JPH03181552A - Polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having improved vibration-damping property near room temperature and improved impact resistance by compounding a polyphenylene ether resin with a (hydrogenated) block copolymer having a specific molecular structure. CONSTITUTION:The objective resin composition contains (A) 97-50 pts.wt. of a polyphenylene ether resin, preferably poly(2,6-dimethyl-1,4-phenylene) ether, etc., and (B) 3-50 pts.wt. of a (hydrogenated) block copolymer having a number- average molecular weight of 30,000-300,000 and composed of (B1) a block having a number-average molecular weight of 2,500-40,000 and composed of a vinyl aromatic monomer (preferably styrene) and (B2) a block composed of isoprene or isoprene-butadiene, having a number-average molecular weight of 10,000-200,000, containing >=40% of 3,4-bond and 1,2-bond and having a principal dispersion peak of tandelta at >=0 deg.C.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention provides polyphenylene ether (
P P E) Regarding a resin composition.

[Conventional technology]

In recent years, the use of plastic materials has become commonplace as casing, inner, and exterior materials for various types of equipment, including office equipment, audio equipment, and household electrical appliances. Among these, PPE resin has excellent mechanical properties and is well balanced including creep and stress relaxation. Furthermore, it has the characteristics of being heat resistant, having little deterioration in physical properties at low temperatures, and having excellent flame retardancy. However, since the PPE resin itself has problems in terms of moldability, modified products with improved moldability are widely used.

In applications where this is used, for example, in office equipment such as copying machines and printers, reduction of noise and vibration generated by these devices is an important issue. In addition, quietness due to low vibration and low noise of household electrical appliances such as refrigerators, washing machines, and vacuum cleaners is also an important product performance.

[Problem to be solved by the invention]

Polymer materials are inherently advantageous in terms of suppressing vibration and noise generation compared to metal materials, but they are not satisfactory in terms of vibration and noise at room temperatures where various equipment is used. There wasn't.

The main object of the present invention is to improve the vibration damping performance of PPE resin, which is commonly used as a material for various types of equipment, at around room temperature.

[Means to solve the problem]

According to the present invention, the above problem can be solved by (a) PPE resin 97-5
0 parts by weight, and (b) number average molecular weight of 2500 to 400
block (A) consisting of a vinyl aromatic monomer of 00 and isoprene or isoprene-butadiene, with a number average molecular weight of 10,000 to 200,000, and 3,4
A block (B
) with a number average molecular weight of 30,000 to 300
000 block copolymer or its hydrogenated product 3~
It is distantly related to compositions containing 50 parts by weight.

The present composition is effective in improving the impact resistance of PPE resin, and is useful as a material that reduces vibration and noise generation.

The present invention will be explained in more detail below.

The PPE resin used in the present invention is composed of 2〇 (one unit of oxygen ether atom is bonded to the benzene nucleus of an adjacent unit, n is an integer of at least 50, and each Q
is a hydrogen atom, a halogen atom, a hydrocarbon group that does not contain a tertiary α carbon atom, a halohydrocarbon group that has at least two carbon atoms between a halogen atom and a phenyl nucleus, a hydrocarbon oxy group, and a halogen atom and a phenyl nucleus. It is a resin having repeating structural units represented by a monovalent substituent selected from the group consisting of halohydrocarbonoxy groups having at least two carbon atoms between them.

Preferred PPE resins are those in which Q is an alkyl group, particularly preferred are those in which Q is an alkyl group having 1 to 4 carbon atoms. For example, poly(2,6-cymethyl-1
, 4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly
(2-methyl-6-propyl-1,4-phenylene) ether, poly (2,6-diprobyl-1,4-phenylene) ether, poly (2-ethyl-6-broby-L4-phenylene) ether, and the like.

Furthermore, in order to improve the processability of the above-mentioned PPB resin, a blend of polystyrene or the like or a graft of polystyrene or the like may also be used.

The second component of the block copolymer used in the present invention is a vinyl aromatic monomer such as styrene, α-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 3-methyl Examples include styrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, and the most preferred is styrene.

The number average molecular weight of the vinyl aromatic block (A) is 2500
~40,000. If the molecular weight is less than 2,500, the performance of the composition will deteriorate, and if it exceeds 40,000, the melt viscosity will be too high, and mixing with the PPE resin will not be successful, making it impossible to obtain a composition with sufficient performance.

The proportion of the vinyl aromatic block (A) in the block copolymer is preferably 5 to 50% by weight. If this ratio is less than 5%, the mechanical properties of the block copolymer will be insufficient, and on the other hand, if it exceeds 50%, the viscosity will become extremely high, making processing such as mixing difficult, and vibration damping performance will decrease. .

Further, as the second component of the block copolymer used in the present invention, isoprene or isoprene-butadiene is preferably used in combination. When other monomers are used, for example, butadiene alone, the temperature at which damping performance is exhibited even if the amount of 1.2 bond is increased is less than 0°C, and the function at the temperature actually used is is not obtained,
It has little practical significance. In the case of isoprene, 3 of the present invention
．． 4 bond and ], 2 bond metal content (hereinafter these may be collectively referred to as vinyl bond metal content), damping vibration in a practical temperature range from approximately O'C to around 50℃. It is extremely meaningful from a practical point of view, as it can demonstrate high performance and can be used in a wide range of applications. When using isoprene-butadiene together, the ratio of isoprene is 4
If it is 0% or more, damping performance will be exhibited at 0°C or higher. Block (B) when isoprene-phtadiene is used together
The format may be random, block, or Cheebird.

The content of 3.4 bonds and 1.2 bonds in the block (B) of the block copolymer of the present invention is 40% or more (100%
) is used. If the vinyl alloy content is less than 40%, sufficient allocation performance cannot be obtained in the normal operating temperature range, which is not preferable.

In addition, t obtained by measuring the viscoelasticity of the block copolymer
The temperature of the peak of the main dispersion of andδ (loss tangent) is O″C0
The above is necessary. Even if there is a peak only at a temperature lower than 0° C., sufficient allocation performance cannot be obtained in the normal temperature range.

Moreover, the number average molecular weight of block (B) is 10,000 to 2
A value in the range 00000 is used. If the molecular weight is smaller than the above range, the elastic properties will be impaired, which is not preferable. Moreover, if it is too large, the fluidity will deteriorate, which is not preferable.

The number average molecular weight of the obtained block copolymer is 30,000
It is necessary to be in the range of ~300,000.

If the molecular weight is less than 30,000, mechanical properties such as strength at break and elongation of the block copolymer itself will be lowered, and the strength of the composition will be lowered, which is not preferable. Also, 3
When it exceeds 00,000, processability deteriorates, mixing with the PPE resin does not work well, and an m-paraboloid having sufficient performance cannot be obtained. From this point of view, the molecular weight of the block copolymer is more preferably in the range of 80,000 to 250,000.

The block form of the block copolymer is A (BA) n
(AB) Indicated by n. Here, A represents a block consisting of a vinyl aromatic monomer, B represents a block consisting of isoprene or isoprene-butadiene, and n is an integer of 1 or more. Among these, the A-B-A form is most preferably used.

In the present invention, the block copolymer can be obtained by the following various methods.

First, the block copolymer is produced by (a) sequentially polymerizing an aromatic vinyl compound, isoprene, or isoprene-butadiene using an alkyllithium compound as an initiator, and (b) polymerizing an aromatic vinyl compound and then isoprene or isoprene-butadiene. However, examples include a method of cambling this with a camping agent, or a method of sequentially polymerizing isoprene or isoprene-butadiene and then an aromatic vinyl compound using (c) a dilithium compound as an initiator.

Examples of alkyl lithium compounds include alkyl compounds in which the alkyl residue has 1 to 10 carbon atoms,
Particularly preferred are methyllithium, ethyllithium, pentyllithium, and butyllithium. As the coupling agent, dichloromethane, dibromomethane, dichloroethane, dibromoethane, dibromobenzene, etc. are used. Examples of dilithium compounds include naphthalene dilithium, dilithiohexylbenzene, and the like. The amount used is determined depending on the desired molecular weight, but approximately 0 parts of initiator is used per 100 parts by weight of all monomers used for polymerization.
．． 01-0.2 parts by weight, campling agent 0.04-0.
It is used in a range of about 8 parts by weight.

The microstructure of the isoprene or isoprene-butadiene moiety contains 40% or more vinyl bonds and 00 or more t.
In order to have a main dispersion peak of and[delta], a Lewis base is used as a cocatalyst during the polymerization of isoprene or isoprene-butadiene. Examples of Lewis bases include ethers such as dimethyl ether, diethyl ether, and tetrahydrofuran, glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, triethylamine, N, N',
N'-tetramethylethylenediamine (TMEDA),
Examples include amine compounds such as N-methylmorpholine. The amount of these Lewis bases used is approximately 0.1 to 1.000 times the number of moles of lithium in the polymerization catalyst.

It is preferable to use a solvent during the polymerization to facilitate control. As the solvent, an organic solvent inert to the polymerization catalyst is used. In particular, aliphatic, alicyclic, and aromatic hydrocarbons having 6 to 12 carbon atoms are preferably used. Examples include hexane, heptane, cyclohexane, methylcyclohexane, benzene, and the like.

Regardless of the polymerization method used, the polymerization is carried out at a temperature of 0 to 80°C for a period of 0.5 to 50 hours.

The block copolymer is hydrogenated by a known method. As the hydrogenation reaction, a method is preferably used in which molecular hydrogen is reacted with a known hydrogenation catalyst in a state dissolved in a solvent inert to the reaction and hydrogenation catalyst. The catalyst used is Raney nickel, PL, Pd.
Heterogeneous catalysts such as metals such as , Ru+Rh, and Ni supported on carbon, aluminum, diatoms, etc.
Alternatively, a Ziegler-based catalyst consisting of a combination of a transition metal and an alkyl aluminum compound, an alkyl lithium compound, etc. is used. The reaction is carried out at a hydrogen pressure of normal pressure to 200 kg/aa, a reaction temperature of normal temperature to 250°C,
The reaction time is in the range of 0.1 to 100 hours.

After the reaction, the block copolymer is produced by coagulating the reaction solution with methanol or the like and then drying it by heating or under reduced pressure.
It can be obtained by pouring the reaction solution into boiling water to azeotropically remove the solvent, followed by drying by heating or under reduced pressure.

The hydrogenation rate is determined by the level of physical properties required, but if heat resistance and weather resistance are important, hydrogenation should be at least 50%, preferably at least 70%.

The composition of the present invention contains 97 to 50 parts by weight of the PPE resin and 3 to 50 parts by weight of the block copolymer. If the proportion of the block copolymer is less than this, the vibration damping performance of the resulting Mi precipitate will be insufficient, and if it is too large, the U paraboloid will become flexible and lose its properties as a plastic, which is the original purpose of the PPE resin. It is not suitable for this and is not desirable.

The composition of the present invention contains a PPE resin and a block copolymer as essential components, but various additives may be mixed and used as necessary. Examples include 5 to 250 parts by weight of carbon blank, reinforcing agents such as silica, calcium carbonate, mica, etc.
Fillers, etc., and 0.01 to 5 parts by weight of antioxidants, ultraviolet absorbers, and the like. Among these, mica is particularly preferably used because it improves allocation performance. When mica is added, the amount is 20 parts by weight or more, more preferably 4 parts by weight.
By using 0 parts by weight or more, it becomes possible to exhibit higher vibration damping performance.

Further, it is also possible to blend and use other polymers as long as the gist of the present invention is not impaired. Examples include polystyrene, ABS resin, styrene-conjugated diene block copolymers, hydrogenated products thereof, and nylon. The blending ratio of these polymers is preferably approximately 30% by weight or less.

The MiK product of the present invention is used by kneading a PPE resin and a block copolymer using a niegu, extruder, injection molding machine, etc., and molding the mixture. The resulting composition can be used for office equipment, audio equipment,
Suitable for use in housings, interior and exterior materials for various devices, interior and exterior materials for automobiles, bumpers, etc., including household electrical appliances.

〔Example〕

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

In addition, each measurement value in an Example was calculated|required by the following method.

Molecular weight was determined by GPC.

The black structure was measured by NMR spectrum and was found to be 4.8 ppm.
, from the ratio of the peaks of 3.4 bonds and 1.2 bonds at 5.13 ppm and the peaks of 1.4 bonds at 5.3 ppm, 3.
The contents of 4 bonds and 1.2 bonds were calculated.

The hydrogenation rate was calculated from the ratio of the measured iodine values of the block copolymer before and after the hydrogenation reaction.

The peak temperature of tan δ was determined by measuring the viscoelastic spectrum using a Rheobipron (manufactured by Orientic Co., Ltd.).

As an index of damping performance, the value of tan δ at 25°C was determined. The larger this value is, the better the damping performance near room temperature is.

[Reference Example 1] In a pressure-resistant reactor that was dried and purged with nitrogen, styrene monomer, isoprene monomer, and styrene monomer were added in this order and polymerized using cyclohexane as a solvent, n-butyllithium as a polymerization catalyst, and TMEDA as a vinylizing agent. death,
A-B-A type block copolymer (1), (IT),
(Iff) was obtained. Table 1 shows their molecular properties.

[Reference Example 2] A, -B -A type block copolymer polymerized in the same manner as in Reference Example 1 was hydrogenated in cyclohexane using pd-c as a hydrogenation catalyst, and water was added at a hydrogen pressure of 20 kg/-. Perform the addition reaction to obtain a hydrogenated block copolymer (■).

(V) and (VI) were obtained. Table 1 shows these molecular properties [Example 1] The block copolymer obtained in Reference Example 1 and poly(2,6-
Modified PPE resin (Silon 500H) with a specific gravity of 1.06 based on dimethyl-1,4-phenylene) ether
, manufactured by Asahi Kasei Kogyo Co., Ltd.) were kneaded at 180° C. using a Brabender plasticorder according to the formulation shown in Table 2 to prepare a composition.

The resulting composition was pressed into a 2xx sheet at 200°C, and the tan δ was measured at 25°C and an impact test (
Izot) was carried out.

In addition, for comparison, a single modified PPE resin, a modified PPE resin and a styrene-isoprene-styrene block copolymer with few vinyl bonds (SIS, TR-1107, l:"
Similar measurements were also performed on a mixture with Nyl bond itz% (manufactured by Shell Chemical Co., Ltd.).

[Example 2] Hydrogenated block copolymer obtained in Reference Example 2 and modified PPE
A composition was prepared by kneading the resin and the resin according to the formulation shown in Table 2 using a Brabender plasticorder at 190''C.

The obtained composition was press-molded at 210°C to produce a 2N sheet, and the tan δ was measured at 25°C and an impact test was conducted.

The measurement results of Example 1.2 are shown in Table 2. From these results, it is clear that the composition of the present invention has an excellent distribution effect and is also excellent in impact resistance.
! /%T9j 6 [Effects of the Invention] The composition of the present invention, which is characterized by combining a polyphenylene ether resin with a block copolymer having a specific molecular structure, improves the impact resistance of the resin and also improves vibration and It can be used as a material that reduces noise generation, and has excellent vibration damping performance especially near room temperature.

Claims (1)

[Claims] 1) (a) 97 to 50 parts by weight of polyphenylene ether,
and (b) a block (A) consisting of a vinyl aromatic monomer having a number average molecular weight of 2,500 to 40,000, and a block (A) consisting of isoprene or isoprene-butadiene, having a number average molecular weight of 10,000 to 200,000, with a 3,4 bond and 1
, 2 bond content is 40% or more, and tan
A polyphenylene ether comprising 3 to 50 parts by weight of a block copolymer having a number average molecular weight of 30,000 to 300,000, or a hydrogenated product thereof, which is composed of a block (B) having a main dispersion peak of δ. Resin composition.