JPS6038417B2 - polyester composition - Google Patents

Description

[Detailed description of the invention]

The present invention relates to polyester compositions, particularly pyrolyzed polyester
ester composition. Aromatic polyesters such as polyethylene terephthalate have many excellent properties and are therefore widely used in fibers, films, and other molded products. However, polyester is easily combustible, and for this reason, in recent years, from a standpoint of respect for humanity, there has been a call for the use of polyester as a combustible material, and various efforts have been made. Conventionally, methods for making polyester flame retardant include adding flame retardant substances during polymer production and blending or copolymerizing them, kneading flame retardant polymers during molding, and imparting flame retardancy through post-processing. Although many methods have been proposed, each method has its own problems, and currently there is still much room for improvement. In other words, the methods of imparting flame retardance through post-processing are complicated, the effects are not uniform, the light resistance and texture of the molded product are impaired, and there are problems with toxicity during use. There are drawbacks. On the other hand, the method of adding a flame retardant imparting substance during polymer production and copolymerizing is the most desirable from a commercial standpoint, but has the drawback that the inherent properties of polyester are impaired by copolymerization. Furthermore, with the method of adding and mixing flame retardant substances to polyester, there are problems with the compatibility of the key flame retardant, difficulty in uniformly mixing the flame retardant, and the conventional flame retardants cause needle wear during knitting of fibers. There are various problems. As a result of deep research into these problems, the present inventors have discovered a flame-retardant polyester composition that does not have the above-mentioned drawbacks and does not impair the performance of the main polyester pot. That is, the present invention provides polyester with the following general formula [1]
A reaction product obtained from a phosphorus compound represented by and a dicarboxylic acid or its ester-forming conductor (or/and) an oxycarboxylic acid or its ester-forming cryptic conductor, (or/and) a diol or its ester-forming conductor and the phosphorus atom content in the polyester is 0.
05-5. This is a polyester composition characterized in that the polyester composition is blended in a proportion of 1% by weight. [In the formula, R1 and R2 are a monovalent alkyl group or phenyl group having 1 to 18 carbon atoms, R3 is a carboxyl group, or an alkyl ester, aryl ester, or cycloalkyl ester thereof, and R4 is a hydrogen atom or a monovalent It is an ester-forming functional group, and A is ÷C ratio n2CR5<, (
R5 to RII represent a hydrogen atom or a lower alkyl group having 1 to 8 carbon atoms, and n2 to M represents 0 or 1. ) 1 and m represent an integer of 0 or 1. ] Regarding the phosphorus compound represented by the above general formula [1], in the formula, R1 and R2 are an alkyl group having 1 to 18 carbon atoms such as methyl, ethyl, butyloctyl group, phenyl group,
Aryl groups such as naphthyl groups, aralkyl groups such as benzyl groups, cycloalkyl groups such as cyclohexyl, haloalkyl groups in which some or all of the hydrogen atoms are substituted with halogen atoms, haloaryl groups, haloaralkyl groups, and halocycloalkyl groups. Two molecules may be bonded to each other to form a ring. As R1 and R2, an alkyl group having 1 to 6 carbon atoms or a phenyl group is particularly preferred. Next, in the formula, R3 is a carboxyl group, or an alkyl ester, aryl ester, or cycloalkyl ester thereof, and R4 is R3 or a monovalent ester-forming functional group such as a hydroxyl group or a hydroxyalkoxycarbonyl group, or a hydrogen atom, or R3, R4 is a divalent ester-forming functional group that can form a ring with A via the groups shown with each other. Note that some or all of the hydrogen atoms of R3 and R4 may be substituted with halogen atoms. Preferred groups for R3 and R4 are a carboxyl group, an alkyl ester thereof, an aryl ester, a hydroxyl group, and a hydroxyalkoxycarponyl group. Preferred specific examples of the phosphorus compound represented by the general formula [1] include dimethyl 2-methoxycarbonylethylphosphonate, dimethyl 2-ethoxycarbonylethylphosphonate, and 2-phenoxycarbonylethylphosphonate when both 1 and m are 1. dimethyl acid, diethyl 2-methoxycarbonylethylphosphonate, diethyl 2-ethoxycarbonylethylphosphonate, diethyl 2-phenoxycarbonylphosphonate, 2
- diisopropyl methoxycarbonylethylphosphonate, diisopropyl 2-ethoxycarbonylethylphosphonate, dibutyl 2-methoxycarbonylethylphosphonate, dibutyl 2-ethoxycarbonylethylphosphonate, diphenyl 2-methoxycarbonylethylphosphonate, Diphenyl 2-ethoxycarbonylethylphosphonate, diphenyl 2-phenoxycarbonylethylphosphonate, dibenzyl 2-methoxycarbonylethylphosphonate, dibenzyl 2-ethoxycarbonylethylphosphonate, dimethyl 2-methyl-2-methoxycarbonylethylphosphonate , diethyl 2-methyl-2-methoxycarbonyl phosphonate, dimethyl 1-methyl-2-methoxycarbonylethylphosphonate, 1-methyl-2-
Examples include diethyl ethoxycarbonyl ethylphosphonate. Two or more of these may be used in combination. If either 1 or m is 1, methyl (2-carboxyethyl)methylphosphinate, ethyl (2-carboxyethyl)methylphosphinate, methyl (2-methoxycarbonylethyl)methylphosphinate, (2 -ethoxycarbonylethyl) ethyl phosphinate, (2-carboxyethyl) ethyl phosphinate, methyl (2-methoxycarbonylethyl) ethyl phosphinate, (2-carboxyethyl) phenyl phosphinate, (2-carboxyethyl) ethyl phosphinate, (2-methoxycarbonylethyl) ethyl phosphinate, -methoxycarbonylethyl) methyl phenylphosphinate, (
Examples include ethyl 2-ethoxycarbonylphenyl)phenylphosphinate, methyl (4-methoxycarbonylphenyl)phenylphosphinate, and the like. When both 1 and m are 0, (1,2-dicarboxyethyl)dimethylphosphine oxide, (1,2-dimethoxycarbonylethyl)dimethylphosphine oxide, (1
・2-diethoxycarbonylethyl) dimethylphosphine oxide, (1,2-diphenoxycarbonylethyl)dimethylphosphine oxide, [1-carboxy, 2
-methoxyethyl]diphenylphosphine oxide, (
1,2-dicarboxyethyl)diethylphosphine oxide, (1,2-dicarboxyethyl)methylphenylphosphine oxide, (1,2-dicarboxyethyl)
Diphenylphosphine oxide, (1,2-dicarboxy-2-methyl-ethyl)dimethylphosphine oxide, (2,3-dicarboxypropyl)dimethylphosphine oxide, (2,3-dimethoxycarbonylpropyl)dimethylphosphine oxide , (2,3-dicarboxypropyl)diphenylphosphine oxide, (carboxyethyl)dimethylphosphine oxide, (methoxycarbonylethyl)dimethylphosphine oxide, (ethoxycarbonylethyl)dimethylphosphine oxide, (phenoxycarbonyl) (Ethyl)dimethylphosphine oxide, (Ruboxyethyl)dimethylphosphine oxide, (Ruboxyethyl)methylphenylphosphine oxide, (Ruboxyethyl)diphenylphosphine oxide, (Ruboxy 2-methyl-ethyl)dimethylphosphine oxide, (carboxypropyl)dimethylphosphine oxide, (methoxycarbonylpropyl)dimethylphosphine oxide, (carpoxypropyl)diphenylphosphine oxide, and the like. The dicarboxylic acids used in the present invention include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenylsulfone 4,4-dicarboxylic acid, diphenyl ether 4,4-dicarboxylic acid, diphenoxychetane 4,
4'-dicarboxylic acid, diphenyldicarboxylic acid, 2.5
- Aromatic dicarboxylic acids such as dibromoterephthalic acid and tetrabromoterephthalic acid, aliphatic dicarboxylic acids such as adipic acid and sebacic acid, and alicyclic dicarboxylic acids such as hexahydroterephthalic acid, but 5-monosodium isophthalic acid etc. can also be used. As the oxycarboxylic acid, p-oxybenzoic acid, p-8
-Includes oxyethoxybenzoic acid, etc. In addition, as the diol component in the present invention, ethylene glycol,
1,2-propylene glycol, 1,3-trimethylene glycol, tetramethylene glycol, neobentyl glycol, 1,4-cyclohexanediol, 1,4
- Cyclohexane dimethanol, diethylene glycol, polyoxyalkylene glycol, or those of the following general formula. [In the formula, X represents bromine and/or chlorine, Y is an alkylene group having 1 to 6 carbon atoms, a cycloalkylidene group, an arylalkylidene group, -S-, -S
O-, 1S02 represents 1 or -0-. m represents an integer from 0 to 4. ] The phosphorus compound represented by the general formula [1] specifically shown above and 'B' dicarboxylic acid or its ester-forming derivative, or/and

[C
'Oxycarboxylic acid or its ester-forming derivatives,
And/or a reaction product obtained from dish diol or its ester-forming derivative (hereinafter referred to as teaching agent) can be synthesized by a known method. That is, in the two-component system of the sail and the plate, a phosphorus compound with a hydroxyalkoxycarbonyl group at the end is obtained, and the wind, {
B} and the three-component system of blood, the two-component system of wind and 'q, ■, [
In the four-component system of B}, {C' and dish, a phosphorus-containing oligomer and a phosphorus-containing polymer are obtained, and the reaction is carried out in each system by transesterification or/and esterification reaction,
Polymerization is carried out under reduced pressure if necessary. In this reaction, a titanium compound is usually used as a catalyst, but if necessary, an alkali metal compound, an alkali metal compound, a metal compound such as zinc, manganese, or cobalt, an antimony compound, or a germanium compound can be used. In the present invention, the phosphorus atom content in the modifier can be changed by adjusting the amount of the above-mentioned Tsukuda, 'C', and plate. Furthermore, by using the acid component and/or diol component of the polyester to be modified as the acid component and/or diol component used in the synthesis of the modifier, the compatibility with the polyester is further improved. Furthermore, the composition of the present invention can be obtained even in the presence of conventionally known phosphoric acid esters and benzenephosphonic acid esters as the phosphorus component. The polyester modified in the present invention is preferably polyethylene terephthalate, but poly(cyclohexylene dimethylene terephthalate)
, poly[ethylene 1,2-bis(phenoxy)ethane p
・p'-dicarboxylate], polytetramethylene terephthalate, polyethylene naphthalate, etc. In addition, some of the dicarboxylic components of each of the above polyesters were added to isophthalic acid, p-3-oxyethoxybenzoic acid, diphenylsulfone 4,4'-dicarboxylic acid, diphenyl ether 4,4'-dicarboxylic acid, diphenyl ether 4,4 '-dicarboxylic acid, diphenoxyethane 4,4'
Dicarboxylic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, 5-sodium sulfisophthalic acid, 2.
It can be replaced by 5-dibromoterephthalic acid, tetrabromoterephthalic acid, adipic acid, azelaic acid, sebacic acid, hexahydroterephthalic acid, etc.
In addition, some of the diol components are propylene glycol, trimethylene glycol, tetramethylene glycol, neobentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexane dimethyl, diethylene glycol, polyethylene glycol, polytetramethylene glycol. , or can be replaced with one of the following general formula. The above polyester is manufactured by a conventionally known method. It also includes so-called modified polyesters for improving the dyeability and antistatic properties of polyesters. [wherein,
Represents 21 or -○-. m represents an integer from 0 to 4. ] The timing of adding the modifier of the present invention to the polyester is not particularly limited, but a method of blending it during molding is particularly preferred. At this time, a chip in which polyester and a modifier are melt-mixed in advance may be used. The modifier of the present invention has a phosphorus atom of 0.05 to 5. It is added in an amount of 0.10 to 1.0% by weight for ordinary fibers. When producing polyester fibers in the present invention,
It is possible to simply form a mixed paper yarn of polyester and a modifier, or to perform two-component yarn extraction of components with different phosphorus atom contents, unstamped polyester and the polyester composition of the present invention. Further, it is not outside the spirit of the present invention to use a conventionally known retardant in combination. Note that additives used in polyester production, such as polysiloxane, titanium oxide, antimony oxide, carbon black, and antistatic agents, can also be used in the present invention. As described above, the composition of the present invention allows the production of flame-retardant polyester of high quality very easily, and is a composition of extremely high industrial value. Next, the present invention will be specifically explained with reference to Examples. Note that in the examples, parts indicate parts by weight, and the intrinsic viscosity indicates the phenol/tetrachloroethane mixed solvent (weight ratio 3:
2) It was determined from the value measured at 30q○. Flame resistance was determined by drawing a polyester polymer using a conventional method, making it into a stockinette wire, rolling it into a length of 10 arcs, inserting it into a wire coil with a diameter of 1 ratio, and making it at an angle of 45o. When the sample is held and ignited from the bottom end and the fire source is moved away, if the sample is extinguished, the ignition is repeated again, and the number of ignitions required to completely burn all the samples is determined and expressed as the average value for the five samples. The test was deemed to have passed if the number of ignitions was 3 or more. Example 1 24 parts of the phosphorus compound shown in Table 1, 18 parts of ethylene glycol, 0.5% by weight of potassium titanyl oxalate and 0.05% by weight of the phosphorus compound
of antimony trioxide, and each mixture was mixed with 150 qo of antimony trioxide.
~20,000°C] was allowed to react for 2 minutes. Subsequently, this reaction mixture was reacted for 4 minutes at a temperature of 20,000 ℃ while gradually reducing the system pressure until it finally reached 1 foot of Hg. The softening point and phosphorus atom content of the obtained reaction products are also listed in Table 1. Then the intrinsic viscosity is 0
．． The above reaction products were added to polyethylene terephthalate No. 65 in an amount of 0.3% by weight as phosphorus atoms in the polyester, and the melt-mixed chips were spun and drawn in a conventional manner to obtain a finished yarn. The properties of the finished yarn obtained are also listed in Table 1. In Table 1, a: diethyl 2-ethoxycarbonylethylphosphonate b: dipheninole methoxycarbonylethylphosphonate c: ethyl (2-carboxyethyl)methylphosphinate d: (2-ethoxycarbonylethyl)ethyl Phenyl phosphinate e: (1,2-dicarboxyethyl)
Dimethylphosphine oxide f: (carboxypropyl) diphenylphosphine oxide *Strength retention: Measured after treating the finished yarn in ion-exchanged water at a temperature below 10,000 for 1 hour. Example 2 50 parts of dimethyl terephthalate, 376 parts of tyrene glycol, and 0 for dimethyl terephthalate, respectively.
．． A mixture of 0.09% by weight zinc acetate, 0.12% by weight potassium titanyl oxalate, and 0.015% by weight antimony trioxide was reacted for 210 minutes at 16,000 to 220% by weight. Nine minutes after the start of the reaction, predetermined amounts of each of the various phosphorus compounds were added. After the above reaction was completed, the temperature of the system was gradually increased over 45 minutes, and at the same time the pressure was gradually reduced to a final value of 245 qo and 0.1 Hg, and the reaction was continued under these conditions for an additional 60 minutes. The softening point and phosphorus atom content of the obtained reaction products are shown in Table 2. Next, the above reaction products were added to polyethylene terephthalate having an intrinsic viscosity of 0.65 in an amount of 0.25% by weight as phosphorus atoms in the polyester, and the melted and combined chips were spun and stretched by a conventional method. A finished yarn was obtained. The properties of the finished yarn obtained are also listed in Table 2. Table 2 Example 3 165 parts of dimethyl terephthalate, 124 parts of ethylene glycol, and 126 parts of 2,2-di(4-hydroxyethoxy-13,5-dibromphenyl)-propane, 0.18 parts of A mixture of zinc acetate, 0.35 parts of potassium titanyl oxalate, and 0.1 parts of antimony trioxide was reacted for 100 minutes at 150°C to 190°C, at which point 35.6 parts of 2-ethoxycarboxylic acid Add diethyl nylethylphosphonate and further add 190-220q
The reaction was carried out for 10 seconds under C. Subsequently, the temperature of the reaction system was raised to 245 qo over 60 minutes while the pressure of the system was gradually reduced, and finally to 0.8 kite Hg. Further, the reaction was carried out for 30 minutes at 245 oo and under 0.8 side Hg. The softening point of the obtained reaction product was 85 pm,
The phosphorus atom content was 1.94%. The above reaction product was added to polyethylene terephthalate having an intrinsic viscosity of 0.65 in an amount of 0.2% by weight as phosphorus atoms, and the melt-mixed chips were drawn in a conventional manner to obtain a polyester thread. The strength of the obtained yarn was 3.6 m/d, the elongation was 27%, and the flame resistance was 4.6. In addition, the strength retention rate of this thread is 97
．． It was 8%. Example 4 A mixture of 11 parts of diethyl 2-ethoxycarbonylethylphosphonate, 172 parts of bis(4-hydroxyethoxyphenyl) sulfone, 0.177 parts of potassium titanyl oxalate, and 0.073 parts of antimony trioxide. After reacting for 12 minutes under 240q0 in a nitrogen atmosphere,
Subsequently, the pressure of the system was gradually reduced to 20 Hg over 68 minutes under 240 qC to complete the reaction. The softening point of the reaction product is 6000, and the phosphorus atom content is 6
．． It was 40%. This reaction product has an intrinsic viscosity of 0.65
of polyethylene terephthalate as phosphorus atoms in the polymer. The chips were added in an amount equal to % by weight of the box, and the chips were melt-mixed and then spun and drawn in a conventional manner to obtain a polyester yarn. The strength of the obtained yarn was 4.2 ta'd, the elongation was 30%, and the flame resistance was 4.8. In addition, the strength retention rate of this thread is Satoshi. 1
%Met. Comparative Example 1 582 parts of dimethyl terephthalate, 372 parts of ethylene glycol, an amount of diethyl 2-ethoxycarbonylethylphosphonate to give a phosphorus atom of 0.3% by weight based on the polymer, and 0% based on dimethyl terephthalate.
．． A mixture of 0% by weight of zinc acetate, 0.0% by weight of titanyl potassium oxalate, and 0.01% by weight of antimony trioxide was reacted at 150 qo to 230 oo for 120 minutes. Subsequently, while increasing the temperature of the system to 275°C for 45 minutes,
The system pressure was gradually reduced to 0.1 Hg, and the reaction was continued for an additional 60 minutes. The intrinsic viscosity of the obtained reaction product (combined polyester) was 0.56. The above-mentioned phosphorus-containing polyester chips were spun and drawn by a conventional method to obtain a polyester thread. The flame resistance of the obtained yarn was 4.6, the strength was 2.7/d, and the elongation was 30%. Moreover, the strength retention rate was 95.3%. Comparative Example 2 50 parts of eaves dimethyl terephthalate, 35 parts of ethylene glycol, 81.5 parts of 2,2-di(4-hydroxyethoxy-3,5-dipromphenyl)propane, 3
A mixture of 3 parts of diethyl 2-ethoxycarbonylethyl phosphinate, 0.09% by weight zinc acetate, 0.0% potassium titanyl oxalate and 0.0% antimony trioxide by weight based on dimethyl terephthalate. 1
The reaction was carried out for 120 minutes at 50 to 230 oO. Subsequently, the temperature of the system was gradually reduced to 275 qo over 45 minutes, and the pressure of the system was gradually reduced to 0.1 Hg. 27 more
The reaction was continued for 65 minutes under 5oo and 0.1 skin Hg, and the obtained reaction product (phosphorus-containing polyester) had an intrinsic viscosity of 0.
．． It was 53. The above-mentioned phosphorus-containing polyester chips were spun and drawn by a conventional method to obtain a polyester thread.

Claims (1)

[Scope of Claims] 1 Polyester, a reaction product obtained from a phosphorus compound represented by the following general formula [I], a dicarboxylic acid or an ester-forming derivative thereof, or/and an oxycarboxylic acid or an ester-forming derivative thereof; A polyester composition characterized in that the following are blended in a proportion such that the phosphorus atom content in the polyester is 0.05 to 5.0% by weight. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, R^1 and R^2 are monovalent alkyl groups having 1 to 18 carbon atoms or phenyl groups, and R^3 is carboxyl groups or their Alkyl ester, aryl ester,
cycloalkyl ester, R^4 is a hydrogen atom or a monovalent ester-forming functional group, and A is -(CH_2)_
n_2-CR^5■, ▲Mathematical formulas, chemical formulas, tables, etc.▼(R^5~R^1^1 is a hydrogen atom or the number of carbon atoms
~8 lower alkyl groups, n_2 to n_7 are 0 or 1
represents. ) Also, l and m represent integers of 0 or 1. ]