WO2018095356A1 - Fluorine-titanium hybrid flame retardant and method for fabrication thereof - Google Patents

Abstract

The present invention relates to a fluorine-titanium hybrid flame retardant and method for fabrication thereof, characterized in that: the molecular structural formula is: (I), wherein R is CH₃CH₂CH₂CH₂ ^- or (II); the reaction conditions for said fluorine-titanium hybrid flame retardant to fabricate a flame-retardant epoxy resin are simple and mild, and yield is high; product purification is simple and is readily made commercially viable; the fabricated epoxy resin has high transparency and guarantees excellent heat resistance and mechanical properties; the invention has good flame retardancy performance and a broad range of applications, and satisfies environmental protection requirements.

Description

Fluorine-titanium hybrid flame retardant and preparation method and application thereof Technical field

The invention belongs to the technical field of organic flame retardant, and particularly relates to a fluorine titanium hybrid flame retardant and a preparation method and application thereof.

Background technique

Epoxy resins include both epoxy-based oligomers and epoxy-containing low molecular compounds. The epoxy resin has good mechanical properties, strong adhesion, small cure shrinkage, excellent electrical insulation performance, good processability, stability and chemical resistance. Epoxy resin is widely used in the fields of water conservancy, transportation, machinery, electronics, home appliances, automobiles and aerospace as a resin matrix for adhesives, coatings and composite materials. With the increasing requirements for the reliability and safety of epoxy resins in these fields, heat resistance and flame retardancy have become more and more important. A widely used method for improving the flame retardancy of epoxy resins is to add a flame retardant.

Fluoropolymer, which has many excellent properties such as heat resistance, corrosion resistance, hydrophobic oil, electrical insulation, low friction coefficient, low toxicity, non-combustibility, etc. Large, the heat resistance of the modified epoxy resin is improved, on the other hand, in the high temperature environment, the intermolecular rearrangement can be increased, and a highly stable carbon layer is deposited on the surface to protect the internal polymer crosslinked network. effect. The large volume of trifluoromethyl (CF ₃ ) introduced in the epoxy resin can further hinder the movement of the molecular segment of the polymer, while the CF ₃ group can be enriched on the surface of the epoxy resin, making the ring of high surface energy Oxygen resin has excellent water and oil resistance. Dai Lizong et al. (a fluorine-containing self-lubricating fabric coating material and its preparation method, publication number CN103410003A) synthesized a fluorine-containing epoxy resin coating with a fluorine-containing monomer and epichlorohydrin, and cured with an acid anhydride curing agent. And adding reactive diluent, a green epoxy curing system is obtained.

Titanium is an effective flame retardant element, which can effectively reduce the flame propagation rate. In the 1970s, the flame retardant of titanium flame retardant on wool fiber was studied. Dai Lizong et al. (a silicon-phosphorus titanium three-element synergistic flame-retardant epoxy resin and its preparation method, 201610200021.7) using phosphorus-containing organotitanium hybrid silsesquioxane modified epoxy resin to introduce titanium metal into silicon phosphorus In the synergistic system, the flame retardant effect is improved.

The existing technical solutions for the flame retardant modification of epoxy resin by using fluorine element combined with titanium element have the defects of complex formula and harsh reaction conditions. The present invention is directed to such a deficiency, and adopts two resource-rich, inexpensive and readily available raw materials for mild organic synthesis of the reaction conditions, and the epoxy resin is modified, and the addition of a small amount not only maintains the transparency and mechanical properties of the resin, but also Greatly improved its heat resistance and flame retardancy.

Summary of the invention

It is an object of the present invention to provide a fluorine-titanium hybrid flame retardant.

Another object of the present invention is to provide a process for producing the above fluorine-titanium hybrid flame retardant.

It is still another object of the present invention to provide the use of the above-described fluorine-titanium hybrid flame retardant.

The technical solution of the present invention is as follows:

A fluorine-titanium hybrid flame retardant whose molecular structural formula is:

Wherein R is CH ₃ CH ₂ CH ₂ CH ₂ - or

The preparation method of the above fluorine-titanium hybrid flame retardant is as follows:

details as follows:

Weigh hexafluorobisphenol A in an organic solvent, dissolve and stir at 20 to 50 ° C, then add butyl titanate dropwise, and react at room temperature for 8 to 24 hours after the completion of the addition. Finally, the solvent is removed and purified to obtain a fluorotitanium hybridization resistance. The fuel agent; the molar ratio of the above hexafluorobisphenol A to butyl titanate is 1:4.0 to 5.0, and the volume ratio of hexafluorobisphenol A to the organic solvent is 1 g:30 to 50.

The above fluorine-titanium hybrid flame retardant is used in the preparation of a flame-retardant epoxy resin.

In a preferred embodiment of the present invention, specifically, weigh a certain amount of epoxy resin in a reaction vessel, raise the temperature to 60-110 ° C, and then add the fluorine-titanium hybrid flame retardant according to a ratio of 0.1-50 wt%. The agent is stirred until it is in a uniform transparent state, and then the curing agent is added to the stoichiometric ratio until completely dissolved and uniformly mixed, and then poured into a mold, and a temperature-increasing program is set for curing to obtain the flame-retardant epoxy resin.

Further preferably, the epoxy resin is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin or a novolac type epoxy resin.

Further preferably, the curing agent is an amine curing agent, an acid anhydride curing agent, a boron amine complex or an amine group-containing boric acid ester curing agent.

Further preferably, the heating program is: 120 ° C for 5 h, then at 140 ° C for 2 h, and finally at 180 ° C for 2 h.

The beneficial effects of the invention are:

The flame retardant epoxy resin prepared by using the fluorine-titanium hybrid flame retardant of the invention has simple and mild reaction conditions and high yield; the product purification operation is simple and easy to industrialize; the prepared epoxy resin has high transparency and ensures excellent resistance. Under the premise of thermal and mechanical properties, the flame retardant effect is good, the scope of application is wide, and it meets environmental protection requirements.

DRAWINGS

1 is a synthetic route diagram of a fluorine-titanium hybrid flame retardant synthesized in Example 1.

2 is an infrared spectrum of a fluorine-titanium hybrid flame retardant synthesized in Example 1.

3 is a nuclear magnetic resonance spectrum of a fluorine-titanium hybrid flame retardant synthesized in Example 1.

detailed description

The technical solutions of the present invention will be further described and described below with reference to the accompanying drawings.

Example 1

0.336 g (0.001 mol) of hexafluorobisphenol A and 20 mL of ethanol were added to a 50 mL three-neck round bottom flask, and 0.17 g (0.0005 mol) of butyl titanate was dissolved in 6 mL of ethanol, and dissolved uniformly. The mixed liquid was dropped into the above three-necked flask, and the reaction was stirred at room temperature for 24 hours. After completion of the reaction, the solvent was removed by rotary evaporation to obtain a crude product, which was repeatedly washed three times with ethanol and lyophilized to obtain a fluorotitanium hybrid flame retardant in a yield of about 96%.

The synthetic route diagram of the fluorine-titanium hybrid flame retardant is shown in FIG. The infrared spectrum of the fluorine-titanium hybrid flame retardant is shown in Fig. 2. The 994 cm ^-1 peak is a characteristic absorption peak of the -Ti-OC ₆ H ₄ - group. The nuclear magnetic resonance spectrum of the fluorotitanium hybrid flame retardant is shown in Fig. 3, ¹ H NMR (CDCl ₃ , 500 MHz) δ (ppm): 9.84 (1H, ph-OH), 7.89 (1H, C-CH-CH) ), 7.49 (1H, CH-CH-C), 7.36 (1H, C-CH-CH), 6.74 (1H, CH-CH-C), 3.48 (2H, O-CH ₂ -CH ₂ ), 1.46 ( 4H, CH ₂ -CH ₂ -CH ₂ ), 0.92 (3H, CH ₂ -CH ₃ ).

Example 2

Preparation of pure epoxy resin

Pure epoxy resin is the control group, weigh 20g epoxy resin E-51, raise the temperature of 90 ° C, add 5g curing agent 4,4 '-diaminodiphenylmethane, stir evenly, pour into the mold, keep at 120 ° C 5h, then incubated at 140 ° C for 2 h, and finally at 180 ° C for 2 h.

The prepared flame retardant epoxy resin was tested to have an oxygen index of 25.4% according to the method of GB/T 2406.2-2009.

The results of the vertical burning grade of the prepared flame-retardant epoxy resin according to the method of GB/T 2408-2008 are shown in Table 1.

Example 3

Weigh 20g epoxy resin E-51, heat up to 100 ° C, add 0.25g of the fluorine-titanium hybrid flame retardant prepared in Example 1, the addition quality of the flame retardant is calculated according to the mass percentage, and the fluorine-titanium hybrid flame retardant is 1% of the epoxy resin, while vacuuming to remove small molecules, after completely dissolving, add 5g of 4,4'-diaminodiphenylmethane, stir well, pour into the mold, keep at 120 ° C for 5h, then Insulation at 140 ° C for 2 h, and finally at 180 ° C for 2 h, flame retardant epoxy resin.

The prepared flame retardant epoxy resin was tested to have an oxygen index of 28.9% according to the method of GB/T 2406.2-2009.

The results of the vertical burning grade of the prepared flame-retardant epoxy resin according to the method of GB/T 2408-2008 are shown in Table 1.

Example 4

Weigh 20g epoxy resin E-51, heat up to 100 ° C, add 0.77g of fluorine titanium hybrid flame retardant, the addition quality of flame retardant is calculated according to the mass percentage, and the fluorine titanium hybrid flame retardant is epoxy resin 3 %, vacuuming to remove small molecules while stirring, after completely dissolving, adding 5g of 4,4'-diaminodiphenylmethane, stirring evenly, pouring into the mold, keeping at 120 ° C for 5h, then holding at 140 ° C for 2h, Finally, it is kept at 180 ° C for 2 h, flame retardant epoxy resin.

The prepared flame retardant epoxy resin was tested to have an oxygen index of 27.8% according to the method of GB/T 2406.2-2009.

The results of the vertical burning grade of the prepared flame-retardant epoxy resin according to the method of GB/T 2408-2008 are shown in Table 1.

Example 5

Weigh 20g epoxy resin E-51, heat up to 100 ° C, add 1.316g of fluorine-titanium hybrid flame retardant, the addition quality of flame retardant is calculated according to the mass percentage, and the fluorine-titanium hybrid flame retardant is epoxy resin 5 %, vacuuming to remove small molecules while stirring, after completely dissolving, adding 5g of 4,4'-diaminodiphenylmethane, stirring evenly, pouring into the mold, keeping at 120 ° C for 5h, then holding at 140 ° C for 2h, Finally, it is kept at 180 ° C for 2 h, flame retardant epoxy resin.

The prepared flame retardant epoxy resin was tested to have an oxygen index of 27.8% according to the method of GB/T 2406.2-2009.

The results of the vertical burning grade of the prepared flame-retardant epoxy resin according to the method of GB/T 2408-2008 are shown in Table 1.

Table 1

Burning Grade t ₁ (s) t ₂ (s) Dripping Control group NR >30s / Yes Example 2 V-1 12 2 NO Example 3 V-1 11 twenty one NO Example 4 V-1 twenty two 12 NO

The above is only the preferred embodiment of the present invention, and thus the scope of the present invention is not limited thereto, and equivalent changes and modifications made in accordance with the scope of the present invention and the contents of the specification should still be covered by the present invention. In the range.

Claims (7)

A fluorine-titanium hybrid flame retardant characterized in that the molecular structural formula is:

Wherein R is CH ₃ CH ₂ CH ₂ CH ₂ - or

The method for preparing a fluorine-titanium hybrid flame retardant according to claim 1, wherein the synthesis reaction formula is as follows:

details as follows: Weigh hexafluorobisphenol A in an organic solvent, dissolve and stir at 20 to 50 ° C, then add butyl titanate dropwise, and react at room temperature for 8 to 24 hours after the completion of the addition. Finally, the solvent is removed and purified to obtain a fluorotitanium hybridization resistance. The fuel agent; the molar ratio of the above hexafluorobisphenol A to butyl titanate is 1:4.0 to 5.0, and the volume ratio of hexafluorobisphenol A to the organic solvent is 1 g:30 to 50. Use of the fluorotitanium hybrid flame retardant of claim 1 for the preparation of a flame retardant epoxy resin. The application according to claim 3, characterized in that: a certain amount of epoxy resin is weighed in a reaction vessel, heated to 60-110 ° C, and then added to the fluorotitanium in a proportion of 0.1 to 50 wt%. The flame retardant is stirred until it is in a uniform transparent state, and then the curing agent is added to the stoichiometric ratio until completely dissolved and uniformly mixed, and then poured into a mold, and a temperature rising program is set for curing to obtain the flame retardant epoxy resin. The use according to claim 4, wherein the epoxy resin is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin or a novolac type epoxy resin. The use according to claim 4, wherein the curing agent is an amine curing agent, an acid anhydride curing agent, a boron amine complex or an amine group-containing borate curing agent. The application according to claim 4, wherein the temperature increasing program is: 120 ° C for 5 h, then at 140 ° C for 2 h, and finally at 180 ° C for 2 h.

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