JPH02296867A - Liquid polymer composition - Google Patents

Abstract

PURPOSE:To obtain a liquid polymer composition which can give a cured product excellent in mechanical and magnetic properties as well by adding a polyisocyanate compound to a composition comprising a specified liquid polymer and a ferrite. CONSTITUTION:A polyisocyanate compound (e.g. tolylene diisocyanate or diphenylmethane diisocyanate) is added to a composition comprising a hydroxylated liquid diene polymer or its product of hydrogenation (e.g. butadiene homopolymer, butadiene/styrene copolymer or a product of hydrogenation of hydroxy-terminated liquid polybutadiene) and a compound of the formula: MO.Fe2O3 (wherein M is a bivalent metal). In this way, a liquid polymer composition which can give a cured product having excellent mechanical properties and good magnetic properties can be obtained.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a liquid polymer composition, and more specifically, a liquid polymer composition that can provide a cured product with excellent mechanical properties and good magnetic properties. It is related to.

[Prior Art and Problems to be Solved by the Invention] Compositions in which ferrite powder is blended with a rubber matrix or a plastic matrix are known as compositions used for magnetic core materials, magnets, and the like.

In order to improve the moldability of such ferrite-containing compositions, it is also known to use liquid polybutadiene having hydroxyl groups as a matrix (Japanese Patent Publication No. 58-2444).

Although this composition consisting of a liquid polybutadiene having a hydroxyl group and ferrite can be said to be excellent in its moldability and the magnetic properties of the resulting cured product, it has the drawback of poor mechanical properties of the cured product. However, there was also the disadvantage that it was difficult to obtain a cured product unless the curing conditions were made severe.

The object of the present invention is to provide a liquid polymer composition that eliminates these drawbacks and provides a cured product with excellent mechanical properties and also good magnetic properties.

[Means to solve problems]

In order to achieve the above object, the present inventor conducted various studies on the components constituting a liquid polymer composition that provides a cured product, and as a result, added a polyisocyanate compound to a composition consisting of a specific liquid polymer and ferrite. It was discovered that the above objective could be achieved by blending
Based on this knowledge, we have completed the present invention.

That is, according to the present invention, a liquid polymer comprising a hydroxyl group-containing liquid diene polymer or its hydride, a polyisocyanate compound, and a ferrite represented by the general formula MO-Fe*Os (M represents a divalent metal). A composition is provided.

The present invention will be explained in detail below.

The hydroxyl group-containing liquid diene polymer in the present invention has a hydroxyl group inside or at the end of the molecular chain and has a number average molecular weight of 300 to 25,000, preferably 500 to 1
0,000 liquid diene polymer is used. Here, the content of hydroxyl groups is usually 0.1 to xomeq/y, preferably 0.3 to 7meq/y.

These liquid diene polymers include diene polymers and diene copolymers having 4 to 12 carbon atoms, and copolymers of these diene monomers and a-olefinic addition-polymerizable heptamers having 2 to 22 carbon atoms. and so on. Specific examples include butadiene homopolymer isoprene homopolymer, chloroprene homopolymer, butadiene-styrene copolymer, butadiene-isoprene copolymer, butadiene-acrylonitrile copolymer, butadiene-2-ethylhexyl acrylate copolymer, butadiene-n-octadecyl acrylate copolymer, etc. be able to. These liquid diene polymers can be produced, for example, by subjecting a conjugated diene monomer to a heating reaction in the presence of hydrogen peroxide in a liquid reaction medium.

In the present invention, a hydride thereof can be used instead of the hydroxyl group-containing liquid diene polymer. This hydride can be obtained by hydrogenating a hydroxyl group-containing liquid diene polymer.

Hydrogenation of the hydroxyl group-containing liquid diene polymer is carried out by dissolving the hydroxyl group-containing liquid diene polymer in a solvent and at a temperature of 20 to 300°C in the presence of a known hydrogenation catalyst such as nickel, palladium, ruthenium, or platinum. , preferably 30-20
At 0°C, hydrogen pressure 0 to 200 Jn/cs+”G,
Preferably, the reaction can be carried out at 0 to 100 kg/ca''G for 0.1 to 10 hours.

After the reaction is completed, the catalyst is filtered off and the solution is distilled under reduced pressure to remove the solvent and obtain a hydride of a liquid diene polymer containing hydroxyl groups.

The hydrogenated product of the hydroxyl group-containing liquid diene polymer has a number average molecular weight of 300 to 25,000°, preferably 500°.
~10,000, and the hydroxyl group content is 0.1~tom
eq/g, preferably 0.3 to 7 meq/9.

Next, the polyincyanate compound used in the present invention is an organic compound having two or more incyanate groups in one molecule, which has reactive incyanate groups with respect to the hydroxyl groups of the hydroxyl group-containing liquid diene polymer. It is something that you have.

Examples of this polyisocyanate compound include the usual aromatic, aliphatic and cycloaliphatic ones,
For example, tolylene diisocyanate (TDI), hexamethylene diisocyanate, diphenylmethane diisocyanate (MDI), carbodiimide-modified diphenylmethane diisocyanate, polymethylene polyphenylisocyanate, xylylene diisocyanate (XDI)
, transcyclohexane-1,4-diisocyanate, phenylene diisocyanate, naphthalene-1,5-
Diisocyanate, o-toluidine diincyanate,
Lysine diisocyanate, triphenylmethane triisocyanate, tris(incyanate phenyl)thiophosphate, tetramethylxylene diisocyanate,
lysine ester triisocyanate), 1,6.11-undecane triisocyanate, l,8-diisocyanate-4-incyanate methyloctane, 1.3.6-
Hexamethylene triisocyanate, bisic abutane triisocyanate, isopropylbenzene-2,4-
diisocyanate, trimethylhexamethylene diisocyanate, inphorone diisocyanate) (IPDI),
Hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, cyclized trimer of the above polyisocyanate compound (incyanurate modified product), ethylene glycol, trimethylolpropane, polyether polyol, polymer polyol, polytetramethylene ether glycol, polyester Addition reaction products of polyol compounds such as polyols, acrylic polyols, polyalkadiene polyols, partially melted ethylene-vinyl acetate copolymers, castor oil-based polyols, and the above polyisocyanate compounds are used. Especially MDI.

Carbodiimide MDI, TDI, etc. are preferred.

In addition, these polyisocyanate compounds can be used as a mixture of two or more types, and furthermore, so-called blocked isocyanate compounds in which the incyanate groups of these polyisocyanate compounds are blocked with a blocking agent such as phenol, xylenol, methyl ethyl ketone oxime, ε-caprolactam, etc. can also be used.

There is no particular restriction on the blending ratio of these components, but usually the ratio of the isocyanate group (N G O) of the polyisocyanate compound to the hydroxyl group (OH) of the hydroxyl group-containing liquid diene polymer or its hydride (N
Olo H) in a molar ratio of 0.5 to 25, preferably 0.
Blend so that it becomes 5-15.

In the present invention, a liquid polymer composition is prepared by further blending ferrite with the hydroxyl group-containing liquid diene polymer, its hydride, and polyisocyanate compound.

Ferrite has the general formula MO-Fe, 0. A group of iron oxides having the composition where M represents a divalent metal such as manganese, iron, cobalt, nickel, copper, zinc, etc.

This ferrite is usually blended as a powder, and the powder has an average particle size of 0.5 to 10 μm.

Preferably it is 1 to 3 μm.

There are no particular restrictions on the blending ratio of ferrite, but it is usually 3 to 50 parts by weight, preferably 5 to 50 parts by weight, per 100 parts by weight of the hydroxyl group-containing liquid diene polymer or its hydride.
It is blended in a range of 30 parts by weight.

The liquid polymer composition of the present invention is composed of the hydroxyl group-containing liquid diene polymer or its hydride, a polyisocyanate compound, and a ferrite, and optionally a polyol compound, a polyamine compound, an inorganic filler,
Other additives may also be blended.

As the polyol compound, any of primary polyol, secondary polyol, and tertiary polyol may be used. Specifically, for example, 1.2-propylene glycol, diglobylene glycol, 1.2-butanediol, 1.3-
Butanediol, 2.3-butanediol, 1,2-bentanediol, 2.3-bentanediol, 2.5-
Hexanediol, 2,4-hexanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, glycerin, N,N-bis-2-hydroxypropylaniline, N,N'-bis-hydroxyisopropyl-2- Examples include low molecular weight polyols having a hydroxyl group bonded to at least one secondary carbon, such as methylpiperazine and a propylene oxide adduct of bisphenol A.

Furthermore, ethylene glycol, 1.3-propylene glycol, 1.4-butanediol, 1.5-bentanediol, 1.6-hexanediol, etc. that do not contain a hydroxyl group bonded to a secondary carbon can also be used as the polyol. . Diols are usually used as polyols, but triols and tetraols may also be used, and their molecular weights range from 50 to 500.

Note that these polyol compounds do not include the hydroxyl group-containing liquid diene polymer or its hydride.

The polyamine compound may be any of diamine, triamine, and tetraamine. Furthermore, primary polyamine,
Either a secondary polyamine or a tertiary polyamine can be used. Examples of polyamine compounds include aliphatic amines such as hexamethylene diamine; alicyclic amines such as 3,3'-dimethyl-4,4'diaminodicyclohexylmethane; aromatic amines such as 4,4°-diaminodiphenyl; , 4.6-), triamines such as (dimethylaminomethyl)phenol, and the like.

There are no particular restrictions on the blending ratio of these polyol compounds and polyamine compounds, but usually 1-1 parts of the polyol compound or polyamine compound is added to 100 parts by weight of the above-mentioned hydroxyl group-containing liquid diene polymer or its hydride.
000 parts by weight, preferably 3 to 200 parts by weight.Inorganic fillers of concern include zinc, asbestos, alumina, aluminum, kaolin clay, glass spheres, glass flakes, carbon (channel black, furnace black, acetylene black, sabre). nephrite, cryolite, graphite, silica, wollastonite, diatomaceous earth, zinc oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, aluminum hydroxide, slate powder, ceolite, quartz powder, carbonate Examples include calcium, magnesium carbonate, talc, potassium titanate, boron nitride, feldspar powder, copper, nickel, molybdenum disulfide, barium sulfate, whiting, waxite sauce, mica, and ceracola.

There are no particular restrictions on the amount of inorganic filler, but it is usually a hydroxyl group-containing liquid diene polymer or its hydride.
00 parts by weight, 1 to 500 parts by weight, preferably 10 parts by weight
~200 parts by weight.

In the present invention, a liquid polymer composition is prepared by blending the above-mentioned components in the above-mentioned proportions, but as other additives that may be added as desired, a plasticizer such as dioctyl phthalate may be added as a viscosity modifier, or an aromatic , naphthenic oils, paraffinic oils, and other softening agents, and to adjust adhesive strength and adhesion, alkylphenol resins, terpene resins, terpenephenol resins, xylene formaldehyde resins, rosins, hydrogenated rosins, coumaron resins, aliphatic It is also possible to add tackifying resins such as and aromatic petroleum resins. Further, curing accelerators such as dibutyltin dilaurate, stannous octoate, polyethylene diamine, etc. can also be added. Furthermore, an anti-aging agent may be added to improve weather resistance, and red phosphorus, hexabromobenzene, etc. may be added as a flame retardant imparting agent.

A liquid polymer composition that becomes a cured product can be obtained by blending and mixing the above components. Usually, first, the above components except for the polyincyanate compound are blended and stirred and blended at 15 to 120'0, preferably 70 to 100°C, for 5 to 240 minutes, preferably 30 to 180 minutes, and then this mixture is mixed. by adding a polyisocyanate compound to 0.5°C at 0 to 70°C, preferably 15 to 50°C.
A liquid polymer composition is obtained by stirring and mixing for 1 second to 120 minutes, preferably 1 second to 120 minutes.

There are no particular restrictions on the conditions for curing, but usually 0~
0.5-75 at 120°C, preferably 15-70"0
time, preferably 1 to 72 hours.

[Examples] Hereinafter, the present invention will be explained in more detail by giving Examples and Comparative Examples.

The hydroxyl group-containing liquid diene polymer and its hydride used are as follows.

i) Liquid polybutadiene with hydroxyl group at the end of the molecular chain Manufactured by Idemitsu Atochem Co., Ltd. R-45HT.

Number average molecular weight 2800, hydroxyl group content 0.79 meq/g i) 100 g of liquid polybutadiene having a hydroxyl group at the end of the molecular chain, cyclohexane 1009 and nickel catalyst with diatomaceous earth, nickel content 5% by weight) 10
9 into an autoclave, 140℃, hydrogen pressure 50℃
The reaction was carried out for 4.5 hours at kg/cta"G.

After the reaction is complete, remove the contents from the autoclave and
．． The catalyst was filtered off using a 45 μm membrane filter, and the solvent was distilled off from the filtrate at 110° C. under a reduced pressure of 2 tmtaHg to obtain a liquid polybutadiene hydride having a hydroxyl group at the end of the molecular chain.

The bromine number of this hydride was 1 or less, the number average molecular weight was 2850, and the hydroxyl group content was 0.78 meq/g.

i) Molecular chain Production example of liquid polyisoprene having hydroxyl groups at the ends 2.
00g, 50% by weight hydrogen peroxide solution 169 and n-butyl alcohol 1009 were prepared, and at a temperature of 120°C, 2
The polymerization reaction was carried out while stirring for hours.

The reaction pressure rose to a maximum of 8 kg/crm''G.

After the reaction was completed, the reaction product was cooled to room temperature and taken out from the reaction vessel. The reaction product was added to and mixed with 600 g of water in a separatory funnel, and the mixture was thoroughly shaken and allowed to stand at room temperature for 3 hours. The separated oil layer was heated at a temperature of 100°C under a reduced pressure of 2ta*Hy.
Volatile components (solvent, imprene, low pancreatic point components, etc.) were removed by evaporation for a period of time, and liquid polyisoprene having a hydroxyl group at the end of the molecular chain was obtained as a residue with a yield of 68% by weight.

This liquid polyisoprene had a number average molecular weight of 2150, a hydroxyl group content of 0.96 meq/IF, and a viscosity of 62 poise/30°C.

The bromine number of this material was 240.

iv) Liquid polyisopropylene having a hydroxyl group at the end of the molecular chain i)
100g of the liquid polyisoprene having a hydroxyl group at the end of the molecular chain produced in 109, 100g of cyclohexane, nickel catalyst with Kkeru diatomaceous earth, and nickel content of 5% by weight) were placed in an autoclave at a temperature of 140°C and a hydrogen pressure of 50kg/cm"G. The reaction was carried out for 4.5 hours.

After the reaction is complete, remove the contents from the autoclave and
．． The catalyst was filtered through a 45 μm membrane filter, and the solvent was distilled off from the filtrate at 110° C. under a reduced pressure of 2 mmHg to obtain a hydrogenated liquid polyisoprene having a hydroxyl group at the end of the molecular chain.

The bromine number of this hydride is 1 or less, the number average molecular weight is 2210, and the hydroxyl group content is 0.94 m eq / 9
Met.

Examples 1 to 6 Predetermined amounts of the components shown in Table 1 except for the polyincyanate compound were blended, and the mixture was stirred and mixed at 100° C. for 30 minutes. Next, a predetermined amount of the polyisocyanate compound shown in Table 1 was added, and the mixture was stirred and mixed at 25° C. for 5 minutes to prepare a liquid polymer composition.

Next, this liquid polymer composition was poured into a mold and heated at 120
℃, 200 kg (/cm"G) for 1 hour, and the length was 300 cm, the width was 150 am, and the thickness was 2 r.
A plate-shaped test piece of ata was obtained.

This test piece was cured at 70° C. for 15 hours to obtain a cured product.

Table 1 shows the magnetic properties and mechanical properties of this cured product.

(The following is a blank space) 100 parts by weight of the hydroxyl-terminated liquid polybutadiene described in Comparative Example i), 50 parts by weight of iron/ferrite 1-Fe. (Average grain i1.5μm)
500 parts by weight and 2 parts by weight of dicumyl peroxide were kneaded at room temperature using a kneader, then extruded into a rod shape using an extruder and cut to produce a cylindrical chip with a diameter of 2 ram and a length of 5 m#I. .

This chip is placed at a cylinder temperature of 50℃, a mold temperature of 20℃,
Injection molded at an injection pressure of 500 kg/cm.
Vertical 120+1111. A plate-shaped test piece with 50 scrap layers horizontally and 2 yrta thick was obtained.

A cured product was obtained by heating this test piece at 150° C. for 3 hours.

Table 2 shows the magnetic properties and mechanical properties of this cured product.

Table 1 [Effects of the Invention] According to the present invention, a liquid polymer composition is provided which provides a cured product having excellent mechanical properties and good magnetic properties. Furthermore, when producing a cured product from this liquid polymer composition, the curing treatment conditions may be mild.

Therefore, it is extremely useful as a composition for materials such as magnetic core materials, magnets, and radio interference prevention materials.

(Margin below)

Claims (1)

[Claims] 1 Hydroxyl group-containing liquid diene polymer or its hydride, polyisocyanate compound and general formula MO・Fe_
A liquid polymer composition consisting of ferrite represented by 2O_3 (M represents a divalent metal).