JPH04139246A - Production of poly 1-butene resin for yarn - Google Patents

Abstract

PURPOSE:To obtain a composition providing yarn having high-speed spinning properties, extremely improved drawing properties and high productivity by reacting a poly 1-butene resin with a propylene-based resin in the presence of an organic peroxide. CONSTITUTION:A composition comprising poly 1-butene having >=93% isotactic value and 0.01-5g/10 minutes melt flow rate and a propylene-based resin is heated and reacted in the presence of an organic peroxide. The propylene-based resin used has >=125 deg.C melting point and 0.1-20g/10 minutes melt flow rate. Dicumyl peroxide is used as the organic peroxide and is premixed with the composition, fed to an extruder and heated at 180-230 deg.C.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention relates to a method for producing a poly-1-butene resin composition for textiles, and particularly to a poly-1-butene resin composition for textiles that has excellent high-speed spinnability and stretchability. Relating to a manufacturing method.

<Prior Art> Poly-1-butene resin has excellent heat resistance, creep resistance, stress cracking resistance, flexibility, etc., and is therefore used for hot water pipes, food packaging films, and the like. In recent years, studies have been made to take advantage of the above-mentioned excellent characteristics of poly-1-butene resin to make it into fibers and use it for various purposes.

By the way, poly-1-butene resin is characterized by a slower crystallization rate than polyethylene and polypropylene, which are the same type of polyolefin resins. Therefore, when making poly-1-butene resin into fibers, it is necessary to
In the spinning process, in which butene is extruded through a large number of fine nozzles and wound while being cooled, if the threads come into contact with each other before they crystallize, they will stick together, which is a disadvantage. It becomes a problem in some cases.

In addition, the yarn that has been melt-spun and wound may be used as undrawn yarn without being stretched.
Treatments such as stretching 0 to 400% to make thin fibers and improving strength are also performed.

<Problem to be solved by the invention> However, conventionally, poly-1-butene resins have been produced by polymerization methods using Ziegler catalysts, and the stereoregularity is too low, or even if the stereoregularity is high, Since the molecular weight distribution was too wide, it was not possible to achieve both high-speed melt spinnability and stretchability.

Therefore, an object of the present invention is to provide a method for obtaining a poly-1-butene resin composition for fibers that has excellent high-speed spinnability and stretchability.

<Means for Solving the Problems> In order to solve the above problems, the present invention provides an isotactic value of 93% or more and a melt flow rate of 0.01.
Provided is a method for producing a poly-1-butene resin composition for laM, which includes a step of heating and reacting a composition containing a poly-1-butene resin and a propylene resin of ~5g710min in the presence of an organic peroxide. It is something.

The propylene resin has a melting point of 125°C or higher and a melt flow rate (ASTM DI238, E) of 0.
It is preferable that it is 1 to 20 g/l 0 min.

Hereinafter, the method for producing the poly-1-butene resin composition for fibers of the present invention will be explained in detail.

Poly 1, which is the main component of the composition used in the method of the present invention
-Butene resin has 1-butene as a main component, and contains 0 to 5 mol% of α-olefin having 2 to 12 carbon atoms other than 1-butene.
It contains.

The isotactic value (II), which is an index of stereoregularity, of this poly-1-butene resin is 93% or more, and a poly-1-butene resin composition for fibers with excellent melt-spinning stability can be obtained. Preferably, it is 95% or more.

This isotactic @1 (II) is measured by the following method.

After dissolving 1 g of poly-1-butene resin in 100 ml of n-decane, it was cooled to 0°C and left at 0°C for 24 hours to precipitate highly stereoregular components, and the weight percent of the insoluble portion was set as (II). .

In addition, the melt flow rate of this poly-1-butene resin is 0.01 to 5 g 710 min, and the melt flow rate can be easily controlled during thermal decomposition using an organic peroxide. 01~1 g/l 0mi
Preferably, it is n. This melt flow rate is ASTM D1238. This is a value measured according to H.

The ratio of the weight average molecular weight (Mw) to the number average molecular weight ('n) representing the molecular weight distribution of this poly-1-butene resin (Mw/xn)
) is usually about 4 to 20, and it is about 4 to 15 in that a poly-1-butene resin composition for wa textiles having an appropriate melt fluorate and molecular weight distribution can be obtained by thermal decomposition. It is preferable to have one.

The propylene resin, which is another main component of the composition used in the method of the present invention, is a propylene homopolymer or a copolymer of propylene and another compound copolymerizable with the propylene. It is.

Examples of other compounds copolymerizable with the propylene include ethylene, butene, and the like. These are 1
f! It may be used alone or two or more types may be contained in the propylene resin. When the propylene resin contains this copolymerizable compound, the content thereof is about 1 to 20 mol%.

This propylene-based resin has a melting point of 125°C or higher, and also has a melting point of 125°C or higher and a
Preferably, the temperature is 30°C or higher.

In addition, this propylene resin has similar melting characteristics to poly-1-butene resin, and has a melt flow rate of 0.1 to 20 g/10 min, and further 1 to 10 g/10 min.
10 min is preferable.

Said poly 1 in the composition used in the method of the invention
-The content ratio of butene resin/propylene resin is usually
60/40 to 98/2, and 7 in that it maintains the properties of poly-1-butene resin and accelerates the crystallization rate.
It is preferable that it is 0/30-9515.

The composition may also contain an antioxidant commonly added to polyolefins to prevent oxidation.

Examples of the antioxidant include 2,6-di-t-butyl-4-hydroxybenzoate, n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, and 1,3.5-trimethyl- 2,4,6-tris(3
, 5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(t-butyl-3-hydroxy-2,6-dimethylphenyl)incyanate, tris(3,5-di-t -butyl-4-hydroxyphenyl) isocyanate, n-octadecyl-3-(3,5-
Di-t-butyl-4-hydroxyphenyl) propionate, nickel salt of bis(3,5-di-t-butyl-4-hydroxybenzoylphosphonic acid) monoethyl ester, 2,2'-dihydroxy-3,3'-di(α-methylcyclohexyl)-5,5'-dimethyl-diphenylmethane, 4,4-thio-bis(3-methyl-6-7-
butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-t-butyl-phenyl)butane, tetrakis[methylene-3(3,5-di-t-butyl-4-hydroxyphenyl) propionate comethane,
2.6-di-t-butyl-p-cresol, 4,4'-
Examples include phenol-based antioxidants such as methylenebis(2,6-di-t-butyl-phenol), tris(2,4-di-t-butyl-phenyl)phosphite, and vitamin E, and phosphorus-based antioxidants. These are 1f! Even alone 2
It can also be used in combination of more than one species.

When containing an antioxidant, the content is usually 0.0 parts by weight per 100 parts by weight of poly-1-butene resin in the composition.
The amount is about 5 to 0.8 parts by weight, preferably about 0.1 to 0.5 parts by weight.

Furthermore, in addition to the above-mentioned antioxidants, this composition may contain ultraviolet absorbers, crystal nucleating agents, fungicides, rust inhibitors, lubricants, fillers, pigments, heat stabilizers, etc. as necessary. agent,
It may be included as long as it does not impair the purpose of the present invention.

Further, this composition may contain polyethylene or olefin elastomer in order to improve moldability or adjust various physical properties within a range that does not impair the object of the present invention. When these olefin elastomers are included, the content is usually 20 parts by weight or less based on 100 parts by weight of the poly-1-butene resin.

The method of the present invention is a method for producing a poly-1-butene resin composition for fibers by adding an organic peroxide to the above-mentioned composition and causing a heating reaction.

The organic peroxide used is, for example, 3.5.5
- trimethylhexanoyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, succinic acid peroxide, acetyl peroxide, t-butyl peroxide (2-ethylhexanoate), meta-toluoyl peroxide, Benzoyl peroxide, t-butyl peroxyisobutyrate, 1,
1-bis(t-butylperoxy)3,3.5-)-limethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, t-butylperoxymaleic acid, t-butylperoxylau rate, t-butylperoxy-3,3,5-trimethylhexanoate, cyclohexanone peroxide, t-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-
Di(benzoylperoxy)hexane, t-butylperoxyacetate, 2,2-bis(t-peroxy)butane, t-butylperoxybenzoate, n-butyl-4,4-bis(t-butylperoxy) Valerate,
Di-t-butylshiba-oxyisophthalate, methyl ethyl ketone peroxide, α,α-bis(t-butylperoxyisopropyl)benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butyl) peroxy)hexane, t-butylcumyl peroxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, p-menthane hydroperoxide,
2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3,1,1,3,3-tetramethylbutylhydroperoxide, 2,5-dimethylhexane-2,
Examples include 5-dihydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, and the like.

Among these, dicumyl peroxide, 2,5-dimethyl-2,5 -di(t-butylperoxy)hexane and α,α-bis(t-butylperoxyisopropyl)benzene are preferred.

The amount of organic peroxide used is usually determined by
-0.01 to 0.3 parts by weight, preferably 0.02 parts by weight, based on a total of 100 parts by weight of butene resin and propylene resin
The proportion is ~0.1 part by weight.

The heating reaction may be carried out by supplying the composition and the organic peroxide to an extruder, for example, and heating and melting them to cause the reaction. Providing a spinning nozzle at the exit of the extruder and performing spinning continuously is advantageous for improving productivity.

The organic peroxide may be mixed with the composition in advance and the mixture may be supplied to the extruder, or the composition and organic peroxide may be separately supplied to the extruder at a predetermined ratio and then fed into the extruder. You may also mix it with

The heating temperature in the extruder is appropriately selected depending on the type, amount, etc. of the organic peroxide used, and is not particularly limited as long as it is a temperature at which the composition is decomposed by the organic peroxide. Usually, the temperature is about 180 to 250°C, preferably about 180 to 230°C.

The poly-1-butene resin composition for fibers obtained by the above method usually exhibits a high melt flow rate of about 1 to 50 g710 min, and exhibits a molecular weight distribution (
Mw/Mn) has a narrow molecular weight distribution of about 2 to 6. Therefore, the poly-1-butene resin composition for fibers obtained by the method of the present invention can be
Melt spinning at a high speed of n or more becomes possible, and fibers containing poly-1-butene resin can be obtained with high productivity.
The resulting fibers can also withstand stretching of 200% or more.

The poly-1-butene resin composition for fibers obtained by the present invention can be made into fibers alone, but composite fibers can be obtained by coextruding other thermoplastic resins such as polyethylene, polypropylene, nylon, and polyester. It is also possible.

<Example> Hereinafter, the present invention will be specifically explained by giving examples and comparative examples of the present invention.

(Examples 1 to 3) Organic peroxide was added to a raw material composition consisting of a poly-1-butene resin having an isotactic value (II) melt flow rate and M w / M n shown in Table 1 and a propylene resin. α,α-bis(t-butylperoxyisopropyl)benzene (manufactured by Kayaku Nouri Co., Ltd., Percadox 14) was mixed together, and the resulting mixture was fed to an extruder (screw diameter: 65 mm). Poly 1-
A butene resin composition was obtained.

The melt flow rate (MFR) and the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (M w / M n ) of the obtained wa textile poly-1-butene resin composition were measured, and high-speed spinning was performed. The properties and stretchability were evaluated according to the following methods. The results are shown in Table 1.

The poly-1-butene resin composition for jtL Gogo fibers is supplied to an extruder (screw diameter + 40 mm), melted and kneaded at 200°C, extruded through a die having many pores with a diameter of 0.5 mm, and cooled with air. 300 m/m m on the take-up roll
The yarn was wound up at a take-up speed of 30 to 50 μm in fiber diameter.

Yarn breakage and the state of fusion between threads during this melt-spinning process were observed, and the state of fusion between the wound threads was also examined. High-speed spinnability was considered to be good if melt spinning was possible without yarn breakage and there was only slight fusion between yarns.

Stretchability: The yarn obtained by melt spinning was stretched while passing it through a hot water bath at 80 to 100°C. For stretching, feed speed is 200m/
By changing the take-up speed as min, the highest draw ratio until yarn breakage: was measured, and the case where it was possible to draw at a draw ratio of 200% or more was considered to have good drawability.

(Comparative Example 1) Poly-1-butene resin having the isotactic value (II), melt flow rate, and M W / M n shown in Table 1 was used, except that propylene resin and organic peroxide were not used. Poly 1 for fibers was prepared in the same manner as in Example 1.
- A butene resin composition was obtained.

Melt flow rate (MFR) and ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (M
w/M n ) and evaluated high speed spinnability and drawability. The results are shown in Table 1. As a result, high-speed spinnability was good, but the maximum draw ratio was 110.
%, and the stretchability was insufficient.

(Comparative Example 2) The same procedure as Example 1 was carried out except that a poly-1-butene resin having the isotactic value (II), melt flow rate, and M W / Mn shown in Table 1 was used, and a propylene resin was not used. A poly-1-butene resin composition for fibers was obtained.

Melt flow rate (MFR) and ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw) of the poly-1-butene resin composition for fibers obtained in the same manner as in Example 1
/Mn), and high-speed spinnability and drawability were evaluated. The results are shown in Table 1. As a result, the yarns were severely fused together during spinning, and a good yarn could not be obtained.
Therefore, it was not possible to evaluate the stretchability.

<Effects of the Invention> According to the method of the present invention, a poly-1-butene resin composition for fibers having excellent high-speed spinnability and drawability can be obtained.

\Yoni

Claims (2)

[Claims] (1) Poly 1 having an isotactic value of 93% or more and a melt flow rate of 0.01 to 5 g/10 min
- a composition containing a butene resin and a propylene resin,
A method for producing a poly-1-butene resin composition for fibers, which includes a step of heating and reacting in the presence of an organic peroxide. (2) The method for producing a poly-1-butene resin composition for fibers according to claim 1, wherein the propylene resin has a melting point of 125° C. or higher and a melt flow rate of 0.1 to 20 g/10 min.