A glycosyl sorbitol epoxy resin flame retardant polymer and preparation method thereof

Abstract

The present invention discloses a glycosyl sorbitol epoxy resin flame retardant polymer and a preparation method thereof. The glycosyl sorbitol epoxy resin polymer is a binary polymer consisting of a first unit and a second unit, or a ternary polymer consisting of a first unit, a second unit, and a third unit; the first unit is unit A, the second unit is unit B or unit C, and the third unit is unit D; in the binary polymer, the first unit and the second unit are bonded by a C-N bond; in the ternary polymer, the first unit and the second unit are bonded by a C-N bond, and the third unit and the second unit are also bonded by a C-N bond. The epoxy resin material synthesis steps of the present invention are simple, the raw material sources are wide, and the product has a high degree of greenness; the prepared epoxy resin polymer has excellent heat resistance and flame retardant effect, and has great advantages over existing petroleum-based epoxy resins.

Description

Technical Field

[0001] The present invention relates to the field of polymer materials, and in particular to a glycosyl sorbitol epoxy resin flame retardant polymer and a preparation method thereof. Background Art

[0002] In recent years, with the rise of environmental awareness, waste disposal, and the shortage of non-renewable resources, the demand for natural products in industry has continued to increase. There is growing interest in preparing bio-based polymers from renewable resources to replace petroleum-based polymers. Bio-based polymers are produced from natural resources such as sugars, polysaccharides, vegetable oils, lignin, lipids, and other monomers. Due to their high sustainability, low cost, strong competitiveness, and high performance and greenness, they can partially or even completely replace petroleum-based polymers and have attracted great interest in both research and industrial applications. In particular, sorbitol has great potential to replace petroleum-based thermosetting resins due to its versatility, renewability, and biodegradability.

[0003] Sorbitol, also known as D-sorbitol, is a monosaccharide alcohol with five hydroxyl groups. It is an odorless, sweet white crystalline powder with a wide range of applications in medicine, food, cosmetics, and other fields. It is environmentally friendly and has excellent plasticizing properties. In addition to being used as a sugar substitute in foods, a plasticizer in polymers, polyester resins, and polyurethane materials, sorbitol can also be used in the manufacture of biocomposites. Sorbitol reacts with epichlorohydrin to produce a novel bio-based aliphatic epoxy resin, sorbitol glycidyl ether. Compared to traditional epoxy resins, sorbitol glycidyl ether has low viscosity, low shrinkage, and strong compatibility with other resins, facilitating mixing and shaping during polymer preparation. It can also be used in conjunction with various resin systems such as polyurethanes and acrylates, exhibiting excellent composite properties.

[0004] Thomazine et al. [Physical properties of gelatin films plasticized by blends of glycerol and sorbitol. Journal of Food Science, 2005, 70(3):E172-E176.] studied the effects of sorbitol and glycerol blends on the physical properties of gelatin films. The study found that increasing the amount of sorbitol increased the film's flexibility, but its barrier properties decreased. Therefore, sorbitol can be used to improve the properties of the original resin system, enhancing its toughness and biodegradability.

[0005] Sorbitol is also used in the field of nanocomposites. Schmitt et al. [Preparation and Characterization of Plasticized Starch / Halloysite Porous Nanocomposites Possibly Suitable for Biomedical Applications [J]. Journal of Applied Polymer Science, 2015, doi.org / 10.1002 / app.41341] prepared porous nanocomposites using mixed raw materials such as sorbitol, glycerol and plasticized starch. The study showed that the composite material has the advantages of large pore size, high porosity and good mechanical properties, and has broad application prospects in the fields of drug delivery and bone cement.

[0006] Regarding sorbitol polyesters, Barrett et al. [One-Step Syntheses of Photocurable Polyesters Based on a Renewable Resource[J]. Macromolecules 2010, 43, 9660-9667] found that itaconic acid, as a dibasic acid, could be used in the synthesis of a photocurable polyester with sorbitol, resulting in a high-biobased content. Therefore, sorbitol, due to its advantages such as being green, convenient, economical, and having good mechanical properties, has become an important raw material in the green polyester industry.

[0007] Currently, global annual sorbitol consumption is around 2 million tons, providing ample raw material for the research and preparation of sorbitol-based polymers. Sorbitol's unique polyhydroxy structure can impart a higher crosslink density to the polymer network. Polymers with higher crosslink density tend to possess greater resistance to thermal degradation, further broadening their application range. Considering the development trend of bio-based polymers, sorbitol-based biomass thermosetting resins (especially high-performance types) will have broad prospects for development. Summary of the Invention

[0008] Purpose of the invention: The technical problem to be solved by the present invention is to provide two types of glycosyl sorbitol epoxy resin polymers in response to the shortcomings of the existing technology.

[0009] The technical problem that the present invention also aims to solve is to provide a method for preparing the above-mentioned glycosyl sorbitol epoxy resin flame retardant polymer.

[0010] In order to solve the above-mentioned first technical problem, the present invention discloses a glycosyl sorbitol epoxy resin polymer, which is a binary polymer composed of a first unit and a second unit, or a ternary polymer composed of a first unit, a second unit, and a third unit; the first unit is unit A, the second unit is unit B or unit C, and the third unit is unit D; in the binary polymer, the first unit and the second unit are bonded via a CN bond; in the ternary polymer, the first unit and the second unit are bonded via a CN bond, and the third unit and the second unit are also bonded via a CN bond;

[0011]

[0012] Wherein, the binary polymer has repeating structural units represented by formulas I-1 and I-2, and the ternary polymer has repeating structural units represented by formulas II-1 and II-2;

[0013]

[0014] In formula I-1 and formula I-2, m and n represent the molar equivalents of epoxy functional groups and NH in the raw materials, respectively, maintaining m / n = 0.8 to 1.5:1;

[0015]

[0016] In formula II-1 and formula II-2, m, n, and k represent the molar equivalent of epoxy functional groups, NH, and epoxy functional groups in the raw materials, respectively, maintaining (m+k) / n=0.8~1.5:1, and n:k=3~30:1.

[0017] In order to solve the second technical problem mentioned above, the present invention discloses a method for preparing the above-mentioned glycosyl sorbitol epoxy resin flame retardant polymer.

[0018] The binary polymer is prepared by mixing sorbitol glycidyl ether GluEP with an aromatic sulfone diamine curing agent, heating the mixture to completely melt the mixture, uniformly injecting the mixture into a mold, and then continuing to heat the mixture to cure the mixture, thereby obtaining glycosyl sorbitol epoxy resin polymers I-1 and I-2.

[0019] The ternary polymer is prepared by mixing sorbitol glycidyl ether GluEP, DOPO-based epoxy resin monomer EP-DOPO and aromatic sulfone diamine curing agent, heating to completely melt, uniformly injecting into a mold, and then continuing to heat and cure to obtain glycosyl sorbitol epoxy resin flame retardant polymers II-1 and II-2;

[0020] The sorbitol glycidyl ether GluEP is a commercially available chemical. The epoxy value is 0.6 mol / 100 g and its infrared spectrum is shown in FIG. Figure 1 shown.

[0021] The structure of the DOPO-based epoxy resin monomer EP-DOPO is as follows, and it can be produced by existing technology (CAS: 102486-95-3). The infrared properties of the monomer are as follows: Figure 2 As shown;

[0022]

[0023] Wherein, the aromatic sulfone diamine curing agent is 4,4'-diaminodiphenyl sulfone and 3,3'-diaminodiphenyl sulfone;

[0024]

[0025] In the binary polymer, the molar ratio of the epoxy groups in the sorbitol glycidyl ether to the NH in the aromatic sulfone diamine curing agent is 0.8 to 1.5:1; in the ternary polymer, the molar ratio of the sum of the epoxy groups in the bio-based sorbitol glycidyl ether GluEP and the DOPO-based epoxy resin monomer EP-DOPO to the NH in the aromatic sulfone diamine curing agent is 0.8 to 1.5:1, preferably 1:1.

[0026] The molar ratio of the aromatic sulfone diamine curing agent to the DOPO-based epoxy resin monomer EP-DOPO is 3 to 30:1, preferably 6:1.

[0027] In the ternary polymer, the feeding amount and ratio of bio-based sorbitol glycidyl ether GluEP, DOPO-based epoxy resin monomer EP-DOPO and aromatic sulfone diamine curing agent are determined by the mass of phosphorus element in all the resin materials, wherein the mass content of phosphorus is 0.11% to 1.1% of the total mass of the polymer of bio-based sorbitol glycidyl ether GluEP, DOPO-based epoxy resin monomer EP-DOPO and aromatic sulfone diamine curing agent, preferably 0.55% to 0.59%.

[0028] The melting temperature is 90-110°C, preferably 95-105°C.

[0029] The curing temperature is 150-230°C, preferably 180-210°C, and more preferably 180-195-210°C in a stepwise manner.

[0030] The curing time is 2 to 5 hours, preferably 3 to 5 hours, and more preferably 4 hours.

[0031] The curing is performed at 175-185° C. for 1.5-2.5 h, 190-200° C. for 0.5-1.5 h, and 205-215° C. for 0.5-1.5 h, preferably at 180° C. for 2 h, 195° C. for 1 h, and 210° C. for 1 h.

[0032] Beneficial effects: Compared with the prior art, the present invention has the following advantages:

[0033] (1) In the present invention, a thermosetting polymer material with a novel structure is constructed based on sorbitol glycidyl ether. The obtained polymer material has excellent thermal stability and excellent flame retardant properties.

[0034] (2) The sorbitol of the present invention can be produced by fermentation bioproduction, using microorganisms (such as actinomycetes) to ferment renewable plant substrates (such as corn or sugar beets). This method has the advantages of low cost, sustainability, and environmental protection. Therefore, sorbitol has a high biological added value and good biosafety.

[0035] (3) The epoxy resin material in the present invention has simple synthesis steps, a wide range of raw material sources, a high degree of greenness of the product, and is biodegradable. The prepared bio-based epoxy resin has a novel structure, excellent heat resistance, and excellent flame retardant properties, and has greater advantages than existing petroleum-based epoxy resins. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, and the above and / or other advantages of the present invention will become more apparent.

[0037] Figure 1 This is the Fourier infrared spectrum of sorbitol glycidyl ether.

[0038] Figure 2 This is the Fourier infrared spectrum of the epoxy resin monomer EP-DOPO.

[0039] Figure 3 This is the Fourier transform infrared spectrum of the epoxy resin polymer in Example 1.

[0040] Figure 4 This is the Fourier transform infrared spectrum of the epoxy resin polymer in Example 2.

[0041] Figure 5 This is the Fourier transform infrared spectrum of the epoxy resin polymer in Example 3.

[0042] Figure 6 This is the Fourier transform infrared spectrum of the epoxy resin polymer in Example 4.

[0043] Figure 7 This is the TGA diagram of the epoxy resin polymer in Example 1.

[0044] Figure 8 This is the TGA diagram of the epoxy resin polymer of Example 2.

[0045] Figure 9This is the TGA diagram of the epoxy resin polymer of Example 3.

[0046] Figure 10 This is the TGA diagram of the epoxy resin polymer of Example 4.

[0047] Figure 11 The DSC graphs of the epoxy resin polymers of Examples 1 to 4 are shown.

[0048] Figure 12 These are combustion test diagrams of the epoxy resin polymers of Examples 1 to 4. DETAILED DESCRIPTION

[0049] The experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials are commercially available unless otherwise specified.

[0050] Example 1 (GluEP-44DDS)

[0051] Bio-based sorbitol glycidyl ether GluEP (9.83 g, epoxy value 0.6 mol / 100 g) was weighed into the reaction flask, and the curing agent 4,4'-diaminodiphenyl sulfone (3.66 g, 14.74 mmol) was measured and added at 25 ° C under air atmosphere. The temperature was raised to 95-105 ° C and mixed evenly. After removing bubbles, the above materials were evenly poured on the metal template. The material was moved into the curing box and slowly heated. The temperature was cured for 4 h at a rate of 180 ° C for 2 h to 195 ° C / 1 h to 210 ° C / 1 h. After completion, it was naturally cooled to obtain an epoxy resin polymer material.

[0052] Analysis of the thermogravimetric data under nitrogen, such as Figure 7 As shown, the initial decomposition temperature is 289.0℃, T d30 The decomposition temperature is 403.8℃, the maximum decomposition temperature is 425.1℃, and the residual carbon content is 26.5% at 750℃. The obtained material has good heat resistance.

[0053] The differential scanning calorimetry test data analysis, such as Figure 11 As shown, the phase transition temperature of the polymer is 136.5°C, indicating that the obtained material has a wide operating temperature.

[0054] In the vertical combustion test of resin, Figure 12 -a, the polymer is ignited by an open flame and the combustion is observed after 10 seconds. In this experiment, after the fire source is removed, the flame of the polymer slowly spreads upward and extinguishes after burning for 60 seconds, indicating that the resin has relatively general flame retardant properties.

[0055] By judging its infrared data, such as Figure 3 As shown, the infrared peaks of ethylene oxide (853.9 and 909.8 cm-1 ) disappears, indicating that the epoxy groups and amine groups of the epoxy resin have been completely polymerized.

[0056] Polymer infrared data attribute: 1508,1590cm -1 Belongs to the characteristic peak of benzene ring; 1105cm -1 The carbon-oxygen characteristic peak of 2°ROH generated by epoxy ring opening; 3407 cm -1 The strong broad absorption peak at is the peak formed by the appearance of -OH group after the ring opening of ethylene oxide.

[0057] Example 2 (GluEP-0.55P-44DDS)

[0058] Bio-based sorbitol glycidyl ether GluEP (9.83 g, epoxy value 0.6 mol / 100 g) was weighed into the reaction flask, and the curing agent 4,4'-diaminodiphenyl sulfone (4.00 g, 16.11 mmol) and EP-DOPO (1.17 g, 2.68 mmol) were measured and added at 25 ° C under air atmosphere. The temperature was raised to 95-105 ° C and mixed evenly. After removing bubbles, the above materials were evenly poured on the metal template. The material was moved into the curing box, slowly heated, and cured for 4 h at a program of 180 ° C / 2 h ~ 195 ° C / 1 h ~ 210 ° C / 1 h, and then naturally cooled to obtain an epoxy resin polymer material.

[0059] Analysis of the thermogravimetric data under nitrogen, such as Figure 8 As shown, the initial decomposition temperature is 282.9℃, T d30 The decomposition temperature is 390.3℃, the maximum decomposition temperature is 404.0℃, and the residual carbon content is 26.9% at 750℃. The obtained material has good heat resistance.

[0060] The differential scanning calorimetry test data analysis, such as Figure 11 As shown, the phase transition temperature of the polymer is 141.4 °C, indicating that the obtained material has a wide operating temperature.

[0061] In the vertical combustion test of resin, Figure 12 -b, the polymer was ignited by an open flame and the combustion was observed after 10 seconds. In this experiment, after the fire source was removed, the flame of the polymer began to shrink and went out after 9 seconds, indicating that the resin has good flame retardant properties.

[0062] By judging its infrared data, such as Figure 4 As shown, the infrared peaks of ethylene oxide (853.9 and 909.8 cm -1 ) disappears, indicating that the epoxy groups and amine groups of the epoxy resin have been completely polymerized. The epoxy infrared peaks of EP-DOPO (859 and 918 cm -1) also disappeared, indicating that EP-DOOPO participated in the reaction.

[0063] Polymer infrared data attribute: 1510, 1592 cm -1 Belongs to the characteristic peak of benzene ring; 1103cm -1 The carbon-oxygen characteristic peak of 2°ROH generated by epoxy ring opening; 3413 cm -1 The strong broad absorption peak at is the peak formed by the appearance of -OH group after the ring opening of ethylene oxide.

[0064] Example 3 (GluEP-33DDS)

[0065] Bio-based sorbitol glycidyl ether GluEP (9.83 g, epoxy value 0.6 mol / 100 g) was weighed into the reaction flask, and the curing agent 3,3'-diaminodiphenyl sulfone (3.66 g, 14.74 mmol) was measured and added at 25°C under an air atmosphere. The temperature was raised to 95-105°C and mixed evenly. After removing bubbles, the above materials were evenly poured on a metal template. The material was moved into a curing box, slowly heated, and cured for 4 hours at a program of 180°C / 2h~195°C / 1h~210°C / 1h. The material was naturally cooled to obtain an epoxy resin polymer material.

[0066] Analysis of the thermogravimetric data under nitrogen, such as Figure 9 As shown, the initial decomposition temperature is 292.5℃, T d30 The decomposition temperature is 400.8℃, the maximum decomposition temperature is 426.8℃, and the residual carbon content is 23.8% at 750℃. The obtained material has good heat resistance.

[0067] The differential scanning calorimetry test data analysis, such as Figure 11 As shown, the phase transition temperature of the polymer is 123.5°C, indicating that the obtained material has a wide operating temperature.

[0068] In the vertical combustion test of resin, Figure 12 -c, the polymer was ignited by an open flame and the combustion was observed after 10 seconds. In this experiment, after the fire source was removed, the flame of the polymer slowly spread upward and extinguished after burning for 49 seconds, indicating that the resin has relatively general flame retardant properties.

[0069] By judging its infrared data, such as Figure 5 As shown, the infrared peaks of ethylene oxide (853.9 and 909.8 cm -1 ) disappears, indicating that the epoxy groups and amine groups of the epoxy resin have been completely polymerized.

[0070] Polymer infrared data attribute: 1491, 1616 cm -1 Belongs to the characteristic peak of benzene ring; 1109cm -1The carbon-oxygen characteristic peak of 2°ROH generated by epoxy ring opening; 3413 cm -1 The strong broad absorption peak at is the peak formed by the appearance of -OH group after the ring opening of ethylene oxide.

[0071] Example 4 (GluEP-0.55P-33DDS)

[0072] Bio-based sorbitol glycidyl ether GluEP (9.83 g, epoxy value 0.6 mol / 100 g) was weighed into the reaction flask, and the curing agent 3,3'-diaminodiphenyl sulfone (4.00 g, 16.11 mmol) and EP-DOPO (1.17 g, 2.68 mmol) were measured and added at 25 ° C under air atmosphere. The temperature was raised to 95-105 ° C and mixed evenly. After removing bubbles, the above materials were evenly poured on the metal template. The material was moved into the curing box, the temperature was slowly raised, and the curing was performed for 4 h at a program of 180 ° C / 2 h ~ 195 ° C / 1 h ~ 210 ° C / 1 h. The epoxy resin polymer material was naturally cooled to obtain.

[0073] Analysis of the thermogravimetric data under nitrogen, such as Figure 10 As shown, the initial decomposition temperature is 302.3℃, T d30 The decomposition temperature is 405.0℃, the maximum decomposition temperature is 426.2℃, and the residual carbon content is 26.0% at 750℃. The obtained material has good heat resistance.

[0074] The differential scanning calorimetry test data analysis, such as Figure 11 As shown, the phase transition temperature of the polymer is 133.2°C, indicating that the obtained material has a wide working temperature range.

[0075] In the vertical combustion test of resin, Figure 12 -d, the polymer was ignited by an open flame and the combustion was observed after 10 seconds. In this experiment, after the fire source was removed, the flame of the polymer began to shrink and went out after 11 seconds, indicating that the resin has good flame retardant properties.

[0076] By judging its infrared data, such as Figure 6 As shown, the infrared peaks of ethylene oxide (853.9 and 909.8 cm -1 ) disappears, indicating that the epoxy groups and amine groups of the epoxy resin have been completely polymerized. The epoxy infrared peaks of EP-DOPO (859 and 918 cm -1 ) disappeared, indicating that EP-DOOPO participated in the reaction.

[0077] Polymer infrared data attribute: 1492,1599cm -1 Belongs to the characteristic peak of benzene ring; 1108cm -1The carbon-oxygen characteristic peak of 2°ROH generated by epoxy ring opening; 3415 cm -1 The strong broad absorption peak at is the peak formed by the appearance of -OH group after the ring opening of ethylene oxide.

[0078] The present invention provides a flame-retardant glycosyl sorbitol epoxy resin polymer and a method for preparing the same. Numerous methods and approaches exist for implementing this technical solution. The foregoing merely represents a preferred embodiment of the present invention. It should be noted that those skilled in the art may make various improvements and modifications without departing from the principles of the present invention, and such improvements and modifications are also within the scope of protection of the present invention. Any components not specified in this embodiment may be implemented using existing technologies.

Claims

1. A glycosyl sorbitol epoxy resin polymer, characterized in that: A binary polymer consisting of a first unit and a second unit, or a ternary polymer consisting of a first unit, a second unit, and a third unit; the first unit is unit A, the second unit is unit B or unit C, and the third unit is unit D; in the binary polymer, the first unit and the second unit are bonded via a CN bond; In the terpolymer, the first unit and the second unit are bonded via a CN bond, and the third unit and the second unit are also bonded via a CN bond; 2. The polymer according to claim 1, characterized in that The binary polymer has a repeating structural unit represented by formula I-1 or formula I-2, and the ternary polymer has a repeating structural unit represented by formula II-1 or formula II-2; In formula I-1 and formula I-2, m and n represent the molar equivalents of epoxy functional groups and NH in the raw materials, respectively, and m / n = 0.8 to 1.5:1; In formula II-1 and formula II-2, m / k and n represent the molar equivalents of epoxy functional groups and NH in the raw materials, respectively, and (m+k) / n=0.8~1.5:

1.

3. The method for preparing the glycosyl sorbitol epoxy resin polymer according to claim 1 or 2, characterized in that: The sorbitol glycidyl ether and the aromatic sulfone diamine curing agent are mixed, melted, injection molded, and cured to obtain a binary polymer.

4. The method for preparing the glycosyl sorbitol epoxy resin polymer according to claim 1 or 2, characterized in that: Sorbitol glycidyl ether, DOPO-based epoxy resin monomer EP-DOPO and aromatic sulfone diamine curing agent are mixed, melted, injection molded, and cured to obtain a terpolymer; 5. The preparation method according to claim 3, characterized in that: In the binary polymer, the molar ratio of the epoxy group in the sorbitol glycidyl ether to the NH in the aromatic sulfone diamine curing agent is 0.8 to 1.5:

1.

6. The preparation method according to claim 4, characterized in that: In the terpolymer, the molar ratio of the sum of the epoxy groups in the sorbitol glycidyl ether and the DOPO-based epoxy resin monomer EP-DOPO to the NH in the aromatic sulfone diamine curing agent is 0.8 to 1.5:

1.

7. The preparation method according to claim 6, characterized in that: The molar ratio of the aromatic sulfone diamine curing agent to the DOPO-based epoxy resin monomer EP-DOPO is 3 to 30:

1.

8. The preparation method according to claim 3 or 4, characterized in that The aromatic sulfone diamine curing agent is 4,4'-diaminodiphenyl sulfone and 3,3'-diaminodiphenyl sulfone.

9. The preparation method according to claim 3 or 4, characterized in that: The melting temperature is 90-110°C.

10. The preparation method according to claim 3 or 4, characterized in that: The melting temperature is 95-105°C.

11. The preparation method according to claim 3 or 4, characterized in that: The curing temperature is 150-230°C.

12. The preparation method according to claim 3 or 4, characterized in that: The curing temperature is 180-210°C.

13. The preparation method according to claim 3 or 4, characterized in that: The curing time is 2 to 5 hours.

14. The preparation method according to claim 3 or 4, characterized in that: The curing time is 3 to 5 hours.

15. The preparation method according to claim 3 or 4, characterized in that: The curing time is 4 hours.

16. The preparation method according to claim 3 or 4, characterized in that: The curing is performed at 175-185° C. for 1.5-2.5 hours, at 190-200° C. for 0.5-1.5 hours, and at 205-215° C. for 0.5-1.5 hours.

17. The preparation method according to claim 3 or 4, characterized in that: The curing is performed at 180° C. for 2 hours, at 195° C. for 1 hour, and at 210° C. for 1 hour.

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