JPS5812908B2 - Flame retardant polyester composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyester compositions, particularly flame retardant polyester compositions.

Polyester containing polyalkylene terephthalate has high crystallinity, high softening point, and excellent strength and chemical resistance, so it has great industrial value as a fiber or film molding material. What you are doing is well known.

However, polyester is inherently flammable;
Once ignited, it burns violently.

In recent years, from the viewpoint of flame prevention, methods of imparting flame retardancy to fibers or films made of easily combustible polymers have been studied.
A method of making polyester flame retardant using a halogen-containing compound, a phosphorus-containing compound, etc. has been proposed.

However, these methods have drawbacks such as decreased light resistance of the fibers, difficulty in spinning, and decreased physical properties of the obtained fibers.

As a method for imparting relatively good flame retardancy and fiber physical properties, Patent Publication No. 46-41696 discloses that polyphosphonates or polyphosphonites containing halogenated hydroquinones and/or halogenated bisphenols as diol components are commonly used. A method of compounding with flammable organic polymers is disclosed.

Further, Patent Publication No. 46-41699 discloses a polyphosphite containing halogenated hydroquinone and/or halogenated bisphenols as a diol component,
Alternatively, a method is disclosed in which a polyphosphate is blended with an organic polymeric substance that is normally easily combustible.

Furthermore, Patent Publication No. 47-32297 discloses a method of blending a polyarylphosphonate having a degree of polymerization of 6 or more with an aromatic diol as a diol component into a thermoplastic polyester, in which all or part of the diol component is blended. A method is disclosed in which a polyarylphosphonate having a degree of polymerization of 6 or more is blended into a polyester.

However, the polyester compositions obtained by these methods have poor molding processability, and therefore, yarn breakage, cutting, fluffing, etc. occur frequently when spinning and drawing the compositions.

The present inventors have conducted extensive research on flame-retardant polyester compositions free from such drawbacks. As a result, compositions containing polyphosphates or polyphosphonates containing diols obtained by adding epoxy to aromatic diols have excellent flame retardancy, fiber properties, and The present invention was developed based on the knowledge that both moldability was good.

That is, the present invention relates to the following general formula [■] [wherein R is an aryl group, an alkyl group, an allyloxy group, or an alkoxy group, R' is H or
represents an alkyritene group, a sulfone group, an ether group or a carbonyl group.

X represents a lower alkyl group or a chlorine atom.

1, 1', m, m' are integers from 0 to 4.

n is an integer of 5 or more. ] or the following general formula [■] [However, in the formula, R is an aryl group, an alkyl group, an allyloxy group, or an alkoxy group, R' is H, and
represents a lower alkyl group or a chlorine atom.

m is an integer from 0 to 4, and n' is an integer of 5 or more.

] The phosphorus atoms in the entire composition are 0.3 to 0.
This is a flame-retardant polyester composition blended with polyalkylene terephthalate in a proportion of 3% by weight.

The compound represented by the general formula [■] or [■] used in the present invention is the application No. 4-9-1 previously filed by the present inventors.
46758, aliphatic diols and R-P-
X2 (wherein R represents an aryl group, an alkyl group, an alkoxy group, or an allyloxy group, and X represents a chlorine atom.

] and hexamethylphosphoryl (
It can be obtained by reacting in tri)amide,
The reaction solvent is not limited to hexamethylphosphoryl(tri)amide, but compounds prepared in other solvents such as N-methylpyrrolidone, N-N-dimethylacetamide, etc. can also be used. Needless to say.

Examples of the compound [■] that can be used in the present invention include the following.

The degree of polymerization of the compound is preferably 5 or more.

If less than 5 is used, the molding processability of the vine will deteriorate, and the physical properties of the fiber will also be greatly reduced.

The polyalkylene terephthalate used in the present invention is mainly a polyalkylene terephthalate made using a terephthalic acid derivative as an acid component and a linear diol derivative having 2 to 12 carbon atoms or dicyclohexane 14 dimethanol as a diol component. The polyester may be a polyester copolymerized with a third component.

The amount of the compound [■] or [■] used in the present invention relative to the polyalkylene terephthalate is preferably such that the amount of phosphorus atoms in the entire composition is 0.3 to 3% by weight.

0.3% by weight, more preferably 0.5-2% by weight
If the amount is smaller, sufficient flame retardancy cannot be imparted.
Moreover, if the amount is more than 30% by weight, the flame retardancy is already saturated,
A decrease in moldability and fiber properties is observed.

The timing of blending the compound [■] or [■] into the polyalkylene terephthalate can be selected at any stage before the synthesis of the polyester is completed or after the synthesis is completed and until the molding is completed.

The first feature of the method of the present invention is that it has good moldability and excellent yield during spinning and stretching.

The second feature of the method of the present invention is that there is little deterioration in physical properties due to blending.

According to the method of the present invention, excellent flame retardance can be imparted to polyester very easily, and its industrial value is extremely high.

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples.

The intrinsic viscosity (η) of the polyester is a value measured at 35° C. using an O-chlorophenol solvent in a conventional manner.

Moreover, flame retardancy was evaluated by the following method.

Flame retardant (45° coil method) TC-H2 manufactured by Tsutsumi Seiki with a diameter of 3.75 inches drawn yarn
It was knitted into a sock shape using a cylinder knitting machine, and measured in accordance with the disaster prevention performance standards specified in Section 4, Section 3, Item 4 of the Fire Service Act.

The test method is as follows. The test specimen support coil is JIS
Diameter 0.0 that meets standard G-4309. 5 mm hard stainless steel wire, inner diameter 10 mm, distance between wires 2 mm,
It has a length of 150 mm.

The fuel is liquefied petroleum gas No. 5 according to JIS standard K-2240.

The test specimen was randomly cut from cloth, 10 cm wide, and weighing 1.
The length of the flame was 45 mm, the burner was fixed so that the tip of the flame was in contact with the lower end of the specimen, and the specimen was heated until it stopped melting.

Then, the flame is applied until 9 cm from the lower end of the specimen is completely melted, and the number of times the flame is applied is determined.

In addition, the total combustion time is measured, and the value obtained by dividing this by the number of times of flame contact is determined as the number of seconds for ignition.

Example 1 A 1 liter three-necked flask was equipped with a dropping funnel and an efficient stirring device, and 158 parts of 2.2 di(4-β-
Take hydroxyethoxy-phenyl)propane and 0.4 part of calcium chloride, add and dissolve 277 parts of HMPA, cool the reaction vessel sufficiently in a water cooling bath, and while stirring, phenylphosphonic acid dichloride. 96.7 parts were added from the dropping funnel.

An exotherm started and the liquid became cloudy and the viscosity increased within a few minutes.

The reaction was completed about 20 minutes after the dropwise addition.

When the resulting polymer was poured into about 10,000 parts of cold water under vigorous stirring, a white precipitate formed.

The resulting precipitate was washed with an aqueous sodium bicarbonate solution, then washed twice with water, filtered with suction to remove the polymer, and dried under reduced pressure at 120°C for 2 hours and at 190°C for 30 minutes to obtain 195 parts of a transparent solid. (yield 90%).

The softening point was 98°C, and the molecular weight was 14,100 (degree of polymerization: 32).

Add the flame retardant obtained by the above reaction to molten polyethylene terephthalate with [η] = 0.72 held at 280°C so that the weight percent of phosphorus atoms contained therein becomes the value shown in Table 1. After mixing for 30 minutes under reduced pressure, the mixture was discharged into cold water and cut into chips.

The pellets were dried at 115°C and 0.5mmHg for 24 hours, and then melt-spun using a 65mmφ extra-goo spinning machine in a conventional manner.The spinning conditions were: polymer melt temperature 280°C;
The spinning speed was 1000 m/min.

Table 1 shows the number of undrawn yarns (spinning yield) in which yarn breakage and single yarn breakage occurred during spinning per 100 undrawn yarns (2 kg roll) obtained.

The resulting undrawn yarn was heated at a pin temperature of 90°C and a plate temperature of 15°C.
Stretching was carried out at 0° C., at a stretching speed of 520 m/min, and at a stretching ratio of 3.5 times.

[η], physical properties, flame retardance, yield of the obtained yarn (undrawn yarn 1
Table 1 also shows the number of yarn breakage and single yarn breakage during stretching per 00 yarns) and the occurrence rate of fuzz.

Comparative Example 1 Bis(4-hydroxyphenyl)propane 25% was placed in a 1 liter reactor equipped with a stirring device, a nitrogen inlet tube, and a reflux condenser.
1 part, 210 parts of phenylphosphonic acid dichloride, 0.7 parts of calcium chloride, and 250 parts of 1,1,2,2-tetrachloroethane were taken, and the temperature was gradually raised under a nitrogen stream.
After 4 hours, the tetrachloroethane reflux temperature (approximately 148°C)
Make it so that

After that, the reaction was continued by keeping the temperature at reflux temperature for 16 hours, and then the 1,1,2,2-tetrachloroethane 6
The solution was further injected into 10,000 parts of methanol, and the resulting precipitate was taken out and heated to 110~
By drying under reduced pressure at 120° C. for 48 hours, 342 parts of a yellow solid (yield 90%) was obtained.

It had a softening point of 117°C and a molecular weight of 7000 (degree of polymerization 20).

The flame retardant obtained by this method was blended with polyethylene terephthalate in the same manner as in Example 1, and the mixture was spun and stretched.

The results obtained are shown in Table 2. Example 2 In place of 2,2-di(4-β-hydroxyethoxy-phenyl)propane used in Example 1, 2,2-di(4-
Using 169 parts of β-hydroxyethoxyphenyl) sulfone, 223 parts (yield 97%) with a softening point of 110
A transparent polymer having a molecular weight of 15,200 was obtained.

Static melt mixing shown in Figure 1, that is, element L/D = 1.5, D = 5, n = 15 (dividing width 0.8 μ)
and a mixer where the external heating of the pipe is an electric heater
mmφ extruder spinning machine (screw L/D=2
6), and supply the polyphosnate with a gear pump from just before the static melt mixer.
Polyethylene terephthalate with η]0.72 was melt-spun.

The spinning conditions were as follows: the average temperature of the screw part was 300°C, the screw rotation speed was 15 times/min, the internal temperature of the mixer was 280°C, the nozzle part was 280°C, and the spinning speed was 1000 rrt/min.

The obtained undrawn yarn was heated at a pin temperature of 90°G and a plate temperature of 1
It was stretched at 50° C., at a stretching speed of 520 m/min, and at a stretching ratio of 3.5 times.

The results obtained are shown in Table 3.

Comparative Example 2 In the same manner as in Comparative Example 1, 274 parts of 2,2-di(4-hydroxyphenyl)sulfone was used instead of 2,2-di(4-hydroxyphenyl)propane. 3
38 parts (yield 90%) of a yellow solid was obtained.

It had a softening point of 182°C and a molecular weight of 10,050.

The flame retardant obtained by this method was blended with polyethylene terephthalate in the same manner as in Example 2, and the mixture was spun and stretched.

The results obtained are shown in Table 4. Example 3 The additives shown in Table 5 were synthesized in the same manner as in Example 1, and blended into polyethylene terephthalate in the same manner as in Example 1 so that the phosphorus content in the entire composition was 1% by weight. Then, it was spun and stretched.

The results obtained are shown in Table 5.

As can be seen from the examples, the composition to which the flame retardant shown in the method of the present invention is added has improved moldability and spinnability compared to polyphosphonates containing conventional aromatic diols as the diol component. , not only has an excellent yield during stretching, but also has features such as less fluff and less deterioration of physical properties, indicating that it has extremely high industrial utility value.

[Brief explanation of the drawing]

FIG. 1 is a sectional view showing an example of a static melt mixer according to the present invention. 1... Pipe, 2, 3... Mixing element, 4... Heating body.

Claims (1)

[Scope of Claims] 1 The following general formula [■] [However, in the formula, R is an aryl group, an alkyl group, an allyloxy group, or an alkoxy group, R' is H or, and Y is an alkylidene group, a sulfone group, Indicates an ether group or a carbonyl group. X represents a lower alkyl group or a chlorine atom. 1, 1', m, m' are integers from 0 to 4. n is an integer of 5 or more. or the following general formula [■] [However, in the formula, R is an aryl group, an alkyl group, an allyloxy group, or an alkoxy group, R' is H or less, and X represents a lower alkyl group or a chlorine atom. m is an integer from 0 to 4. n' is an integer of 5 or more. ] The phosphorus atoms in the total composition are 0.3 to 3
A flame-retardant polyester composition blended with polyalkylene terephthalate in a proportion by weight.