A cyclic multi-functional epoxy modified self-emulsifying sizing agent for carbon fiber precursor filaments and its preparation method

Abstract

The invention discloses a kind of cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil agent and preparation method thereof, wherein, the cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil agent is composed of the following components: It is composed of the following components: 100 weight portions of aminosilicone oil, 50 100 weight portions of multifunctional epoxy, 3 5 weight portions of silane coupling agent, 3 5 weight portions of acid modifier, 0.2 0.5 weight portion of catalyst, 1 3 weight portion of neutralizer, 50 weight portions of acetone solvent, 50 weight portions of butanone solvent and 200 weight portions of deionized water. The present invention utilizes solvent method so that acid modifier opens an epoxy group of multifunctional epoxy, links a carboxyl group, and the remaining epoxy reacts with the amino group on aminosilicone oil, while adding a small amount of silane coupling agent to introduce multiple hydroxyls, then add alkali to neutralize the carboxyl group and transfer water, and the introduction of hydrophilic carboxylate and hydroxyl makes it possible to obtain a stable emulsion without adding emulsifier.

Description

Technical Field

[0001] The invention relates to the technical field of industrial fiber additives, and in particular to a cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil and a preparation method thereof. Background Art

[0002] The oil used in the production of carbon fiber precursor is loaded on the surface of the precursor through a coating process. It mainly improves the strength of the carbon fiber precursor and prevents fuzzing and static electricity on the fiber surface. In particular, it prevents the fiber from sticking, doubling, melting and burning due to high temperature (200-400℃) in the precursor pre-oxidation furnace. Therefore, the requirements for the precursor oil are good temperature resistance and good wettability on the surface of the precursor fiber.

[0003] Traditional carbon fiber precursor oils are usually obtained by compounding and emulsifying epoxy-modified silicone oils, amino-modified silicone oils, and polyether-modified silicone oils. Silicone oils are also modified with polyurethane, acrylic acid, etc., but these will reduce the oil's temperature resistance. Summary of the Invention

[0004] To this end, the technical problem to be solved by the present invention is to provide a cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil agent and a preparation method thereof. A solvent method is used to allow an acid modifier to open the ring of an epoxy group of the multifunctional epoxy and connect a carboxyl group. The remaining epoxy reacts with the amine group on the amino silicone oil. At the same time, a small amount of silane coupling agent is added to introduce multiple hydroxyl groups. Then, a base is added to neutralize the carboxyl groups and then water is converted. The introduction of hydrophilic carboxylates and hydroxyl groups makes it possible to obtain a stable emulsion without adding an emulsifier.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0006] A cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil comprises the following components: 100 parts by weight of amino silicone oil, 50-100 parts by weight of multifunctional epoxy, 3-5 parts by weight of silane coupling agent, 3-5 parts by weight of acid modifier, 0.2-0.5 parts by weight of catalyst, 1-3 parts by weight of neutralizer, 50 parts by weight of acetone solvent, 50 parts by weight of butanone solvent, and 200 parts by weight of deionized water.

[0007] In the above-mentioned cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil, the amine value of the amino silicone oil is between 0.5 and 1.

[0008] The cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil agent is one of nitrogen-hybridized polyglycidyl ether, resorcinol diglycidyl ether and tetrahydrophthalic acid diglycidyl ester.

[0009] The cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil agent, the silane coupling agent is KH550 or KH560.

[0010] In the above-mentioned cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil, the acid modifier is maleic anhydride or succinic anhydride.

[0011] The catalyst of the cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil is one of sulfuric acid, phosphoric acid and oxalic acid.

[0012] In the above-mentioned cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil, the neutralizer is one of 25wt% ammonia water, N,N-dimethylethanolamine and 20wt% sodium hydroxide aqueous solution.

[0013] The preparation method of the cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil comprises the following steps:

[0014] 1) Add multifunctional epoxy to a three-necked flask, add acetone and butanone, heat to dissolve, start stirring, pass nitrogen, control the reaction temperature at 50-70°C, add acid modifier and catalyst, and keep the temperature to react for 2 hours;

[0015] 2) Connect the buffer bottle, receiving bottle, and vacuum pump, continue to heat and keep warm, and quickly remove the solvents acetone and butanone;

[0016] 3) Add amino silicone oil and silane coupling agent, continue the reaction at 80-100°C for 2-4 hours, add neutralizer after the reaction is completed, and pour the mixture into a beaker while hot;

[0017] 4) Under high-speed dispersion at 2000 rpm, water was slowly dripped into the beaker to perform phase inversion to obtain a raw silk oil emulsion.

[0018] The technical solution of the present invention achieves the following beneficial technical effects:

[0019] The present invention uses a cyclic epoxy prepolymer to modify amino silicone oil to prepare a water-based carbon fiber precursor oil. First, a solvent method is used to open the ring of an epoxy group of a multifunctional epoxy with an acid modifier, linking it to a carboxyl group. The remaining epoxy reacts with the amine group on the amino silicone oil. A small amount of silane coupling agent is added to introduce multiple hydroxyl groups. After adding a base to neutralize the carboxyl groups, the water is converted. The introduction of hydrophilic carboxylates and hydroxyl groups makes it possible to obtain a stable emulsion without adding an emulsifier. The removal of the small molecule emulsifier and the introduction of a heterocyclic structure into the main structure of the silicone oil can improve the heat resistance of the oil in the pre-oxidation furnace. At the same time, the hydrophilic anionic structure of the silicone oil itself facilitates dispersion and emulsification in water, thereby improving the wettability on the surface of the carbon fiber precursor. DETAILED DESCRIPTION

[0020] Example 1

[0021] In this embodiment, the cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil is composed of 100 parts by weight of amino silicone oil with an amine value of 0.75, 50 parts by weight of multifunctional epoxy nitrogen hybridized polyglycidyl ether, 4 parts by weight of silane coupling agent KH550, 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, 50 parts by weight of solvent acetone, 50 parts by weight of solvent butanone and 200 parts by weight of deionized water. The specific process is as follows: add multifunctional epoxy to a three-necked flask, add acetone and butanone, heat and dissolve, start stirring, pass nitrogen, control the reaction temperature at 50-70 degrees, add acid modifiers and catalysts, and keep warm for 2 hours; add a buffer bottle, a receiving bottle, and a vacuum pump, continue heating and keeping warm, and quickly remove the solvents acetone and butanone; add amino silicone oil and silane coupling agent, continue to react at a temperature of 80-100 degrees for 2-4 hours, add a neutralizer after the reaction is completed, and pour it into a beaker while hot; under high-speed dispersion at 2000 rpm, slowly drip water into the beaker for phase inversion to obtain a raw silk oil emulsion.

[0022] Example 2

[0023] The cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil in this embodiment is different from that in Example 1 in that the amount of multifunctional epoxy-nitrogen hybridized polyglycidyl ether added in this embodiment is changed to 75 parts by weight.

[0024] Example 3

[0025] The cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil in this embodiment is different from that in Example 1 in that the amount of multifunctional epoxy-nitrogen hybridized polyglycidyl ether added in this embodiment is changed to 100 parts by weight.

[0026] Example 4

[0027] The cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil in this embodiment is different from that in Example 1 in that the cyclic multifunctional epoxy in this embodiment is replaced by resorcinol diglycidyl ether.

[0028] Example 5

[0029] The cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil in this embodiment is different from that in Example 1 in that the cyclic multifunctional epoxy in this embodiment is replaced with diglycidyl tetrahydrophthalate.

[0030] Example 6

[0031] The cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil in this embodiment is different from that in Example 1 in that the silane coupling agent is replaced with KH560 in this embodiment.

[0032] Example 7

[0033] The cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil in this embodiment is different from that in Example 1 in that the acid modifier in this embodiment is replaced by succinic anhydride.

[0034] Example 8

[0035] The cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil in this embodiment is different from that in Example 1 in that the catalyst in this embodiment is changed to phosphoric acid.

[0036] Example 9

[0037] The cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil in this embodiment is different from that in Example 1 in that the catalyst in this embodiment is changed to oxalic acid.

[0038] Example 10

[0039] The cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil in this embodiment is different from that in Example 1 in that the neutralizing agent in this embodiment is changed to N,N-dimethylethanolamine.

[0040] Example 11

[0041] The cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil in this embodiment is different from that in Example 1 in that the neutralizing agent in this embodiment is changed to a 20% sodium hydroxide aqueous solution.

[0042] Comparative Example 1

[0043] The difference between Comparative Example 1 and Example 1 is that the formula does not contain cyclic multifunctional epoxy.

[0044] Comparative Example 2

[0045] The difference between Comparative Example 2 and Example 1 is that no solvent is added during the process of modifying the cyclic multifunctional epoxy in the formulation, and bulk polymerization is adopted.

[0046] Test method:

[0047] The broken yarn and yarn condition, oiling rate and heat resistance of the raw yarn during the pre-oxidation process were determined as follows:

[0048] Determine whether there are broken silk and wool in the pre-oxidation process: Observe whether there are broken silk and wool in the pre-oxidation process;

[0049] Heat resistance: Dry in a 350℃ oven for 30 minutes and calculate the residual mass before and after drying.

[0050] The results are as follows:

[0051] Table 1 Performance test results of cyclic multifunctional epoxy modified self-emulsified carbon fiber precursor oil

[0052] Broken wire wool Oiling rate (%) Mass residue (%) Example 1 none Small amount 1.6 83.3 Example 2 none Small amount 1.5 84.1 Example 3 none Small amount 1.6 83.9 Example 4 none Small amount 1.4 82.9 Example 5 none Small amount 1.5 83.1 Example 6 none Small amount 1.6 83.5 Example 7 none Small amount 1.4 84.0 Example 8 none Small amount 1.6 83.5 Example 9 none Small amount 1.5 83.7 Example 10 none Small amount 1.6 83.4 Example 11 none Small amount 1.5 83.6 Comparative Example 1 Small amount Large quantities 1.2 74.5 Comparative Example 2 none More 1.4 82.5

[0053] It can be seen from the results recorded in Table 1 that the number of hairs in the precursor using the cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil of the present invention decreased significantly during the pre-oxidation process.

[0054] 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 cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil, characterized in that: The invention is prepared from the following components: 100 parts by weight of amino silicone oil, 50-100 parts by weight of multifunctional epoxy, 3-5 parts by weight of silane coupling agent, 3-5 parts by weight of acid modifier, 0.2-0.5 parts by weight of catalyst, 1-3 parts by weight of neutralizer, 50 parts by weight of acetone solvent, 50 parts by weight of butanone solvent and 200 parts by weight of deionized water, wherein the multifunctional epoxy is one of resorcinol diglycidyl ether and tetrahydrophthalic acid diglycidyl ester, and the acid modifier is maleic anhydride or succinic anhydride; the cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil is prepared by the following steps: 1) Add multifunctional epoxy to a three-necked flask, add acetone and butanone, heat to dissolve, start stirring, pass nitrogen, control the reaction temperature at 50-70°C, add acid modifier and catalyst, and keep the temperature to react for 2 hours; 2) Connect the buffer bottle, receiving bottle, and vacuum pump, continue to heat and keep warm, and quickly remove the solvents acetone and butanone; 3) Add amino silicone oil and silane coupling agent, continue the reaction at 80-100℃ for 2-4 hours, add neutralizer after the reaction is completed and pour into a beaker while hot; 4) Under high-speed dispersion at 2000 rpm, slowly drip water into the beaker to perform phase inversion to obtain a raw silk oil emulsion.

2. The cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil according to claim 1, characterized in that: The amine value of the amino silicone oil is between 0.5 and 1.

3. The cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil according to claim 1, characterized in that: The silane coupling agent is KH550 or KH560.

4. The cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil according to claim 1, characterized in that , the catalyst is one of sulfuric acid, phosphoric acid and oxalic acid.

5. The cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil according to claim 1, characterized in that The neutralizing agent is one of 25wt% ammonia water, N,N-dimethylethanolamine and 20wt% sodium hydroxide aqueous solution.

6. The method for preparing the cyclic multifunctional epoxy-modified self-emulsifying carbon fiber precursor oil according to any one of claims 1 to 5, characterized in that: The steps include: 1) Add multifunctional epoxy to a three-necked flask, add acetone and butanone, heat to dissolve, start stirring, pass nitrogen, control the reaction temperature at 50-70°C, add acid modifier and catalyst, and keep the temperature to react for 2 hours; 2) Connect the buffer bottle, receiving bottle, and vacuum pump, continue to heat and keep warm, and quickly remove the solvents acetone and butanone; 3) Add amino silicone oil and silane coupling agent, continue the reaction at 80-100℃ for 2-4 hours, add neutralizer after the reaction is completed and pour into a beaker while hot; 4) Under high-speed dispersion at 2000 rpm, slowly drip water into the beaker to perform phase inversion to obtain a raw silk oil emulsion.