JPS6315823A - Flame-retarding polyester resin - Google Patents

Abstract

PURPOSE:To obtain a flame-retarding resin useful as a flame retardant for moldings such as films and fibers, by using a polyester obtained by reacting a polyester having two specified kinds of repeating units with a specified phosphorus compound as a component. CONSTITUTION:A flame-retarding polyester resin comprising a polyester obtained by reacting a polyester having repeating units of formulas I and II with a phosphorus compound of formula III and having an average degree of polymerization of 3-300. In the formulas, R<1> and R<2> are each a bivalent saturated aliphatic group, R<3> and R<4> are each a bivalent saturated or unsaturated aliphatic group, at least either R<3> or R<4> is an unsaturated aliphatic group, R<5> and R<6> are alkyl, aryl, alkoxy or aryloxy and they may be combined together to form a ring. When the average degree of polymerization of this polyester resin is below 3, the resin is viscous liquid and so can be not be easily handled, and when this degree is above 300, the melt viscosity of the resin is so high that the fluidity is improved or the solubility in a solvent is lowered undesirably.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a flame-retardant polyester resin that is particularly useful as a flame retardant for molded products such as films and fibers.

(Prior Art) Due to its excellent mechanical and chemical properties, polyester is used as a fiber for clothing, industrial use, etc.

It is widely used as films for magnetic tapes, photographs, capacitors, etc., and molded products such as bottles.

Incidentally, in recent years, there has been an increasing demand for synthetic fibers and various plastic products to be flame resistant from the viewpoint of fire prevention.

Conventionally, various methods for imparting flame resistance to polyester have been proposed, but a method of incorporating a phosphorus compound into polyester is considered to be effective.

Various phosphorus compound flame retardants have been proposed.

For example, in JP-A-54-116052, 9.10-
It is obtained by reacting dihydro-9-oxa-10-fluoride (called dihydro-9-oxa-10-fuoxide (1)01) or its benzene-nuclear substituted product with a compound having a vinyl group or a vinylidene group. A polyester phase separating flame agent consisting of a phosphorus compound has been proposed.

Mata, special release RL? +52 No. 652711 tlJ Niha, DOP and derivatives of maleic acid, fumaric acid, A flame retardant consisting of a reaction product with a condensate) has been proposed.

However, when the retardants proposed in the prior art 1 are added to polyester to form a molded article, it causes thermal decomposition.

This may cause undesirable coloring on the molded product.

There are drawbacks such as lowering the degree of polymerization and deterioration of the mechanical properties of molded products, and also drawbacks such as insufficient solubility and compatibility when used as a coating on molded products such as films. was there.

(Problems to be Solved by the Invention) The present invention solves the drawbacks of conventional phosphorus compound-based flame retardants and provides a method of coating or compounding molded products such as films and fibers to impart high flame retardancy. The purpose of this project is to provide a flame-retardant polyester resin that can be used.

(Means for Solving the Problems) ' The present invention achieves the objects set forth in item L, and its gist is as follows.

A flame-retardant polyester resin having an average degree of polymerization of 3 to 300, which is made of a polyester having repeating units represented by the following formulas (■) and [2] and reacted with a phosphorus compound represented by the following formula (○).

-0C-R'-CoO-R2-0-■ -0C-R'-COO-R4-0-■ I? 5 (R', R'' is a divalent aliphatic group R3, R4 is a divalent saturated aliphatic group or a divalent unsaturated aliphatic group, R3゜R4
At least one of them is an unsaturated aliphatic group, R5,
R' is an alkyl group, an aryl group, an alkoxy group, or an allyloxy group, and BS and Rh mutually form a ring)), 1. ) In the present invention, the polyester C11 with which the phosphorus compound of ゛ζ and 2〇 is reacted must have an unsaturated bond in some of the repeating positions 7j' and 1, and must not have unsaturated bonds in all of them. However, it is not possible to obtain a polyester resin that can be converted into one-two-dimensional material and used as a practical flame retardant. It is suitable that the proportion of the 11i-position in formula (1) accounts for 5 to 95 mol%, preferably 5 to 50 mol% of the total repeating units.

Further, the polyester resin of the present invention needs to have an average degree of polymerization of 3 to 300, preferably 4 to 150.
．． Optimally, it should be between 5 and 100. If the average degree of polymerization is less than 3, it becomes a viscous liquid and difficult to handle; if it exceeds 300, the melt viscosity becomes too high and fluidity is impaired.

This is not preferable because the solubility in solvents may decrease.

In the present invention, the polyester to be reacted with the compound of the formula It can be produced by reacting according to a method.

Specific examples of aliphatic dicarboxylic acids include fumaric acid, maleic acid, mesaconic acid, citraconic acid, glutaconic acid,
Examples include unsaturated aliphatic dicarboxylic acids such as itaconic acid, and saturated aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, and sebacic acid. (These may be used in the form of ester-forming derivatives such as acid anhydrides and esters.) Specific examples of aliphatic diols include:
Ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol.

Propylene glycol, ■, 4-butanediol.

1. Saturated aliphatic diols such as 2-butanediol and 2
-butene-1,4-diol, 3-butene-1,2-
Examples include saturated aliphatic diols such as diols. (
These may be used in the form of ester-forming derivatives such as esters. ) Furthermore, as a specific example of the phosphorus compound represented by 2〇, 41
The following four examples are listed below.

1-I II (e
)◎ (fl QC old ○-P-OII O-13-0C1l.

Hl1 111] (11(CI+□).

The aliphatic polyester with an unsaturated bond H in the 0.
Add 2 phosphorus compounds and react.
When making a polyester, the superesterification or transesterification reaction is completed approximately 1' after the end of the reaction.

It may be added at a time when a desired polymer having an average degree of polymerization of 3 to 300 can be obtained, but it is preferable to add it as soon as the average degree of polymerization becomes high.

The amount of phosphorus compound added in No. 2 is 1.50 (1 to 50.000 ppm, preferably 1,000 to 10,000 ppm) is appropriate for the heavy use of polyester as a phosphorus atom.The amount of phosphorus compound is very small. If the amount is too large, the flame retardant performance of the resulting polyester resin will be insufficient.On the other hand, if the amount is too high, the flame retardant performance will not only be saturated, but also the physical properties of the resulting polyester resin may be impaired, which is not preferable. , the amount of the phosphorus compound added is 70.5 to 2 times the equivalent of the unsaturated bond of the polyester,
It is preferably 0.8 to 1.4 times equivalent, most preferably 1 times equivalent.

The polyester resin of the present invention is suitable as an H retardant to be coated or blended into molded products such as films and fibers, but those with a relatively high degree of polymerization can be molded independently. It can also be used to obtain molded articles.

(Function) The polyester resin of the present invention is obtained by reacting the phosphorus compound (2) with the unsaturated bond portion of a polyester (including oligomers) having two partially unsaturated bonds. That is, the phosphorus compound is bonded to the polyester main chain in a bendane-like manner, and exhibits good flame retardancy.

For example, it is presumed that the reaction occurs according to a quadratic equation in which DOP is reacted with a polyester made of succinic acid, maleic acid (or fumaric acid), and ethylene glycol.

OO (Example) Next, examples are given to describe the invention.

In addition, in the examples, the average degree of polymerization of the polyester resin was determined using a chloroform solution containing 2.5% hexafluoroisopropanol as a solvent using 1-f L C801 type gel permeation coomadography manufactured by Toyo Soda Co., Ltd. It was determined by dividing the number average molecular weight measured at 39°C by the molecular weight of the repeating unit.

The polyester resin pedestal foot was run using a fluorescent X-ray method.

In addition, the flame retardant performance is UL-
1'M-0.94 standard combustion test. shi1'M1
．． Evaluation was performed by determining the grade of TM-2.

Example 1 124g of ethylene glycol was charged into a reactor and heated to 80°C.
11.13+r of succinic acid and 98 g of maleic anhydride were added to this, and while stirring, the temperature was reduced to 140 g in 1 hour.
The esterification reaction was carried out at ~160°C under a nitrogen atmosphere for 3 hours. Thereafter, germanium dioxide was added as a catalyst in an amount of 2.5 x 10-' mol per mol of the acid component, the temperature of the system was warmed to 2DO"c over 2 hours, and the pressure of the system was gradually reduced and the temperature was increased for 1 hour. 50-100mm 1llH and 1
1 in another hour. Omml! g, and the polycondensation reaction was continued under these conditions for an additional hour.

After that, the 9 reaction system was brought to normal pressure with nitrogen gas, and 'D OP.

That is, 216 g of the phosphorus compound of formula (h) was added, stirred for 20 minutes, and then heated at 200°C and 1.0 mmH.
Polycondensation was carried out for 3 hours under the conditions of g.

The obtained polyester resin was a substantially linear polymer with an average degree of polymerization of 108, and a phosphorus residual rate of 99%.

This polyester resin was heated at 230°C for 3 hours in a sealed tube.
After methanol decomposition, only compounds containing phosphorus atoms were separated using a gask 1-coat gel column.

One type of compound accounts for more than 95 mol% of these phosphorus compounds, and as a result of analysis with an infrared spectrophotometer, this compound has a concentration of 2960 cm-' and 1380 cn+.
Absorption of C-CH, at -', absorption of ■)-0 at 1735 cm-'.

Absorption of p-o-c at 1210 cm”, 760 cm-
' P-C absorption was observed. In addition, as a result of 9 elemental analysis, P = 8.57%, c-6o, 3o%,
H-=4.68%.

Theoretical value P = 8.60%, C-6'0.00%, H
=4.76%, which showed good agreement. From these results, it was confirmed that this metal phosphide was a compound having the following structural formula, and that DOP added to the polyester reacted with the unsaturated bonds in the polyester main chain.

Further, the above polyester resin was dissolved in tetrahydrofuran, and coated on a polyethylene terephthalate film with a thickness of 100 μm using a bar coater so that the phosphorus content was about 7% of the weight of the film. It was applied to give OOOppm and air-dried.

The flame retardant performance of the obtained film was TM-0 class, indicating a high degree of flame retardancy, and the mechanical properties of the film were also good.

Example 2 A polyester resin was produced in the same manner as in Example 1, except that DOP was added after the esterification reaction was completed.
The obtained polyester resin had an average degree of polymerization of 93. The phosphorus residual rate was 98%.

Further, Example 1-: Similarly, when this polyester resin was coated on a polyethylene terephthalate film at 2°ζ, the flame retardant performance of the film was VTM-0 grade.

Example 3 After the esterification reaction, a polycondensation reaction was carried out at 200° C. and 50 to 100 mJg for 2 hours. 1. The reaction system was brought to normal pressure with nitrogen gas, and DOP was added. f! A polyester resin having an average degree of polymerization of 10 was obtained in the same manner as in Example 1 except that the condensation time was adjusted. The phosphorus residual rate of the obtained polyester resin was approximately 100%.

This polyester resin is made of polyethylene terephthalate, and the total phosphorus content is about 7.0% of the total weight of the polyester.
00 (lp) was added to form a concave shape, and formed into a film with a thickness of 110 μm.

The flame retardant performance of the obtained fill J1 was VTM-, grade 0.

Examples 4 to 8 Polyester resins were produced in the same manner as in Example 1 except that the dicarboxylic acid component and diol component were changed to those shown in Table 1.

Table 1 shows the average degree of polymerization of the obtained polyester resin and the flame retardant performance of a polyethylene terephthalate film coated with this resin in the same manner as in Example 1.

Examples 9 to 16 Polyester resins were produced in the same manner as in Example 1 except that the phosphorus compounds were changed to those shown in Table 2.

Table 2 shows the average degree of polymerization of the obtained polyester resin and the flame retardant performance of polyethylene terephthalate film 1 coated with this resin in the same manner as in Example 1.

Table 2 Comparative Example 1 124 g of ethylene glycerol was charged into a reactor, and 80 g of
℃, and add 11 succinic acid to it. Fl+t, 98 g of maleic anhydride and 216 g of I) OI) were added one by one, and while stirring, the temperature was reduced to 1110 1 (io'c) in 1 hour.
The esterification reaction was carried out for 3 hours under a nitrogen atmosphere. Thereafter, 2.5XIO-' mole of germani dioxide/'Tum was added as a catalyst per mole of acid component, and /I of the yarn was added.
The temperature was raised to 200°C in 2 hours, the pressure of the system was gradually reduced to 50-100 mm 11 g in 1 hour, and then 11 g.
．． '1 Omm11H and polyconistel resin ii↑.

The obtained polyvarnish film resin had a degree of homopolymerization of V of 1.5° and a residual rate of phosphorus of 98%.

When this polyester resin was applied to a polyethylene terephthalate film in the same manner as in Example 1, the applied surface was sticky and blocking occurred. (The flame retardant performance number was VTM-0 grade.) Comparative Example 2 A polyester resin with an average degree of polymerization of 34) was obtained in the same manner as in Example 1, except that the polycondensation time was 5 hours.

When this polyester resin was applied to polyethylene terephthalate filno in the same manner as in Example 1, the fluidity of the resin was poor, uneven thickness of the applied resin occurred, and the flame retardant performance was VTM, -1 grade. Ta.

Comparative Example 3 A polyester resin was produced in the same manner as in Example 1 except that succinic acid was not added.

The resulting polyester resin has a marked three-dimensional structure, is insoluble in solvents and cannot be coated, and has extremely poor fluidity, making it difficult to mix it into polyethylene terephthalate as a flame retardant.

It could not be put to practical use.

(Effects of the Invention) According to the present invention, flame-retardant polyester can be coated or blended into molded products such as films and fibers to impart high flame retardancy without impairing the properties of the molded products. A resin is provided.

Claims (1)

[Claims] (1) Consisting of a polyester having repeating units represented by the following formulas [1] and [2] and a phosphorus compound represented by the following formula [3], the average degree of polymerization is 3.
~300 flame retardant polyester resin. -OC-R^1-COO-R^2-O-[1] -OC-R^3-COO-R^4-O-[2] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[3] ( R^1, R^2 are divalent saturated aliphatic groups, R^3, R^
4 is a divalent saturated aliphatic group or a divalent unsaturated aliphatic group,
At least one of R^3 and R^4 is an unsaturated aliphatic group, R^5 and R^6 are an alkyl group, aryl group, alkoxy group, or allyloxy group, and R^5 and R^6 are They may mutually form a ring. )