JPS596203A - Method for producing new polymer composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel polymer composition in which carbon fibers (hereinafter abbreviated as CF) and an organic polymer are strongly integrated.

Regarding the polymerization of vinyl monomers, various polymerization methods such as radical polymerization, ionic polymerization, and coordination polymerization are known.

There are not necessarily many industrially convenient polymerization methods that require the addition of some kind of polymerization initiator or a water management cycle in the polymerization of polymers. Moreover, although two or three non-catalytic polymerization methods that do not use a polymerization initiator have been reported in unique systems, from an industrial point of view.

could hardly be put to practical use.

In view of the above-mentioned current situation, as a result of intensive studies, the present inventors have discovered that a vinyl monomer capable of radical polymerization in the presence of a specific sulfonic acid monomer or sulfonate monomer is contacted with CF as a third component. By this method, the polymerization activity of the monomer is significantly increased, CF and the organic polymer are strongly integrated, and a novel polymer composition with excellent granulation properties that cannot be obtained by conventional methods can be obtained. This discovery led to the completion of the present invention.

Conventionally, the development of composite fillers that mutually complement the properties of the constituent materials and create new effective functions by combining two or more types of materials has been actively conducted. Regarding compounding with inorganic compounds useful as
For example, improvements in performance over the range of elastic modulus and heat distortion temperature of 2Mt gas-temporal properties have been reported. However, in this case,
Since the properties of the composite materials are significantly different, interfacial compatibility such as compatibility and adhesion is poor, and sufficient composite effects cannot be achieved. Especially when using powdered inorganic fillers, It also has some essential drawbacks, such as the unavoidable deterioration of some of its physical properties, such as its toughness.

To improve this point, a mechanochemical method involves grinding an inorganic compound in the presence of a reactive monomer to graft an organic polymer, and a radiation method involves irradiating an inorganic compound with high-energy radiation to graft an organic polymer. Attempts have been made to improve the interfacial affinity between organic polymeric substances and inorganic compounds by methods such as methods, but these require pulverization processes, radiation generation equipment, etc., resulting in complicated processes and a significant increase in manufacturing costs. There are major problems in terms of practicality.

As a result of intensive studies to improve this point, the present inventors discovered a practical method for producing composites in which various powdered inorganic compounds and nil polymers are firmly integrated in the presence of a specific sulfonic acid monomer. First, we filed a patent application No. 1983-937. Subsequently, as a result of further studies, it was found that CF is particularly rich in polymerization activity as an inorganic compound, has excellent interfacial cohesiveness, and has a unique and pronounced formation even in relatively long fibers, including powdered fine fibers. The present invention was completed based on the discovery that it exhibits graininess.

That is, the present invention provides the following general formula %formula%] (In the formula, R1 is H, an alkyl group having 1 to 20 carbon atoms.

Phenyl group and its derivatives or halogen radicals it.

Take (CH,)n, R1 and R3 are each ■ or an alkyl group having 1 to 15 carbon atoms, R4 is an alkylene group having 1 to 15 carbon atoms, m is an integer of 1 to 20, and n is 0
In the presence of a sulfonic acid or sulfonate monomer, an integer of ~20, Y being H, NI (or an alkali metal atom), and in a polymerization system in which CF is dispersed.

The present invention provides a method for producing a novel polymer composition in which CF and an organic polymer are strongly integrated, characterized by polymerizing at least one radically polymerizable vinyl monomer.

Generally, when vinyl monomers are simply polymerized in the presence of an acid under temperature conditions that do not cause a thermal polymerization reaction, the polymerization rate remains at an extremely low level even after several days of polymerization time. On the other hand, according to the present invention, by adding CF as a third component, a very specific polymerization activity is brought about, and a polymer with a high polymerization rate that is of practical value can be obtained in a few hours. In addition, it provides an extremely clean polymerization form without current generation due to gas phase polymerization.

Furthermore, the present invention is characterized by: 1. The interaction between the CF surface and the polymer applied by the method of the present invention is strongly integrated beyond adhesion in the sense of simple adsorption. At the point.

In addition, it can be applied not only to fine powder CF but also to relatively long CF such as chopped strand fibers, which are normally difficult to process in a medium due to reduced cohesiveness, entanglement and agglomeration between fibers. This can be said to be a great practical value of the present invention.

An example of an embodiment when carrying out the present invention is as follows:
After suspending and dispersing the organic vinyl monomer and CF in the water matrix r'11 under temperature conditions that do not cause the PA polymerization reaction, a nulphonic acid monomer or a sulfonate monomer is added and stirred to form an aqueous system. As a result of the heterogeneous polymerization reaction, the CF-i surface is uniformly coated with the vinyl monomer at a high polymerization rate over a predetermined polymerization time.
Moreover, it can be firmly fixed.

At this time, it is an essential condition that the three components mentioned above are brought into contact with each other in coexistence, but it is not necessarily necessary to bring them into contact at the same time.

Request 1: Even if CF pretreated with, for example, a sulfonic acid monomer or a sulfonate monomer is used, 9 the method of the present invention can be used without adding any new sulfonic acid monomer or sulfonate monomer during the polymerization of the monomers. Similar polymer compositions can be obtained.

Conventionally, a method for obtaining a similar polymer composition in the presence of hydrogen sulfite ions is known, but since a large amount of cullet from gas phase polymerization adheres and the product is extremely fine particles, it requires washing and recovery. It has a disadvantage in terms of industrial practicality in that post-processing is not easy. Regarding these problems, the method of the present invention uses the specific sulfonic acid monomer or sulfonate monomer represented by the above general formula [1], thereby resulting in a clean polymerization form with almost no current generation, and is even more surprising. (Preferably, since the resulting polymer composition has excellent granulation properties, it provides a method for obtaining a product with extremely easy subsequent steps such as washing and recovery.

The specific sulfonic acid monomer used in the present invention has a sulfonic acid group as an active side that brings about monopolymerization activity as a sulfonate monomer, and an active side that exhibits strong bonding properties between the produced polymer and CF. The presence of a double bond is essential, and a compound having the structure represented by the above general formula LIE that has both of these two types of functional groups can be applied. Propanesulfonic acid (hereinafter referred to as A
(abbreviated as MPS), sodium 2-methacrylethanesulfonate (hereinafter referred to as

SEM-Na), sodium 3-methacrylicpropanesulfonate (hereinafter referred to as sps), sodium 2-propenesulfonate (hereinafter referred to as NaAS)
), sodium 2-methyl-2-propenesulfonate (hereinafter abbreviated as NaMS), etc., but AMPS containing an amide bond, SFM-Na containing an ester bond, and sps have particularly remarkable granulation properties. It is preferable because it expresses the following properties and has a high polymerization activity.

The CF used in the present invention is a high-strength or high-elastic carbon made of polyacrylonitrile or a copolymer thereof.
F. Petroleum pyrolysis pitch.

C made from coal tar pitch and coal depolymerized products
Examples include F, and CF produced by a vapor phase growth method, 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 morphology ranges from powdery O, lynyx to large chopped strands with an aspect ratio of 3 to 20 ttnn, with a wide range of fiber lengths suitable for convenient oJ performance. Not limited. All of the composites obtained by the present invention are obtained in the form of granules that have good interfacial adhesion and are easy to handle. Among them, when chopped strand-like CF is stirred in water or an organic solvent, the single fibers generally coagulate and are difficult to blend with resin, but according to the present invention, its excellent granulation properties By taking advantage of this and adjusting the conditions, it is possible to obtain pellets with a size of approximately 1 to 2 mm, which are easy to handle and work. However, when the pitch-based CF reaches a fiber length of about 1 inch or more, the CF itself is already flocculent and agglomerated, so it cannot normally be pre-coated with a resin, but when the formulation of the present invention is applied, it can be extruded. Alternatively, since a pellet-like composite with good injection molding processability is easily torn, the present invention has extremely high practical value as a method for adjusting the shape of the composite in addition to the interfacial effect. Eggplant・I roving-shaped long moro 1
The present invention can also be applied to these materials by static treatment or gentle stirring conditions, and excellent interfacial effects can be obtained.

The vinyl used in the present invention is an integral part of the vinyl.

Any of the usual radically polymerized vinyl monomers can be used, but methyl methacrylate is especially suitable! 1″, ge?-
It is particularly preferable because it has high polymerization activity and good coalescence between the carbon-forming polymer and CF. When a mixture of two or more monomers is used, it is preferable to use methyl methacrylate as one component, particularly from the viewpoint of polymerization activity.

According to the present invention, the concentration of sulfonic acid or sulfonate monomers is about 0.05-10% based on the total weight of CF and monomer.

Preferably 0.1 to 50 weight ratio, particularly preferably 0.5
Used in amounts of ~30 Jyugenka. In most cases, it is preferred to increase the amount of sulfonic acid or sulfonate monomer as the monomer component increases. C to use
The weight ratio of monomer or monomer mixture to F can vary within a wide range, from about 500:1 to 1:5.
Preferably the ratio is from about 50:1 to about 1:1. The amount of water is
It is about 1% to several hundred times, preferably about 10% to 10 times, based on the total weight of CF and monomer. The reaction is preferably
For example, under an atmosphere of inert gas such as nitrogen,
The temperature is about 10-100°C, preferably 20-80°C. The specific reaction temperature here is selected as appropriate depending on the vinyl monomer used, but it is important to carry out the reaction at a temperature that suppresses thermal polymerization to a negligible extent, and it is important to carry out the reaction at a temperature that is extremely high so that thermal polymerization does not occur. In this case, the integrity and homogeneity of the resulting complex is inhibited. Reaction time is 30 minutes to about 15 hours. The resulting complex is approximately 10-300°C,
Preferably, drying can be performed at a temperature range of about 5() to 200°C. It should be noted that the interaction between the surface of CF and the polymer applied by the method of the present invention goes beyond adhesion in a physical sense due to simple adsorption or van der Waals forces, and this fact is true for vinyl. This is clear from the fact that a large amount of unextracted polymer is observed even after extraction with a good solvent for the polymer.

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

Example 1. Comparative Examples 1 to 6 500m/! set with cooling pipe, nitrogen introduction pipe, stirring rod, and thermocouple for internal temperature detection! In the fourth flask, add pitch-based graphite CF (manufactured by Kureha Chemical Industry Co., Ltd.) and chop M2O1.
) The suspension was dispersed in 270 ml of deionized water, followed by purging with nitrogen for 30 minutes. Next, 30.07 g of methyl methacrylate was added together with the vinyl monomer while stirring vigorously under nitrogen flow. Next, in a hot water bath, the temperature of the reaction solution was not raised to 50"C. After confirming that the added monomer was uniformly dispersed, the sulfonate monomer was dissolved in deionized water. lomi
Gradually add the solution dissolved in

The polymerization reaction was carried out at the same temperature for 8 hours. After the polymerization was completed, about 21- was sampled from one reaction solution, and the remaining unreacted monomer was measured by gas chromatography using dioxane as an internal standard reagent to determine the polymerization rate. For comparison, the polymerization behavior when no CF is added, polymerization without the addition of sulfonic acid monomer or sulfonate monomer, polymerization with the addition of ethane sulfonic acid, which is a saturated organic sulfonic acid, and polymerization behavior when sulfite water is added, is also shown. A similar combination operation and post-polymerization evaluation were performed and investigated. The results are shown in Table 1. Note that all parts indicate the weighing part.

No. +16% H, So3 aqueous solution +2 MMA: Methyl methacrylate 3.Cullet adhesion 0... is almost impossible.

×... It sticks quite a bit.

XX... A large amount adheres.

Granulation property ◎: Good and very easy to wash and collect.

×... It is defective and it is difficult to recover it by cleaning.

XX... It is defective, and cleaning and recovery are extremely difficult.

As is clear from Table 1, the system shown in Comparative Example 4 in which no sulfonic acid monomer or sulfonate monomer was added did not show any polymerization activity; Whereas a simple two-component system with CF has extremely low polymerization activity, the method of the present invention in which CF is added as a third component significantly increases the monomer polymerization rate. Although the polymerization system has a high monomer polymerization rate, the polymerization conditions such as current adhesion and secondary aggregation performance are significantly inferior to the method of the present invention. It shows.

Examples 2-5. Comparative Examples 7 to 9 SPS, AM instead of SEM-Na as the sulfonic acid monomer or sulfonate monomer in Example 1
Polymerization was carried out in the same manner as in Example 1 except that PS, NaAS, and NaMS were used, and the monomer polymerization rate was measured and evaluated. The results were compared with Example 1 and are shown in Table 2.

Table 2 As is clear from Table 2, the monopolymerization activity is SEN・Na, S
PS, AMPS are extremely high in temperature (, NaAS.

NaMS showed a slightly lower level.

Polymer composition 1 obtained by the method of Examples 1 to 5
The polymer extraction of the composition was measured by weighing 07' together with a cylindrical opening paper and conducting a 24-hour Nxhlet extraction test using be/zene, which is a good solvent for methyl methacrylate polymer, as an extraction solvent. For comparison, a composition coated with polymethyl methacrylate prepared by dispersing an inorganic powder (pitch thread CF) in a methylene chloride solution of polymethyl methacrylate and then evaporating the solvent was prepared (Comparative Example 7). ) Comparative Examples 8.9 and 4.) Comparative Examples 8 and 9 were also evaluated and studied in the same manner. The results are shown in Table 3. The polymer components in the composites shown in the comparative example were completely extracted in the 24-hour extraction test, whereas the polymer components obtained by the method of the present invention were completely extracted by the method of the present invention. The extraction rate of the components is small, and most of them are not extracted and are strongly integrated into CF.

Table 3 *1 Manufactured by Mitsubishi Rayon Co., Ltd., using Acrybet VH *
2 AIBN: Azobisisobutyronitrile *3
KPS: Potassium Persulfate Example 6 The reaction was carried out in the same manner as in Example 1 except that the type of CF was changed, and the resulting composition was evaluated. The results are shown in Table 4.

*l Kureka Chop manufactured by Kureha Chemical Industry Co., Ltd. *2 Manufactured by Mitsubishi Rayon Co., Ltd. *3 Extrusion workability 0 Extremely easy to extrude and shape.

Q: It's easy.

△ It is difficult.

× It is impossible.

*4 Polymerization conditions CF 10 parts SEM-Na 6.5 parts MMA monomer 30 parts Deionized water 280 parts It is clear from Table 4 that in the case of untreated CF, especially pitch-based CF, fibers of about I 11 or more When the length becomes long, the CF itself is already flocculent and agglomerated, so it cannot be blended with resin and extruded. However, by applying the method of the present invention, a pellet-like composite with good extrusion or injection molding processability can be obtained. As a result, blend extrudability becomes extremely easy. In addition, in the method of the present invention, CF selectivity regarding monopolymerization activity was not observed, and the monomer polymerization rate was generally good, and
It can be seen that the extraction rate of the polymer component in the produced complex is small, most of it is not extracted, and it is strongly integrated with CF.

Example 7 In place of methyl methacrylate as the vinyl monomer,
The reaction was carried out in the same manner as in Example 1 except that one type of vinyl monomer or a mixture of two types shown in the table was used, and the results of evaluation of the obtained compositions are shown in Table 5.

Table 5 *l The weight ratio of the mixed system is 5 o15 QST: styrene, /BuA n-butyl acrylate, /M
MA: Methyl methacrylate Example 8 In a Henschel mixer for powder kneading, pitch-based CF (M
-201) 38.7JP and SEM-Na6.5P were added and stirred thoroughly for 10 minutes. Using a reactor set in the same manner as in Example 1, the entire amount of the treated filler was mixed with 280m7 of deionized water! The mixture was suspended and dispersed in the solution, and the atmosphere was replaced with nitrogen for 30 minutes.

Then, 30. methyl methacrylate was used as the vinyl monomer.
07 was added with vigorous stirring under nitrogen flow. Next, the temperature of the reaction solution was raised to 50°C in a hot water bath, and a polymerization reaction was carried out at the same temperature for 8 hours. After the polymerization was completed, the monomer polymerization rate was evaluated in the same manner as in Example 1. 80.5%, and the obtained composite was a composition in which the surface of the inorganic substance was uniformly and firmly fixed with the polymer of the vinyl monomer.

Example 9 The polymer composition obtained according to the present invention was blended with a general-purpose polymer pellet, the CF content was adjusted to 30 cIb, a composite molded article was prepared using an extruder, and the mechanical properties and thermal properties of the molded article were evaluated. Characteristics were evaluated.

For comparison, untreated CF (shown as a simple blend in the table) was similarly blended and evaluated. The results are shown in Table 6.

Table 6 *1 Manufactured by Ube Industries, Ltd. *2 Measurement of bending strength and impact strength is as per ASTM
D790 and ASTM I) 256 (without notch)
I did it.

*3 Measurement of heat distortion temperature is based on ASTMI) 648 (18,
6 kg/C1n').

It was shown that the composite composition produced by the method of the present invention is an excellent composition in terms of practicality such as mechanical properties and heat resistance. ing.

Procedure Ura City 1'l' (voluntary) 11□100 II
57 '8 II%bit1.11? 'r Agency Director Kazuo Wakasugi Tono 1゜・l+fi table・jgu'F♀Kasho 57 ] ] No. 5246? Invention 09
Name (;1, Manufacturing method of new electrolyte composition: 1.1 Mountain 11/Shi・Suru person'1 Eye cow and υ) Related Patent applicant Jujube Chuka 1beichi;-(To 1, J l 1.”=ii〒
Enshi J (60a) Mitsubishi Rayon Book End Ceremony Company 11 ShifLii i Length 111 1n l°1000' [1
Tani-jyo” 1! People (lj I; <Tokyo history 1be+111r< 11+:s
City 10 Yumi Mitsubishi Rayon Co., Ltd. Spontaneous Amendment 6, r+Ii City's Karii 5 Specification■ "Detailed Description of the Invention" Column 7, Supplement j1 °1.zu (1) Page 19 of the specification is attached as an attached sheet. Correct the entire sentence as follows.

(2) The entire text of page 21 of the specification should be corrected as shown in the attached sheet.

(3) Mei 9 (I) Book Box 25, Lines 8 to 11: ``Moreover, the obtained polymer has a composition in which the surface of the inorganic material is uniformly and firmly fixed with the polymer of the vinyl monomer. [Moreover, the obtained composite was a composition in which the surface of the CF coating was uniformly and firmly fixed by the 71'I coalescence of the vinyl monomer. ].

(4) Specifications ■ “Naron-6” listed in Table 6 on page 26
．． 6" is corrected to "nylon-6,6".

8.Inventory of attached bedding (1) Correction No. 19 Page 1 copy (2) Correction No. 2
1 page 1st copy 3 Table 1＼ I゛□ 1゜＋' 〼＊1 Mitsubishi Rayon Co., Ltd. Ate, using Acrybet VH＊
2 AIBN: Azobisin butyronitrile *3
KPS: potassium persulfate

Claims (1)

[Claims] 1. The following general formula %) (In 'i, R, is H, an alkyl group having 1 to 2 carbon atoms, a phenyl group and its derivatives, or halo R. Gen atom, X is C0NH , cONH-C-R,, Co. 3 (Ci'it)nl or (CH2)n, R2 and R3 are each H or an alkyl group having 1 to 15 carbon atoms, and R is an alkyl group having 1 to 15 carbon atoms. alkylene group. m is an integer of 1 to 20, n is an integer of 0 to 2o, Y is H, NH, or an alkali metal atom). The fibers are dispersed in a polymerization system,
1. A method for producing a novel polymer composition, which comprises polymerizing at least one radically polymerizable vinyl monomer. 2. A patent claim characterized in that the sulfonic acid monomer or sulfonate monomer is 2-acrylamido-2-methylzolopanesulfonic acid, sodium 2-methacrylethanesulfonate, or sodium 3-methacrylpropanesulfonate. A method for producing the novel polymer composition according to item 1. 3. Claim 1 or 2, characterized in that the main component of the vinyl monomer is methyl methacrylate.
2. Method for producing the novel polymer composition described in Section 1.