JP2001187805A - New polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a useful polymer excellent in antistaticity, heat resistance and flame retardancy. SOLUTION: The new polymer is prepared by copolymerizing bis(4- vinylphenyl) sulfone with another ethylenically unsaturated monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel polymer obtained by copolymerizing bis (4-vinylphenyl) sulfone with another ethylenically unsaturated monomer. The polymer is a compound that is extremely useful industrially as a novel resin.

[0002]

2. Description of the Related Art Polymers using bis (4-vinylphenyl) sulfone are not known. On the other hand, divinylbenzene is generally and widely used as a cross-linking agent for the purpose of improving physical properties such as styrene-based resin and mechanical strength and heat resistance. However, copolymers crosslinked with divinylbenzene have problems in that physical properties such as mechanical strength and heat resistance are not sufficient, and that the resin itself is charged.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel polymer (resin) having excellent antistatic properties, heat resistance and flame retardancy.

[0004]

Means for Solving the Problems The present inventors have made intensive studies in view of the above problems, and as a result, the above effects can be expected by polymerizing a monomer component containing bis (4-vinylphenyl) sulfone. We succeeded in developing a resin and completed the present invention. That is, the present invention is a novel polymer obtained by copolymerizing bis (4-vinylphenyl) sulfone and another ethylenically unsaturated monomer.

Hereinafter, the present invention will be described in detail.

Other ethylenically unsaturated monomers used in the present invention include various monomers having a carbon-carbon double bond copolymerizable with bis (4-vinylphenyl) sulfone. Preferably, aromatic vinyl monomers, vinyl cyanide monomers, acrylate monomers and methacrylate monomers are used.

As the aromatic vinyl monomer, for example,
Styrene, α-methylstyrene, o-methylstyrene,
m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene,
p-tert-butylstyrene, chloromethylstyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, p-methoxystyrene,
p-ethoxystyrene, 3,4-dimethoxystyrene,
m-tert-butoxystyrene, p-tert-butoxystyrene, p-acetoxystyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o
-Bromostyrene, m-bromostyrene, p-bromostyrene, o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, vinylnaphthalene, styrenesulfonic acid, divinylbenzene, divinylbiphenyl, divinyltoluene, divinylxylene, divinylnaphthalene , Trivinylbenzene and the like, preferably styrene, methylstyrene, chloromethylstyrene,
Hydroxystyrene, tert-butoxystyrene, acetoxystyrene, chlorostyrene, divinylbenzene or divinylbiphenyl.

The vinyl cyanide monomer includes, for example, acrylonitrile, allyl cyanide, methacrylonitrile, cinnamonitrile, crotonnitrile and the like, and preferably acrylonitrile, allyl cyanide and methacrylonitrile.

Examples of the acrylate-based monomers include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, lauryl acrylate, and tridecyl acrylate. , Stearyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, acrylamide, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate Acrylate, vinyl acrylate, trifluoroethyl acrylate, etc., preferably alkyl acrylate and hydroxyalkyl acrylate.

The methacrylic acid ester monomers include:
For example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, lauryl methacrylate, tridecyl methacrylate,
Stearyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, methacrylamide, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, Vinyl methacrylate, trifluoroethyl methacrylate and the like,
Preferred are alkyl methacrylate and hydroxyalkyl methacrylate.

These other ethylenically unsaturated monomers copolymerizable with bis (4-vinylphenyl) sulfone can be used alone or in combination of two or more.

In the present invention, the mixing ratio of the other ethylenically unsaturated monomer copolymerizable with bis (4-vinylphenyl) sulfone is such that bis (4-vinylphenyl) sulfone is 0.01% by weight or more. , Preferably 0.1% by weight
That is all. If the amount of bis (4-vinylphenyl) sulfone is less than 0.01% by weight, the effects of antistatic properties, heat resistance, and flame retardancy cannot be sufficiently expected.

In the method of the present invention, the copolymerization reaction of bis (4-vinylphenyl) sulfone with other ethylenically unsaturated monomers can be carried out according to a known method. For example, a solution reaction in an organic solvent, emulsion polymerization in water, suspension polymerization, or the like, or solution polymerization in a mixed solvent of a water-soluble organic solvent and water, emulsion polymerization, suspension, can be performed according to a known method. it can. For example, solution reaction in an organic solvent, emulsion polymerization in water, suspension polymerization, or the like, or solution polymerization in a mixed solvent of water-soluble organic solvent and water, emulsion polymerization,
Suspension polymerization and the like can be mentioned. Alternatively, solution polymerization may be performed using an ethylenically unsaturated monomer as a solvent. The organic solvent that can be used is not particularly limited as long as bis (4-vinylphenyl) sulfone and other ethylenically unsaturated monomers can be dissolved or mixed, and examples thereof include aromatic hydrocarbons, ethers, and esters. , Ketones and alcohols.

In the method of the present invention, the polymerization temperature is not particularly limited, but it is preferable to select a temperature at which the decomposition of the polymerization initiator occurs immediately.

In the method of the present invention, the polymerization initiator that can be used includes a conventionally known polymerization initiator.
2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis-
Examples include azo-based polymerization initiators such as 2,4-dimethylvaleronitrile, and organic peroxide-based polymerization initiators such as benzoyl peroxide, lauryl peroxide, and bis (4-t-butylcyclohexyl) peroxydicarbonate. . These polymerization initiators can be used alone or in combination of two or more. The amount of the polymerization initiator to be used is usually 0.0
It is 1 to 20 parts by weight, preferably 0.1 to 10 parts by weight.

[0016]

EXAMPLES Hereinafter, the method of the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 Polyvinyl alcohol (Poval PVA manufactured by Kuraray Co., Ltd.)
-224) Styrene 1 in 500 g of 0.1 wt% aqueous solution
8.0 g, bis (4-vinylphenyl) sulfone 2.0
g, and a mixture of 0.2 g of benzoyl peroxide, followed by nitrogen replacement, followed by slowly raising the temperature with stirring and polymerizing at 80 ° C. for 10 hours. The polymerization liquid was cooled to room temperature, and the generated polymer was separated by filtration and dried to obtain 16.1 g of a white solid.

As shown in Table 1 below, the white solid was confirmed to be a styrene / bis (4-vinylphenyl) sulfone copolymer.

[0019]

[Table 1]

Example 2 The procedure of Example 1 was repeated except that a mixture of 18.0 g of styrene, 1.6 g of divinylbenzene, 0.4 g of bis (4-vinylphenyl) sulfone and 0.2 g of benzoyl peroxide was added. When the same operation was performed, a white solid 1 was obtained.
7.7 g were obtained.

As shown in Table 2 below, the white solid was confirmed to be a styrene / divinylbenzene / bis (4-vinylphenyl) sulfone copolymer.

[0022]

[Table 2]

Example 3 In 200.0 g of toluene, 38.0 g of styrene and bis (4
-Vinylphenyl) sulfone (2.0 g) and azobisisobutyronitrile (1.0 g) were added, and after nitrogen substitution, the temperature was slowly raised while stirring, and polymerization was carried out at 80 ° C. for 5 hours. After cooling to room temperature, the polymerization liquid was added to methanol to precipitate the polymer. The polymer was separated by filtration and dried to obtain 34.8 g of a white solid.

As shown in Table 3 below, the white solid was confirmed to be a styrene / bis (4-vinylphenyl) sulfone copolymer.

[0025]

[Table 3]

Example 4 Example 4 was repeated except that 38.0 g of styrene, 1.6 g of divinylbenzene, 0.4 g of bis (4-vinylphenyl) sulfone and 1.0 g of azobisisobutyronitrile were added. By performing the same operation as described above, 35.6 g of a white solid was obtained.

As shown in Table 4 below, the white solid was confirmed to be a styrene / divinylbenzene / bis (4-vinylphenyl) sulfone copolymer.

[0028]

[Table 4]

<Evaluation of Antistatic Property> Examples 1 to 4
Was hot-pressed at 300 ° C. × 9.9 MPa under pressure to produce a square test piece of 100 × 100 × 2 mm. The test piece was held at 25 ° C. and a relative humidity of 50% for 24 hours, and a surface high resistance meter Hireta HT-
Surface resistivity was measured at an applied voltage of 500 V using a 210 (manufactured by Mitsubishi Yuka), and the results are shown in Table 5.

[0030]

[Table 5]

<Evaluation of heat resistance> In order to evaluate the thermal properties of the resins obtained in Examples 1 to 4, Rigaku Corporation
Using a Thermoflex 8100 manufactured by
0 mg, at a heating rate of 10 ° C./min, measure the thermal decomposition temperature,
Table 6 shows the results.

[0032]

[Table 6]

Comparative Example 1 38.0 g of styrene, 2.0 g of divinylbenzene, 1.0 g of azobisisobutyronitrile in 200.0 g of toluene
g was added, and after purging with nitrogen, the temperature was slowly raised while stirring, and polymerization was carried out at 80 ° C. for 5 hours. After cooling to room temperature, the polymerization liquid was added to methanol to precipitate the polymer. The polymer was separated by filtration and dried to obtain 36.3 g of a styrene / divinylbenzene copolymer. Using this resin composition, antistatic properties and heat resistance were evaluated in the same manner as in the above examples, and the results are shown in Tables 5 and 6.

[0034]

As described above, the novel polymer of the present invention is excellent in antistatic properties, heat resistance, flame retardancy, etc., and is therefore suitable for electric, electronic parts, automobile parts, packaging materials, building materials and electronic materials. Can be used as sealant, paint, adhesive, etc.
It is an extremely useful compound in industry.

Claims (6)

[Claims] 1. A novel polymer obtained by copolymerizing bis (4-vinylphenyl) sulfone with another ethylenically unsaturated monomer. 2. The other ethylenically unsaturated monomer is a group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer, an acrylate monomer and a methacrylate monomer. The novel polymer according to claim 1, wherein the polymer is at least one member selected from the group consisting of: 3. The method according to claim 1, wherein the aromatic vinyl monomer is styrene, methylstyrene, chloromethylstyrene, hydroxystyrene, tert-butoxystyrene, acetoxystyrene, chlorostyrene, divinylbenzene or divinylbiphenyl. Claim 1 or Claim 2
3. The novel polymer according to 1.). 4. The novel polymer according to claim 1, wherein the vinyl cyanide monomer is acrylonitrile, allyl cyanide, or methacrylonitrile. 5. The novel polymer according to claim 1, wherein the acrylate monomer is an alkyl acrylate or a hydroxyalkyl acrylate. 6. The novel polymer according to claim 1, wherein the methacrylate monomer is an alkyl methacrylate or a hydroxyalkyl methacrylate.