A reactive chelated aramid oil agent and preparation method thereof

Abstract

The invention discloses a reactive chelated aramid oil agent and a preparation method thereof, wherein the reactive chelated aramid oil agent is composed of the following components: 100 parts by weight of a multifunctional epoxy, 1 5 parts by weight of a titanate coupling agent, 3 5 parts by weight of an acid modifier, 0.2 0.5 parts by weight of a catalyst, 1 3 parts by weight of a neutralizer, 3 10 parts by weight of a hyperbranched emulsifier, 1 3 parts by weight of an auxiliary emulsifier, and 200 parts by weight of deionized water. The present invention imparts good compatibility and reactivity between the oil agent and the epoxy resin through the epoxy group on the main resin structure, and the phosphoric acid acyloxy group, titanate group, etc. introduced by the titanate coupling agent have a chelating effect, further enhancing the interfacial strength between the fiber and the resin, thereby improving the performance of the composite material.

Description

Technical Field

[0001] The invention relates to the technical field of industrial fiber additives, and in particular to a reactive chelated aramid oil agent and a preparation method thereof. Background Art

[0002] Aramid is a specialty fiber made from a polymer obtained through the polycondensation reaction of aromatic diamines and aromatic dicarboxylic acids or aromatic aminobenzoic acid. The main varieties are para-aramid fiber and meta-aramid fiber.

[0003] Meta-aramid fiber is primarily poly(m-phenylene isophthalamide) fiber. It is produced by dissolving a polymer obtained by the polycondensation of m-phenylenediamine and isophthaloyl chloride in organic solvents such as tetrahydrofuran, dimethylacetamide, and N-methylpyrrolidone, and then spinning it through dry or wet spinning. It is primarily used in workwear for flammable and explosive environments, as well as spacesuits and firefighter uniforms. It can also be used as industrial filter media and fillers, and paper made from this fiber is widely used in electrical insulation. Para-aramid-poly(m-phenylene terephthalamide) fiber can also be used as a reinforcement material, boasting a strength 50% higher than that of fiberglass cloth. It is used as a cement reinforcement or as a partial replacement for steel bars in super-high-rise buildings. This fiber is also used in high-pressure hoses, conveyor belts, air-supported roofing materials, high-pressure vessels, rocket engine casings, and radar antenna covers.

[0004] Aramid fibers are spun at high temperatures and have strong rigidity. During the winding process, a layer of oil must be applied to the surface to prevent defects and lint from forming during winding, storage, transportation, and downstream use, which can lead to a decrease in the physical and mechanical properties of the fibers. This requires the oil to have good wettability on the fiber surface and a certain degree of bundling. In addition, when aramid fibers are used downstream to make epoxy composites, a certain degree of compatibility and reactivity between the fiber interface and the epoxy resin is required. Currently, most oils can only provide surface protection, and downstream companies also need to wash them clean, dry them, and then directly or after surface treatment, compound them with epoxy resin. This process is complex, and the interlayer bonding between the resin and the fiber is also low. Summary of the Invention

[0005] To this end, the technical problem to be solved by the present invention is to provide a reactive chelated aramid oil agent and a preparation method thereof. The epoxy groups on the main resin structure give the oil agent and the epoxy resin good compatibility and reactivity. The phosphate acyloxy group, titanate group, etc. introduced by the titanate coupling agent have a chelating effect, further enhancing the interface strength between the fiber and the resin, thereby improving the performance of the composite material.

[0006] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0007] A reactive chelated aramid oil agent is composed of the following components: 100 parts by weight of a multifunctional epoxy, 1-5 parts by weight of a titanate coupling agent, 3-5 parts by weight of an acid modifier, 0.2-0.5 parts by weight of a catalyst, 1-3 parts by weight of a neutralizer, 3-10 parts by weight of a hyperbranched emulsifier, 1-3 parts by weight of an auxiliary emulsifier, and 200 parts by weight of deionized water.

[0008] In the above-mentioned reactive chelated aramid oil agent, the multifunctional epoxy is one or more of trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, pentaerythritol glycidyl ether and azo-hybridized polyglycidyl ether.

[0009] The above-mentioned reactive chelated aramid oil agent, the titanate coupling agent is one of trialkoxy butyl phosphate titanate dimer, isopropyl tris (dioctyl pyrophosphate acyloxy) titanate, tetraisopropyl di (dioctyl phosphite acyloxy) titanate, di (triethylamine) diisopropyl titanate and bis (dioctyl pyrophosphate) ethylene titanate.

[0010] In the reactive chelated aramid oil agent, the acid modifier is maleic anhydride or succinic anhydride.

[0011] The catalyst in the reactive chelated aramid oil agent is one of sulfuric acid, phosphoric acid and oxalic acid.

[0012] The above-mentioned reactive chelated aramid oil agent, the neutralizing agent is one of 25wt% ammonia water, N,N-dimethylethanolamine, and 20wt% sodium hydroxide aqueous solution.

[0013] In the above-mentioned reactive chelated aramid oil agent, the auxiliary emulsifier is one or more of alkyl polyoxyethylene ether, polyoxyethylene sorbitan fatty acid ester, fatty alcohol polyoxyethylene ether sulfate, alkyl polyoxyethylene ether sulfate, sodium dodecyl sulfate and sodium dodecylbenzene sulfonate.

[0014] The preparation method of the reactive chelated aramid oil comprises the following steps:

[0015] 1) Add multifunctional epoxy and titanate coupling agents into a three-necked flask, start stirring and heating, vent nitrogen, control the reaction temperature at 70-90°C, add acid modifier and catalyst, and keep the temperature to react for 2 hours to obtain modified epoxy resin;

[0016] 2) mixing and stirring the modified epoxy resin and hyperbranched emulsifier prepared in step 1) to obtain a mixed material A;

[0017] 3) dissolving the auxiliary emulsifier in deionized water to obtain a mixed material B;

[0018] 4) Pour the mixture A prepared in step 2) into a high-speed shear emulsifier at a shear stirring rate of 1500-2500 rpm / min, and slowly add the mixture B prepared in step 3) dropwise into the mixture A in the high-speed shear emulsifier for phase inversion emulsification for 1-2 hours to obtain an aqueous reactive chelated aramid oil.

[0019] The technical solution of the present invention achieves the following beneficial technical effects:

[0020] The present invention uses a titanate coupling agent to modify a multifunctional epoxy, and emulsifies it to obtain a low-particle-size oil emulsion to obtain a reactive chelated aramid oil agent that can be directly compounded with an epoxy resin without cleaning. First, an acid modifier is used to open the ring of some epoxy groups, which are then connected to active groups such as alkoxy and amino groups of the titanate coupling agent. After that, a designed and synthesized hyperbranched emulsifier and an auxiliary emulsifier are added, and the oil is emulsified into an aramid oil agent with a particle size of less than 100 nm under a phase inversion process. The epoxy groups on the main resin structure impart good compatibility and reactivity between the oil agent and the epoxy resin. The phosphatoxy and titanate groups introduced by the titanate coupling agent have a chelating effect, further enhancing the interfacial strength between the fiber and the resin, thereby improving the performance of the composite material. In addition, the addition of a functional emulsifier and the optimization of the emulsification process formula make the particle size of the oil emulsion below 100 nm, which can improve the wettability and uniformity of the oil agent on the surface of the aramid precursor. DETAILED DESCRIPTION

[0021] Example 1

[0022] In this embodiment, the reactive chelated aramid oil agent is composed of 100 parts by weight of multifunctional epoxy trimethylolpropane triglycidyl ether and glycerol triglycidyl ether, 3 parts by weight of titanate coupling agent trialkoxy butyl phosphate titanate dimer, 4 parts by weight of acid modifier maleic anhydride, 0.35 parts by weight of catalyst sulfuric acid, 2 parts by weight of neutralizing agent ammonia water, 3 parts by weight of hyperbranched emulsifier (the hyperbranched emulsifier uses the one prepared in authorized patent ZL201910124536.7), 2 parts by weight of auxiliary emulsifiers alkyl polyoxyethylene ether and polyoxyethylene anhydrous sorbitan fatty acid ester and 200 parts by weight of deionized water. The specific process is as follows: add a multifunctional epoxy and titanate coupling agent into a three-necked flask, start stirring and heating, pass nitrogen, control the reaction temperature at 70-90°C, add an acid modifier and a catalyst, and then keep the reaction warm for 2 hours; mix and stir the modified epoxy resin and the hyperbranched emulsifier to obtain a mixture A; dissolve the auxiliary emulsifier in deionized water to obtain a mixture B; pour the obtained mixture A into a high-speed shear emulsifier at a shear stirring rate of 1500-2500 rpm / min, and slowly add the obtained mixture B dropwise to the mixture A in the high-speed shear emulsifier for phase inversion emulsification for 1-2 hours to obtain a water-based reactive chelated aramid oil agent.

[0023] Example 2

[0024] The reactive chelated aramid oil in this embodiment differs from that in Example 1 in that in this embodiment, the cyclic multifunctional epoxy is replaced with trimethylolpropane triglycidyl ether and pentaerythritol glycidyl ether.

[0025] Example 3

[0026] The reactive chelated aramid oil agent in this embodiment differs from that in Example 1 in that in this embodiment, the cyclic multifunctional epoxy is replaced with trimethylolpropane triglycidyl ether and azo-polyglycidyl ether.

[0027] Example 4

[0028] The reactive chelated aramid oil agent in this embodiment differs from that in Example 1 in that the titanate coupling agent in this embodiment is replaced with isopropyl tris(dioctyl pyrophosphate) titanate.

[0029] Example 5

[0030] The reactive chelated aramid oil agent in this embodiment differs from that in Example 1 in that the titanate coupling agent in this embodiment is replaced with diisopropyl di(triethylamine) titanate.

[0031] Example 6

[0032] The reactive chelated aramid oil agent in this embodiment differs from that in Example 1 in that the acid modifier in this embodiment is replaced by succinic anhydride.

[0033] Example 7

[0034] The reactive chelated aramid oil agent in this embodiment differs from that in Example 1 in that the catalyst in this embodiment is changed to phosphoric acid.

[0035] Example 8

[0036] The reactive chelated aramid oil agent in this embodiment differs from that in Example 1 in that the neutralizing agent in this embodiment is changed to N,N-dimethylethanolamine.

[0037] Example 9

[0038] The reactive chelated aramid oil agent in this embodiment differs from that in Example 1 in that the amount of the hyperbranched emulsifier added in this embodiment is changed to 6.5 parts by weight.

[0039] Example 10

[0040] The reactive chelated aramid oil agent in this embodiment differs from that in Example 1 in that the amount of the hyperbranched emulsifier added in this embodiment is changed to 10 parts by weight.

[0041] Example 11

[0042] The reactive chelated aramid oil agent in this embodiment differs from that in Example 1 in that the auxiliary emulsifier in this embodiment is changed to alkyl polyoxyethylene ether and alkyl polyoxyethylene ether sulfate.

[0043] Example 12

[0044] The reactive chelated aramid oil agent in this embodiment differs from that in Example 1 in that the auxiliary emulsifiers in this embodiment are replaced with alkyl polyoxyethylene ether and sodium dodecylbenzene sulfonate.

[0045] Comparative Example 1

[0046] The difference between the comparative example and Example 1 is that no titanate coupling agent is contained.

[0047] Comparative Example 2

[0048] The difference between the comparative example and Example 1 is that no hyperbranched emulsifier is contained.

[0049] Test method:

[0050] The broken yarns, wool yarns and oiling rate of the raw yarn during the pre-oxidation process were determined as follows: Observe whether there were broken yarns or wool yarns during the pre-oxidation process;

[0051] Epoxy equivalent refers to the epoxy equivalent of the oil, which is titrated according to GB / T4612-2008;

[0052] The particle size of the emulsion was measured using a Malvern laser particle size analyzer.

[0053] The results are as follows:

[0054] Table 1 Parameters and performance test of reactive chelated aramid oil

[0055]

[0056] It can be seen from the data recorded in Table 1 that the reactive chelated aramid oil agent of the present invention can significantly reduce the breakage and yarn-making conditions during the pre-oxidation process of the precursor yarn, and can provide better protection for the precursor yarn.

[0057] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will readily appreciate that other variations or modifications based on the above descriptions are possible. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the claims of this patent application.

Claims

1. A reactive chelated aramid oil agent, characterized in that: The invention comprises the following components: 100 parts by weight of a multifunctional epoxy, 1-5 parts by weight of a titanate coupling agent, 3-5 parts by weight of an acid modifier, 0.2-0.5 parts by weight of a catalyst, 1-3 parts by weight of a neutralizer, 3-10 parts by weight of a hyperbranched emulsifier, 1-3 parts by weight of an auxiliary emulsifier and 200 parts by weight of deionized water, wherein the multifunctional epoxy is one or more of trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, pentaerythritol glycidyl ether and azo-hybridized polyglycidyl ether, and the titanate coupling agent is one of trialkoxy butyl phosphate titanate dimer, isopropyl tris(dioctyl pyrophosphate acyloxy) titanate, tetraisopropyl di(dioctyl phosphite acyloxy) titanate, diisopropyl di(triethylamine) titanate and bis(dioctyl pyrophosphate) ethylene titanate; and the reactive chelated aramid oil is prepared by the following steps: 1) Add multifunctional epoxy and titanate coupling agents into a three-necked flask, start stirring and heating, vent nitrogen, control the reaction temperature at 70-90°C, add acid modifier and catalyst, and keep the temperature to react for 2 hours to obtain modified epoxy resin; 2) mixing and stirring the modified epoxy resin and hyperbranched emulsifier prepared in step 1) to obtain a mixed material A; 3) dissolving the auxiliary emulsifier in deionized water to obtain a mixed material B; 4) Pour the mixture A prepared in step 2) into a high-speed shear emulsifier at a shear stirring rate of 1500-2500 rpm / min, and slowly add the mixture B prepared in step 3) dropwise into the mixture A in the high-speed shear emulsifier for phase inversion emulsification for 1-2 hours to obtain a reactive chelated aramid oil agent.

2. The reactive chelated aramid oil according to claim 1, characterized in that The acid modifier is maleic anhydride or succinic anhydride.

3. The reactive chelated aramid oil according to claim 1, characterized in that The catalyst is one of sulfuric acid, phosphoric acid and oxalic acid.

4. The reactive chelated aramid oil according to claim 1, characterized in that The neutralizing agent is one of 25 wt% ammonia water, N,N-dimethylethanolamine, and 20 wt% sodium hydroxide aqueous solution.

5. The reactive chelated aramid oil according to claim 1, characterized in that: The auxiliary emulsifier is one or more of alkyl polyoxyethylene ether, polyoxyethylene sorbitan fatty acid ester, fatty alcohol polyoxyethylene ether sulfate, alkyl polyoxyethylene ether sulfate, sodium lauryl sulfate and sodium dodecylbenzene sulfonate.

6. The method for preparing the reactive chelated aramid oil agent according to claim 1, characterized in that: The steps include: 1) Add multifunctional epoxy and titanate coupling agents into a three-necked flask, start stirring and heating, vent nitrogen, control the reaction temperature at 70-90°C, add acid modifier and catalyst, and keep the temperature to react for 2 hours to obtain modified epoxy resin; 2) mixing and stirring the modified epoxy resin and hyperbranched emulsifier prepared in step 1) to obtain a mixed material A; 3) dissolving the auxiliary emulsifier in deionized water to obtain a mixed material B; 4) Pour the mixture A prepared in step 2) into a high-speed shear emulsifier at a shear stirring rate of 1500-2500 rpm / min, and slowly add the mixture B prepared in step 3) dropwise into the mixture A in the high-speed shear emulsifier for phase inversion emulsification for 1-2 hours to obtain an aqueous reactive chelated aramid oil.

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