JPH11236453A - Rosin derivative, flame-retardant plasticizer and flame-retardant plastic composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a rosin derivative capable of exhibiting an excellent plasticization effect, an excellent flame retardation effect and an excellent smoke-reducing effect, and useful as a flame-retardant plasticizer for plastics by condensing a rosin alcohol with a specific diaryl phosphate halide. SOLUTION: This rosin derivative is obtained by condensing (A) a rosin alcohol [for example, (dehydro, dihydro or tetrahydro)abietyl alcohol) with (B) a compound of the formula [X is Cl or Br; R is a 1-4C alkyl; (n) is 0-3] (for example, diphenylphosphate chloride). The condensation reaction is preferably carried out in the presence of a basic substance. The rosin derivative is, for example, used in an amount of about 10-200 pts.wt. per 100 pts.wt. of a plastic.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a rosin derivative, a flame-retardant plasticizer for plastics comprising the rosin derivative, and a flame-retardant plastic composition containing the rosin derivative.

[0002]

2. Description of the Related Art Conventionally, various plasticizers have been added to plastics in order to improve plasticity and moldability. However, when flame retardancy is required for plastics, triphenyl phosphate is used. Phosphate-based flame-retardant plasticizers such as glycerol and tricresyl phosphate have been used. In recent years, simply making plastic flame-retardant is not enough from the viewpoint of fire safety.
It is required to reduce smoke emission in consideration of fire safety. However, the above-mentioned phosphate ester-based flame-retardant plasticizer cannot satisfy the requirement for low smoke emission. In response to such a demand for reducing the smoke emission of the flame-retardant plasticizer, 2-ethylhexyldiphenyl phosphate and the like [J. Vinyl Tec
hnol. (1979), 1 (3), 172-5] is known to be relatively effective, but its smoke reducing effect is insufficient.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a new compound which can be used as a flame-retardant plasticizer for plastics having excellent low smoke emission.

[0004]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the following rosin derivatives can be used as a flame-retardant plasticizer and have excellent smoke reducing effect. The present invention has been found to be very effective in reducing the smoke emission of the compounded plastic, and has completed the present invention.

That is, the present invention relates to a rosin alcohol having the general formula (1):

[0006]

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(Wherein X represents a chlorine atom or a bromine atom, R represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 3). The present invention relates to a rosin derivative obtained, a flame-retardant plasticizer for plastics comprising the rosin derivative, and a flame-retardant plastic composition obtained by blending the rosin derivative with a plastic.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The rosin alcohol used in the present invention is obtained by hydrogenating a carboxyl group of various rosins into a hydroxymethyl group. Examples of the rosin alcohol include abiethyl alcohol, dehydroabiethyl alcohol, dihydroabiethyl alcohol, and tetrahydroabiethyl alcohol. These rosin alcohols can be used alone or as a mixture of two or more.

The diaryl phosphate halide represented by the general formula (1) used in the present invention includes, for example, diphenyl phosphate chloride, diphenyl phosphate bromide, dicresyl phosphate chloride, dicresyl phosphate bromide, dixylenyl phosphate chloride, dixylenyl phosphate. Bromide, di (isopropylphenyl) phosphate chloride, di (isopropylphenyl) phosphate bromide, di (t-butylphenyl) phosphate chloride and di (t-butylphenyl) phosphate bromide. Among these diaryl phosphate halides, diphenyl phosphate chloride is preferred because it is industrially easily available and inexpensive.

The rosin derivative of the present invention is produced by condensing the rosin alcohol with a diaryl phosphate halide. For the condensation of rosin alcohol and diaryl phosphate halide, generally, general conditions for condensation of alcohol and phosphate halide may be employed. For example, in order to suppress a side reaction or a by-product due to hydrogen halide released by condensation, a method in which a basic substance is present in the reaction system (for example, the fourth edition of Experimental Chemistry Course 22 Organic Synthesis IV, The method described in p. 339-340) is preferable, and good results can be obtained in terms of shortening the reaction time and improving the yield.

The rosin derivative thus obtained is blended with various plastics as a flame-retardant plasticizer for plastics, and makes the plastic flame-retardant. Such a flame-retardant plastic composition generally contains about 10 to 200 parts by weight of a rosin derivative per 100 parts by weight of plastic.

Specific examples of the plastic include nitrocellulose, acetylcellulose, ethylcellulose, acrylic resin, styrene resin, vinyl acetate resin, vinyl butyral resin, polyvinyl alcohol, vinyl chloride resin, vinyl chloride and vinyl acetate, acryl and vinylidene chloride. And vinylidene chloride resin, polycarbonate, polyamide, polyurethane, epoxy resin, phenol resin, melamine resin, polyvinylpyrrolidone and the like.

The flame-retardant plastic composition generally contains various additives used for flame-retardant plastics, such as stabilizers, fillers, reinforcing agents, antioxidants,
An ultraviolet absorber, a foaming agent, a flame retardant, an antistatic agent, a lubricant, a coloring agent, an antibacterial / antifungal agent and the like can also be added.

[0014]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.

Example 1 (Production of Rosin Derivative) Rosin alcohol (abitol / Abito) was placed in a 2 L separable flask equipped with a stirrer, a condenser, and a dropping funnel.
175 g of pyridine and 728 g of pyridine were added and dissolved. After cooling to 4 ° C. in an ice bath, a solution of 157 g of diphenylphosphoric chloride in 157 g of pyridine was added dropwise over 4 hours. Thereafter, the reaction was carried out at room temperature for 4 hours. The reaction was performed under a nitrogen stream. To hydrolyze excess diphenylphosphoric acid chloride, 607 g of ion-exchanged water was added, and the mixture was stirred at room temperature for 2 hours. Then, pyridine and 1134 g of water were distilled off under reduced pressure (oil bath 60).
C, 100-300 Torr), 1200 ml of toluene
, 800 ml of 10% hydrochloric acid, 800 ml of a saturated aqueous solution of sodium hydrogen carbonate, 1200 ml of ion-exchanged water
And the toluene solution is concentrated by an evaporator,
304 g of a pale yellow oil was obtained. This was distilled under reduced pressure (170 ° C., 0.2 Torr) to remove low boiling components, and 257 g of the target rosin derivative was obtained as a residue. From the NMR chart shown in FIG. 1, the peak around 3.0 to 3.7 ppm derived from rosin alcohol disappears, and 3.5 to 4.2 p based on the formation of a new phosphate ester bond.
Since the appearance of a peak near pm was observed and the peak indicating the rosin skeleton and the like was not significantly changed, it was confirmed that the obtained rosin derivative was a condensate of rosin alcohol and diphenyl phosphate chloride. did. NM
R is 1 in the 1H nucleus using deuterated chloroform as a solvent.
The dimensional spectrum was measured. The apparatus used was VXR300 manufactured by Japan Bruker Co., Ltd.

In addition, rosin alcohol (abitol / A
bitol, manufactured by Hercules) is 14 to 23% by weight.
Of dehydroabiethyl alcohol, 36 to 39% by weight of dihydroabiethyl alcohol, 38 to 50% by weight of tetrahydroabiethyl alcohol, 3 to 8% by weight of esters and 7 to 12% by weight of hydrocarbon. .

Example 2 100 parts by weight of polyvinyl chloride (manufactured by Aldrich)
50 parts by weight of the rosin derivative obtained in Example 1, 3 parts by weight of a calcium-zinc composite stabilizer (OW-5000, manufactured by Sakai Chemical Industry Co., Ltd.) and a phosphorus-based stabilizer (CHELEX)
-300, manufactured by Sakai Chemical Industry Co., Ltd.), and then kneaded in a roll at 160 ° C.
A test piece was prepared by press molding under the condition of 5 minutes. A kneading roll was used for testing, and a mini-test press (manufactured by Toyo Seiki Co., Ltd.) was used for press molding.

Comparative Examples 1-2 The test pieces were prepared in the same manner as in Example 2 except that the rosin derivative obtained in Example 1 was replaced with a flame-retardant plasticizer shown in Table 1. It was created.

Using the test pieces prepared in Example 2 and Comparative Examples 1 and 2, the following tests were performed and evaluated. Table 1 shows the results.

Flame retardancy: A combustion test was performed according to JIS K7201, and the oxygen index was determined. (ON-1 type, manufactured by Suga Test Instruments Co., Ltd.) was used as a flammability tester.

Smoke emission (Dm): Measured under the combustion conditions of the NBS smoke chamber method.

[0022]

[Table 1]

In Table 1, DOP: di-2-ethylhexyl phthalate (manufactured by Tokyo Chemical Industry Co., Ltd.) and ODP: 2-ethylhexyl diphenyl phosphate (manufactured by Tokyo Chemical Industry Co., Ltd.) are shown.

[0024]

According to the present invention, it is possible to provide a flame-retardant plasticizer for plastics having excellent low-smoke-generating properties. It is possible to provide a plastic material having excellent fire safety.

[Brief description of the drawings]

FIG. 1 is an NMR chart of a rosin derivative obtained in Example 1.

Claims (5)

[Claims] 1. Rosin alcohol and general formula (1): (Wherein, X represents a chlorine atom or a bromine atom, R represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 3). Derivatives. 2. The rosin derivative according to claim 1, wherein the rosin alcohol is at least one selected from abiethyl alcohol, dehydroabiethyl alcohol, dihydroabiethyl alcohol and tetrahydroabiethyl alcohol. 3. The rosin derivative according to claim 1, wherein the compound of the formula (1) is diphenyl phosphate chloride. 4. A flame-retardant plasticizer for plastics comprising the rosin derivative according to claim 1, 2 or 3. 5. A flame-retardant plastic composition comprising the rosin derivative according to claim 1, 2 or 3 incorporated in a plastic.