JPS58179255A - Nitrile copolymer composition - Google Patents

Abstract

PURPOSE:To prepare the titled copolymer composition having high thermal stability and excellent moldability, by adding a fatty acid nitrile monomer unit having two or more nitrile groups per one molecule to the base resin. CONSTITUTION:The objective composition is prepared by adding 0.1-8pts.wt. of an aliphatic nitrile monomer having 1-32 carbon atoms (excluding the nitrile carbon atom) and two or more nitrile groups per one molecule (e.g. malononitrile) to 100pts.wt. of (A) a nitrile-type copolymer composed of (i) 45-90wt% of one or more nitrile monomers of formula (R is H, 1-4C lower alkyl or halogen) (e.g. acrylonitrile) and (ii) 55-10wt% of a polymerizable monomer copolymerizable therewith (e.g. acrylic acid ester) or (B) a nitrile-type copolymer obtained by reinforcing the component (A) with a rubbery polymer (e.g. a diene rubber) wherein the ratio of the nitrile monomer in the copolymer is 45-90wt%.

Description

[Detailed description of the invention] The present invention provides thermally stable and excellent moldability 2) IJ
This invention relates to a copolymer composition.

In general, nitrile polymers containing a high proportion of IJ monomers such as acrylonitrile and methacrylonitrile, or compositions containing the same, have excellent mechanical properties,
It has characteristics such as low gas permeability and chemical resistance. However, this type of polymer has the problem that it is difficult to mold because it is unstable and tends to discolor or decompose when heated. Particularly when heat molding is performed at high temperatures, for example when extrusion molding or injection molding, discoloration and decomposition are significant.

As a result of intensive research to improve the molding difficulties of nitrile polymers, the present inventors have found that nitrile polymers with a carbon number of 1 to 32 (d) having two or more IJ groups per molecule ! The present invention has been based on the discovery that when an aliphatic nitrile compound (excluding the carbon in the JR group) is added to a polymer containing a high proportion of nitrile monomer units, heat moldability is significantly improved and discoloration can also be prevented. completed.

That is, the present invention provides at least one dihydrogen compound represented by the horizontal bending formula co2=c-CN (where R is water-(Z is a lower alkyl group having 1 to 4 carbon atoms or a halogen radical f-)).
-IJ spinning wheel polymer or copolymer thereof consisting of 45 to 90% by weight of an IJ-based monomer and 545 to 10% by weight of another polymerizable monomer that can be copolymerized with it A copolymer in which the polymer is reinforced with a rubber-like polymer, and the ratio of the nitrile main polymer having the above structural formula to the Imaichi polymer is 45 to 45.
90% by weight of the nitrile copolymer (hereinafter referred to as "the nitrile copolymer of the present invention") 1004ii Otori,
1 carbon number with 2 nitrile groups on I'l per molecule
~32' (2) A nitrile-based polymer composition prepared by adding 1 to 8 parts of an aliphatic nitrile compound (excluding carbon in IJ).

The polymers used in the present invention include acrylonitrile, bemethacrylonitrile, ethacrylonitrile, α□-chloroacrylonitrile, α-fluoroacrylonitrile, and others. Among these, acrylonitrile and himetacrylonitrile are particularly preferred.

Other monomers that can be copolymerized with this include acrylic esters, methacrylic esters, alkyl vinyl ethers, aromatic vinyl compounds, a-olefins, and others. Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and methyl methacrylate. As alkyl vinyl ether IV, methyl vinyl ether,
Examples of aromatic vinyl compounds such as ethyl vinyl ether and propyl vinyl ether include styrene, α-methylstyrene, nuclear-substituted alkylstyrene, nuclear-substituted halo)y'-y, and tyrene. α-olefin toshi is 2
-Methyl-1-butene and isobutyne are preferred. In addition, vinyl acetate, vinyl propionate, indene, etc. can also be used.

In the present invention, 2) The IJJ copolymer is preferably reinforced by containing a rubbery polymer in order to improve impact resistance. Methods for incorporating a rubbery polymer include a method of blending a rubbery polymer and a nitrile copolymer, a method of graft polymerizing a nitrile monomer, etc. in the presence of a rubbery polymer, and A method of blending this graft copolymer with a di-IJ-based copolymer, and any other suitable method may be employed.

Suitable rubber J-like polymers include diene thread rubber, acrylic ester rubber, olefin rubber, urethane rubber, and mixtures thereof. The amount of these rubbery polymers is determined depending on the purpose, but in order not to significantly impair the properties of the nitrile copolymer, it is necessary to It is preferably 30% by weight or less, more preferably 15% or less and 7% by weight or less.

The aliphatic nitrile compound used in the present invention has two or more, preferably 2 to 4, nitrile groups per molecule, and has 1 to 62 carbon atoms (excluding carbon in the nitrile group), It may not only be linear but also branched.

Specifically, malononitrile, suberonitrile, geltalonitrile, adiponitrile, pimelonitrile, suberonitrile, azelaonitrile, sepaconitrile, nonane-
1,9-dinitrile, decane-1,10-dinitrile,
undecane-1,11-dinitrile, dodecane-1,1
2-dinitrile, tridecane-1,13-dinitrile,
Tetradecane-1,14-dinitrile, pentadecane-
1,15-dinitrile, hexadecane-1,17-dinitrile, octadecane-1,18-dinitrile, nonatecane-1,19-dinitrile, icosane-1,20
-dinitrile, heneicosane-1,21-dinitrile, tocosan-1,22-dinitrile, tetracosane-1
, 24-dinitrile, octacosane-1,28-dinitrile, todoriacontane-1,32-dinitrile, methylcultalonitrile, pentane-1,4-dinitrile,
Furopane-1,1,2-trinitrile, nonane-1,3
, 3-trinitrile, butane i, i, 4,4-tetranitrile, pentane-1,2,2,5-tetranitrile, etc. can be used. Particularly preferred are adiponitrile, pimelonitrile, subnitrile, acrylonitrile, and sepaconitrile. The amount used is "2) of the present invention"
The amount is 0.1 to 8 small parts, preferably 0.6 to 5 parts by weight, per 100 parts by weight of the IJ-based copolymer. If the amount is less than 0.01 parts by weight, the effect in improving heat moldability and heat coloring will be small, and if it exceeds 8 parts by weight, mechanical properties such as tensile strength will be impaired.

Any known method may be used for mixing [the nitrile copolymer of the present invention] and the aliphatic nitrile compound, and methods such as powder blending, melt mixing, solution blending, and aqueous dispersion blending are employed. When forming the desired molded product by injection molding, extrusion molding, etc., there are methods using heated rolls, a Banbury mixer 1 extruder, a kneader-pre-noder, and others. In addition, when mixing [the nitrile copolymer of the present invention] and the aliphatic nitrile compound, an aliphatic 2) IJ compound is added before or during the polymerization reaction of the "nitrile copolymer of the present invention". It may be a method. However, in that case, it is preferable to add it so as not to cause a large change in the polymerization behavior, and in particular, it is necessary to prevent the aliphatic nitrile compound from substantially reacting in the polymerization system.

Furthermore, if necessary, a heat stabilizer, ultraviolet absorber, oxidation inhibitor, lubricant, pigment, etc. may be added to the composition.

The composition thus obtained has excellent thermal stability and good moldability without impairing the excellent properties of the nitrile copolymer, and can be formed into films, sheets, bottles, etc. using a general molding machine. It is possible to provide useful materials for

The present invention will be explained below with reference to Examples.

Examples 1 to 5, Comparative Examples 1 to 2 In the presence of 10% by weight (solid content) of nutyrene-butadiene combination latex with a styrene content of 25% by weight,
A monomer mixture consisting of 65% by weight of acrylonitrile, 13% by weight of methylene chloride, and 12% by weight of methyl methacrylate was subjected to emulsion graft polymerization to obtain a nitrile copolymer powder.

The conversion rate of the tl'-bt form was 950% by weight. To 100 parts by weight of this copolymer powder, 05 parts by weight of a dioctyltin malate stabilizer and a stabilizer as shown in Table 1 were added,
The pellets were fed into an extruder and made into pellets at 200'C. The pellets were fed into a 20-screw extruder heated to 240'C and the steady torque during extrusion was compared. Five cabinet plates were injection molded at 210°C, and the tensile strength and yellowness at 23'C were measured.

vi chromaticity was measured using a colorimetric colorimeter (ND-11 manufactured by Nippon Heavy Industries Co., Ltd.).
JID type) based on JIS K 7103. In other words, the yellowness is the standard machinium oxide,
#16 Visible wavelength range for whiteness plate (400-703
The tristimulus values X, Y, and Z for standard light were determined from the spectral reflection characteristic curve at mμ) and calculated using the following formula.

1°28X-1,0622 Yellowness=-X100 Comparative Examples 1 and 2 were also prepared and measured in the same manner. The results are shown in Table 1.

As is clear from Table 1, by blending an aliphatic nitrile compound, "the nitrile copolymer of the present invention" can be
Molding fluidity and yellowness were improved with almost no decrease in tensile strength.

Claims (1)

[Claims] One or more nitrile monomers represented by the general formula 〇l(22C-ON (where 1 is hydrogen, a lower alkyl group having 1 to 4 carbon atoms, or a halogen atom) and 55 to 90% by weight of other small polymerizable substances that can be copolymerized therewith.
A nitrile-based copolymer consisting of 0M amount%, or a copolymer in which this copolymer is reinforced with a rubber-like polymer, in which the proportion of the nitrile-based monomer having the above general formula to the total polymer is Nitrile copolymer 100 which is 45-90% by weight
Add an aliphatic nitrile compound having 1 to 62 carbon atoms (excluding the carbon in the J group) and having two or more nitrile groups per minute to the overlapping part. A nitrile copolymer composition comprising: