JPS59120620A - Production of new polymer composition - Google Patents

Abstract

PURPOSE:To obtain a polymer consisting of carbon fiber and an epoxy polymer which are strongly united, by using a cycloaliphatic epoxy compound as at least part of a reactive monomer and electrolytically polymerizing the monomer by using carbon fiber as an electrode. CONSTITUTION:A cycloaliphatic epoxy compound of, for example, formula I or II(wherein R1 is a group of formula III, R3 is a 1-20C alkylene, R2 is a 1-30C alkyelen, and R4 is a 30C or lower alkylene) is used as at least part of a reactive monomer, and the monomer and a strongly electrolytic inorganic salt (e.g., sodium nitrate) are dissolved in a solvent. The resulting solution is poured into a electrolytic polymerization apparatus 5 as an electrolyte 4. Carbon fiber rovings 3 are immersed in the electrolyte 4 and a D.C. current is passed between the electrolyte 4 and the carbon fiber 3. Thus the reaction mixture is electrolytically polymerized to obtain the purpose polymer composition consisting of the carbon fiber 3 and the epoxy polymer which are strongly united.

Description

[Detailed Description of the Invention] The present invention uses electrolytic polymerization to produce carbon fiber (abbreviated as CF).
This invention relates to a method for producing a novel polymer composition in which the organic polymer and the organic polymer are strongly combined and combined.

Conventionally, there has been a known method for producing metal-organic polymers by electrolytically polymerizing reactive monomers of metals such as iron, copper, and silver with electrodes and I~, but the polymerization activity of the monomers is low and Since the amount of polymer attached to the metal was still 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 conducted intensive study 1, and determined that C11'' with ψ, C2 city, ↑/1 has 7111 poles and 1 ~, ring fat tlJ-i group]-bogin By using the compound as a reactive monomer, a part of the reactive monomer, a part of the 11 □f part and 1.-U, the polymerized oil of the reactive monomer is created. It has been shown that a large amount of I'-type polymers are strongly integrated with Cp', and that a new polymer composition which cannot be obtained by conventional methods and which has superior effects of 7j-1 is obtained. Heading 7: The present invention has now been completed.

Conventionally, by compositing materials of 2f'J'i or more, the development of composite materials H that mutually complement each other and bring out new effective functions has been actively carried out. Regarding compounding with C11'', which is useful as reinforcement and filler for organic polymers, for example, mechanical strength, Lili I percentage,
A wide range of thermal deformation temperatures, electrical properties, etc.
li improvements have been reported. However, in this case, since the properties of the composite materials are significantly different from each other, interfacial compatibility such as compatibility and adhesiveness is poor, and the full composite effect is not fully exerted. -The current situation is that it is impossible to do so.

In order to improve this point, oxidation treatment with inorganic acids was carried out immediately (~da (31P surface...) 1 Granod method,
c
Attempts have been made to improve the interfacial affinity between substances and CF; This solves major problems in terms of practicality, such as the shift to 4F and the large increase in manufacturing costs.

The present invention solves the above-mentioned problems and is characterized by using a cycloaliphatic epoxy compound as part of the reaction f4 monomer or as the entire C1 (Book C and epoxy polymer). The present invention provides a method for producing a polymer composition that is strongly integrated.

In general, even if a supporting electrolyte is added, when carrying out electrolytic polymerization of 1,000 reactive polymers, even after a polymerization time of 15 minutes has elapsed, the proportion C' In contrast, according to the present invention, by adding a cycloaliphatic ebon compound to part or all of the reactive monomer, a very specific polymerization activity can be achieved. In a few seconds, a polymer with a high polymerization rate, which is of practical value, is produced in large quantities on the surface of the CF coating, and because of its excellent size effect, the focusing 1'1 is greatly improved.

Furthermore, the present invention is characterized in that the interaction between the surface of the OF and the polymer applied by the method of the present invention goes beyond adhesion in the sense of pure adsorption, and is strongly integrated. It is in.

To give an example of an embodiment of the present invention, a CF roping is immersed in an electrolytic bath prepared by dissolving a reactive monomer and a supporting electrolyte (-) and a strong electrolyte inorganic salt in a solvent,
By applying a DC voltage between the electrolyte and the CF, an electrolytic polymerization reaction of the reactive monomer on the surface of the OF coating is caused, and the reactive monomer on the surface of the OF coating is produced at a high polymerization rate within a predetermined polymerization time. Polymer monomers can be used to bond uniformly, in large quantities, and firmly (-).In this case, it is an essential condition that the above three components are energized together, but it is necessary to
It is not necessary to energize 'L at the same time. That is, for example, some of the OFs pretreated with inorganic salts can be used in the same way without adding new inorganic salts during monomer polymerization according to the method of the present invention. A polymer composition can be obtained.

Conventionally, there is a known method of obtaining a similar polymer composition using an inorganic acid or an inorganic salt as a supporting electrolyte, but the polymerization activity of the polymer is low, and the amount of polymer adhering to the a1r is significant. Since it is small, it has a disadvantage in terms of industrial practicality, such as not exhibiting a size effect. Regarding these problems, the method of the present invention uses a specific epoxy compound as part or all of the reactive monomer, so that the surface of the CF coating and the produced organic polymer are often and strongly integrated. More surprisingly, the size effect of the resulting polymer composition is so outstanding that it provides a method for obtaining a product with very good convergence between c]t' fibers.

The specific epoxy compound used in the present invention [7]
It has a polyfunctionality (-, preferably a cyclic compound, and a bis-epoxy Hexyl-11-hexyllupoglycylates, bis-evoxozochlores, key-le-di-carb-1-1, and hibis-evogysyl-11-hexyldiogysanes have a remarkable effect. 7, and the electrolytic polymerization activity was also very high (7).

The carbon fibers used in the present invention (・) include polyacrylic fibers, polyacrylic fibers, polyacrylic fibers, high-strength carbon fibers made of a combination of both, high-elastic CF, petroleum high-temperature decomposition pitch, coal tar pinot. °f and O made from coal depolymerized material
Examples include F, and further CF produced by a vapor phase growth method, and carbonaceous and graphite OF is also applicable. Various types of CF may be subjected to a commonly performed surface oxidation treatment17. In addition, there are 41 conductive metals such as iron, silver, stainless steel,
Metal fibers such as copper aluminum can also be applied. The fiber form is preferably a roving-like long fiber form, and the fiber diameter V1 is not particularly limited. The complex obtained by the present invention is
1 can also be obtained as a convergent composition with good interfacial adhesion and excellent handling workability.

The co-reactive polymer used in the present invention is not particularly limited, but specifically, common radical polymerizable monomers, aziridine ring-containing compounds, etc. can be used.

According to the present invention, the concentration of the cycloaliphatic compound in the electrolyte is approximately ()05 to 100 wt.
It is used at a concentration of 1 to 50% by weight, particularly preferably 05 to 30% by weight. The reactive monomer (cycloaliphatic epoxy compound) to cF used can also be used. : 5 (1 (1, good i Lll
JJ5 o: 1-no'! Approximately 1. : 5.

It is. The amount of solvent is about 0.9"1% to several thousand times, preferably about 1 to iooo times, based on the total weight of OF and monomers. Electrolytic polymerization A direct current is applied between the electrolyte containing the CF and the CF, and the current density V at that time is usually 001~2°A
dn? , preferably 0.1- = 2 A/d
yyz2, and the voltage is usually about 5 to 25V. If the current density is too low, the polymerization rate will be slow, resulting in a good size (-<
No (7. Conversely, if the current density becomes too high,
This is not preferable because OF' itself deteriorates. Furthermore, CF can be applied at either positive or cathodic potential. Reaction time is about 0.1 seconds to about 5 hours. Reaction temperature is about -50U
~T-(10C1 good size t, <&, j, OC~SOC
It will be held in The specific reaction temperature here is selected as appropriate depending on the reactivity temperature used, but it is important to carry out the reaction at a temperature that suppresses thermal polymerization to a negligible level, and avoids excessive thermal polymerization. When performing high-temperature-C, the integrity and uniformity of the resulting composite is impaired. The resulting complex is about 10 to 300C1 [7 or about: (0 to
2007: It can be dried in the temperature range of 2007:.

Various solvents can be used in carrying out the present invention. Examples include ketones such as zanone, carboxylic acid esters such as acetic acid ester, and carbonamides such as dimethylformamide.

Note that the interaction between the surface of (F) and the polymer applied by the method of the present invention does not involve simple adsorption (7), but is beyond adhesion in the physical sense due to van der Waals forces, etc. , this fact shows that extraction treatment 1 with a good solvent for polymers
This is evident from the fact that a large amount of unextracted polymer is observed even in ~.

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

Examples 1 to 2, Comparative Examples 1 to 3 Electrode rollers and guide rollers were placed E~ After setting the high-strength gPAN-based CP' roving in the electrolytic polymerization apparatus shown in Figure 1, the cycloaliphatic epoxy compound 50 gr of bis(34-evogycyclohegycyl)adivate and 2.5 gr of sodium nitrate as supporting electrolyte.
9r f: D M F 5 (adjusted by dissolving in +09r).
The injection was continued until F was immersed.

Next, using the CF potential as an anode and a DC converter, OF
A direct current was passed between the electrolyte and the electrolyte (7. The electrolytic polymerization reaction was carried out at room temperature for 1 hour.The current density at that time was adjusted to 0.27 A/di using a variable resistor. .

After completion of the reaction, the product was thoroughly washed with D)A Fi'(・ and dried with hot air at 7.1,0 (lC), and the polymer of C!F-\ was determined by the convergence of CF and 1. The amount of adhesion was determined.

The same procedure was carried out in this case as well, using a monomer mixture of the above-mentioned Evogishi resin 25, j9r and 25 gr of methyl methacrylate (M ra A ) monomer. M
A similar polymerization operation and post-polymerization evaluation were conducted to determine the 7tL decomposition behavior when a reactive monomer was added to a mixture of monomer A and ethyl methyl glycidate, which is a monofunctional aliphatic epoxy compound that is not a cyclic compound. I did a test. The results are shown in Table 1. In addition, parts t and t indicate parts by weight.

As is clear from Table 1, in the case of Comparative Examples 1.2 and 3, O
While the F' convergence is poor and the amount of polymer adhesion is extremely small, -C, by the method of the present invention, the CF convergence is very good and at the same time polymer adhesion (as much as 1% [1]
It is expected that the amount of metal will be increased and the practicality will be dramatically improved.

Table 1: Reactive mono--1: cF111-
: Example 1. , "l fi (1 part l -'
l' (112311 1I"0 copies 〃 1 'J 3: l 2 parts 5 parts: 251 1'
1 rice 2 MMA: Methyl methacrylate rice 8 Monofunctional aliphatic epoxy compound CH (Usol 1-3-0-02H5 powder 11 Mitsubishi Rayon @ high strength PAN type CF+5
, [) Ml (1: N, N-dimethylformamide supporting electrolyte 1 Solvent::;□ Reaction product: ■ Nitric acid (: 0.1.'8 11: ・3' i all ・,: □ ,...:・ 夾′ 1 ′11 1()I +5 Reaction conditions Rice 7 CF convergence Tree 8 Example 'J2h1!1 In Example 1, a cycloaliphatic epoxy compound (Ll,, -r As shown in Table 1, /ζ compounds can be used with reactive monomers and L4.
The market was carried out in the same manner as in Example 1, and the amount of volume per garment was measured using a measuring meter filli I-1'.
+l11 and [, t lp intersection 1. The results are shown in Table 2.

Table 2.
,・Solvent II Nail・He ν 1゜1 □
1 :＼ Vermilion 1 Raw material CF Rin: 1. (+ ('1 part poly-7-4'
\4) Azo Ibate rice 3. B: 2-(a4-Eboxycycline'\Gycinol-55-Spiro-3)To-Eboxy)cyclo-Gyzan-Metadioxane* 4. O: :(,4-epoxycyclohegysylmethino l-34-epoxycycloheyl A-phosphoric carboxylate end!'+l,): Vinylcyclohegycene dioxide As is clear from Table X2, a polyfunctional cycloaliphatic epoxy compound [The amount of polymer adhering to CF was at a high level in all cases, fv.

Approximately 1,1Ex- of the polymer composition obtained by the method of Examples 1 to 5 was weighed together with the cylindrical opening paper, and 1
1. Determination of the polymer extraction rate of the nucleic acid by conducting a 24-hour Soxhlet extraction test using Nyl as the extraction solvent. Ta. For comparison, (
Bu:1 in the presence of 7F' roving. Similar evaluations were made regarding the composition (Comparative Example 4) produced by
Fi to t-j side [7]. The results are shown in Table 3.
The polymer component in the composition shown in the comparative example was completely extracted in a 24-hour extraction test, whereas the extraction rate of the polymer component in the CF complex obtained in Q by the method of the present invention was small. However, most of it is not extracted and is strongly integrated into CF.

Table 3 :　　＼ 1゛＼ □　＼ \ Iゝ 11 JaiflJ ■ 1 --- 1〃 2 − I.

3 1'4 :〃 5 --- jUpper Interchange Example 1 4 Next 1. Example 6: Poor polymer adhesion when raw material OF was 100 parts Table 4 shows the results of evaluating the obtained composition by carrying out the reaction in the same manner as in Example 1 except for changing the type of CF. Shown below.

Part 4 Table 1 Electron W (polymerization conditions CF: 0.123 parts, sodium nitrate: 2.5 parts (ERL-4299: 50 parts, DMF: 500 parts) As is clear from Table 4, the method of the present invention CF regarding polymerization activity
No selectivity was observed, and the amount of polymer deposited was generally good, and the extraction rate of the polymer component in the one-produced polymer was small, and most of it was not extracted, but was strongly combined with OF. I understand.

Example 7 The reaction was carried out in the same manner as in Example 2, except that the reactive monomer shown in Table 5 was used instead of MMA as the co-reactive monomer with the cycloaliphatic epoxy compound, and the resulting composition The results of the evaluation are not shown in Table 5. Table 5 *: 1 8T: Styrene monomer rice 2 tons (u, A: Acrylic acid n-]゛thyl ester rice a MAA: Methacrylic acid 14 GMA: Glycidyl methacrylate, The weight ratio is 5 (1150 pots 5 HDU: 1.6-
Hoxamethylene cLiethylen
From eurea 6 AZM: 2-(1-azi
ridiny:1-)ethy'Lme1;hacry
lat.

TDEI: 2, 4-Dietlylurea,
toluidineTAZO: Tetramet
hylolmethane -tr soil -β --a
ziridinylpropyonate H2 / Polymer tJ coverage when the raw material OF is 100 parts.
Urubi? 1) Compound containing 1 moiety and aziridine ring
1. It can be seen that both are applicable.

Example 8 Zutrium nitrate 2509r as support 4'3 electrolyte
Take off the water! Two PAN threads (Mitsubishi Ray 1 HT) roving 0.123, Q+- were dipped in a solution of 17% dissolved in 100 gr. After being thoroughly dried [7], the same method as in Example 1 was carried out. Also, using a reactor, add the previously prepared reaction solution (ERL-429+, 1 to 1) MF5 (If-1,9
Dissolved in r- (7 solution) immersed in (-d).

Next, a direct current was passed between the treatment ()'' and the reaction liquid using the CI [i'' tube anode and a DC converter, and an electrolytic polymerization reaction was carried out for 1 hour at room temperature. .

In addition, the current density at that time is set to 0, 27 by a variable resistor.
A/Can? I adjusted it so that After polymerization,
Evaluation was made in the same manner as in Example 1; W7, the amount of polymer adhering to the OF was i, t, 8 t, and the resulting composite had the CF surface covered with the weight of the reactive monomer. When combined, the composition is firmly and firmly fixed.
is.

Examples (.

Bisphenol A type pan-FI# = 1'-Beau V resin complex (tlni, d, 1 rectiona, -1 Ca
rdpool, fo ) f was prepared, and the mechanical properties of the shaped product, such as strand strength, interlaminar shear strength, and bending strength, were evaluated as 1 to 1. For comparison, the OF of car processing (simple block/end (indicated by 7) in the table) was similarly combined and evaluated.

The resulting IJ is shown in Table 6.

Table 6 Mechanical properties: 1
0F content 60 VOI % Hr, (As is clear from the table H, the polymer composition produced by the method of the present invention has excellent mechanical properties and other practical properties. There is.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram showing an embodiment of an electrolytic polymerization apparatus for CF raw material according to the present invention. Sign - Explanation of bow (j) ・・・ Electrode j'l - Ra (copper)■ ・
・・ Guy 1 button - ra (made of glass) ■ ・・・ OF
UJ-Ping ■ - Ryukakui polymerization solution (... Reaction tank (stainless steel) (...
DC converter ■ ... Variable resistor ■ ... Current language special ￥r Applicant Mitsubishi Rayon Co., Ltd. Agent Patent attorney 1) Takeshi Mura Stroll 1 Figure / ■ Re°1. Correction () 5 formula) Showa 5ε3 fi-April/枳11 t8i rF I't'f-<Government O Cedar
Aifu 1〆hi1, Fli (Expression 11 of i (1 sum 57 'I Q, X■i+'l application No. 2266
52'> Shin 3 Hangmei σ) Name Y11? Ii f1! ,! Production method of intermediate composition 3. Ura 11
-4 Rir person = Ij ('l Which relationship Special 9'1 Applicant Tokyo Chuo E
Mekyobashii Jl'' 3 No. 19 (60, '3) Kakubishi Shiin F-1 stock company r (enforcement 1st kidnapping fgu) Osamu Kanazawa 2lI, agent Nito 5 Bafilln Aiku Tora ,) Bolt-2 1L No. 18 1″I″
)] 111 sum 5 B 3T33jl 29 to! Lee NJ
Zatsu 6, N+li il's S・1 Elephant
-9 bright ■ 1 μm filter 11 ((no change in content) Pal Example In Example 1, a cycloaliphatic epoxy compound and the compound shown in Table 2 in 17 were combined with a reactive monomer, j, 2 and l1
The entire assembly was carried out in the same manner as in Example 1, except for the i74 Jfit and the mechanism. Table 2 shows the results of measurement and evaluation of polymer adhesion to CF from Evaluation 1 to Example 1. Table 2 Table 3 *1 Amount of polymer gain when thick phase CF is 100 parts Example 6゜The reaction was carried out in the same manner as in Example 1 except that the type of CF was changed. The result of Rf' rating of the obtained composition f:
It is shown in the fourth mourning. Table 4: 7 points 1 i (j total calf CF: 0.
123 parts, sodium nitrate: 2.5 parts (Ele L-4299: 50 parts, DMF: 500 parts As is clear from Table 4, the polymerization activity of the method of the present invention was 4'1.
CF selectivity cannot be expected, and poly=7-i.
1γIF IS order -11, good and in the produced complex *I ST: Styrene monomer *2 BuA n-butyl acrylate *3 MAA
:Methacrylic acid*4 GMA nigericidyl methacrylate, weight ratio is 50150$5 Hl)U : L6- Hexa
Methy! ene dlet, hyleneure
The composition was evenly and firmly fixed. Example 9 A composite with bisphenol A type general-purpose epoxy resin (Unld
A directional composite was prepared, and mechanical properties such as strand strength, interlaminar shear strength, and bending strength of the shaped product were evaluated. For comparison, untreated CF (shown as a simple blend in the table) was similarly composited and evaluated. The results are shown in Table 6. Table 6 *I CF gold content 0Vo1% -I loss-

Claims (2)

[Claims] (1) When electrolytically polymerizing a reactive polymer using carbon fiber as an electrode, a cycloaliphatic epoxy compound is
1. A method for producing a polymer composition in which carbon fiber and epoxy polymer are strongly integrated, characterized by adding the reactive monomer as part or all of the reactive monomer. (2) The cycloaliphatic epoxy compound is the following general C+
) (In the formula, R1 is 7~o -!-r(3-f RsHC+
~C21]': represents a V ren group. R2 is 04-(
Indicates the alkylene group of 3Q. ) or a cycloaliphatic epoxy compound represented by general formula (1) (wherein R4 represents an alkylene group of 030 or less), the method for producing a polymer composition according to claim 1.