CN102108116A - Method for producing polyurethane foaming material by using waste polyester fibers - Google Patents

Abstract

The invention discloses a production method of waste polyester polyurethane foaming material, which relates to the technical fields of polyester degradation and polymer material foaming. The present invention utilizes ethylene glycol alcoholysis method to degrade waste polyester fibers to obtain ethylene terephthalate (BHET), which reacts with -NCO group in polyisocyanate (PAPI) after repeated washing, crystallization and purification , to prepare polyurethane foam material. The present invention utilizes waste polyester fiber to prepare polyurethane foam material, and organically combines waste polyester fiber recovery and polyurethane foam material, not only can solve the problem of waste polyester fiber treatment, but also the obtained polyurethane foam The material is high in strength, light in weight, widely used and low in cost.

Description

A kind of method that utilizes waste polyester fiber to produce polyurethane foam material

technical field

A method for producing polyurethane foam material by using waste polyester fiber, in particular to a method for preparing polyurethane foam material by reacting with polyisocyanate after degrading waste polyester fiber with ethylene glycol to obtain ethylene terephthalate The invention belongs to the technical field of polyester degradation and polymer material foaming.

Background technique

As a polymer material, polyester fiber is widely used in various industries. At the same time, the amount of waste polyester is also increasing. If waste polyester is not recycled, it will not only cause waste of resources, but also harm the environment. Bring a lot of pollution, therefore, the recycling of waste polyester has become a major research topic in the development of the current polyester industry. In addition, in recent years, my country's building energy consumption has continued to increase rapidly, and building energy conservation has become a hot issue of concern to the whole society. Rigid polyurethane foam is a very good thermal insulation material, which is mainly used in industrial applications such as external wall insulation. Increasing the usable square footage inside buildings has particular appeal in cities where land is becoming more and more expensive. Therefore, the organic combination of polyester recycling and polyurethane foam can not only solve the problem of waste polyester disposal, but also obtain foamed materials with high strength, light weight and low cost.

Contents of the invention

The object of the present invention is to provide a kind of method that utilizes waste polyester fiber to produce polyurethane foam material, waste polyester fiber is reacted with ethylene glycol, polyester molecular weight is reduced, obtains its monomer ethylene glycol phthalate ( BHET), after crystallization and purification, the purity of BHET can reach 96%. On this basis, two -OH on BHET react with -NCO in polyisocyanate (PAPI), through a series of chain growth, gas generation and crosslinking reactions to prepare polyurethane foam materials.

The technical scheme of the present invention: a method for producing polyurethane foam materials by using waste polyester fibers, using ethylene glycol alcoholysis process to degrade waste polyester fibers to obtain ethylene terephthalate BHET, and then foaming by BHET Obtain polyurethane foam material, step is as follows: by weight parts:

(1) Degradation of waste polyester fiber:

a. Install the reaction device: take a four-necked flask as a reaction vessel, and three of them are respectively equipped with a thermometer, a reflux condensing device and a nitrogen ventilation device;

b. Degradation reaction: Take 300-500 parts of ethylene glycol and 0.1-0.3 parts of catalyst zinc acetate into a four-necked flask to mix, put the four-necked flask into an oil bath, heat up and heat until the zinc acetate is completely dissolved; take waste polyester After cleaning and drying 100 parts of fiber, add it to the reaction device, open the nitrogen device to ventilate nitrogen to eliminate the oxygen in the flask, slowly raise the temperature to the boiling point of ethylene glycol at 196°C, and keep warm for 2 to 5 hours after the reflux phenomenon occurs in the reflux condensing device; Sampling 0.5 ~ 1mL every half hour since the reflux phenomenon;

c. Sample treatment: Mix gasoline and xylene in an equal volume ratio to make a solvent; cool the sample obtained in step b to room temperature, and then add the prepared solvent to dissolve the sample; until the sample can be completely dissolved in the solvent stop reacting when

(2) Preparation of BHET monomer: Cool the mixed solution obtained in step (1) to 140-160°C, pour it into a beaker filled with distilled water, heat it to 90-100°C, and filter when the solution is transparent to obtain the filtrate. Put the filtrate in an ice bath for 8-10 hours, precipitate needle-like crystals, and then filter; repeat the above operation 3-4 times to obtain BHET monomer;

(3) Preparation of polyurethane foam material: Take 100 parts of BHET monomer obtained in step (2), 90 to 110 parts of foaming agent polyisocyanate PAPI, 2 to 4 parts of water, 2 to 6 parts of stannous octoate as catalyst, and 2 to 6 parts of solubilizer Add 1 to 3 parts of silicone oil into the reaction flask in turn, mix and stir evenly, and then start the foaming reaction. After 0.5 to 2.5 minutes of reaction, the foaming is completed, and the crude polyurethane foam material is obtained; Put it aside for 24-48 hours to mature to obtain the product polyurethane foam material.

The properties of the polyurethane foam material prepared by the above steps: the melting point is 150-158°C, the initial decomposition temperature is 230-245°C, the compressive strength is 700-735KPa, and the density is 92-100kg·m ^-3 .

Advantages of the present invention: the present invention utilizes waste polyester fibers to prepare polyurethane foam materials, and organically combines the recycling of waste polyester fibers and polyurethane foam materials, which can not only solve the problem of waste polyester fiber disposal, but also The obtained polyurethane foam material is high in strength, light in weight, widely used and low in cost.

Detailed ways

The present invention is further elaborated below by embodiment, and its purpose is for better understanding content of the present invention. Therefore, the examples cited do not affect the protection scope of the present invention.

Example 1

(1) Degradation of waste polyester fiber:

a. Install the reaction device: take a four-necked flask as a reaction vessel, and three of them are respectively equipped with a thermometer, a reflux condensing device and a nitrogen ventilation device;

b. Degradation reaction: Take 400 parts of ethylene glycol and 0.2 parts of catalyst zinc acetate and mix them in a four-necked flask, put the four-necked flask into an oil bath, heat up and heat until the zinc acetate is completely dissolved; take 100 parts of waste polyester fiber for cleaning , After drying, add to the reaction device, open the nitrogen device to feed nitrogen to eliminate the oxygen in the flask, slowly raise the temperature to the boiling point of ethylene glycol of 196 °C, keep warm for 5 hours after the reflux phenomenon occurs in the reflux condensation device; Sampling 0.8mL in half an hour;

c. Sample treatment: Take No. 94 gasoline and xylene in an equal volume ratio to fully mix and configure as a solvent; after cooling the sample obtained in step b to room temperature, add the configured solvent to dissolve the sample; until the sample can be completely dissolved in Stop reaction when in solvent;

(2) Preparation of BHET monomer: Cool the mixed solution obtained in step (1) to 150°C, pour it into a beaker filled with distilled water, and heat it to 95°C. When the solution is transparent, filter it to obtain the filtrate, and put the filtrate in ice In the bath for 9 hours, precipitate needle crystals, and then filter; repeat the above operation 4 times to obtain BHET monomer;

(3) Preparation of polyurethane foam material: 100 parts of BHET monomer obtained in step (2), 100 parts of blowing agent polyisocyanate PAPI, 2 parts of water, 3 parts of catalyst stannous octoate, and 2 parts of solubilizer silicone oil are added to the reaction in turn In the flask, mix and stir evenly to start the foaming reaction, and the foaming is completed after 1.5 minutes of reaction to obtain a polyurethane foam material crude product; place the obtained polyurethane foam material crude product under normal temperature and pressure for 24 hours to mature to obtain the product polyurethane foam material.

The obtained polyurethane foam material had a melting point of 156°C, an initial decomposition temperature of 240°C, a compressive strength of 724KPa, and a density of 99kg·m ^-3 .

Example 2

(1) Degradation of waste polyester fiber:

a. Install the reaction device: take a four-necked flask as a reaction vessel, and three of them are respectively equipped with a thermometer, a reflux condensing device and a nitrogen ventilation device;

b. Degradation reaction: Take 300 parts of ethylene glycol and 0.1 part of catalyst zinc acetate and add them into a four-necked flask to mix, put the four-necked flask into an oil bath, heat up and heat until the zinc acetate is completely dissolved; take 90 parts of waste polyester fiber for cleaning , After drying, add to the reaction device, open the nitrogen device and feed nitrogen to eliminate the oxygen in the flask, slowly raise the temperature to the boiling point of ethylene glycol 196 ° C, keep warm for 2 hours after the reflux phenomenon occurs in the reflux condensation device; Sampling 1mL in half an hour;

c. Sample treatment: Take No. 94 gasoline and xylene in an equal volume ratio to fully mix and configure as a solvent; after cooling the sample obtained in step b to room temperature, add the configured solvent to dissolve the sample; until the sample can be completely dissolved in Stop reaction when in solvent;

(2) Preparation of BHET monomer: Cool the mixed solution obtained in step (1) to 160°C, pour it into a beaker filled with distilled water, and heat it to 100°C. When the solution is transparent, filter it to obtain the filtrate, and put the filtrate in ice In the bath for 8 hours, precipitate needle crystals, and then filter; repeat the above operation 3 times to obtain BHET monomer;

(3) Preparation of polyurethane foam material: 100 parts of BHET monomer obtained in step (2), 90 parts of foaming agent polyisocyanate PAPI, 2 parts of water, 2 parts of catalyst stannous octoate, and 1 part of solubilizer silicone oil are added to the reaction in turn In the flask, mix and stir evenly to start the foaming reaction. After 1 minute of reaction, the foaming is completed to obtain a crude polyurethane foam material; place the obtained crude polyurethane foam material under normal temperature and pressure for 36 hours to mature to obtain the product polyurethane foam material.

The obtained polyurethane foam material had a melting point of 153°C, an initial decomposition temperature of 235°C, a compressive strength of 700KPa, and a density of 95kg·m ^-3 .

Example 3

(1) Degradation of waste polyester fiber:

a. Install the reaction device: take a four-necked flask as a reaction vessel, and three of them are respectively equipped with a thermometer, a reflux condensing device and a nitrogen ventilation device;

b. Degradation reaction: Take 500 parts of ethylene glycol and 0.2 parts of catalyst zinc acetate and add them into a four-necked flask to mix, put the four-necked flask into an oil bath, heat up and heat until the zinc acetate is completely dissolved; take 100 parts of waste polyester fiber for cleaning , After drying, add to the reaction device, open the nitrogen device and feed nitrogen to eliminate the oxygen in the flask, slowly raise the temperature to the boiling point of ethylene glycol 196 ° C, keep warm for 3 hours after the reflux phenomenon occurs in the reflux condensation device; Sampling 0.5mL in half an hour;

c. Sample treatment: take No. 94 gasoline and xylene in an equal volume ratio and fully mix it into a solvent; after cooling the sample obtained in step b to room temperature, add the prepared solvent to dissolve the sample; until the sample can be completely dissolved in Stop reaction when in solvent;

(2) Preparation of BHET monomer: Cool the mixed solution obtained in step (1) to 140°C, pour it into a beaker filled with distilled water, and heat it to 90°C. When the solution is transparent, filter it to obtain the filtrate, and put the filtrate in ice In the bath for 10 hours, the needle-like crystals are precipitated, and then filtered; the above operation is repeated 3 times to obtain the BHET monomer;

(3) Preparation of polyurethane foam material: 100 parts of BHET monomer obtained in step (2), 110 parts of foaming agent polyisocyanate PAPI, 4 parts of water, 6 parts of catalyst stannous octoate, and 3 parts of solubilizer silicone oil are added to the reaction in turn In the flask, mix and stir evenly to start the foaming reaction. After 2 minutes of reaction, the foaming is completed, and the crude polyurethane foam material is obtained; the obtained polyurethane foam material is placed at normal temperature and pressure for 48 hours to mature to obtain the product polyurethane foam material.

The obtained polyurethane foam material had a melting point of 155°C, an initial decomposition temperature of 239°C, a compressive strength of 733KPa, and a density of 98kg·m ^-3 .

Example 4

(1) Degradation of waste polyester fiber:

a. Install the reaction device: take a four-necked flask as a reaction vessel, and three of them are respectively equipped with a thermometer, a reflux condensing device and a nitrogen ventilation device;

b. Degradation reaction: Take 300 parts of ethylene glycol and 0.1 part of catalyst zinc acetate and add them into a four-necked flask to mix, put the four-necked flask into an oil bath, heat up and heat until the zinc acetate is completely dissolved; take 100 parts of waste polyester fiber for cleaning , After drying, add to the reaction device, open the nitrogen device and feed nitrogen to eliminate the oxygen in the flask, slowly raise the temperature to the boiling point of ethylene glycol 196 ° C, keep warm for 4 hours after the reflux phenomenon occurs in the reflux condensation device; Sampling 0.6mL in half an hour;

c. Sample treatment: Take No. 94 gasoline and xylene in an equal volume ratio to fully mix and configure as a solvent; after cooling the sample obtained in step b to room temperature, add the configured solvent to dissolve the sample; until the sample can be completely dissolved in Stop reaction when in solvent;

(2) Preparation of BHET monomer: Cool the mixed solution obtained in step (1) to 145°C, pour it into a beaker filled with distilled water, and heat it to 95°C. When the solution is transparent, filter it to obtain the filtrate, and put the filtrate in ice In the bath for 9 hours, precipitate needle crystals, and then filter; repeat the above operation 3 times to obtain BHET monomer;

(3) Preparation of polyurethane foam material: 100 parts of BHET monomer obtained in step (2), 100 parts of foaming agent polyisocyanate PAPI, 2 parts of water, 3 parts of catalyst stannous octoate, and 3 parts of solubilizer silicone oil are added to the reaction in turn In the flask, mix and stir evenly to start the foaming reaction, and the foaming is completed after 2.5 minutes of reaction to obtain a polyurethane foam material crude product; place the obtained polyurethane foam material crude product under normal temperature and pressure for 48 hours to mature to obtain the product polyurethane foam material.

The obtained polyurethane foam material had a melting point of 152°C, an initial decomposition temperature of 232°C, a compressive strength of 713KPa, and a density of 93kg·m ^-3 .

Claims (1)

1. method of utilizing waste polyester fiber production polyurethane foam material, it is characterized in that utilizing glycolysis process degradation waste polyester fiber, obtain ethylene glycol terephthalate BHET, obtain polyurethane foam material by the BHET foaming again, step is as follows: count by weight:

(1) waste polyester degradation of fiber:

A, installation reaction unit: getting four-hole boiling flask is reaction vessel, wherein settles thermometer, reflux condensate device and logical nitrogen device respectively for three mouthfuls;

B, DeR: get 300～500 parts of ethylene glycol, the mixing of 0.1～0.3 part of adding of catalyst acetic acid zinc four-hole boiling flask, four-hole boiling flask is put into oil bath pan, intensification is heated to zinc acetate and dissolves fully; Get 100 parts of cleanings of waste polyester fiber, dry back adds reaction unit, opens logical nitrogen device and feeds nitrogen to get rid of the oxygen in the flask, slowly is warming up to 196 ℃ of the boiling points of ethylene glycol, insulation continues reaction 2～5h behind the reflux condensate device generation backflow phenomenon; Own backflow phenomenon plays the 0.5～1mL that takes a sample per half an hour;

C, sample preparation: gasoline and the dimethylbenzene thorough mixing of getting the equal-volume ratio are configured to solvent; Behind the sample cool to room temperature of obtaining among the step b, add the dissolution with solvents sample that is disposed; Stopped reaction when institute's sample thief can be dissolved in the solvent fully;

(2) the monomeric preparation of BHET: step (1) gained mixing solutions is cooled to 140～160 ℃, pours in the beaker that distilled water is housed, be heated to 90～100 ℃, filter when solution is transparence and obtain filtrate, filtrate is put into ice bath 8～10h, separates out the spicule crystal, refilters; Repeat aforesaid operations 3～4 times, can obtain the BHET monomer;

(3) preparation of polyurethane foam material: get 100 parts of step (2) gained BHET monomers, 90～110 parts of whipping agent polyisocyanates PAPI, 2～4 parts in water, 2～6 parts in the inferior tin of octoate catalyst, solubilizing agent silicone oil adds in the reaction flask for 1～3 part successively, mixing and stirring promptly begins foamable reaction, react 0.5～2.5 minute post-foaming and finish, obtain the thick product of polyurethane foam material; The thick product normal temperature and pressure of gained polyurethane foam material is placed 24～48h slaking down obtain the product polyurethane foam material.