Composite glass fiber material containing thermosetting polymer

Abstract

The composite glass fiber material comprises a thermosetting polymer, which is a mixture of (i) an ethylenically unsaturated resin and (ii) an N-vinyloxazolidinone of formula (I), where 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), and the reactive diluent (ii) is present in an amount of at least 0.5 wt % based on the total amount of the reactive diluent (ii) and the further reactive diluent. [Formula 1] TIFF2025531083000038.tif27170

Description

[Technical Field]

[0001] The present invention relates to a composite glass fiber material comprising a thermosetting polymer, a method for producing the composite glass fiber material, the use of N-vinyloxazolidinone in the process for obtaining the composite glass fiber material, and a curable resin composition. [Background technology]

[0002] Composite fiber materials comprise a fiber-reinforced polymer matrix and are used as molded parts in many applications, including, for example, automotive manufacturing and engineering. The polymer in composite fiber materials is typically a thermosetting polymer, such as an epoxy, vinyl ester, or polyester-based thermosetting polymer.

[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 production of composite fiber materials containing thermosetting polymers involves the curing of a prepolymer resin, which is suitably flexible or liquid before curing. To optimize the rheology and thereby improve the processability of the resin, at least one reactive diluent (diluent) 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, especially styrene.

[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.

[0007] There is a need for additional bicomponent fiber materials derived from reactive diluents that address at least some of the above-mentioned shortcomings. Summary of the Invention [Means for solving the problem]

[0008] The present invention provides a composite glass fiber material comprising a thermosetting polymer, the thermosetting polymer comprising: (i) an ethylenically unsaturated resin; and (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 independently selected from a hydrogen atom and an organic moiety containing 1 to 10 carbon atoms; obtained from a curable resin composition comprising A composite glass fiber material is provided in which the reactive diluent (ii) is present in an amount of at least 0.5 wt. % based on the total amount of reactive diluent (ii) and any further reactive diluents. DETAILED DESCRIPTION OF THE INVENTION

[0009] It has been found that composite glass fiber materials containing thermosetting polymers can be advantageously obtained from curable resin compositions containing reactive diluents (ii). One particular advantage is the ability of N-vinyloxazolidinones of formula (I) to solubilize relatively highly polar unsaturated resins. Without wishing to be bound by theory, it is believed that the high polarity of N-vinyloxazolidinones of formula (I) makes these compounds highly compatible with relatively polar unsaturated resins. 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.

[0010] 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.

[0011] 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.

[0012] 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.

[0013] 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").

[0014] 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.

[0015] 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.

[0016] 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).

[0017] The curable resin composition includes an ethylenically unsaturated resin. The ethylenically unsaturated resin has an ethylenically unsaturated double bond in its backbone. 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═CH) double bond.

[0018] The ethylenically unsaturated resin (i) is preferably selected from ethylenically unsaturated polyester resins, vinyl ester resins, and urethane (meth)acrylate resins, and in particular, the ethylenically unsaturated resin (i) is an ethylenically unsaturated polyester resin.

[0019] The ethylenically unsaturated polyester resin can be obtained by reacting (ia) at least one unsaturated dicarboxylic acid, including at least one unsaturated dicarboxylic acid, or its ester or anhydride, with (ib) at least one polyol. Optionally, the monomers for forming the ethylenically unsaturated polyester resin may include a saturated dicarboxylic acid or its ester. The ethylenically unsaturated polyester resin has an ethylenically unsaturated double bond in its main chain derived from the polymerized ethylenically unsaturated dicarboxylic acid of component (ia).

[0020] 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.

[0021] The unsaturated dicarboxylic acid can be 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.

[0022] 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.

[0023] 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.

[0024] 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.

[0025] Compound (ia) is preferably 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, 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.

[0026] In one embodiment, the ethylenically unsaturated polyester resin can be obtained in the presence of a saturated aliphatic dicarboxylic acid. 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. Typically, the amount of saturated dicarboxylic acid 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.

[0027] At least one 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.

[0028] 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.

[0029] 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).

[0030] The ethylenically unsaturated polyester resin (i) can be obtained by reacting the compounds (ia) and (ib) preferably in a molar ratio ranging from 1.2:1 to 1:1.2, more preferably from 1.1:1 to 1:1.1, and most preferably from 1.05:1 to 1:1.05.

[0031] Alternatively, the ethylenically unsaturated resin (i) is a vinyl ester resin. Vinyl ester resins can be obtained by esterifying an epoxy resin with (meth)acrylic acid. The term (meth)acrylic acid is understood herein to refer to both acrylic acid and methacrylic acid.

[0032] The epoxy resin used to prepare the vinyl ester resin is preferably a polyglycidyl ether, which typically has an average of 2 to 4 glycidyl groups per molecule and may also have 1 to 4 esterifiable hydroxyl groups. Preferred vinyl ester resins are aromatic vinyl ester resins. Among these, aromatic polyglycidyl ethers, particularly those based on novolac epoxy resins such as epoxy phenol novolac (EPN) or epoxy cresol novolac (ECN), or those based on bisphenols such as bisphenol A or bisphenol F, are preferred as reaction products with acrylic acid. In a typical embodiment, bisphenol A is reacted with epichlorohydrin to form an epoxide, which is then esterified with acrylic acid.

[0033] Number average molecular weight M n Particularly preferred are vinyl ester resins having an average of 1.9 to 5, especially 2 to 4, acrylate groups.

[0034] Unlike ethylenically unsaturated polyester resins, vinyl ester resins contain only terminal double bonds. The small number of double bonds allows thermosetting polymers to be obtained from vinyl ester resins, which exhibit relatively low crosslink density and therefore high impact strength, elongation at break, and tensile strength. Furthermore, thermosetting polymers obtained from vinyl ester resins exhibit fewer free chain ends than polymers obtained from ethylenically unsaturated polyester resins, making them less susceptible to hydrolysis and more resistant to corrosion. In addition, the glass transition of thermosetting polymers obtained from vinyl ester resins is much more remarkable than that of thermosetting polymers obtained from ethylenically unsaturated polyester resins.

[0035] Suitable commercially available vinyl ester resins include, in particular, Laromer® products LR8765 (aliphatic), LR8986, LR9019, LR9023, EA9081, EA9082, EA9097, EP9124, EA9138, EA9143, and EA9145, EA9148 from BASF SE; AgiSyn® products 1010, 1030, 2020, 3010, 3020, 3051, 9720, 9721, 9750, 9760, 9771, 9790, and 9792 from DSM Coating Resins BV; Allnex Ebecryl® products 113, 600, 604, 605, 608, 609, 640, 641, 648, 860, 1606, 1608, 3105, 3203, 3300, 3416, 3420, 3608, 3639, 3700, 3700, 3701, 3702, 3703, 3708, 3730, 3740, 5848, and 6040 from Eternal Chemical Co., Ltd.'s Etercure® products 621, 621, 622, 622, 623, 623, 624, 624, 625, 923, 6209, 6210, 6211, 6213, 6215, 6219, 6231, 6233, 6233, 6234, 6235, 6241, 6261, and 620; IgM Photomer® products 3005, 3015, 3016, 3072, 3316, 3317, 3620, and 3660; and Miwon Specialty Chemical Co., Ltd.'s Miramer® and Photocryl® products Miramer PE 110H, Photocryl E202, Photocryl E203 / 30PE, and Photocryl E203 / 30PE. E207 / 25TP, Photocryl E207 / 30PE, Photocryl E07 / 25HD, Miramer PE210, Miramer PE210HA, Miramer PE230, Miramer PE250, Miramer PE250LS, Photocryl DP296, Miramer PE310, Photocryl DP460, Miramer PE2100, Miramer PE2120A, Miramer PE2120C, Miramer PE2120B, Miramer PE130, Miramer ME2500, Miramer SC6345, and Miramer SC6400; Genomer® products 2235, 2253, 2255, 2259, 2263, and 2280 from Rahn AG; Sartomer® CN and Kyrarad® products from Sartomer: Sartomer CN104 Y50, Sartomer CN108, Sartomer CN109, Sartomer CNUVE 110 / 95, Sartomer CN111, Sartomer CN112 B70, Sartomer CN12 C60, Sartomer CN113 D70, Sartomer CNUVE 114 / 95, Sartomer CN115, Sartomer CN116, Sartomer CN116 D50, Sartomer CN117, Sartomer CN118, Sartomer CN119, Sartomer CN120, Sartomer CN120 A75, Sartomer CN120 A80, Sartomer CN120 B60, Sartomer CN120 B80, Sartomer CN120 C60, Sartomer CN120 C80, Sartomer CN120 D80, Sartomer CN120 E50, Sartomer CN120 J90, Sartomer CN120 M50, Sartomer CN120 S80, Sartomer CN121, Sartomer CN122 A80, Sartomer CN124, Sartomer CN129, Sartomer CNUVE 130, Sartomer CN131 B, Sartomer CN132, Sartomer CN133, Sartomer CN136, Sartomer CN148, Sartomer CNUVE 150 / 80, Sartomer CN151, Sartomer CNUVE 151, Sartomer CN152, Sartomer CN56, Sartomer CN159, Sartomer CN173, Sartomer CN186, Kayarad R 190, Kayarad R 205, Kayarad TCR 1094, Kayarad TCR1096, Sartomer CN1300, Sartomer CN2003EU, Kayarad EAM2160, and Kayarad EAM2300, and Qualipoly Chemical Corporation's Qualicure® GU products GU1160C, GU1200W, GU1280A, GU1380A, GU1400Z, GU1475A, GU1480A, GU1600Y, GU1650X, GU1700W, GU1700P, GU1700T, GU1700Y, GU1700Z, GU1800W, GU1900W, and GU1900Z, which may be blended with monomers.

[0036] Alternatively, the ethylenically unsaturated resin (i) is a urethane (meth)acrylate resin, which is obtained by reacting an aromatic or aliphatic di- or oligoisocyanate with a hydroxyalkyl (meth)acrylate, such as hydroxyethyl (meth)acrylate or hydroxypropyl (meth)acrylate, and optionally with a saturated polyol selected from aliphatic polyols, alicyclic polyols, polyetherols, polyesterols, polyetheresterols, and polycarbonate diols.

[0037] Suitable commercially available urethane (meth)acrylate resins include urethane (meth)acrylates, more specifically urethane group-containing oligomers and polymers having an average of 1.8 to 10, more specifically 1.9 to 8.5 (meth)acrylate groups, preferably obtainable by reaction of aromatic or aliphatic di- or oligoisocyanates with hydroxyalkyl (meth)acrylates. Examples include Laromer® products UA19T, UA9028, UA9030, UA8987, UA9029, UA9033, UA9047, UA9048, UA9050, UA9072, UA9065, UA9089, UA9073, and UA9136 from BASF SE; Neorad® U products 10, 20, 25, 42, 60, 61, 6282, and 6288 from DSM Coating Resins BV; AgiSyn® products 230, 236, 250, and 670 from DSM Coating Resins BV; Allnex Sarl's Ebecryl® products include 204, 205, 206, 210, 214, 215, 220, 221, 230, 244, 245, 246, 264, 265, 267, 270, 271, 280, 284, 285, 286, 294, 1258, 1290, 1291, 2002, 2003, 2221, 4101, 4150, 4201, 4220, 4250, 4265, and 439 6, 4491, 4501, 4510, 4513, 4587, 4654, 4666, 4680, 4683, 4740, 4765, 4820, 4858, 4859, 5021, 5129, 6202, 8100, 8110, 8210, 8213, 8215, 8232, 8254, 8296, 8301, 8307, 8310, 8311, 8402, 8405, 8413, 8415, 8465, and 8602;Eternal Chemical Co. Ltd.'s Etercure® products are 611, 615, 6072, 6081, 6101, 6112, 6113, 6114, 6115, 6120, 6121, 6122, 6123, 6127, 6130, 6131, 6134, 6141, 6142, 6143, 6144, 6145, 6146, 6147, 6148, 6149, 6150, 6151, 6152, 6153, 6154, 6155, 6156, 6157, 6158, 6159, 6160, 6161, 6162, 6163, 6164, 6165, 6166, 6167, 6168, 6169, 6170, 6171, 6172, 6173, 6174, 6175, 6176, 6177, 6178, 6179, 6180, 6181, 6182, 6183, 6184, 6185, 6186, 6187, 6188, 6189, 6190, 6191, 6192, 6193, 6194, 6195, 6196, 6197, 6198, 6199, 6200, 6201, 6202, 6203, 6204, 6205, 620 148, 6148, 6149, 6150, 6151, 6152, 6153, 6153, 6154, 6154, 6157, 6158, 6160, 6161, 6164, 61 65, 6170, 6171, 6172, 6175, 6175, 6175, 6176, 6181, 6195, 6196, 6197, 6198, 8000, Etercure DR-U 6-1, Etercure DR-U 10, Etercure DR-U 11, Etercure DR-U 20, Etercure DR-U 21, Etercure DR-U 22, Etercure DR-U 24, Etercure DR-U 25, Etercure DR-U 26, Etercure DR-U 57, Etercure DR-U 91, Etercure DR-U 92, Etercure DR-U 95, Etercure DR-U 106, Etercure DR-U 116, Etercure DR-U 300, Etercure DR-U 301;IGM Resins BV Photomer® products 6008, 6009, 6010, 6019, 6184, 6210, 6230, 6625, 6628, 6690, 6720, 6891, 6892, and 6893; Miwon Specialty Chemical Co., Ltd.'s Miramer® products include 256, 307, 320, 340, 360, 375, 610, 620, 622, 662, 664, 2012, 2030, 2100, 2152, 2200, 2404, 2410, 2421, 2510, 2560, 2564, 2565, 2900, 3100, 3195, 3201, 3280, 3304, 3400, 3420, 3440, 3450, 3600, 3603, 3701, 3710, 3722, 4100, 4150, 5000, 5216, 6140, and 9800;Genomer® products 1122, 4188, 4205, 4215, 4217, 4256, 4267, 4269, 4297, 4302, 4312, 4316, 4425, 4590, and 4622 from Rahn AG; Sartomer® CN products 902, 910, 914, 916, 922, 925, 929, 936, 944, 945, 946, 956, 959, 961, 962, 963, 964, 965, 966, 967, 968, 970, 971, 972, 973, 975, 976, 977, 978, 979, 980, 981, 982, 983, 984, 985, 986, 987, 988, 989, 990, 991, 992, 993, 994, 995, 996, 997, 998, 999, 1000, 1001, 1002, 1003, 1004, 1005, 1006, 1007, 1008, 1009, 1010, 1011, 1012, 1013, 1014, 1015, 1016, 1017, 1018, 1019, 1020, 1021, 1022, 1023, 1024, 102 76, 977, 978, 980, 981, 982, 983, 984, 985, 989, 990, 991, 992, 994, 996, 997, 998, 999, 1963, 3000, 3001, 8000, 8001, 8002, 8003, 9001, 9002, 9004, 9007, 901 0, 9014, 9026, 9101, 9102, 9130, 9143, 9165, 9167, 9170, 9196, 9200, 9245, 9245, 9250, 9251, 9260, 9276, 9278, 9293, 9761, 9782, 9783, 9788, 9800, and 9893;Qualicure® GU products from Qualipoly Chemical Corporation include GU3001Z, GU3010Z, GU3030Z, GU3100W, GU3100Y, GU3100Z, GU3185A, GU3185B, GU3285A, GU3290M, GU3300W, GU3300Z, GU3370A, GU3400Y, GU3400Z, GU3501Q, GU4000Y, GU4075B, GU4100Y, GU4175X, GU4200Z, GU4280B, and GU4300. GU4900Y, GU6600Y, and GU7900Z, as well as Qualicure® GS products GS4920C and GS5120C. The aforementioned products may also be blended with monomers. Among these, aliphatic urethane acrylates are preferred. Number average molecular weight M: n Aliphatic urethane (meth)acrylates having a molecular weight in the range of 500 to 4,000 g / mol are particularly preferred.

[0038] Suitable aliphatic polyols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, and polytetrahydrofuran.

[0039] Suitable polyesterols can be derived from adipic acid and a polyol selected from ethylene glycol, propylene glycol, 1,4-butanediol, 1,4-hexanediol, diethylene glycol, and dipropylene glycol.

[0040] Suitable polycarbonate diols include polycarbonates based on 1,5-pentanediol and 1,6-hexanediol.

[0041] In one embodiment, the ethylenically unsaturated resin (i) has at least one of the following characteristics: - Number average molecular weight (M) in the range of 500 to 10,000 g / mol, determined by gel permeation chromatography n ); - an acid number in the range of 5 to 80 mg KOH / g; and - Hydroxyl number in the range of 5 to 80 mg KOH / g.

[0042] Preferably, the ethylenically unsaturated resin (i) has at least one of the following characteristics: a number-average molecular weight (M) in the range of 800 to 8,000 g / mol, preferably 1,000 to 5,000 g / mol, determined by gel permeation chromatography n ); an acid value in the range of 10 to 65 mg KOH / g, preferably 15 to 55 mg KOH / g; and - Hydroxyl number in the range of 10 to 65 mg KOH / g, preferably 15 to 55 mg KOH / g.

[0043] The acid number (neutralization number) is the amount 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. The acid number is particularly relevant for characterizing ethylenically unsaturated polyester resins.

[0044] The hydroxyl number is the amount of potassium hydroxide (KOH) in milligrams required to neutralize the acetic acid incorporated in the acetylation of one gram of a chemical containing free hydroxyl groups. The hydroxyl number indicates the number of free hydroxyl groups per gram of compound and can be determined according to DIN EN ISO 4692-2.

[0045] In a further embodiment, the ethylenically unsaturated resin (i) has an ethylene group density in the range of 0.5 to 10 mol / kg, in particular in the following ranges: - 2.0 to 9.0 mol / kg, for example 4.0 to 7.5 mol / kg, when the ethylenically unsaturated resin (i) is an ethylenically unsaturated polyester resin; - 1.0 to 4.5 mol / kg, for example 2.5 to 4.5 mol / kg, when the ethylenically unsaturated resin (i) is a vinyl ester resin; When the ethylenically unsaturated resin (i) is a urethane (meth)acrylate resin, the amount is 1.0 to 5.0 mol / kg, for example, 3.0 to 5.0 mol / kg.

[0046] The ethylene group density refers to the molar ratio of ethylene groups per kg of resin and can be determined by nuclear magnetic resonance (NMR) spectroscopy.

[0047] 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 resin (i) is particularly suitable for solubilizing an ethylenically unsaturated resin (i) having a Hansen solubility parameter δ. This is particularly applicable when the ethylenically unsaturated resin is an ethylenically unsaturated polyester resin. p indicates the energy due to dipole-dipole intermolecular forces between molecules.

[0048] 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 relatively polar unsaturated resins, which is due to the relatively high Hansen solubility parameters δ of these unsaturated resins. p is reflected in.

[0049] 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.

[0050] 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 h indicates the energy due to intermolecular hydrogen bonds. The unit of the Hansen solubility parameter is MPa. 1 / 2 is.

[0051] 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.

[0052] Hansen solubility parameter δ p If the value is less than the claimed value, the solubility of the ethylenically unsaturated 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, the known reactive diluent styrene has a solubility of at least 5.5 MPa.1 / 2 Hansen solubility parameter δ p It has been found that the ethylenically unsaturated resin (i) having the formula:

[0053] In one embodiment, the ethylenically unsaturated 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 , especially at least 7.0 MPa 1 / 2 , most preferably at least 8.0 MPa 1 / 2 It is characterized by the Hansen solubility parameter δp of 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.

[0054] In a further embodiment, the ethylenically unsaturated 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 It is characterized by the Hansen solubility parameter δd of 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.

[0055] In a further embodiment, the ethylenically unsaturated 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 / 2It is characterized by the Hansen solubility parameter δh. h is preferably at most 30.0 MPa 1 / 2 , more preferably at most 24.0 MPa 1 / 2 , most preferably up to 18.0 MPa 1 / 2 is.

[0056] In one embodiment, the ethylenically unsaturated 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 , 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 .

[0057] The upper limits stated above are preferred.

[0058] In a further embodiment, the ethylenically unsaturated 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 MPa1 / 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 .

[0059] The upper limits stated above are preferred.

[0060] 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.

[0061] 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

[0062] 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.

[0063] 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.

[0064] 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 resin. a Values ​​above 12.65 mean that the RED value is greater than 1 and the material is insoluble in styrene.

[0065] In one embodiment, the ethylenically unsaturated resin (i) has an R of greater than 12.65, preferably greater than 12.70, or greater than 12.80 relative to styrene. a It is characterized by a value.

[0066] If the Hansen Solubility Parameter values ​​of the individual substances are known, the Hansen Solubility Parameter value of the mixture can be calculated. Each parameter is calculated individually by adding the parameters of both substances according to their 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.

[0067] The curable resin composition preferably comprises the ethylenically unsaturated resin (i) in an amount of 15 to 85 wt %, more preferably 15 to 75 wt %, and most preferably 20 to 60 wt %, based on the total weight of the curable resin composition.

[0068] The curable resin composition preferably contains 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 %, for example, 20 to 80 wt %, even more preferably 25 to 80 wt %, and most preferably 40 to 80 wt %, for example, 50 to 75 wt %, based on the total weight of the curable resin composition.

[0069] In addition to the reactive diluent (ii), the curable resin composition 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-butylcyclohexyl acrylate, dimethyl itaconate (DMI), methyl cinnamate, ethyl cinnamate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, isobornyl acrylate, isobornyl methacrylate, 1,4-butanediol dimethacrylate (1,4-BDDMA), triethylene glycol dimethyl acrylate, trimethylolpropane trimethacrylate, and acetoacetoxyethyl methacrylate (AAEMA). 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.

[0070] To achieve high solubilization of the ethylenically unsaturated polyester resin (i), the reactive diluent (ii) is present in an amount of at least 0.5 wt.%, preferably at least 5 wt.%, more 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 the further reactive diluent.

[0071] 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 particularly 30:70 to 70:30 or 30:70 to 60:40.

[0072] In one embodiment, the ethylenically unsaturated polyester resin composition does not include an additional reactive diluent.

[0073] In one embodiment, the composite glass fiber material comprises the thermosetting polymer in an amount in the range of 10 to 90 wt%, preferably 15 to 85 wt%, more preferably 20 to 80 wt%, based on the total weight of the material.

[0074] Composite glass fiber materials contain glass fibers. The fibers enhance the mechanical properties and mechanical stability of the composite glass fiber material. Glass fibers are materials consisting of many ultrafine glass fibers and are formed by extruding thin strands of glass, such as silica-based glass. It has been found that using N-vinyloxazolidinone of formula (I) as a reactive diluent to obtain composite glass fiber materials increases the impact strength of these materials compared to known reactive diluents such as styrene.

[0075] For every 100 parts by weight of the ethylenically unsaturated resin (i) and the total amount of reactive diluent, preferably 10 to 220 parts by weight of glass fiber, more preferably 15 to 200 parts by weight of glass fiber, and most preferably 25 to 180 parts by weight of glass fiber are present. This range of glass fiber amounts allows for the achievement of useful physical properties of the composite glass fiber material.

[0076] In addition to glass fibers, the material may include fibers selected from carbon fibers, ceramic fibers, aramid fibers, boron fibers, basalt fibers, steel fibers, natural fibers, and / or nylon fibers.

[0077] For every 100 parts by weight of ethylenically unsaturated resin (i) and the total amount of reactive diluent, there are preferably 10 to 220 parts by weight of fiber, more preferably 15 to 200 parts by weight of fiber, and most preferably 25 to 180 parts by weight of fiber.

[0078] 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.

[0079] Suitable glass fibers typically have a length in the range of 1 mm to 1 m, preferably 2 mm to 1 m, and most preferably 3 mm to 1 m. Suitable glass fibers typically have a diameter in the range of 6 to 25 μm, preferably 10 to 25 μm, and most preferably 12 to 25 μm.

[0080] 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.

[0081] The compositions may contain additional ingredients, including stabilizers; inhibitors; pigments and dyes; fillers; thickeners; 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. 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® NOR® 356, Tinuvin® 765, and Tinuvin® 770, imines, sulfonamides, oximes, hydroxylamines, urea derivatives, phosphorus-containing compounds, sulfur-containing compounds such as phenothiazines, tetraazaannulenes (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.

[0083] Suitably, the ethylenically unsaturated 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 %, based on the total amount of the ethylenically unsaturated resin composition.

[0084] 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.

[0085] 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.

[0086] 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 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.

[0087] Thickeners increase the viscosity of unsaturated polyester resin compositions, reducing their tackiness and thus improving the handling of the compositions. Examples of thickeners are isocyanates such as 4,4'-methylene-diphenyl-diisocyanate, magnesium oxide (MgO), calcium hydroxide (Ca(OH)2), and calcium oxide (CaO).

[0088] 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®).

[0089] 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.

[0090] 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.

[0091] Toughening agents are used to improve the damage tolerance of cured ethylenically unsaturated polyester resin compositions. In particular, they can reduce crack formation under prolonged static and dynamic loads while improving elongation at break and impact strength. Suitable toughening agents include rubbers, 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 resin (i), and block copolymers other than the ethylenically unsaturated resin (i). The toughening agent may be present in the resin composition in an amount of 2 to 40 wt %, preferably 3 to 30 wt %, and more preferably 5 to 25 wt %, based on the total amount of the curable resin composition.

[0092] 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).

[0093] 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.

[0094] 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 styrene, 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.

[0095] 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.

[0096] A hardener is a compound or mixture of compounds that accelerates the hardening process.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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.

[0101] 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.

[0102] Suitable azo compounds include 2,2'-azobis(2-isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), and 1,1'-azobis(hexahydrobenzo-nitrile).

[0103] Suitable CC labile compounds include 2,3-dimethyl-2,3-diphenylbutane and 3,4-dimethyl-3,4-diphenylhexane.

[0104] 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.

[0105] In one embodiment, the curable resin composition does not include a curing agent.

[0106] The composite glass fiber material can be obtained from the curable resin composition by curing. 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.

[0107] 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.

[0108] 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.

[0109] 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.

[0110] 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.

[0111] The composite glass fiber material according to the present invention can 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 coatings, in-mold coatings and paints, putties, cast products, buttons, porous materials (e.g., foams, membranes, etc.), fiber manufacturing, tool manufacturing, electronic devices, flame retardant thermoset resins, profiles, containers, molded articles, polymer parts, long field lamp carriers, oil sinks, sheets / plates, railway interior parts, bonding, and pipes.

[0112] The present invention further provides a method for manufacturing a glass fiber comprising: (i) an ethylenically unsaturated resin; (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 independently selected from a hydrogen atom and an organic moiety containing 1 to 10 carbon atoms; contacting the curable resin composition comprising the reactive diluent (ii) is present in an amount of at least 0.5 wt. %, based on the total amount of reactive diluent (ii) and further reactive diluents; curing the curable resin composition to form a thermoset polymer, thereby obtaining a composite glass fiber material; The present invention provides a method for producing a composite glass fiber material, comprising:

[0113] It is understood that the above discussion and embodiments relating to the composite glass fiber material of the present invention apply equally to the method of the present invention.

[0114] The term "contacting" as used herein should be interpreted broadly and includes all means of resulting in a material in which glass fibers are present in a matrix of cured resin composition, including mixing glass fibers with a curable resin composition, impregnating a knitted or woven fabric of glass fibers with a curable resin composition, impregnating glass fiber roving with a curable resin composition, and the like.

[0115] The present invention further provides N-vinyloxazolidinones of formula (I): [ka] (In the formula, 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. in a method for obtaining a composite glass fiber material.

[0116] In one embodiment, (i) an ethylenically unsaturated resin as defined above; (ii) a reactive diluent which is an N-vinyloxazolidinone of formula (I) defined above; wherein the reactive diluent (ii) is present in an amount of at least 0.5 wt %, based on the total amount of the reactive diluent (ii) and the further reactive diluent, is used to manufacture a composite glass fiber material.

[0117] It is understood that the above discussion and embodiments relating to the composite glass fiber material of the present invention apply equally to the use of the present invention.

[0118] The present invention further comprises: (i) an ethylenically unsaturated resin; and (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 independently selected from a hydrogen atom and an organic moiety containing 1 to 10 carbon atoms. A curable resin composition comprising: the reactive diluent (ii) is present in an amount of at least 0.5 wt. %, based on the total amount of reactive diluent (ii) and further reactive diluents; A curable resin composition is provided, wherein the ethylenically unsaturated resin (i) is selected from ethylenically unsaturated polyester resins, vinyl ester resins, and combinations thereof.

[0119] It is understood that the above discussion and embodiments relating to the composite glass fiber materials of the present invention apply equally to the curable resin compositions of the present invention.

[0120] The curable compositions described above may be used as matrix polymers for reinforced and non-reinforced thermosetting resins in SMC technology (sheet molding composite 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 manufacturing, filament winding, rotational molding, laminating, vacuum pressure impregnation (VPI process), pultrusion, casting, bundling, bonding, coatings such as gel coating, top coating, spray coating, filling, in-mold coating, knife coating, dipping, dripping, painting, wire coating (enamel coating), fiber spinning, and foaming.

[0121] The present invention is further illustrated in the examples that follow. [Example]

[0122] The ethylenically unsaturated resin was obtained as described below. The following table provides a summary of the reactants, stabilizers and initiators used in the examples.

[0123] [Table 1]

[0124] [Table 2]

[0125] [Table 3]

[0126] A-1. Production of ethylenically unsaturated polyester resin The ethylenically unsaturated polyester resins were obtained by reacting the compounds specified in the table below in the molar ratios specified: The ethylenically unsaturated polyester resins were prepared by melt polycondensation.

[0127] 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.

[0128] At the start of the reaction, 500 ppmw of hydroquinone was added to the entire reaction mixture as a free radical scavenger. 400 ppmw of Fascat 4100 (butylstannoic acid) was added to the entire reaction mixture as an esterification catalyst at the start of the reaction. The reaction was carried out in a four-neck flask (2 L) equipped with a stirrer and thermometer as described above under a nitrogen atmosphere (99.999% nitrogen).

[0129] Heating from room temperature to 80°C was carried out under program control as quickly as possible while avoiding overheating. At 80°C, the ring opening of maleic anhydride occurred, resulting in an exothermic reaction. The heating was switched off to prevent overheating of the melt. After the exothermic reaction was complete, the temperature rose further to 110°C. The reaction temperature was then increased by 10°C per hour to 190°C. The initial formation of water was observed between 135 and 145°C. The reaction was stopped when the unsaturated polyester melt reached 190°C. The polymer was cooled and left overnight in solid form.

[0130] The polymer was then reheated to 190°C to melt. The reaction was continued until the required acid number was achieved. For polyesters using phthalic anhydride, the melt was cooled to 155°C and stirred for 1 hour. The unsaturated polyester was then poured into shallow rectangular molds where it cooled and solidified.

[0131] 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.

[0132] The hydroxyl number is the amount of potassium hydroxide (KOH) in milligrams required to neutralize the acetic acid incorporated during the acetylation of one gram of a chemical containing free hydroxyl groups. The hydroxyl number indicates the number of free hydroxyl groups per gram of compound and was determined by titration according to DIN EN ISO 4692-2.

[0133] The ethylene group density refers to the molar ratio of ethylene groups per kg of resin and was determined by nuclear magnetic resonance (NMR) spectroscopy.

[0134] 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.

[0135] In the first heating cycle, the pan was first cooled to 0°C and then heated to 100°C at 10 K / min. In the second heating cycle, the pan was cooled to -80°C and then heated to 100°C at 10 K / min. g was determined from the second cycle.

[0136] Mass average molecular weight M w and number average molecular weight M nwas 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:

[0137] 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.

[0138] 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.

[0139] The following table shows the composition and properties of the unsaturated resins.

[0140] [Table 4]

[0141] [Table 5]

[0142] B. Prediction of Hansen Solubility Parameters for Unsaturated Resins The Hansen parameters of unsaturated 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.

[0143] [Table 6]

[0144] C. Curable resin composition C-1. Production of curable resin composition The solidified ethylenically unsaturated resin obtained according to Section A-1 was crushed using a hammer. If the unsaturated resin did not solidify at room temperature, it was cooled with liquid nitrogen and then crushed at low temperature. The crushed resin was used to prepare a curable resin composition according to the following table. First, the unsaturated resin particles were weighed into a glass bottle. Then, a reactive diluent or a reactive diluent mixture according to the following table was added. To suppress gelation, Tinuvin® 765 (1,000 ppmw) was added to the resin along with VMOX® as a reactive diluent. The bottle was placed on a roller mixer and mixed for several days. The curable resin composition was considered ready to use when the unsaturated resin particles were completely dissolved in the reactive diluent or reactive diluent mixture.

[0145] C-2. Soluble The bottles obtained according to Section C-1 were placed on a roller mixer and mixed for several days. Bottles obtained according to Section C-1 in which the curable resin composition contained cyclohexyl vinyl ether were then placed in a 60°C oven for 3 hours. The solubility of the ethylenically unsaturated resin particles in the reactive diluent was checked visually at regular intervals.

[0146] The results of the solubility tests are shown in the table below.

[0147] [Table 7]

[0148] [Table 8]

[0149] [Table 9]

[0150] [Table 10]

[0151] The cloudy solution indicates that dissolution is not complete. It is clear that VMOX® allows complete solubilization of the unsaturated resins investigated.

[0152] C-3.Surface adhesion and curing properties The surfaces of unsaturated polyester thermosets made from resins containing acrylates as reactive diluents can become tacky after curing in air. The tackiness of the thermoset surface is induced by oxygen inhibition during the radical curing process. The tackiness of thermoset polymers obtained from curable resin compositions containing tert-butyl acrylate or VMOX® was compared.

[0153] Unsaturated polyester resin 1-2 was dissolved in 60 wt% tert-butyl acrylate or VMOX® as shown in the table below to obtain curable resin compositions. 1 wt% Trigonox 21 was added to each of the curable resin compositions. The curable resin compositions were cured using a cure profile of 60°C for 2 hours, then 80°C for 2 hours, then 100°C for 2 hours. The results are shown in the table below.

[0154] [Table 11]

[0155] Both curable resin compositions can be cured to produce thermoset polymers with smooth surfaces, and the thermoset polymers obtained from the curable resin compositions containing VMOX® do not exhibit surface tackiness. This effect is achieved in the resin compositions containing VMOX® despite the presence of Tinuvin® 765, which can act as an inhibitor in the curing process.

[0156] Furthermore, the curing characteristics of unsaturated resins 1-1 to 1-4 in 1,4-butanediol diacrylate were investigated. Each unsaturated resin was dissolved in 60 wt% 1,4-butanediol diacrylate to obtain a curable resin composition. 1 wt% Trigonox 21 was added to each curable resin composition. The curable resin compositions were cured using a curing profile of 60°C for 2 hours, then 80°C for 2 hours, and then 100°C for 2 hours to obtain a thermosetting polymer.

[0157] Each resin using 1,4-butanediol diacrylate as a reactive diluent was found to foam during thermal curing in air. The resulting thermoset polymers had uneven, rough surfaces and were of insufficient quality for further investigation.

[0158] C-4. Glass transition temperature T g The glass transition temperatures of thermosetting polymers obtained from curable resin compositions containing different reactive diluents were compared according to the table below. The curable resin compositions each contained 1 wt% tert-butyl peroxybenzoate. The curable resin compositions were cured using a curing profile of A) 2 hours at 60°C, then 2 hours at 80°C, then 2 hours at 100°C; or B) 1 hour at 80°C, then 1 hour at 160°C to obtain thermosetting polymers. The results are shown in the table below.

[0159] [Table 12]

[0160] It is clear that VMOX® as a reactive diluent increases the glass transition temperature of the resulting thermoset polymers from Resins 1-3 by at least 40°C more than when 1,4-butanediol dimethacrylate or triethylene glycol dimethacrylate are used as the reactive diluent. Furthermore, it is clear that high concentrations of VMOX® as a reactive diluent result in higher glass transition temperatures that cannot be achieved with 4-methylstyrene or divinylbenzene due to solubility issues at relatively high concentrations of the reactive diluent.

[0161] C-5.Low temperature curing The properties of the thermosetting polymers obtained by low-temperature curing of the curable resin compositions using VMOX® or 1,4-butanediol dimethacrylate (1,4-BDDMA) as reactive diluents were compared according to the table below. Acetoacetoxyethyl methacrylate (AAEMA) and dimethyl itaconate (DMI) were used as additional reactive diluents. Prior to curing, 1.5 wt.% of a cobalt-based accelerator (BUEFA® ​​- Accelerator Co1) was added to the curable resin compositions and homogenized using a roller mixer for 1 hour. Then, 1.5 wt.% of methyl ethyl ketone peroxide (MEKP) was added to the curable resin compositions using a wooden spatula and mixed. The curable resin compositions were processed immediately after adding the MEKP.

[0162] Approximately 10 g of resin was placed on a mold (dimensions: 10 cm x 10 cm). The resin was uniformly distributed and then covered with biaxial glass fiber cloth (831 g / m 2 A layer of fiberglass fabric (0° / 90°, part number S14EB490-00831-01300-474000, manufactured by Saertex, dimensions: 10 cm x 10 cm) was placed into the resin. After removing all air bubbles using a wooden spatula, 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 at 90° to each other and approximately 30 g of resin composition.

[0163] Cold curing was carried out at a temperature of about 25° C. The tack of the resulting samples was controlled by touch at regular intervals of about 6 hours during the daytime. The results are shown in the table below.

[0164] [Table 13]

[0165] It is clear that the low temperature cure of the resin containing VMOX® as the reactive diluent proceeds faster than the cure of the resin containing 1,4-BDDMA as the reactive diluent.

[0166] C-6. Curable resin composition containing additional reactive diluent According to item A-1, fumaric acid and 2-methyl-2-propylpropane-1,3-diol (molar ratio 1.0:1.02, δ p =5.702MPa 1 / 2 ) to obtain an ethylenically unsaturated polyester resin. The unsaturated resin was cooled with liquid nitrogen and then crushed at a low temperature. The crushed unsaturated resin was used to prepare a curable resin composition. First, the unsaturated resin 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.

[0167] 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.

[0168] The results of the solubility tests are shown in the table below. To determine the Hansen solubility parameters of mixtures of styrene and VMOX®, the mass fractions were converted to volume fractions by using the following formula:

number

[0169] Using the Hansen solubility parameters of the mixture of styrene and VMOX® compared to the Hansen solubility parameters of the unsaturated polyester resin, R was calculated according to the following formula: a The values ​​were determined:

number

[0170] [Table 14]

[0171] [Table 15]

[0172] It is clear that the presence of even small amounts of VMOX® improves the solubility of the polyester resins investigated compared to pure styrene.

[0173] C-7. Tensile Test The curable resin composition prepared according to C-1 was used to prepare specimens for tensile testing. Prior to specimen preparation, 0.3 wt% of Irganox® 819 and 1 wt% of tert-butyl peroxybenzoate (TBPB) were added to the curable resin composition. The specimens for tensile testing were prepared by vacuum infusion.

[0174] For this purpose, a glass plate (28 x 17 cm) was covered with sealing tape and two parallel, opposing spiral hoses were attached along its length. The spiral hoses were pressed firmly against the sealing tape to prevent any possible leakage. A vacuum hose was inserted into each spiral hose to a depth of approximately 3 cm. The vacuum hoses were then covered with a small piece of sealing tape and sealed. This construction constituted the framework for the vacuum infusion.

[0175] Then, six layers of glass fiber cloth (24 × 13 cm, 831 g / m 2 , 0° / 90°, product number S14EB490-00831-01300-474000, manufactured by Saertex) was placed on a glass plate. The layers were alternately arranged at a 45° angle. A release film (64 g / m², release layer) of the same size as the fabric layer was placed on the glass plate. 2 A 150 cm (plain weave) sheet (product number 190181-150-5) and a resin bleed layer (INFUPLEX with ISONET, 145 cm wide, product number 3903426) were applied. A release film provided a smooth surface for the specimen. The resin bleed layer consisted of a two-layer system: a perforated flow layer and a flow-assist layer. This system allowed for resin permeability, allowing uniform and complete wetting of the laminate through the finely divided structure. Finally, the mold was tightly sealed with vacuum foil.

[0176] The curable resin composition was degassed using a vacuum pump before the infusion process. For infusion, a shorter vacuum hose was placed in the resin, and a longer vacuum hose was connected to the vacuum circuit. The setup consisted of a vacuum pump, a desiccator, and an intervening cold trap. The desiccator contained a collection container for excess fluid resin. The plates needed to be fabricated in the dark to avoid the possibility of premature curing. After the plates were finally laminated, the vacuum hose was immediately compressed with a clamp and then cut. The plates were then photochemically cured for 20 minutes in a xenon tester (Original Hanau, serial number 7011, overall dimensions 700 × 470 × 350 mm, power supply: 220 V / 50 Hz / 1500 W). The laminate was carefully removed from the glass plate and post-cured in a convection oven at 80 °C for 1 hour and 160 °C for 1 hour to obtain the thermoset resin. The specimen was cut into four equally sized specimens with a length of 200 mm and a width of 25 mm using a CNC machine.

[0177] To evaluate the mechanical properties, tensile tests were performed on a Zwick Z200 according to DIN EN ISO 527-4. Four equally sized specimens were used for each test. The width and thickness of all specimens were measured with calipers and recorded for each test. Each thermoset resin obtained from the curable resin composition was tested at room temperature (approximately 20°C), 100°C, and 120°C. For measurements at 100°C and 120°C, a climate chamber was connected to the Zwick Z200 and preheated for at least 1 hour. Before the start of the measurement, the specimens were heated and clamped in the Zwick Z200 for 10 minutes. When clamping the specimens, it is important to avoid shear forces. This means that the specimens must be mounted perpendicular to the clamping jaws. The draft generated by the oven fan must be switched off during the measurement. The Zwick Z200 loads the specimens until final failure. The tensile modulus (E t ), tensile strength (σ m ), and elongation at maximum tensile stress (ε m ) was recorded.

[0178] The measurement results are shown in the table below.

[0179] [Table 16]

[0180] All thermosetting resins obtained from the curable resin compositions exhibited satisfactory mechanical properties. In particular, the use of dimethyl itaconate (DMI) as an additional reactive diluent was found to improve mechanical properties compared to VMOX® alone. Without wishing to be bound by theory, DMI can function as a copolymerization partner for VMOX in addition to the unsaturated polyester resins 1-3. Therefore, radical copolymerization can occur between the unsaturated polyester resin and VMOX, and between DMI and VMOX. Copolymerization between VMOX and DMI increases the likelihood of reactive diluent crosslinks forming between unsaturated polyester resin chains, thereby enhancing the crosslink density and uniformity of the network.

[0181] D. Composite glass fiber materials D-1.Dynamic mechanical analysis Glass fiber reinforced test specimens were prepared using the resin composition of item C-1, 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.

[0182] 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 removed from its mold and cut into 10 x 50 mm specimens using a table saw.

[0183] 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 value of the tan δ curve (T) corresponds to the glass transition temperature T g was considered to constitute

[0184] [Table 17]

[0185] Glass transition temperature T of composite glass fiber material g are shown in the table below.

[0186] [Table 18]

[0187] D-2. Impact test Composite specimens were prepared using resin compositions derived from unsaturated resins 1-3 according to Section C-1, containing either 60% by weight of VMOX® or styrene. Tinuvin® 765 (1,000 ppmw) was added as a stabilizer to suppress gelation. Chopped glass fibers (HP-GS3, HP-Textiles) with a fiber length of 3 mm and a diameter of 13 μm (length-to-diameter ratio: 231) or talc (fine powder Mg3[(OH)2|SiO4] from Merck) were used. 10The densities of both materials were approximately the same, i.e., 2.4–2.8 kg / cm. 3 It was.

[0188] A cobalt-based accelerator (BUEFA-Accelerator® Co 1, Buefa Chemicals) was added to 400 g of each curable resin composition using a round-hole stirrer at approximately 750 rpm. Methyl ethyl ketone peroxide (MEKP, United Initiators) was then added to the curable resin composition using a wooden spatula and mixed. For the curable resin composition containing styrene, 1.25 wt. % of the cobalt-based accelerator and MEKP were used. For the curable resin composition containing VMOX®, 0.5 wt. % of the cobalt-based accelerator and MEKP were used.

[0189] Finally, 10 wt. % of the aforementioned chopped glass fiber or talc was added to the curable resin composition and mixed at 750 rpm for 120 seconds. After mixing, each curable resin composition was divided into three metal dishes (100 cm diameter) so that the resin was evenly distributed and filled each dish to a height of 10–12 mm. A desiccator was used at 10 mbar pressure to remove air bubbles from the composition during low-temperature curing at room temperature. After the low-temperature curing of the composition was completed (approximately 1 hour), the test specimens were heat-cured at 80°C for 8 hours.

[0190] The cured composite specimens were removed from the metal pan and cut to size using a CNC cutting machine, yielding test bars of approximately 8 mm width, 4 mm height, and 80 mm length for each composite.

[0191] Impact tests were performed using a ZwickRoell impact testing machine. The impact pendulum had an energy of 0.5 joules. Prior to the impact test, the width and height of each test rod were determined using a vernier caliper. The specimen was positioned in the impact testing machine so that the impact pendulum would strike the center of one of its narrow sides, i.e., one of its faces with an area that can be defined as length x height.

[0192] Impact strength was determined using the following formula:

number

[0193] [Table 19]

[0194] [Table 20]

[0195] [Table 21]

[0196] [Table 22]

[0197] [Table 23]

[0198] [Table 24]

[0199] It is clear that glass fiber-based composite materials have higher impact strength than talc-based composite materials. Furthermore, it is clear that N-vinyloxazolidinone of formula (I)-based composite glass fiber materials have higher impact strength than styrene-based composite glass fiber materials. Furthermore, N-vinyloxazolidinone of formula (I)-based composite glass fiber materials require less initiator for low temperature curing than styrene.

Claims

1. 1. A composite glass fiber material comprising a thermosetting polymer, the thermosetting polymer comprising: (i) an ethylenically unsaturated resin; and (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; obtained from a curable resin composition comprising A composite glass fiber material, wherein the reactive diluent (ii) is present in an amount of at least 0.5 wt. %, based on the total amount of the reactive diluent (ii) and any further reactive diluents.

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 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 material of claim 1 which is an alkyl group.

3. 3. The material according to claim 1 or 2, 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 material according to any one of claims 1 to 3, wherein the ethylenically unsaturated resin (i) is selected from ethylenically unsaturated polyester resins, vinyl ester resins, and urethane (meth)acrylate resins.

5. 5. The material according to any one of claims 1 to 4, wherein 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 from 15:85 to 85:15, more preferably from 25:75 to 75:25, especially from 30:70 to 70:30 or from 30:70 to 60:

40.

6. The ethylenically unsaturated resin (i) has the following characteristics: - number average molecular weight in the range of 500 to 10,000 g / mol, determined by gel permeation chromatography; an acid number in the range of 5 to 80 mg KOH / g, determined by titration according to DIN EN ISO 2114; and - a hydroxyl number in the range of 5 to 80 mg KOH / g, determined by titration according to DIN EN ISO 4692-2; The material according to any one of claims 1 to 5, having at least one of:

7. The ethylenically unsaturated resin (i) is in the range of 0.5 to 10 mol / kg, particularly in the range of: 2.0 to 9.0 mol / kg when the ethylenically unsaturated resin (i) is an ethylenically unsaturated polyester resin; - 1.0 to 4.5 mol / kg when the ethylenically unsaturated resin (i) is a vinyl ester resin; 1.0 to 5.0 mol / kg when the ethylenically unsaturated resin (i) is a urethane (meth)acrylate resin; and having an ethylene group density of 7. The material according to any one of claims 1 to 6, wherein the ethylene group density means the molar percentage of ethylene groups per kg of resin as determined by nuclear magnetic resonance spectroscopy.

8. 8. The material of any one of claims 1 to 7, wherein the curable resin composition preferably comprises the ethylenically unsaturated resin (i) in an amount of 15 to 85 wt%, more preferably 15 to 75 wt%, and most preferably 20 to 60 wt%, based on the total weight of the curable resin composition.

9. 9. The material according to any one of claims 1 to 8, wherein the curable resin composition comprises one or more further reactive diluents selected from styrene and styrene derivatives, epoxides, vinyl ethers, acrylates, and methacrylates.

10. A material according to any one of the preceding claims, comprising glass fibres having a length to diameter ratio in the range of 20 to 100,000, preferably 50 to 100,000.

11. The material according to any one of claims 1 to 10, comprising the thermosetting polymer in an amount ranging from 10 to 90% by weight, based on the total weight of the material.

12. Glass fiber, (i) an ethylenically unsaturated resin; (ii) a reactive diluent which is an N-vinyloxazolidinone of formula (I) 【Chemistry 2】 (In the formula, 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; contacting the curable resin composition comprising the reactive diluent (ii) is present in an amount of at least 0.5 wt. %, based on the total amount of reactive diluent (ii) and any further reactive diluents; curing the curable resin composition to form a thermoset polymer, thereby obtaining a composite glass fiber material; 1. A method for producing a composite glass fiber material, comprising:

13. N-vinyloxazolidinone of formula (I) 【Chemistry 3】 (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. in a method for obtaining a composite glass fiber material.

14. The curable resin composition comprises: (i) an ethylenically unsaturated resin; (ii) a reactive diluent which is an N-vinyloxazolidinone of formula (I); wherein the reactive diluent (ii) is present in an amount of at least 0.5 wt. % relative to the total amount of reactive diluent (ii) and further reactive diluents, 14. The use according to claim 13 for producing a composite glass fiber material.

15. (i) an ethylenically unsaturated resin; and (ii) a reactive diluent which is an N-vinyloxazolidinone of formula (I) 【Chemistry 4】 (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. A curable resin composition comprising: the reactive diluent (ii) is present in an amount of at least 0.5 wt. %, based on the total amount of the reactive diluent (ii) and any further reactive diluents; The curable resin composition, wherein the ethylenically unsaturated resin (i) is selected from an ethylenically unsaturated polyester resin, a vinyl ester resin, and combinations thereof.

16. 16. The curable resin composition of claim 15, wherein the curable resin composition comprises the ethylenically unsaturated resin (i) in an amount of 15 to 85 wt%, more preferably 15 to 75 wt%, and most preferably 20 to 60 wt%, based on the total weight of the curable resin composition.

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