC measurement series were performed for each polyester. The chromatograms were evaluated using the PSS WinGPC UniChrom software. Calibration was performed with appropriate standard kits for styrene oligomers and polymers.

[0137] Melt viscosity was determined at 100° C. or 150° C. according to the table below via an ICI-cone and plate viscometer from Epprecht Control & Instrument (FIC). Standard cone C ( The measurement was carried out with a cone angle of 0.5°. About 0.5 g of solid unsaturated polyester resin was used for the measurement.

[0138] The following table shows the properties of unsaturated polyester resins.

[0139]

[0140]

[0141] nm = not measured

[0142] *Q = polydispersity index

[0143] **T V = Temperature at which viscosity measurement is performed

[0144] B. Prediction of Hansen Solubility Parameters of Unsaturated Polyester Resins

[0145] The Hansen parameters of unsaturated polyester resins are predicted based on the corresponding oligomers using the software COSMOquick 2021. First, the molecules are drawn as 12-mer oligomers in the included JChemPaint module. Then, the corresponding SMILES strings are generated. Finally, the quantitative structure-activity relationship (QSPR) model is used to obtain the Hansen solubility parameters. The QSPR results are fitted to the published empirical Hansen values ​​("Hansen Solubility Parameters: A User's Handbook", CM Hansen, 2007, 2nd edition, CRC Press). The results are shown in the table below.

[0146] C1. Production of ethylenically unsaturated polyester resin composition

[0147] The solidified unsaturated polyester resin obtained according to item A was crushed using a hammer. If the unsaturated polyester resins did not solidify at room temperature, they were cooled with liquid nitrogen and then crushed in a cold state. The crushed polyester resin was used to produce an unsaturated polyester resin composition. First, the unsaturated polyester resin particles were weighed into a glass bottle. Subsequently, a reactive diluent was added in an amount of 70 wt.-% of the total composition, followed by 765 (BASF, 1,000ppmw).

[0148] The bottle was placed on a roller mixer. The solubility of the unsaturated polyester resin particles in the reactive diluent or the progress of the dissolution process was visually checked at regular intervals. Once all the material was dissolved, the resin composition was considered ready for use. The results of the solubility test are shown in the table below.

[0149]

[0150]

[0151] *Comparative Examples

[0152] **Contains no stabilizer 765

[0153] It is clear that the reactive diluents of the present invention allow the Hansen solubility parameter δ p At least 5.5MPa 1 / 2 High solubility of ethylenically unsaturated polyester resins, while the same resins are generally insoluble in styrene.

[0154] C2. Production of Additional Ethylenically Unsaturated Polyester Resin Compositions

[0155] The resin 14 according to item A is composed of fumaric acid and 2-methyl-2-propylpropane-1,3-diol (molar ratio 1.0:1.02, δp =5.702MPa 1 / 2 ) The polyester obtained was cooled with liquid nitrogen and then pulverized in a cold state. The pulverized polyester was used to produce an unsaturated polyester resin composition. First, the unsaturated polyester particles were weighed into a glass bottle. Subsequently, a mixture of styrene and VMOX and a stabilizer was added according to the following table.

[0156] 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 visually checked at regular intervals. Once everything was dissolved, the resin composition was considered ready for use.

[0157] The results of the solubility testing are shown in the table below. To determine the Hansen solubility parameters for a mixture of styrene and VMOX, the mass fractions were converted to volume fractions by using the following formula:

[0158]

[0159] in is the volume fraction of component 1, ω 1 is the mass fraction of component 1, ω 2 is the mass fraction of component 2, ρ 1 is the density of component 1 and ρ 2 is the density of component 2. The density of styrene is 0.909 kg / m 3 The density of VMOX is 1.098kg / m 3 .

[0160] R is determined using the following formula using a comparison of the Hansen solubility parameters of a mixture of styrene and VMOX with the Hansen solubility parameters of an unsaturated polyester resin: a value:

[0161]

[0162]

[0163]

[0164] It is clear that the presence of even small amounts of VMOX improves the solubility of the polyester resins examined compared to pure styrene.

[0165] D. Production of composite fiber materials

[0166] Glass fiber reinforced test specimens were made using the resin composition of item C1 containing 70 wt.-% of VMOX. As a first step, tert-butyl peroxybenzoate (Acros Organic Reagents, 98%) was added to the resin in an amount of 1 wt.-%. Then, about 10 g of the resin was placed in a metal pan (diameter: 10 cm; depth: 1 cm). The resin was evenly distributed and a layer of biaxial glass fiber fabric of the same diameter (831 g / m 2 , 0 ° / 90 °, product number S14EB490-00831-01300-474000, from Saertex (Saertex)) is placed in the resin. Once all bubbles are removed using a wooden scraper, a second layer of resin is added. The second glass fiber fabric layer is placed at a 90 ° angle to the first layer and is also wetted with resin. The process is repeated again so that the metal tray contains three layers of glass fibers at 90 ° to each other and about 30 g of the resin composition.

[0167] The obtained sample was pressed with a weight (about 500 grams) wrapped in aluminum foil to squeeze the excess resin composition out of the mold and obtain a smooth sample surface. Finally, the sample and the weight were wrapped in aluminum foil. The sample was thermally cured at 100°C for 1 h and at 160°C for 1 h in a laboratory oven under air. After cooling, the obtained composite fiber material was removed from the mold and cut into 10×50 mm samples using a table saw.

[0168] Subsequently, the samples were subjected to dynamic mechanical analysis (DMA) using a DMA 242C from NETZSCH. A three-point bending specimen holder was used. The samples were measured under a nitrogen flow of 83 mL / min according to the methods 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 composition was determined. The maximum value of the tan δ curve (T) is considered to constitute the glass transition temperature T G .

[0169]

[0170] The glass transition temperatures of the composite fiber materials are shown in the table below.

[0171]

[0172]

[0173]

[0174] *Comparative Examples

[0175] **Contains no stabilizer 765

Claims

1. An ethylenically unsaturated polyester resin composition comprising (i) an ethylenically unsaturated polyester resin which can be obtained by reacting: (ia) at least one unsaturated dicarboxylic acid, or an ester or anhydride thereof, wherein the unsaturated dicarboxylic acid comprises at least one ethylenically unsaturated dicarboxylic acid; and (ib) at least one polyol; and (ii) a reactive diluent which is an N-vinyl oxazolidinone having the formula (I) Where R 1 , R 2 , R 3 and R 4 are independently selected from a hydrogen atom and an organic moiety containing 1 to 10 carbon atoms; wherein the ethylenically unsaturated polyester resin (i) is characterized by a Hansen solubility parameter δ p At least 5.5MPa 1 / 2 .

2. The composition according to claim 1, wherein -R 1 , R 2 , R 3 and R 4 At least two of 1 , R 2 , R 3 and R 4 each of which is a hydrogen atom; or -R 1 , R 2 , R 3 and R 4 each of which is a hydrogen atom; or -R 1 is a C1-C4 alkyl group and R 2 , R 3 and R 4 is a hydrogen atom; or -R 4 is a C1-C4 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 It is a C1-C4 alkyl group.

3. A composition according to any one of the preceding claims, 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. A composition according to any one of the preceding claims, 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. A composition according to any one of the preceding claims, wherein The compound (ia) is selected from maleic acid, maleic anhydride, fumaric acid, dimethyl fumarate, itaconic acid, dimethyl itaconate, 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 comprising: at least one compound selected from maleic acid, maleic anhydride, fumaric acid, dimethyl fumarate, itaconic acid, dimethyl itaconate, mesaconic acid, citraconic acid, and tetrahydrophthalic anhydride; and at least one compound selected from the group consisting of phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, dimethyl terephthalate, 2,5-furandicarboxylic acid, and dimethyl 2,5-furandicarboxylate.

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

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

2.

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

11. The composition according to any of the preceding claims, 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 according to any of the preceding claims, 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 according to any one of the preceding claims, further comprising a stabilizer.

14. Use of the ethylenically unsaturated polyester resin composition according to any of the preceding claims for reinforced and non-reinforced thermosetting materials in SMC technology (sheet molding composite technology), BMC technology (bulk molding technology), resin transfer molding (RTM), compression molding, hot molding, FCS technology (fiber composite spray technology), injection molding, vacuum assisted resin infusion, continuous sheet production, filament winding, rotational molding, lamination, vacuum pressure impregnation (VPI process), pultrusion, casting, strapping, bonding, gel coating, top coating, spraying, filling, in-mold coating, doctor blade coating, dip coating, drip coating, painting, line painting (enamel coating) and the like coating, fiber spinning and foaming.

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

Images