JPS5817485B2 - Stand Yuno Seizouhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to a polyester resin having a cis-1,4 structure of 50% or more and a viscosity of 3.
2 centipoise to 5,000 centipoise at 0°C,
A method for producing stand oil, which comprises mixing liquid polybutadiene with a number average molecular weight of 150 to 3,000 and natural drying oil in any proportion and heating the mixture to 100 to 350°C under normal pressure or reduced pressure. It is something.

According to the present invention, graft copolymers consisting of anti-core products of butadiene polymers and natural drying oils or derivatives thereof can be synthesized.

Japanese Patent Publication No. 42-19255 describes a method of preparing stand oil by mixing a polybutadiene polymer having a molecular weight of 2,000 to 200,000 with an organic unsaturated oil.

However, this method includes only examples using high molecular weight polybutadiene, and in particular, only methods using normally solid rubber components are described.

Therefore, when stand oil is synthesized, it has an extremely high viscosity, and the resulting oil is too viscous and unsuitable for use as a paint vehicle.

However, according to the method of the present invention, when a liquid polybutadiene has a low viscosity, especially a polymer with a viscosity of 1007 centipoise or less, even if the grafting reaction by heating sufficiently proceeds and the viscosity increases, the viscosity value will be 3,000 centipoise or less. Moreover, even when a film is formed as a paint, the physical properties of the film are excellent.

Furthermore, when mixing and heating low molecular weight liquid polybutadiene and natural drying oil as in the method of the present invention, the following advantages can be obtained by distilling off the low molecular weight liquid polybutadiene that has not undergone the graft reaction under reduced pressure. arise.

First of all, if ungrafted low molecular weight polybutadiene remains in the stand oil, the physical properties of the coating film will deteriorate when used as a paint, but this can be improved by removing it under reduced pressure.

Second, if low molecular weight ungrafted polyphtadiene remains in the stand oil, the bad odor of liquid polybutadiene will remain in the stand oil, and the odor will remain even when used as a paint, but it can be removed by vacuum. This problem is solved.

Thirdly, since low molecular weight polybutadiene has a wide molecular weight distribution, it also contains polymers with a molecular weight of about 200 to 400, but if these are removed under reduced pressure before making stand oil, there is a heat source that heats it to high temperatures. However, when synthesizing stand oil, usually 100 to 3
Since the reaction is carried out by heating to 50°C, particularly 200 to 330°C, unreacted low molecular weight polybutadiene can be simultaneously removed by utilizing this heat and reducing the pressure during the reaction.

The physical properties of the Sukhnod oil produced by the method of the present invention are that it dries much faster than natural drying oil alone or a mixture of natural drying oil and liquid polybutadiene, and the resulting film has excellent gloss, and is resistant to alkali and water. It also has the advantage of being superior in quality.

Natural drying oils or their derivatives used in the present invention include soybean oil, linseed oil, tung oil, castor oil, dehydrated castor oil, soybean oil fatty acids, linseed oil fatty acids, and derivatives thereof.

In addition, liquid polybutadiene with a cis-1,4 structure of 50% or more, a viscosity of 30'C, 27 to 5,000 inches, and a number average molecular weight of 150 to 3,000,
For example, Japanese Patent Publication No. 48-43084, Japanese Patent Publication No. 49-26396, Japanese Patent Publication No. 49-89
788, but also includes liquid polybutadiene obtained by other methods.

The microstructure of polymers is usually 50% cis-1,4 structure.
Above, the vinyl structure is 10% or less, the others are I.Lance-1,
There are 4 structures.

Stand oil contains 5 to 80% of liquid polybutadiene, but it can be blended in any proportion to make stand oil.

The conditions for synthesizing stand oil are that natural drying oil or its derivatives and liquid polybutadiene are mixed, and the mixture is heated to 100% in an inert gas such as nitrogen, -\lium, or argon.
The grafting reaction is carried out by heating to ~350°C for 7 J[].

At this time, stirring is usually performed to promote the reaction.

The reaction time is 20 minutes to 20 hours, usually 1 hour to 6 hours.

In addition, a radical initiator is added to carry out the graft reaction at a low temperature.

Such catalysts include diternary butyl peroxide, azobisisophthyronitrile benzyl peroxide, cumene hydroperoxide, dicumyl peroxide, and the like.

Furthermore, one of the features of the method of the present invention is that during or after the reaction of stand oil, the mercury column is
．． Unreacted low molecular weight liquid polybutadiene is removed while the stand oil is heated under reduced pressure of OO1++tm, usually 50 mnL to 1 rnTL.

Usually, low molecular weight polybutadiene having a molecular weight of about 150 to 400 is distilled out.

Whether or not this grafting reaction has occurred can be confirmed by gel perminiscence chromatography (GPC), solvent extraction, infrared spectroscopy, etc.

The stand oil obtained in this way is used as a substitute for natural drying oils and stand oils obtained from natural drying oils, and is characterized by quick drying and good gloss as a raw material for paints and printing inks. .

Examples are shown below, but the present invention is not limited thereto.

Example 1 Liquid polybutadiene with cis-]s4 structure 58%
A polyester having a microstructure of 9% vinyl, 33% trans-1,4 structures, a viscosity of 427 inch at 30°C, and a number average molecular weight of 630 was used.

Linseed oil was used as the natural drying oil. [4 L of 5QQml] Attach a stirring rod to the flask and add 140g of linseed oil,
Add the above liquid polybutadiene 61, perform nitrogen substitution,
The reaction was carried out at 280 to 300°C for 4 hours under a nitrogen stream.

Thereafter, the pressure was reduced to 20 mml (g) to remove unreacted low molecular weight polybutadiene for 1 hour.

Thereafter, it was cooled to room temperature and the viscosity was measured.

A liquid of 3,500 centipoise of 308C was obtained.

The obtained stand oil (2) does not have the characteristic odor of liquid polybutadiene, and the odor of linseed oil is considerably low, indicating that kraft has occurred.

When the reaction of the obtained stand oil I was followed by GPC, the peak of linseed oil alone disappeared, and the individual peak of liquid polybutadiene also disappeared, indicating that the combined peak was distributed on the high molecular weight side. confirmed.

Therefore, it was confirmed that a graft reaction was occurring.

Next, the stand shaft I obtained in this way was made into a paint.
General coating film performance was measured.

01 parts by weight of naphthenic acid Mn as Mn and 1 part by weight of naphthenic acid P as Pb in 1100 parts by weight of stand oil.
Add b.

Further, 12 parts by weight of xylene was added for dilution, and then 100 parts by weight of titanium oxide was added as a pigment.

The dispersion particle size of pigment and resin is 1 in paint conditioner.
Disperse until the particle size becomes 0 μ or less to create a paint.

At the same time, a comparison paint was prepared using commercially available stand oil in the same formulation as above.

The paint prepared in this way was applied to a mild steel plate to a film thickness of 25μ using an applicator, and left for 7 days under normal use at room temperature (25°C ± 2°C) to completely cure. The table below shows the general coating performance measured on a dry coating.
The measurement results shown in I were obtained.

Example 2 Liquid polybutadiene with 76% cis-1,4 structure,
1% vinyl structure, 23% trans-1,4 structure, viscosity 750 centipoise at 30°C, number average molecular weight 170
Use - with 0 poly.

A 500 m1 four-roof flask was equipped with a stirrer rod, and 120 g of soybean oil and 80 g of liquid polybutadiene were mixed, the mixture was replaced with nitrogen, and the mixture was reacted with mixing at 280 to 300°C for 3 hours under a nitrogen stream, and the pressure was reduced to 15 Hg. Unreacted low molecular weight polybutadiene was removed for 30 minutes.

After that, it was cooled to room temperature and the viscosity was measured: 28 at 30°C.
It was 00 centiboise.

The obtained stand oil ■ had no odor of liquid polybutadiene at all, and the odor of soybean oil was also reduced.

As with stand oil ■ in Example 1, stand oil ■ was made into a paint and the general physical properties of the coating were measured. As a result, the drying property reached a touch-dry state in 120 minutes and a semi-cured dry state in 7 hours. It was 6 hours.

The gloss of the dried film (60 cross) was 86, and a film with excellent gloss was obtained.

Good coating film performance results were obtained in terms of flexibility, hardness, impact resistance and chemical resistance, which were almost equivalent to those of Stand Oil I of Example 1.

Claims (1)

[Claims] 1. A mixture of liquid polyphtadiene with a cis-1,4 structure of 50% or more, a viscosity of 2 centipoise to 5000 centipoise at 30°C, and a number average molecular weight of 150 to 3,000, and a natural drying oil or its derivative is heated in an inert gas. 1. A method for producing stand oil, which comprises heating at 100 to 350° C. for reaction, and then distilling off unreacted liquid polybutadiene under reduced pressure.