A phenoxy resin containing triazine structure with ultraviolet shielding function and a preparation method thereof

Abstract

This invention belongs to the field of thermoplastic polymer materials and discloses a triazine-containing phenoxy resin with ultraviolet shielding function and its preparation method. The compound has the general chemical formula shown below, where m and n are the number of repeating units, m+n=50~360, m≥0, n≥1, R1 is a phenyl, cycloalkyl, or ester group, R2 is a polyphenyl, polycycloalkyl, or naphthyl group, and R3, R4, and R5 are aromatic ether groups containing a triazine structure. R3, R4, and R5 are all linked to the structure via ether groups. This phenoxy resin exhibits excellent ultraviolet shielding, mechanical strength, and thermal stability, making it particularly suitable for applications in engineering plastics, composite materials, adhesives, coatings, and other fields.

Description

Technical Field

[0001] This invention belongs to the field of thermoplastic polymer materials, specifically relating to a triazine-containing phenoxy resin with ultraviolet shielding function and its preparation method. Background Technology

[0002] Phenoxy resin, a thermoplastic polymer material possessing strength, toughness, adhesion, and easy processability, perfectly fills the performance gap between ordinary plastics and thermosetting epoxy resins, playing a crucial role in specific high-end manufacturing fields such as aerospace and high-end electronic packaging. However, due to its similar structure to epoxy resin, phenoxy resin is highly susceptible to UV-induced degradation in the natural environment. Small-molecule UV absorbers are typically added during its processing to improve weather resistance. These absorbers protect the substrate by converting high-energy UV radiation into harmless heat or long-wavelength light energy. However, this approach has significant drawbacks: small-molecule absorbers are prone to migration during processing and use, leading not only to a gradual decline in the material's protective performance but also, more alarmingly, the leaked absorbers exhibit high persistence and bioaccumulation, potentially causing ecotoxicity and endocrine disruption risks. Summary of the Invention

[0003] The purpose of this invention is to propose a triazine-containing phenoxy resin with ultraviolet shielding function and its preparation method.

[0004] The objective of this invention is achieved through the following technical solution:

[0005] A triazine-containing phenoxy resin with ultraviolet shielding function, the compound having the following formula: The general chemical structural formula shown is:

[0006] Mode ,

[0007] Where m and n are the number of repeating units, m+n=50~360, m≥0, n≥1, R1 is a phenyl or cycloalkyl or ester group, R2 is a polyphenyl or polycycloalkyl or naphthyl group, R3, R4, and R5 are aromatic ether groups containing a triazine structure, and R3, R4, and R5 are all connected to the formula via ether groups. In the structure.

[0008] Preferably, R1 is one or more of the following structures:

[0009] .

[0010] Preferably, R2 is one or more of the following structures:

[0011] .

[0012] Preferably, R3 is one or more of the following structures (-C2H5 and -C4H9 are both straight-chain alkane groups):

[0013]

[0014] Preferably, R4 and R5 are one or more of the following structures:

[0015] .

[0016] Preferably, R4 and R5 contain -C2H5, -C4H9, and -C6H 13 -C8H 17 All are straight-chain alkane groups.

[0017] The preparation method of the triazine-containing phenoxy resin with ultraviolet shielding function includes the following steps: Add, by molar ratio, 21 mol of epoxy prepolymer, 0–10.3 mol of bisphenol monomer, 0.1–10.4 mol of triazine monomer containing bifunctional groups, and solvent to a reactor; heat to 100–130°C and stir to dissolve for 30–60 min; heat to 140–200°C, add catalyst in batches, react for 30–120 min, add 0.2 mol ± 0.1 mol of triazine monomer containing monofunctional groups for end-capping, continue reaction for 10–60 min, remove solvent under vacuum, and granulate by screw extrusion to obtain phenoxy resin; the reaction is carried out under a protective atmosphere, and the monofunctional and bifunctional groups are both phenolic hydroxyl groups.

[0018] Preferably, the epoxy prepolymer is one or a mixture of two or more of the following: bisphenol A glycidyl ether, bisphenol F glycidyl ether, bisphenol S glycidyl ether, hydrogenated bisphenol A glycidyl ether, tetrabromobisphenol A glycidyl ether, hexafluorobisphenol A glycidyl ether, tetramethylbiphenyl diglycidyl ether, biphenyl diglycidyl ether, resorcinol diglycidyl ether, diglycidyl phthalate, tetrahydrophthalic acid diglycidyl ester, and hexahydrophthalic acid diglycidyl ester.

[0019] Preferably, the bisphenol structural monomer is one or a mixture of two or more of the following: bisphenol A, bisphenol F, bisphenol S, hydrogenated bisphenol A, tetrabromobisphenol A, hexafluorobisphenol A, tetramethylbiphenyl, biphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, bisphenol AP, 4,4'-(1-methylethylidene)bis(2-methylphenol), 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylanthraquinone oxide, bisphenol fluorene, 1,5-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene.

[0020] Preferably, the triazine monomer containing a bifunctional group is one or a mixture of two or more of 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine and 2,4-bis[2-hydroxy-4-(2-ethylhexyloxy)phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine.

[0021] Preferably, the monofunctional triazine monomer is one or a mixture of two or more of the following: 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxy-phenol, 2,4-bis(4-biphenyl)-6-(2,4-dihydroxy)phenyl-1,3,5-triazine, 2-[2-hydroxy-4-[3-(2-ethylhexyloxy)-2-hydroxypropoxy]phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-methoxyphenol, and 2,4-bis(2,4-dimethylyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine.

[0022] Preferably, the catalyst is one or a mixture of two or more of the following: methyltriphenylphosphine chloride, methyltriphenylphosphine bromide, ethyltriphenylphosphine chloride, ethyltriphenylphosphine bromide, propyltriphenylphosphine chloride, propyltriphenylphosphine bromide, butyltriphenylphosphine chloride, butyltriphenylphosphine bromide, (methoxymethyl)triphenylphosphine chloride, (methoxymethyl)triphenylphosphine bromide, 4-carboxybutyltriphenylphosphine chloride, 4-carboxybutyltriphenylphosphine bromide, benzyltriphenylphosphine chloride, and benzyltriphenylphosphine bromide; the amount added is 1 / 190 to 1 / 1610 of the molar ratio with the epoxy prepolymer.

[0023] Preferably, the solvent is one or a mixture of two or more of ethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether acetate, propylene glycol n-propyl ether, and propylene glycol monobutyl ether.

[0024] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0025] (1) UV shielding performance: This phenoxy resin has excellent UV resistance and can almost completely shield ultraviolet rays in the wavelength range of 200~400nm, making it suitable for applications that require UV protection.

[0026] (2) Mechanical and thermal stability: Phenoxy resin has excellent mechanical properties, with a tensile strength of 74~86MPa and a 5% thermal decomposition temperature of 385~439℃, indicating that it has high strength and good thermal stability. Attached Figure Description

[0027] Figure 1 The infrared spectra of phenoxy resin are shown in (a) for Example 1 and (b) for Control Example 1.

[0028] Figure 2 The images show the UV-Vis absorption spectra of phenoxy resin. (a) Sample from Example 1, (b) Sample from Control Example 1. Detailed Implementation

[0029] The present invention will be further described below with reference to specific embodiments, but the content of the present invention is not limited to the following embodiments.

[0030] Example 1

[0031] Bisphenol A glycidyl ether (NPEL-128) containing 21 mol of epoxy groups, 10.3 mol of bisphenol A, 0.1 mol of 2,4-di(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 1000 g of propylene glycol methyl ether propionate, and 500 g of propylene glycol monobutyl ether were added to a horizontal polymerization reactor. The temperature was raised to 110 °C, and the mixture was stirred and dissolved for 45 min. The temperature was then raised to 150 °C, and 40 g of butyltriphenylphosphine chloride was added in four batches. The reaction was carried out for 100 min, and then 0.2 mol of 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-hexyloxy-phenol was added for end-capping. The reaction was continued for another 45 min. The solvent was removed under vacuum, and the mixture was granulated by screw extrusion to obtain phenoxy resin with the following structural formula:

[0032]

[0033] Using polystyrene (PS) as a reference, the relative molecular weight and distribution of phenoxy resin were determined using an ACQUITY APC ultra-high performance polymer chromatograph. The tensile properties of the resin were tested according to GB / T 1040.1-2025 (Determination of tensile properties of plastics—Part 1: General). The glass transition temperature of the resin was tested according to GB / T 19466.1-2004 (Differential scanning calorimetry (DSC) of plastics—Part 1: General). The decomposition temperature of the resin was tested according to GB / T 33047.1-2025 (Thermogravimetric analysis (TG) of plastics—Part 1: General). The transmittance was tested using a UV-Vis spectrophotometer in the wavelength range of 200–800 nm, according to the standard test method for haze and transmittance of transparent plastics in ASTM D1003-21, with a resin thickness of 1.0 mm.

[0034] Example 2

[0035] The difference between this embodiment and Example 1 is that 10.4 mol of 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine is used instead of 10.3 mol of bisphenol A and 0.1 mol of 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine. The resulting phenoxy resin has the following structural formula:

[0036]

[0037] The testing method is the same as in Example 1.

[0038] Example 3

[0039] 21 mol of bisphenol F glycidyl ether (NPEF-170) containing epoxy groups, 5.2 mol of tetrabromobisphenol A, 5.2 mol of 2,4-bis[2-hydroxy-4-(2-ethylhexyloxy)phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine, and 2000 g of propylene glycol methyl ether acetate were added to a horizontal polymerization reactor. The temperature was raised to 120 °C, and the mixture was stirred and dissolved for 30 min. The temperature was then raised to 140 °C, and 30 g of (methoxymethyl)triphenylphosphine bromide was added in three batches. The reaction was carried out for 120 min, and then 0.2 mol of 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-methoxyphenol was added for end-capping. The reaction was continued for 60 min. The solvent was removed under vacuum, and the mixture was granulated by screw extrusion to obtain phenoxy resin with the following structural formula:

[0040]

[0041] The testing method is the same as in Example 1.

[0042] Example 4

[0043] Hydrogenated bisphenol A glycidyl ether (ADEKA EP-4080E) containing 21 mol of epoxy groups, 7.8 mol of bisphenol S, 2.6 mol of 2,4-di(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 300 g of ethylene glycol butyl ether acetate, and 200 g of propylene glycol monobutyl ether were added to a horizontal polymerization reactor. The temperature was raised to 100℃, and the mixture was stirred and dissolved for 50 min. The temperature was then raised to 170℃, and 15 g of ethyltriphenylphosphine bromide was added in three batches. The reaction was carried out for 50 min, and then 0.2 mol of 2,4-bis(2,4-xylyl)-6-(2-hydroxy-4-n-octyloxophenyl)-1,3,5-triazine was added for end-capping. The reaction was continued for another 30 min. The solvent was removed under vacuum, and the mixture was granulated by screw extrusion to obtain phenoxy resin with the following structural formula:

[0044]

[0045] The testing method is the same as in Example 1.

[0046] Example 5

[0047] 21 mol of tetramethylbiphenyl diglycidyl ether (jER™ YX4000) containing epoxy groups, 2.6 mol of biphenyl, 7.8 mol of 2,4-bis[2-hydroxy-4-(2-ethylhexyloxy)phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine, and 2000 g of propylene glycol ethyl ether acetate were added to a horizontal polymerization reactor. The temperature was raised to 130 °C, and the mixture was stirred and dissolved for 60 min. The temperature was then raised to 190 °C, and 6 g of benzyltriphenylphosphine bromide was added in two batches. The reaction was carried out for 30 min, and then 0.2 mol of 2,4-bis(4-biphenyl)-6-(2,4-dihydroxy)phenyl-1,3,5-triazine was added for end-capping. The reaction was continued for 10 min. The solvent was removed under vacuum, and the mixture was granulated by screw extrusion to obtain phenoxy resin with the following structural formula:

[0048]

[0049] The testing method is the same as in Example 1.

[0050] Compare with Example 1

[0051] The difference between this comparative example and Example 1 is that 10.5 mol of bisphenol A was used instead of 10.3 mol of bisphenol A, 0.1 mol of 2,4-di(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, and 0.2 mol of 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxy-phenol. The structural formula of the obtained phenoxy resin is as follows:

[0052]

[0053] The testing method is the same as in Example 1.

[0054] Compare with Example 2

[0055] The difference between this comparative example and Example 3 is that 10.5 mol of tetrabromobisphenol A was used instead of 5.2 mol of tetrabromobisphenol A, 5.2 mol of 2,4-bis[2-hydroxy-4-(2-ethylhexyloxy)phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine, and 0.2 mol of 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-methoxyphenol. The resulting phenoxy resin has the following structural formula:

[0056]

[0057] The testing method is the same as in Example 1.

[0058] Compare with Example 3

[0059] The difference between this comparative example and Example 4 is that 10.5 mol of bisphenol S was used instead of 7.8 mol of bisphenol S, 2.6 mol of 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, and 0.2 mol of 2,4-bis(2,4-xylyl)-6-(2-hydroxy-4-n-octyloxophenyl)-1,3,5-triazine. The resulting phenoxy resin has the following structural formula:

[0060]

[0061] The testing method is the same as in Example 1.

[0062] Compare with Example 4

[0063] The difference between this comparative example and Example 5 is that 10.5 mol of biphenyl hydroquinone was used instead of 2.6 mol of biphenyl hydroquinone, 7.8 mol of 2,4-bis[2-hydroxy-4-(2-ethylhexyloxy)phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine, and 0.2 mol of 2,4-bis(4-biphenyl)-6-(2,4-dihydroxy)phenyl-1,3,5-triazine. The resulting phenoxy resin has the following structural formula:

[0064]

[0065] The testing method is the same as in Example 1.

[0066] Table 1 Comparison of Phenoxy Resin Performance

[0067]

[0068] Figure 1 , 2 The results in Table 1 show that, compared with Control Example 1, Examples 1 and 2, Example 3, Example 4, and Example 5, the phenoxy resin prepared by the present invention has excellent shielding effect (almost completely shielding ultraviolet light) in the ultraviolet wavelength range (200~400nm); the phenoxy resin prepared by the present invention has excellent mechanical properties (tensile strength reaches 74~86MPa) and thermal stability (5% thermal decomposition temperature is 385~439℃), and the thermal stability is 6~17℃ higher than that of the control example.

[0069] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A triazine-containing phenoxy resin with ultraviolet shielding function, characterized in that, The compound has the following formula: The general chemical structural formula shown is: Mode , Where m and n are the number of repeating units, m+n=50~360, m≥0, n≥1, R1 is a phenyl or cycloalkyl or ester group, R2 is a polyphenyl or polycycloalkyl or naphthyl group, R3, R4, and R5 are aromatic ether groups containing a triazine structure, and R3, R4, and R5 are all connected to the formula via ether groups. In the structure.

2. The triazine-containing phenoxy resin with ultraviolet shielding function according to claim 1, characterized in that, R1 can be one or more of the following structures: 。 3. The triazine-containing phenoxy resin with ultraviolet shielding function according to claim 1, characterized in that, R2 can be one or more of the following structures: 。 4. The triazine-containing phenoxy resin with ultraviolet shielding function according to claim 1, characterized in that, R3 can be one or more of the following structures (-C2H5 and -C4H9 are both straight-chain alkane groups):

5. The triazine-containing phenoxy resin with ultraviolet shielding function according to any one of claims 1 to 4, characterized in that, R4 and R5 are one or more of the following structures: 。 6. The triazine-containing phenoxy resin with ultraviolet shielding function according to claim 5, characterized in that, -C2H5, -C4H9, -C6H in R4 and R5 13 -C8H 17 All are straight-chain alkane groups.

7. The method for preparing the triazine-containing phenoxy resin with ultraviolet shielding function according to any one of claims 1 to 6, characterized in that, The steps are as follows: Add 21 mol of epoxy prepolymer containing epoxy groups, 0–10.3 mol of bisphenol monomer, 0.1–10.4 mol of triazine monomer containing bifunctional groups, and solvent to a reactor using a molar ratio. Heat to 100–130°C and stir to dissolve for 30–60 min. Heat to 140–200°C and add catalyst in batches. React for 30–120 min. Add 0.2 mol ± 0.1 mol of triazine monomer containing monofunctional groups for end-capping. Continue reaction for 10–60 min. Remove solvent under vacuum and granulate by screw extrusion to obtain phenoxy resin. The reaction is carried out under a protective atmosphere, and the monofunctional and bifunctional groups are all phenolic hydroxyl groups.

8. The preparation method according to claim 7, characterized in that, The epoxy prepolymer is one or a mixture of two or more of the following: bisphenol A glycidyl ether, bisphenol F glycidyl ether, bisphenol S glycidyl ether, hydrogenated bisphenol A glycidyl ether, tetrabromobisphenol A glycidyl ether, hexafluorobisphenol A glycidyl ether, tetramethylbiphenyl diglycidyl ether, biphenyl diglycidyl ether, resorcinol diglycidyl ether, diglycidyl phthalate, tetrahydrophthalic acid diglycidyl ester, and hexahydrophthalic acid diglycidyl ester.

9. The preparation method according to claim 7, characterized in that, The bisphenol monomers are one or a mixture of two or more of the following: bisphenol A, bisphenol F, bisphenol S, hydrogenated bisphenol A, tetrabromobisphenol A, hexafluorobisphenol A, tetramethylbiphenyl, biphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, bisphenol AP, 4,4'-(1-methylethylidene)bis(2-methylphenol), 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylanthraquinone oxide, bisphenol fluorene, 1,5-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene. The bifunctional triazine monomer is one or a mixture of two or more of 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-bisbutoxyphenyl)-1,3,5-triazine and 2,4-bis[2-hydroxy-4-(2-ethylhexyloxy)phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine. The monofunctional triazine monomer is one or a mixture of two or more of the following: 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxy-phenol, 2,4-bis(4-biphenyl)-6-(2,4-dihydroxy)phenyl-1,3,5-triazine, 2-[2-hydroxy-4-[3-(2-ethylhexyloxy)-2-hydroxypropoxy]phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-methoxyphenol, and 2,4-bis(2,4-dimethylyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine.

10. The preparation method according to claim 7, characterized in that, The catalyst is one or a mixture of two or more of the following: methyltriphenylphosphine chloride, methyltriphenylphosphine bromide, ethyltriphenylphosphine chloride, ethyltriphenylphosphine bromide, propyltriphenylphosphine chloride, propyltriphenylphosphine bromide, butyltriphenylphosphine chloride, butyltriphenylphosphine bromide, (methoxymethyl)triphenylphosphine chloride, (methoxymethyl)triphenylphosphine bromide, 4-carboxybutyltriphenylphosphine chloride, 4-carboxybutyltriphenylphosphine bromide, benzyltriphenylphosphine chloride, and benzyltriphenylphosphine bromide; the amount added is 1 / 190 to 1 / 1610 of the molar ratio with the epoxy prepolymer. The solvent is one or a mixture of two or more of the following: ethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether acetate, propylene glycol n-propyl ether, and propylene glycol monobutyl ether.

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