CN101492530B - Ion type copolyester and method for preparing the same - Google Patents

Abstract

The invention discloses an ionic copolyester and a preparation method thereof, more specifically an ionic copolyester containing sodium sulfonate groups and a preparation method thereof, belonging to the field of polymer synthesis. High-purity terephthalic acid PTA and ethylene glycol EG are added in the reactor according to the mass ratio of 50-70%: 30-50%. After the esterification is completed, the pressure of the reactor is drained, and 5- 100mol% of the third comonomer isophthalic acid-5-sodium ethylene glycol sulfonate in the reaction system, when the polymer melt reaches the set viscosity, the molten polymer is extruded from the casting belt, After cooling and pelletizing, it becomes the ionic copolyester containing sodium sulfonate group. In the present invention, by changing the macromolecular chain arrangement mode of the blended fiber and adding the polar structure of the sulfonic acid group itself, the blended modified fiber has special properties and has a high market development prospect.

Description

Ionic copolyester and its preparation method

technical field

The invention relates to a polymer, more specifically an ionic copolyester containing sodium sulfonate groups and a preparation method thereof, belonging to the field of polymer synthesis.

Background technique

In the modification of polyester fiber (PET), the blending modification method is a relatively stable and effective method, and the most widely used modification component is the ionic copolymer containing the structural unit of sodium isophthalic acid sulfonate. The addition of this component can change the structure and form of PET to realize the dyeing modification of PET, and even a high content of ionized copolyester component can realize the low-temperature dyeable effect of the fiber. At the same time, the amount of caustic soda can be greatly reduced in the alkali weight reduction treatment of the polyester fiber fabric processed by the blending modification method, which is beneficial to environmental protection.

To prepare high-performance polyester fibers, the key is to solve the problem of high-performance blended component products. Therefore, different polymerization methods must be adopted for different modification requirements. The high-comfort cationic dyeable polyester product prepared by Toyobo Co. contains about 5 mol% of sodium sulfonate groups and is copolymerized by adding 5%-8 mol% of isophthalic acid (IPA). Mitsubishi rayon products are copolymerized with 5 mol% adipic acid as the fourth monomer. A small amount of trimethyl trimellitate is added to the core layer of the sheath-core fiber prepared by Toray and the cationic dyeable polyester used for the conjugate component to improve performance.

Contents of the invention

The purpose of the present invention is to provide a novel ionic copolyester polymer containing sodium sulfonate groups, which provides greater possibility for the modification of polyester fibers.

The technical scheme adopted for realizing the object of the present invention is as follows, a kind of ionic copolyester adopts the high-purity terephthalic acid (PTA) that mass ratio is 50-70%, and the mass ratio is 30-50% ethylene glycol Alcohol (EG) undergoes esterification reaction, and the product of the esterification reaction is prepared by polymerization reaction with the comonomer 5-sodium ethylene glycol isophthalate. Its structure is shown in formula 1:

Formula 1, where: 0<X<100

Another object of the present invention is to provide a kind of preparation method of above-mentioned ionic copolyester, comprising the following steps:

Add high-purity terephthalic acid PTA and ethylene glycol EG into the reactor according to the mass ratio of 50-70%: 30-50%, and at the same time add 0.1-0.6g of toner cobalt acetate, 1.0 -5.0g diethylene glycol inhibitor sodium acetate and 1.0-5.0g polycondensation catalyst antimony triacetate, introduce N2, maintain the pressure at 0.1-0.35MPa/cm ² , fully stir at 150-280°C for 30-80min, then gradually Raise the temperature to 200-300°C. After 80-120 minutes of reaction, the temperature gradually reaches 260-350 ° C, and when the water output reaches the theoretical value, the reaction stops; under the condition of excess EG, all PTA is esterified;

After the esterification is completed, drain the pressure of the reactor, and add 5-100mol% of the third comonomer isophthalic acid-5-sodium ethylene glycol sulfonate to the reaction system while stirring, and simultaneously add 1.0-5.0 g heat stabilizer triphenyl phosphate, the system is fully stirred at 200-300°C for 50-70min, then heated to 260-350°C, vacuumed to 10-20Pa, and reacted for a period of time (70-100min) until the polymer melt reaches When the viscosity is set, N2 is introduced to stop the reaction, the molten polymer is extruded into a casting belt, cooled, and pelletized to form an ionic copolyester containing sodium sulfonate groups.

The beneficial effects of the present invention are: the ionic copolyester containing sodium sulfonate group prepared by the present invention changes between 0.35 and 0.70 along with the difference of the added sodium sulfonate group quantity (dL/ g), the glass transition temperature of the polymer varies between 74°C and 79°C, which is close to that of conventional polyester chips. The ionized copolyester prepared by this invention is used as a new type of polyester blending modification component in the preparation of functional polyester fibers. By changing the macromolecular chain arrangement of the blended fibers, and the sulfonic acid group itself has The polar structure makes the blended modified fiber have special properties, such as easy dyeing at room temperature, easy alkali hydrolysis, etc., which can endow the fiber with better processing performance, so it has a high market development prospect.

Detailed ways

Example 1

5kg of PTA, 3kg of excess EG were added to the small polymerization kettle, and 0.35g of toner cobalt acetate, 2.5g of diethylene glycol inhibitor sodium acetate and 2.5g of polycondensation catalyst antimony triacetate were added at the same time. Introduce N2, maintain the pressure at 0.25Mpa/cm ² , fully stir at 180°C for 60min, and then gradually increase the temperature to 250°C. After about 100 minutes of reaction, the temperature gradually reached 275°C, and the reaction stopped when the water output reached about 1200ml. Under the condition of excess EG, all PTA is esterified.

After stopping the esterification, vent the pressure of the reactor, add 5mol% isophthalic acid-5-sodium ethylene glycol sulfonate and 2.0g heat stabilizer triphenyl phosphate in the reaction system under stirring situation, in Fully stir at 250°C for 50-60min, then heat up to 275°C, evacuate to 10-20Pa, polymerize for about 100min, introduce N2 to stop the reaction, extrude the molten polymer into a casting belt, cool, and cut into pellets. The intrinsic viscosity of the copolymer is is 0.453.

Example 2

7kg of PTA and 5kg of EG were added to the small polymerization kettle, and 0.6g of toner cobalt acetate, 5g of diethylene glycol inhibitor sodium acetate and 5g of polycondensation catalyst antimony triacetate were added at the same time. Introduce N2, maintain the pressure at 0.35Mpa/cm ² , fully stir at 280°C for 80min, and then gradually increase the temperature to 300°C. After about 120 minutes of reaction, the temperature gradually reached 350°C, and the reaction stopped when the water output reached about 1500ml. Under the condition of excess EG, all PTA is esterified.

After stopping the esterification, vent the pressure of the reactor, add 5mol% isophthalic acid-5-sodium ethylene glycol sulfonate and 5.0g heat stabilizer triphenyl phosphate in the reaction system under stirring situation, in Fully stir at 300°C for 70 minutes, then raise the temperature to 350°C, evacuate to 10-20Pa, polymerize for about 100 minutes, introduce N2 to stop the reaction, extrude the molten polymer into a casting belt, cool, and cut into pellets. The intrinsic viscosity of the copolymer is 0.560 .

Example 3

5kg of PTA and 5kg of EG were added to a small polymerization kettle, along with 0.1g of toner cobalt acetate, 1g of diethylene glycol inhibitor sodium acetate and 1g of polycondensation catalyst antimony triacetate. Introduce N2, maintain the pressure at 0.1Mpa/cm ² , fully stir at 150°C for 30min, and then gradually increase the temperature to 200°C. After about 80 minutes of reaction, the temperature gradually reached 260°C, and the reaction stopped when the water output reached about 1000ml. Under the condition of excess EG, all PTA is esterified.

After stopping the esterification, vent the pressure of the reactor, add 5mol% isophthalic acid-5-sodium ethylene glycol sulfonate and 1.0g heat stabilizer triphenyl phosphate in the reaction system under stirring situation, in Fully stir at 200°C for 50 minutes, then raise the temperature to 260°C, evacuate to 10-20Pa, polymerize for about 70 minutes, introduce N2 to stop the reaction, extrude the molten polymer into a casting belt, cool, and pelletize. The intrinsic viscosity of the copolymer is 0.428 .

Example 5

The esterification reaction is the same as in Example 1. After the esterification is stopped, the pressure of the reactor is vented, and 10mol% of isophthalic acid-5-sulfonic acid sodium ethylene glycol ester and 2.0g of heat stabilizer phosphoric acid triphosphate are added under stirring conditions. Phenyl ester into the reaction system, fully stirred at 250°C for 50-60min, then heated up to 275°C, vacuumed to 10-20Pa, polymerized for about 70min, introduced N2 to stop the reaction, extruded the molten polymer into a casting belt, cooled, cut Granules, the intrinsic viscosity of the copolymer is 0.397.

Example 6

The 20% ethylene glycol solution of 5-sodium sulfonate-diethylene glycol isophthalate is directly added in the small polymerization kettle, and 2.0g heat stabilizer triphenyl phosphate, 2.5g sodium acetate etc. are added, and the Examples 1 and 2 were polymerized for about 20-25 minutes under milder polymerization conditions to obtain polyisophthalic acid-5-sodium sulfonate-diethylene glycol ester polymers containing partial oligomers. The copolymer intrinsic viscosity is 0.373.

Claims (2)

1. the preparation method of an ion type copolyester, it is characterized in that: with 7kg PTA, the EG of 5kg joins in the small-sized polymerization kettle, adds 0.6g toning agent Cobaltous diacetate, 5g glycol ether hold back agent sodium-acetate and 5g condensation polymerization catalyzer Antimony Triacetate simultaneously; Import N ₂, keep pressure at 0.35MPa/cm ², fully stirring 80min down at 280 ℃, temperature rises to 300 ℃ gradually then; After the 120min reaction, temperature reaches 350 ℃ gradually, and when aquifer yield reached 1500ml, reaction stopped; Under the excessive condition of EG, the whole esterifications of PTA; After stopping esterification, release the pressure of reactor, the 5-sodium sulfo isophthalate glycol ester of adding 5mol% and 5.0g thermo-stabilizer triphenylphosphate are in reaction system under stirring state, fully stir 70min at 300 ℃, be warmed up to 350 ℃ then, be evacuated to 10-20Pa, polymerization 100min imports N ₂Stopped reaction is extruded Cast Strip, cooling, pelletizing with molten polymer, and this multipolymer limiting viscosity is 0.560.

2. the preparation method of an ion type copolyester, it is characterized in that: with 5kg PTA, the EG of 5kg joins in the small-sized polymerization kettle, adds 0.1g toning agent Cobaltous diacetate, 1g glycol ether hold back agent sodium-acetate and 1g condensation polymerization catalyzer Antimony Triacetate simultaneously; Import N ₂, keep pressure at 0.1MPa/cm ², fully stirring 30min down at 150 ℃, temperature rises to 200 ℃ gradually then; After the 80min reaction, temperature reaches 260 ℃ gradually, and when aquifer yield reached 1000ml, reaction stopped; Under the excessive condition of EG, the whole esterifications of PTA; After stopping esterification, release the pressure of reactor, the 5-sodium sulfo isophthalate glycol ester of adding 5mol% and 1.0g thermo-stabilizer triphenylphosphate are in reaction system under stirring state, fully stir 50min at 200 ℃, be warmed up to 260 ℃ then, be evacuated to 10-20Pa, polymerase 17 0min imports N ₂Stopped reaction is extruded Cast Strip, cooling, pelletizing with molten polymer, and this multipolymer limiting viscosity is 0.428.