JPS6159337B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a phosphorus-containing polyester polyether, in particular a phosphorus-containing polyester polyether comprising a polyester polyether containing a limited amount of a polyalkylene ether component and an alkali metal salt of a specific phosphorus compound. The present invention relates to a method for producing polyester polyether.

In recent years, thermoplastic polymers such as polyester, polyamide, and polyolefin have been used for molded products and other materials due to their excellent mechanical strength, chemical resistance, and heat resistance.
Huge amounts are used especially in the textile and film fields.

However, these thermoplastic polymers tend to generate static electricity, and there are various problems that have not yet been fully resolved, such as reduced operability due to static electricity during molding, dust absorption during actual use, and discomfort when worn. .

Antistatic agents conventionally used to prevent such static build-up include polyalkylene ethers, polyester polyethers containing polyalkylene ethers, and combinations of polyalkylene ethers with organic sulfonic acids or phosphates. Although systems using polyester polyethers in combination with organic sulfonic acids or phosphates have been used, none of them are satisfactory in terms of performance, durability, and operability during use. In order to be used as an antistatic agent for thermoplastic polymers, it must be possible to obtain a high level of antistatic performance with as little amount as possible, the antistatic agent must not fall off during use, and it must have excellent durability. It must satisfy the requirements that it is practical as an agent and does not cause decomposition or coloring of the thermoplastic polymer when added to the thermoplastic polymer.

From the above point of view, although it is easy to obtain polyalkylene ethers that have traditionally been used as antistatic agents alone or in combination with polyalkylene ethers and salts of general organic acids,...
does not satisfy the conditions. Furthermore, it cannot be said that the conditions for polyester polyether systems containing polyalkylene ether are fully satisfied. The most desirable antistatic agent is a combination system of polyester polyether and an organic acid salt. It is desirable that the acid salt is uniformly dispersed, that it can be produced as easily as when polyester polyether is used alone, and that there are no quality problems due to the addition of the organic acid salt. That is, it is important to find an organic acid salt that can be added and copolymerized during or immediately after polyester polyether polymerization.

The present inventor has conducted extensive research on polyester polyether copolymers containing organic sulfonic acids, phosphoric acids, phosphorous acids, and alkali metal salts of phosphonic acids in order to find antistatic agents that do not cause problems in production. They have discovered that if an alkali metal salt of the compound is used, it can be added during or immediately after the production of polyester polyether, and the desired antistatic agent can be obtained. That is, the present invention involves subjecting an aromatic dicarboxylic acid or its ester-forming conductor and an aliphatic diol to a transesterification or esterification reaction, and then producing an aliphatic polyether diol or its ester-forming derivative and the compound represented by the following general formula []. A method for producing a phosphorus-containing polyester polyether, which comprises blending an alkali metal salt of a phosphorus compound having an ester-forming functional group and causing a polymerization reaction.

(However, R ₁ is a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms that may contain an ester-forming functional group, or M ₂ and R ₂ are divalent or trivalent hydrocarbon groups having 1 to 6 carbon atoms. , R ₃ is a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms that may contain a hydroxyl group, or
M ₃ , M ₁ , M ₂ and M ₃ are alkali metal atoms, m is 0 or 1, and n is an integer of 1 or 2. ) Examples of the polyester segment of the polyester polyether in the present invention include polyethylene terephthalate, poly-1,4-cyclohexane dimethylene terephthalate, poly-p-ethyleneoxybenzoate, and copolymers with conventionally known dicarboxylic acids. . The polyalkylene ether preferably has an ethylene oxide chain content of 50% or more and an average molecular weight of 500 to 500.
25000, polyethylene glycol,
polyethylene glycol monophenyl ether,
Examples include, but are not limited to, block copolymers of ethylene oxide and propylene oxide, block copolymers of ethylene oxide and tetrahydrofuran, and the like. In addition, if the ethylene oxide chain content is less than 50%, the hydrophilicity will decrease and the performance as an antistatic agent will also decrease.
Undesirable.

The polyalkylene ether may be added to the polyester polyether at any stage before the completion of the polymerization reaction, but it is preferably added at the initial stage of the polymerization, ie, after the transesterification reaction or after the esterification reaction. The amount of polyalkylene glycol contained in the polyester polyether is 10-90% by weight. If the content is less than 10%, the original performance as an antistatic agent will be low, and if it is more than 90%, the softening point will be low and the hydrophilicity will be too high, making it unsuitable as an antistatic agent.

Examples of the alkali metal salt of the specific phosphorus compound to be copolymerized into the phosphorus-containing polyester polyether of the present invention include alkali metal salts of phosphinic acid and phosphonic acid derivatives having ester-forming functional groups, but are of course not limited to these. It's not something you can do. That is, 2-carboxyethylmethylphosphinic acid, 2
-carboxyethyl phenylphosphinic acid, 4-
Carboxyphenylphenylphosphinic acid, carboxymethylphosphonic acid, 2-carboxyethylphosphonic acid, 2-carboxypropylphosphonic acid, 3-carboxypropylphosphonic acid, 4-carboxyphenylphosphonic acid, 2,3-dicarboxypropylmethyl Examples include alkali metal salts of phosphinic acid, 2,3-dicarboxypropylphosphonic acid, and alcohol, phenol, or glycol esters thereof.

Structural formulas of representative examples of these compounds are shown below.

The alkali metal atom to phosphorus atom equivalent ratio (M/
P) is preferably 2.2 at maximum. If it is 2.2 or more, the inorganicity will be high, and the reactivity and uniform dispersibility for polyester polyether will be extremely low. In addition to sodium salts, potassium salts and lithium salts are used as alkali metal salts.

The alkali metal salt of the phosphorus compound used in the present invention can be obtained by reacting the phosphorus compound with an alkali metal compound such as sodium hydroxide in water, alcohol, glycol or polyalkylene glycol, and can also be obtained by reacting the phosphorus compound with an alkali metal compound such as sodium hydroxide in advance. It is also possible to add each at the time of ether production and react in a polymer system. When the alkali metal salt of the phosphorus compound used in the present invention is synthesized in advance, it can be added to the polyester polyether system either in powder form or in the form of a solution or dispersion of water, polyester, glycol, or polyalkylene glycol. can do.

The most preferable method for producing the phosphorus-containing polyester polyether of the present invention is to react a lower alkyl ester of a phosphorus compound and an alkali metal hydroxide in advance using the glycol component of the polyester polyether as a solvent, and to prepare a solution or a solution of the glycol. This is a method in which a dispersion liquid is added during polyester polyether polymerization. These alkali metal salts of phosphorus compounds can be added at any stage before the completion of the polymerization of polyester polyether or immediately after the completion of the polymerization. Preferably, it is added in stages.

The blending ratio of polyester polyether and alkali metal salt of a phosphorus compound is 99.5/0.5 to 50/50, and if the blending ratio is lower or higher than this, the antistatic effect of the resulting phosphorus-containing polyester polyether will be reduced. It may be insufficient, or the solubility or dispersibility of the alkali metal salt of the phosphorus compound in the polyester polyether may become poor.

Note that it is desirable that all the alkali metal salts of the phosphorus compound be copolymerized with the polyester polyether, but if the phosphorus compound is in excess, it may be dispersed in the polyester polyether.

Further, the relative viscosity of the phosphorus-containing polyester polyether is 1.10 or more, preferably 1.35 to 3.0. When the relative viscosity is 1.10 or less, the dispersibility and workability when blended into polyester are poor, and the durability of the antistatic effect is also unfavorable. On the other hand, in order to obtain a high viscosity phosphorus-containing polyester polyether with a relative viscosity of 3.0 or more, a long time is required for polymerization, which causes discoloration. Moreover, it is undesirable because it has poor solubility and is difficult to mix with polyester.

Examples of the thermoplastic polymer modified by the phosphorus-containing polyester polyether of the present invention include polyester, polyamide, polyurethane, polyolefin, polyacrylonitrile, etc. Examples of the polyester include polyethylene terephthalate, polyethylene terephthalate/isophthalate, Examples include poly-1,4-cyclohexane dimethylene terephthalate, poly-p-ethylene oxide benzoate, and copolymers thereof, such as copolymers with sodium sulfoisophthalic acid and polyethylene glycol.

The amount of the antistatic agent of the present invention to be blended into the thermoplastic polymer is such that the content of the polyalkylene glycol component is 0.1 to 50% by weight based on the total composition,
Moreover, it is desirable that the content as phosphorus atoms is 50 to 5000 ppm. Below this range, a sufficient antistatic effect cannot be obtained, and above this range, the physical properties of the thread etc. will deteriorate.

The phosphorus-containing polyester polyether of the present invention can be obtained using a conventionally known polyester production catalyst under normal polyester production conditions. The composition may also contain a heat stabilizer, a light stabilizer, and other additives.

The present invention will be specifically explained with reference to Examples above. In the examples, all parts and percentages are by weight. Relative viscosity is 0.4g of sample in phenol/tetrachloroethane (=6/4) mixed solvent.
Calculated by measuring at 30°C using a solution dissolved in 100ml.

The cleansing voltage is 40%RH at 20℃.
This is a value measured with a Faraday gauge after rubbing with nylon taffeta for 12 times/12 seconds, and a value of 7V or less indicates that the antistatic effect is present. The frictional charging voltage was measured using a frictional charging voltage measuring device (rotary static tester) at a load of 500g and a rotational speed of 400 times.
The value was measured by rubbing with a cotton cloth for 1 minute at 40% RH and 20°C, and a value of 600V or less indicates an antistatic effect. The half-life is determined to be 30 by a high electrostatic field charge measuring device (honest meter).
This is a value measured at %RH 20°C, and if it is 100 seconds or less, it indicates that the antistatic effect has appeared.

Example 1 120 parts of dimethyl terephthalate, 72 parts of ethylene glycol, 0.2 parts of zinc acetate, 0.2 parts of antimony trioxide
Place the sample in a reaction vessel equipped with a distiller and raise the temperature to 150~
The transesterification reaction was carried out at 230°C for 2 hours. Next, 0.2 parts of INOX 330 (phenolic stabilizer, trade name), 280 parts of polyester glycol (average molecular weight 8000), and 21.1 parts of the compound represented by the above structural formula (E) were added, and the mixture was heated at a temperature of 230 to 275°C under reduced pressure. The initial polymerization reaction was carried out for 40 minutes, and the polymerization reaction was further carried out for 42 minutes at 275°C and under a reduced pressure of 0.2 mmHg. The obtained phosphorus-containing polyester polyether had a softening point of 205.7°C, an intrinsic viscosity of 1.53 calculated from a relative viscosity of 1.756, and no coloration.

Example 2 120 parts of dimethyl terephthalate, 72 parts of ethylene glycol, 0.2 parts of zinc acetate, 0.2 parts of antimony trioxide
A portion of the mixture was placed in a reaction vessel, and the transesterification reaction was carried out at a temperature of 150 to 230°C for 2 hours. Next, 0.2 parts of Ionox 330, 280 parts of polyethylene glycol (average molecular weight 8000), and 89 parts of a 57% ethylene glycol solution of the compound represented by the above structural formula (F) were added, and initial polymerization was carried out for 40 minutes under reduced pressure at 230 to 275°C. The reaction was carried out, and further polymerization was carried out at 275°C and 0.2 mmHg for 65 minutes. The resulting polymer has a softening point
The intrinsic viscosity calculated from 200.7℃ and relative viscosity 1.705 is
It was 1.44 and slightly yellow.

Example 3 120 parts of dimethyl terephthalate, 72 parts of ethylene glycol, 0.2 parts of zinc acetate, 0.2 parts of antimony trioxide
A portion of the mixture was placed in a reaction vessel, and transesterification was carried out at a temperature of 150 to 230°C for 2 hours. Next, 0.2 parts of Ionox 330, 280 parts of polyester glycol (average molecular weight 8000), and 21.1 parts of the compound represented by the above structural formula (C) were added, and an initial polymerization reaction was carried out for 40 minutes at a temperature of 230 to 275°C under reduced pressure. Furthermore
Polymerization reaction was carried out for 85 minutes at 275°C under a reduced pressure of 0.2 mmHg. The obtained polymer had a softening point of 207.5°C, an intrinsic viscosity of 1.08 calculated from a relative viscosity of 1.505, and a slightly yellow color.

Comparative Example 1 The same procedure as in Example 1 was carried out except that 36 parts of amylphosphonic acid monoamyl monosodium salt was added instead of the sodium salt of the phosphorus compound of the present invention in Example 1, and the mixture was heated at a temperature of 230 to 275°C under reduced pressure. The cut-off polymerization reaction was carried out for 40 minutes while heating at 275℃.
Polymerization was carried out for 120 minutes under a reduced pressure of 0.2 mmHg, but the viscosity did not increase at all.

Comparative Example 2 The same procedure as in Example 1 was carried out except that 37 parts of benzenephosphonic acid monomethyl monosodium salt was added instead of the sodium salt of the phosphorus compound of the present invention in Example 1, and the mixture was heated at a temperature of 230 to 275°C under reduced pressure. Initial polymerization reaction was carried out for 40 minutes, and further 275
The polymerization reaction was carried out for 45 minutes at a temperature of 0.2 mmHg. In the product, the sodium salt of the phosphorus compound aggregated and became granular, and was completely separated from the polyester polyether. The softening point of the product is 204.6℃, and the intrinsic viscosity is 1.36, calculated from the relative viscosity of 1.658.

Comparative Example 3 The same procedure as in Example 1 was repeated except that 34 parts of dimethyl monosodium phosphate was added instead of the sodium salt of the phosphorus compound of the present invention in Example 1, and the mixture was heated for 40 minutes at a temperature of 230 to 275°C under reduced pressure. A truncated polymerization reaction was carried out at 275° C. and a reduced pressure of 0.2 mmHg for 120 minutes, but the viscosity did not increase at all.

Comparative Example 4 Example 1 except that 100 parts of sodium dodecylbenzenesulfonate was added instead of the sodium salt of the phosphorus compound of the present invention in Example 1.
When the initial polymerization reaction was carried out in the same manner as above at a temperature of 230 to 275°C under reduced pressure, the polymerization reaction could not be continued due to severe foaming.

Reference Example 1 5 parts of the phosphorus-containing polyester polyether chips obtained in Example 1 were mixed with 95 parts of polyester chips having an intrinsic viscosity of 0.62 and a softening point of 261°C, and after drying, 290°C was mixed using an extruder type spinning machine. ℃
The filament was spun, stretched 4.5 times at 90°C, and then heat-set at 150°C to obtain a filament with a strength of 5.04 g/d and an elongation of 27.4%. This filament was knitted into a double-sided knitted fabric, refined, washed 20 times at home, and then the charged voltage was measured.
5.2V, frictional charging voltage of 510V, and half-life of 64.2 seconds, demonstrating excellent antistatic performance.

Reference Example 2 5 parts of the phosphorus-containing polyester polyether chips obtained in Comparative Example 2 were mixed with 95 parts of polyester chips having an intrinsic viscosity of 0.62 and a softening point of 261°C, and spinning was carried out in the same manner as in Reference Example 1. , the nozzle back pressure increased significantly, and thread breakage occurred frequently, making it impossible to obtain a normal filament.

Claims (1)

[Scope of Claims] 1. After subjecting an aromatic dicarboxylic acid or its ester-forming derivative and an aliphatic diol to a transesterification or esterification reaction, the aliphatic polyether diol or its ester-forming derivative and the following general formula [] 1. A method for producing a phosphorus-containing polyester polyether, which comprises blending an alkali metal salt of a phosphorus compound having an ester-forming functional group represented by the formula and carrying out a polymerization reaction. (However, R ₁ is a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms that may contain an ester-forming functional group, or M ₂ and R ₂ are divalent or trivalent hydrocarbons having 1 to 6 carbon atoms. group, R ₃ is a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms that may contain a hydroxyl group, or M ₃ , M ₁ , M ₂ , M ₃ is an alkali metal atom, m is 0
Alternatively, 0 and n represent an integer of 0 or 2. ) 2 The method for producing a phosphorus-containing polyester polyether according to claim 1, wherein the atomic equivalent ratio of the phosphorus atom to the alkali metal atom in the general formula [] is represented by the following formula []. 1.0≦M ₁ +M ₂ +M ₃ /P≦2.2 [] 3 The method for producing a phosphorus-containing polyester polyether according to claim 1, wherein in the general formula [], R ₂ is an ethylene group. 4. The method for producing a phosphorus-containing polyester polyether according to claim 1, wherein in the general formula [], the alkali metal atom is sodium.