JPS5974117A - Production of new polymer composition - Google Patents

Abstract

PURPOSE:To produce the titled composition containing carbon fiber and an organic polymer strongly united therewith, by electrolytically polymerizing an aliphatic epoxy compound by using carbon fiber as an electrode. CONSTITUTION:As a reactive monomer, 0.1-50wt% aliphatic diepoxy compound of the formula (wherein R1-4 are each H, a 1-20C alkyl, phenyl or its derivative, or a halogen, and n is 0-50) is added to an electrolytic solution prepared by dissolving 0.01-30wt% inorganic salt of a strong electrolyte (e.g., KI) in a solvent (e.g., tetrahydrofuran). Then, carbon fiber as an electrode is immersed in this electrolytic solution, and the mixture is electrolytically polymerized at -50-100 deg.C for 0.1sec-5hr by passing a direct current between the electrolytic solution and the electrode under conditions including a current density of 0.01- 20A/dm<2>, and a voltage of 5-25V to fix an organic polymer strongly, uniformly, and sufficiently on the surface of the carbon fiber.

Description

[Detailed Description of the Invention] The present invention produces carbon mechanical fibers (hereinafter abbreviated as CF) using an electrolytic polymerization method.
This invention relates to a method for producing a novel polymer composition in which organic polymers and organic polymers are strongly integrated.

Conventional methods for producing metal-organic polymers by electrolytically polymerizing reactive monomers using metals such as iron, copper, and silver as electrodes are known, but the bundling activity of the monomers is low, and it is difficult to bond to metals. Because the amount of N attached to the polymer is extremely small,
From an industrial point of view, it could hardly be put to practical use.

In view of the above-mentioned current situation, the present inventors have made extensive studies and have discovered that the polymerization of reactive monomers can be achieved by using conductive CF as an electrode as part or all of the reactive monomer of aliphatic epoxy compound 2. Significantly increases activity,
We have discovered that a new 72M composite composition, which cannot be obtained by conventional methods, has a large amount of organic polymer and is strongly integrated with the CF, which is an electrode, and has an excellent size effect, leading to the completion of the present invention. Ta.

Conventionally, the development of composite materials that complement two or more materials to create new effective functions by mutually complementing the properties of the constituent materials has been actively conducted. Regarding composites with CF, which is useful as a material, improvements in performance over a wide range of areas, such as mechanical strength, elastic modulus, heat distortion temperature, and electrical properties, have been reported. However, in this case, since the brain properties of the composite leaf materials are significantly different from each other, interfacial compatibility such as compatibility and adhesion is poor, and a sufficient composite effect cannot be exerted.

In order to improve this point, organic polymer materials can be grafted onto CF surfaces that have been oxidized with inorganic acids by vinyl grafting, and radiation methods in which CF is irradiated with high-energy radiation to graft organic polymers. Attempts have been made to improve the interfacial affinity with CF, but the reaction takes a long time and requires a radiation generator, etc., making the process complicated and manufacturing costs significantly increased. There are major problems in terms of gender.

The present invention solves the above-mentioned problems, and is characterized in that an aliphatic epoxy compound is used as part or all of the reactive monomer. A method of making a combined composition is provided.

In general, when electrolytic polymerization of reactive monomers is carried out even under conditions in which a supporting electrolyte is added, the polymerization rate remains at a fairly low level even after a long polymerization time has elapsed. According to the authors, the use of an aliphatic epoxy compound as part or all of the reactive monomer brings about extremely specific polymerization activity, and a polymer with a high polymerization rate that is of practical value can be produced in a few seconds on the CF surface. Since it is produced in large quantities and has an excellent size effect, the convergence is extremely improved.

Furthermore, the present invention is characterized in that the interaction between the surface of the CF and the polymer applied according to the present invention goes beyond a contact layer in the sense of simple adsorption, and is strongly integrated. The point is that

To carry out the present invention, to give an example of an embodiment, a CF roving is immersed in an electrolytic solution prepared by dissolving a reactive monomer and a strong electrolyte inorganic salt as a supporting electrolyte in a solvent, and the gap between the electrolytic solution and the CF is By applying a DC voltage to the CF surface, the CF surface is uniformly and abundantly covered with a polymer of reactive monomers at a high polymerization rate within a predetermined time without producing an electrolytic polymerization reaction of reactive monomers on the CF surface. In addition, it is possible to firmly fix the components.At this time, it is an essential condition that the three components described above be energized in coexistence, but it is not necessarily necessary to energize them at the same time. That is, even if CF pretreated with a strong electrolyte inorganic salt is used, a similar polymer composition can be obtained by the production method of the present invention without adding a new inorganic salt during monomer polymerization. can.

Conventionally, a method for obtaining a similar polymer composition using an inorganic acid or inorganic salt as a supporting electrolyte is known, but the size effect is not expressed because the polymerization activity of the monomer is low and the amount of polymer adhesion to the CF is extremely small. It has drawbacks regarding industrial practicality. Regarding these problems, the present invention uses a specific epoxy compound as a part or all of the reactive monomer, so that a large amount of the organic polymer formed on the CF surface is strongly integrated, which is surprising. In particular, because the size effect of the resulting polymer composition is outstanding, it is possible to obtain a product with extremely good convergence between CF fibers.

The specific epoxy compound used in the present invention has strong compatibility between the produced polymer and CF, and
It has polyfunctionality as an active size that exhibits reactivity with SOCS resin. Preferably, the following general formula...CI) (In the formula, RI+ R2+ Rs and R4 are an alkyl group, a phenyl group and a derivative thereof, or a halogen atom having H1 carbon number/~-〇↓, and n is θ Indicates an integer from f) to SO. ) is an aliphatic co-functional epoxy compound represented by n.

The CF used in the present invention is a high-strength or high-elastic carbon made of polyacrylonitrile or a copolymer thereof.
Examples include CF made from F, high-temperature cracked petroleum pitch, coal tar pitch, and coal depolymerized products, and CF produced by vapor phase growth, and both carbonaceous and graphitic CF are applicable. Further, various types of CF may be subjected to a commonly performed surface oxidation treatment. The fiber form is preferably a roving-like long fiber form, and the fiber diameter is not particularly limited. Both composites &1 obtained by the present invention have good surface layer properties and are obtained as convergent compositions with excellent handling and workability σ].

The co-reactive monomer used in the present invention is not particularly limited, but specifically, ordinary radically polymerizable vinyl monomers, aziridine ring-containing compounds, etc. can be used.

Specific examples of the compounds include ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether; propylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether; neopentyl glycol diglycidyl ether;
Gly70-/-polyglycidyl ethers; trimethylolbroban glycidyl ethers; pentaerythritol polyglycidyl ethers; diglycerol polyglycidyl ethers.

Examples include sorbitol polyglycidyl ethers,
These are preferable because they exhibit a remarkable size effect and have high electrolytic polymerization activity.

The concentration of the reactive monomer in the electrolyte in the present invention is approximately O,OS to ioo%, preferably 0,/-&
0% by weight, particularly preferably o, S to 30% by weight. The weight ratio of reactive heptad/mer epoxy compound or reactive monomer mixture to CF used can vary within a wide range and range from about soo:i to /:! 00.
Preferably &1 about so:/ to about/:A:0. The solvent world is approximately 0,000 based on the total weight of CF and monomer.
/ to several thousand times, preferably about 00 to 100 times.

What is the purpose of the present invention as a solvent used in the present invention? There are no particular limitations as long as they do not inhibit the use of alcohol, for example, water; alcohols such as methyl alcohol, ethyl alcohol, glycerin, cellosolve; diethyl ether, tetrahydrofuran, /. ll--Ethers such as dioxane Nitriles such as acetonitrile, butyrocetonitrile, and benzacetonitrile; Amines such as ammonia, ethyleneamine, and pyridine; Formamide,
Amides such as dimethylformamide and dimethylacetamide; sulfur compounds such as sulfur dioxide, dimethylsulfoxide, and sulfolane; acetone, dichloromethane, nitromethane, nitrobenzene, propylene carbonate, and the like.

Examples of strong electrolyte inorganic salts used to form the electrolytic solution include potassium iodide, sodium nitrate, lithium chloride, potassium chloride, ammonium chloride, ammonium nitrate, sodium hydroxide, lithium bromide, and tetraethylammonium perchlorate. salts, etc., and the concentration in the remission solution is 0.0/~30% by weight, preferably θ/
~5% overlapping. Electrolytic polymerization is carried out by passing a direct current between the electrolytic solution containing the reactive monomer and the CF, and the current density is usually 0. 0/~. 20 A/cli,
Preferably Ha0/~. 2A/dm2, and the voltage is usually S
It is about 100mV. If the current density is too low, the polymerization rate will be slow; conversely, if the current density is too high,
This is not preferable because the CF itself deteriorates. Also CF&'i
It can be applied at either anode or cathode potential. The reaction time is approximately 0. /second to about S hours. The reaction temperature is about -!
QC-10OC, preferably oC-g.

It is done in C. The specific reaction temperature here is selected as appropriate depending on the reactive monomer used, but it is important to carry out the reaction at a temperature at which thermal polymerization is suppressed to a negligible extent. When carried out, the integrity and homogeneity of the resulting complex is limited. The resulting complex is about 70~. 300C, preferably about 3θ~20
0CQ] Can be dried within a temperature range.

In the novel polymer composition obtained by the present invention, the interaction between the surface of CF and the polymer is beyond simple adsorption or physical contact N in the sense of 'fi' due to van der Waals forces, etc. This fact shows that even if the polymer is extracted and treated with a good solvent, a large amount of unextracted polymer remains.

Next, the present invention will be explained in more detail with reference to Examples.

The novel polymer compositions of the present invention are useful in a variety of applications, such as aviation, space/sports leisure goods, automobiles, audio, and general industrial applications.

Parts in the examples represent 2 parts by weight.

Examples/~a1 Comparative Examples 1 to 3 High-strength PAN-based CF roving (manufactured by Mitsubishi Rayon Co., Ltd.) was added to an electrolytic polymerization apparatus equipped with an electrode roller (made of copper) and a guide roller (made of glass) as shown in FIG. ), polyethylene glycol (n=lI) diglycidyl ether (manufactured by Nagashio Sangyo Co., Ltd., Bunacol EX-g: 1l) A;
Og and sodium nitrate Sg as supporting electrolyte.
MF! Electrolytic reaction adjusted by dissolving in 00Li? The solution was injected into the reaction species (made of stainless steel) until the CF was immersed.

Next, an electrolytic polymerization reaction was carried out at room temperature for 7 hours by passing a direct current between the CF and the electrolytic solution using a direct current exchanger using the CF% as an anode. Incidentally, the current density σ at that time was adjusted to ox 7 h7a,1 using a variable resistor.

After the reaction, the product was thoroughly washed with DMF/00U
By drying with hot air and measuring the convergence and weight of CF,
The amount of N attached to the polymer on CF was determined. Also EX-g, 2/
, 2j and methyl methacrylate (MMA) monomer Co S9 were used in the same manner.

For comparison, ordinary vinyl monomer T al MMA monomer, polyethylene glycol (average molecular weight 3OO), which is an aliphatic ether compound without epoxy functional group, and a mixture of MMA monomer and polyethylene glycol were added as reactive monomers. Regarding the electrolytic polymerization behavior in the case, the same polymerization operation and post-polymerization evaluation 'f:' were conducted and the results are shown in Table 7.

As is clear from Table 1, the lyethylene glycol shown in Comparative Example 2 shows no Togane activity, and the MMA 1,000/mer alone shown in Comparative Example 2 has considerably poor CF convergence. At the same time, there are very few spots of polymer adhesion to CF, whereas the production method of the present invention has very good CF convergence, and at the same time greatly increases the number of polymer adhesion, dramatically improving practicality. It shows that it will improve.

*/ Aliphatic epoxy compound manufactured by Nagashio Sangyo Co., Ltd. *2
MMAI methyl methacrylate *3 Excess aliphatic ether compound Mitsubishi Rayon Co., Ltd. High-strength PAN-based CF roving *! DMF: N, N-dimethylformamide Hata Otsu
Reaction conditions Temperature: , 2! ;7:CFt rank:
Pole current, current density: 0 Coff A/V'Voltage; , 2 ov When energized Nj: to min 07 CF convergence ◎...Very good ×...Very poor X...Very high *g How many layers of polymer when the raw material CF is 100 parts Examples 3 to 7 In Example/, Bunacol EX-g1 was used instead of Bunacol EX-g2/ as the aliphatic epoxy compound.
0, Denacol EX-g da 01 Denacol EX-J/g, Denacol EX-A/Hedenacol EX-32/i Polymerization was carried out in the same manner as in Example/, except that Denacol EX-A/Hedenacol EX-32/i was used as the reactive monomer. The amount of polymer attached to the CF was measured and evaluated, and the results of comparison with Example/2 are shown in Table 2.

No. λ Table vase / Polymer adhesion amount when raw material CF is 700 parts *Yubunacol EX-112/ *3 Bunnacol EX-g10 *Da Bunnacol EX-411O 1tf5 Denacol/l'EX-J/47 Hata A Bunnacol EX -A/1 H Hata Ri Bunacol EX-32/ As is clear from the table, Company N attaches polymer to CF.
EX-11:l/, EX-glo, and EX-glo were quite large, and EX-3/41. EX-6t/, EX
- Jcol showed a slightly low level 0 Next, about θ12 of the polymer composition obtained by the method of Examples 7 to 70 was weighed together with a cylindrical opening paper, and a 21-hour Soxhlet extraction test was carried out using chloroform as an extraction solvent. By performing this, the polymer extraction rate of the composition was measured. For comparison, a composition produced by bulk polymerization in the presence of CF roving using a conventional radical polymerization catalyst (Comparative Example D) was also evaluated and investigated in the same way.The results are shown in Table 3. The polymer component in the composition shown in is completely extracted in the Judas time extraction test, whereas the extraction rate of the polymer component in the CF complex obtained by the present invention is small and most of it is not extracted. Table 3 */ AIBN: Azobisisobutyronitrile*
Polymer-attached N firefly example g when the raw material CF was 100 parts The reaction was carried out in the same manner as in Example 1, except that the type of CF was changed, and the results of evaluating the obtained composition are shown in Table 9. Shown below.

Table q *l Manufactured by Kureha Chemical Industry Co., Ltd. Rekatou *Yu Manufactured by Mitsubishi Rayon Co., Ltd. Hata 3 Electrolytic polymerization conditions CF2θ 1.23 parts, sodium nitrate: 25 parts.

(DIVIF:!;00 copies, EX-4,2/: 30
As is clear from the % table, the foil manufacturing method of the present invention has no CF selectivity regarding polymerization activity, and generally the MW with polymer
It can be seen that the extraction rate of the polymer component in the produced composite was small, and most of it was not extracted but was strongly combined with CF.

Example 9 A composition obtained by reacting in the same manner as in Example 1 except that reactive monomer 2 shown in Table 3 was used as a co-reactive monomer with an aliphatic epoxy compound (;l!;9) The evaluation results are shown in Table 3.

Table S *l ST: Styrene monomer *, 2EuA n-butyl acrylate summer JMA
A: Methacrylate 11!4'GMA nigericidyl methacrylate weight ratio is sO/s.

*5 I(,D,U: /,A-hexamethylene diethylene urea A, Z, M: 2-(/-aziridinyl)ethyl methacrylate T, D, E, I: 2.II-diethyl 11 g of ureatoluidine T, A, Z, O: Tetramethylolmethane-tri-β-aziridinylpropionate As is clear from Table 5, the co-reactive monomers used in the present invention include the usual co-reactive monomers. It can be seen that both radical-combined vinyl monomers and aziridine ring-containing compounds are applicable.

Example 10 Support 1!1 Sodium nitrate as solute, 2! PAN yarn CF (HT manufactured by Mitsubishi Rayon Co., Ltd.) roving O/23 was immersed in a solution dissolved in 300 g of r09 total deionized water, thoroughly dried, and then subjected to reaction polymerization set in the same manner as in Example 1. The total amount of CF treated using the device is the reaction solution prepared in advance [Bunacol EX-g, 2/! rO
DMF! 00σ solution]. Next, using the CF potential as an anode, a DC converter was used to pass a DC current between the treated CF and the electrolytic solution to carry out an electrolytic polymerization reaction at room temperature for 7 hours.

In addition, the current density after that is 0.27A/ by a variable resistor.
I adjusted it so that it became dm'. After the polymerization was completed, evaluation was carried out in the same manner as in Example 1. As a result, the amount of polymer added to the CF was AO part, and the resulting composite was uniformly coated with the polymer of the reactive monomer on the CF coating surface. It was a strongly fixed composition.

EXAMPLE // Using the polymer composition obtained according to the present invention, a resin and σ0 composite (IJnidivectional Composite) of Pisfer/-A type general-purpose epoxy resin was prepared.
e) was produced, and the mechanical properties of the shaped product, such as strand strength, interlaminar shear strength, and bending strength, were evaluated.

For comparison, untreated σ)C:F (shown as a simple blend in the table) was similarly composited and evaluated. The results are shown in Table 1.

Table 6 As is clear from Table 6, the polymer composition according to the present invention is a composition that is excellent in practicality such as mechanical properties.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram showing one embodiment of an electrolytic polymerization apparatus for CF roving according to the present invention. tz)... Electrode roller (2)... Guide roller (3)... CF roving (S... Electrolytic polymerization liquid (S)... Reactive species (phantom... DC converter (7) ... Variable resistor (g) ... Ammeter (9) ... Electrode

Claims (1)

[Claims] /] A novel polymer composition characterized in that an aliphatic epoxy compound is used as part or all of the reactive monomer in electrolytically polymerizing the reactive monomer using carbon fiber as an electrode. Manufacturing method of 0. 2) The aliphatic epoxy compound has the following general formula % formula %
) (wherein R,, R2, R3 and R4 are H1 carbon numbers/~
20 alkyl groups, phenyl groups and derivatives thereof, or halogen atoms, and n represents an integer from O to SO. ) A method for producing a novel polymer composition according to claim 7), which is a u-functional epoxy compound represented by: 3) The method for producing a novel polymer composition according to claim 2), wherein n of the epoxy compound represented by the general formula CI) is an integer from O to θ.