JPS60259622A - Polymonovinyl aromatic compound fiber and its manufacture - Google Patents

Abstract

PURPOSE:To obtain the titled fiber having excellent heat-resistance and excellent durability against solvents and chemicals such as strong acids, strong alkalis, etc., by irradiating a fiber composed of a polymonovinyl aromatic compound and PE with electron beam, thereby crosslinking the PE. CONSTITUTION:A fiber composed of a polymonovinyl aromatic compound (preferably PS, etc.) and PE (e.g. a multi-core sea-and-island composite fiber wherein the sea component is PS and the island component is PE) is irradiated with electron beam preferably at a dose of 5-50Mrad to effect the crosslinking of the PE and obtain the objective fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a polymonovinyl aromatic compound fiber having excellent chemical resistance and heat resistance, and a method for producing the same.

(Prior art) Conventionally, polymonovinyl aromatic compound 1 [4T IE string made of polymonovinyl aromatic compound and polyolefin, which was applied by binding, such as composite or mixed fibers as seen in Japanese Patent Publication No. 18139/1983, Polystyrene and polyoletene are easily attacked by organic solvents such as M sulfuric acid, aliphatic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons, resulting in poor morphological stability and problems with heat resistance. That's right. For example, if aromatic hydrocarbons are used as a solvent, the j! In a reaction system where an ion exchange group is introduced downstream, the polyolefin is eluted, so there are problems such as not being able to maintain the [F shape] after introduction, and there are constraints that the reaction system must be selected. child .

(Problems to be Solved by the Invention) The present invention provides excellent chemical resistance and heat resistance to fibers made of polymonovinyl aromatic compounds and polyolefins, thereby making effective use of their excellent reactivity and mechanical strength. The present invention provides five fibers that can be used in a wide range of reaction systems.

Polymonovinyl aromatic compound obtained by the present invention
jA 14 hs + U is not only capable of producing ultra-fine cross-linked and insolubilized ultra-fine 1.71 non-fibers, but also to introduce functional groups into the polymonovinyl aromatic compound. i・I)E! Product f1 can provide fibers that can be applied to a wide range of uses depending on heat resistance.

(Means to Solve the Problem) (1) A polymonovinyl aromatic compound binding string made of a polymonovinyl aromatic compound and crosslinked insolubilized polyethylene.

(2) A polymonovinyl aromatic compound that is characterized by crosslinking the polyethylene by subjecting fibers made of the polymonovinyl aromatic compound and polyethylene to electron beam irradiation. Miscellaneous manufacturing methods.

The fiber made of polymonovinyl aromatic compound (A) and polyethylene (B) as used in the present invention has a sea-island fiber structure in which a plurality of Bs are dispersed in Δ at a3 in the fiber cross section, and B is a core component of one tree and Δ It has a core-sheath structure with a sheath component, and can be manufactured by composite spinning or mixed spinning. Among these, those of the Mukojima type cord type are particularly preferred.

1.) In the present invention, as the polyvinyl aromatic compound, small monopolymers such as styrene and vinyl 1-luene, as well as copolymer 7- and monopolymers thereof, are preferably used from the viewpoint of stability against electron beams.

Any of low-density, medium-density, and high-density polyethylene may be used, but Hatamizumaro's polyethylene is preferred from the viewpoint of silk-spinning properties. Note that if the number average degree of polymerization is too low, insolubilization will not be achieved sufficiently, and conversely, if the number average degree of polymerization is too low, it will not be possible to spin sufficiently thin fibers.
A polyethylene having a number average degree of polymerization of .

The content of polyethylene in the fiber is determined by the desired mechanical strength and use of the fiber, for example, when the purpose is to introduce a functional group, the content of polyethylene in the fiber is determined by the content of the functional group, but it is usually 10-10.
It is selected in the range of 90%, preferably 20 to 80%.

In the first aspect of the present invention, polyethylene can be crosslinked, for example, by electron beams.

, 1. Yo-,) T,,□□O1□1. It is thought that structures such as -1-a, a (to CH2-CH-CH2) mainly occur.

The fibers of the present invention may have any diameter as long as they are permeable to electron beams, but are usually 500 μm or less, preferably 1 μm or less.
It is about ~100μ. Regarding the islands of the sea-island type fiber structure, it is possible to make them even thinner dramatically, but in the present invention, even if the thickness of the Ili miscellaneous is changed as appropriate depending on the application, the effect of the present invention will not be affected in any way. It is not a hindrance.

Examples of the shape of such a van include a short length of 11 feet, a filament, a fiber bundle, a knitted fabric, a nonwoven fabric, a paper-like material, a string-like material, etc., but the present invention is not limited to these shapes.

Polyvinyl aromatic compound of the present invention! Melt is effective as a precursor for obtaining ultrafine cross-linked and insolubilized polyethylene V&navy blue. Moreover, by eluting the polymonovinyl aromatic compound in the fiber of the present invention, chemical resistance fl
In addition, polyethylene fibers with excellent heat resistance can be easily obtained, which has the advantage of being able to be used as a substitute for conventional fibers used for chemical and heat resistant applications, and this is compatible with the fact that polyethylene is extremely inexpensive. In other words, people are the main influence on the development of its uses.

However, the main field of application of the fiber of the present invention [J] is the field in which the polymonovinyl aromatic compound is applied as a functional group-introduced piece, and it can be used extremely effectively in place of the conventional polymonovinyl aromatic compound fiber. applicable. In this case, the polyethylene has the effect of reinforcing the aromatic compound.

When introducing a functional group, there is a method of crosslinking the aromatic compound and introducing the functional group at the same time, but it is usually a safe and stable method to introduce the functional group after crosslinking the aromatic compound. It is preferably adopted as

When the fiber of the present invention is applied as a fiber for government use, a preferable embodiment is that the polymonovinyl y) group compound of the fiber is also insolubilized.

The general method for crosslinking and insolubilizing such a compound is the I-J method using a chemical reaction, but other methods may also be used as long as the compound is crosslinked.

Examples of the crosslinking group C in the case of a chemical reaction include a methylene group and a dihexymethylene group. Such a crosslinking group is practically preferably formed by an aldehyde compound, particularly formaldehyde.

The degree of such crosslinking and insolubilization can be expressed as the toluene insoluble fraction, but in the case of introducing a functional group, this fraction is at least 70%, preferably 80% or more, and more preferably 90% or more of the total fiber weight. 'b' is preferred.

If the toluene insoluble fraction is less than 70%, the shape stability will deteriorate.
tb<, huh? Yo'J a'A□, L□ya. Good, good 9
In addition, the fibers tend to become powdery and lose their characteristics as fibers.

Such cross-linked and insolubilized fibers have excellent chemical resistance, have sufficient durability against various chemicals and solvents used in -C during the introduction of functional groups, and have extremely low deterioration in fiber properties. The functional group-introduced fibers obtained in this way may change from insoluble to soluble depending on the type and amount of functional groups introduced, but they retain their insolubility and are comparable to conventional fibers (fibers before insolubilization). It is also applicable to a reaction system in which the reaction system is dissolved, and it is also possible to increase the number of functional groups of the same kind or other kinds. In some cases, it is also possible to form a special 81-layer having multiple functional groups at the same time.

Here, the toluene insoluble fraction is determined by sufficiently drying the fiber and measuring its weight (Wo),
After adding 1 ton of toluene from 100ml and running it for 2 hours, it was taken out, washed with dry toluene, dried under vacuum, and the weight of the insoluble residue was reduced.
When measured, ri<w) is the percentage of insoluble residue expressed by the following formula:

h)Lr　I　　　, y 工ゎ ゎ ゎ ゎ 　 　7., 8..

. l゛Functional groups that can be introduced into the 11th category of the present invention include, for example, sulfonic acid groups, phosphonic acid groups, carboxylic acid groups, chloromethyl groups, primary to tertiary amino groups, quaternary ammonium groups, chelate groups, and phosphonium groups. , crown ether v4 structural unit, cryptand structural unit, organometallic complex,
All functional groups such as metal colloids that can be introduced into ordinary styrene polymers and styrene/divinylbenzene copolymers can be mentioned.

Next, the method for producing the polymonovinyl aromatic compound m-fiber of the present invention will be explained.

Harari fiber is an Il fiber made of polymonovinyl aromatic compound and polyethylene.

The second feature of the present invention is that an electron beam is applied to crosslink the polyethylene in the raw II fiber.

- However, the electron beam has a small effect on polymonobinyl aromatic hexagroup compounds such as polystyrene, and focuses on the specificity that it acts selectively on poly-1-dylene. In that case, irrespective of whether or not the bolimonobicol aromatic compound is crosslinked, only the polyethylene will be crosslinked when irradiated with the electron beam. Therefore, the irradiation can be performed at any time and by any method, but since the crosslinking reaction tends to be inhibited by oxygen, it is preferable to perform the irradiation in an inert gas such as a nitrogen stream or in a vacuum.

Any known electron beam irradiation device may be used, and a typical example is a van de Graaf electron beam accelerator.

The electron beam absorption dose when the object to be treated is irradiated for 1 minute while moving at a linear velocity of 40 cm/min under conditions of an output of 1 MeV and 100 μA is expressed as 1 Mrad.

The higher the absorbed dose, the more the crosslinking progresses, but if it is too high, fiber deterioration occurs. Therefore, usually 1~100Mra
d, preferably in the range of 5-50M rad is selected.

The method for crosslinking the polymonovinyl aromatic compound in the IN of the present invention may be a commonly used chemical reaction method, such as the method described in Japanese Patent Publication No. 56-18139. It is preferable to carry out crosslinking in an aqueous solution (water: 5 to 20% by volume) system containing the following from the viewpoint of ease of controlling the degree of crosslinking and chemical stability.

(Example) Example 1 Sea component is 50 parts of polystyrene, island component is polyethylene (
The number average degree of polymerization is -1300) 50 parts, and the Shimamoto number is 16.
In this book, a knitted fabric made of multicore sea-island type composite fibers with a fiber diameter of 34xl (approximately 9:1) was heated at 20°C in a nitrogen stream (oxygen 'fA') using a van de Graaf type accelerator. Melon 20
The knitted structure was irradiated with an electron beam three times under the conditions of IMeV and 100 tlA (0 ppm or less) while moving at a linear velocity of 8 cm7'In r n. The absorbed dose of this fiber was 15M rad.

Even when this electron beam irradiated 04 fiber was treated with boiling 1-Lune, the polystyrene was dissolved, but the poly-1-Dylene remained in the form of fibers. However, if the electron beam is not irradiated, the boiling point 1
~In one run, both fiber components are completely dissolved.

Next, the electron beam irradiation @It) AtA1a/T:
1iltl acid 5ml, paralumnofluj” human
200 mg and 0.5 ml of water were added and reacted at 100° C. for 4 hours to obtain crosslinked fibers.

When we measured the toluene-insoluble fraction of this crosslinked fiber, we found that almost no polybrene or polyethylene was dissolved! 71'9
G%tea-]. The appearance of Ii miscellaneous was also very good.

Comparative Example 1 Without electron beam treatment, 1 g of the knitted material used in Example 1 was added with 5 ml of sulfuric acid, 200+ ng of parabomaldehyde, and 0.51 ng of water, and reacted at 100° C. for 4 hours.

When the toluene insoluble fraction of this fiber was measured, it was 59%.
Met. When observed with the naked eye, almost all of the polyethylene in the fibers was dissolved, and the fibers did not quickly change into a fibrous form, but were instead powdery.

Example 2 Using 10 g of the crosslinked fiber of Example 1, it was immersed in a solution consisting of 100 ml of chloromethyl ether and 10 ml of stannic chloride, and reacted at 30° C. for 1 hour. 10 pieces of this fiber
% hydrochloric acid, distilled water, and acetone. Next, 1 tlh of this chloromethyl synthetic fiber was immersed in 30% trimethylamine aqueous solution 1001 and aminated at 30° C. for 1 hour.

The resulting anion exchange fiber had an exchange capacity of 2.5 mcq/g.

In addition, the toluene insoluble fraction at the stage of introducing functionalities j and I is 98% at the stage of chloromethylation, and finally)
It was 100% at the miniaturization stage.

Example 3 Using the knitted fabric 4 made of the multicore sea-island composite fiber shoulder r used in Example 1, the same electron beam irradiation treatment as in Example 1 was applied to Mb L
, 3. This knitted fabric was immersed in methyl edyl ketone and refluxed to dissolve and remove the polystyrene. The obtained knitted fabric is a cross-linked polynylene 1-
It was made of ultrafine fibers and had high elasticity. This knitted material had a morphological stability with a toluene insoluble content of 80%.

(Effects of the Invention) The present invention provides a polymonovinyl aromatic compound S which is not only heat resistant but also extremely durable against various chemicals and solvents including strong acids and strong alkalis.
The degree of freedom in conventional functional group introduction operations has been greatly expanded, making it applicable to a variety of reactions. Additionally, the present invention has the advantage that ultrafine crosslinked and insolubilized polyethylene fiber moldings can be easily obtained.

Patent applicant Higashi Shikikai Co., Ltd.

Claims (2)

[Claims] (1) Poly-[novinyl aromatic compound fibers made of polymonovinyl aromatic compound and crosslinked insolubilized polyethylene. (2) A method for producing a polymonovinyl aromatic compound fiber, which comprises crosslinking the polyethylene by irradiating the fiber made of the polymonovinyl aromatic compound and polyethylene with an electron beam.