KR101468070B1 - Method for manufacturing polyurethane using eco-friendly raw material - Google Patents

Abstract

The present invention relates to a method for producing a polyurethane from a biopolyol, comprising the steps of: (A) hydrolyzing an animal or vegetable oil to prepare a free fatty acid; (B) polymerizing the free fatty acid under high temperature and high pressure to prepare dimeric acid; (C) reacting the dimer acid with propylene oxide to produce polypropylene glycol; And (D) reacting the polypropylene glycol with a diisocyanate to prepare a polyurethane.

Description

METHOD FOR MANUFACTURING POLYURETHANE USING ECO-FRIENDLY RAW MATERIAL BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to a process for producing a polyurethane using an eco-friendly raw material, wherein a dimer acid is produced through an animal and vegetable polymerisation, and then a polyol is synthesized using the dimer acid as a raw material and an environmentally friendly polyurethane is produced through a reaction with a diisocyanate or the like ≪ / RTI >

Polyol is an initiator such as multifunctional alcohols or aromatic amines having two or more hydroxyl groups (-OH) or amine groups (Amine Group, - NH2) in molecules and initiators such as propylene Oxide (PO) or Ethylene Oxide (EO) under appropriate conditions. It is an essential raw material for polyurethane production together with diisocyanate.

Polypropylene glycol (PPG) is generally used as a raw material for polyurethane rather than as a final product. Polyurethane using polypropylene glycol is widely used in coatings, textiles and rubber industries.

Conventional polypropylene glycol is synthesized by opening a ring of propylene oxide (see the following reaction formula). At this time, an alcohol is used as an initiator for the reaction, and generally, glycerin, pentaerythritol, or sorbitol is used. Further, when ethylene glycol is used as the initiator, it has a linear structure. The most commonly used initiator is ethylene glycol, and in addition, propylene glycol, trimethylolpropane and the like can be added.

≪ Preparation of polypropylene glycol >

Ethylene glycol is widely used as a raw material for antifreeze and surfactant, and has a molecular weight of 62.7 g / mol. Ethylene glycol has the advantage of having two alcohols, but it has the disadvantage that it is a hazardous substance with toxicity and must be treated with caution.

Conventionally, polypropylene glycol synthesized with ethylene glycol has two OH groups, and it has been common to synthesize polyurethane by reacting it with diisocyanate. The synthetic reaction formula of the polyurethane is as follows.

<Synthesis of polyurethane>

In recent years, there has been an increasing demand for the development of alternative petroleum products using environmentally friendly materials in response to depletion of petroleum resources. In particular, polymers are derived from the petrochemical product group. Recently, a lot of techniques for manufacturing polymers from starch and natural materials have been studied. Accordingly, a technique for producing a bio-polyol and producing a polyurethane from such a bio-polyol has been studied.

Such technologies include Korean Patent Laid-Open No. 10-2011-0131980 (polyurethane foam for a sound-absorbing material including a bio-polyol and a manufacturing method thereof), Korean Patent Laid-Open No. 10-2012-0038038 (preparation of a bio- Method and a polyurethane produced therefrom) and the like. However, these prior arts have produced a polyol by epoxidizing soybean oil or the like and then using an epoxidizer. When a urethane resin is produced using such a polyol, the quality of the urethane resin is poor and the reaction yield is low there was.

Accordingly, the inventors of the present invention have attempted to establish synthesis reaction conditions for producing urethane resins having excellent physical properties while maximizing the stability of synthesis based on environmentally friendly raw materials.

It is an object of the present invention to provide a method for producing a bio-polyol (polypropylene glycol) using an eco-friendly and toxic raw material, and using the bio-polyol to produce an environment-friendly polyurethane.

In order to achieve the above object, the present invention provides a method for producing a polyurethane from a biopolyol, comprising the steps of: (A) hydrolyzing a plant and animal oil to prepare a free fatty acid; (B) polymerizing the free fatty acid under high temperature and high pressure to prepare dimeric acid; (C) reacting the dimer acid with propylene oxide to produce polypropylene glycol; And (D) reacting the polypropylene glycol with a diisocyanate to prepare a polyurethane.

Specifically, the present invention relates to a method for producing a dimer acid comprising a step of hydrolyzing a vegetable oil, especially a fat containing a large amount of an unsaturated fatty acid, to obtain a fatty acid having a fatty acid content of 99.9% or more and polymerizing the fatty acid under high temperature and high pressure to prepare a dimer acid containing two carboxyl groups, Polypropylene glycol (PPG) is synthesized with propylene oxide. (MDI), toluene diisocyanate (TDI), naphthalene diisocyanate (NDI), or p-phenylene diisocynate (PPDI), and the like. Of diisocyanate to synthesize a polyurethane. The environmentally friendly polyurethane thus obtained can be used as a raw material for general building exterior paint, adhesive, and fiber.

Hereinafter, a method for producing polyurethane from the bio-polyol of the present invention will be described in detail in each step.

(A) a step of hydrolyzing animal and plant oil to prepare a free fatty acid

This step is a step of producing animal and vegetable oils, especially vegetable oils, such as soybean oil, seed oil, palm oil, linseed oil, castor oil, sunflower oil, grape seed oil and waste cooking oil through a hydrolysis process as free fatty acids.

Specifically, 10 to 30% by weight of water is added to the animal and plant oil at a temperature of 100 to 200 ° C under a pressure of 5 to 40 kg / cm ₂ , and hydrolysis is performed for 5 to 20 hours to obtain a free fatty acid. Unsaturated fatty acid is at least 50% by weight fatty acid.

The following is a reaction formula in which the fat is decomposed into fatty acids through a hydrolysis process.

&Lt; Hydrolysis step of fat &

Of these free fatty acids, unsaturated oleic acid, linoleic acid, linolenic acid and the like are used in the subsequent high temperature polymerization.

(B) polymerizing the free fatty acid under high temperature and high pressure to prepare dimeric acid

This step is a step of polymerizing 50% by weight or more of free fatty acids produced in the step (A) under high temperature and high pressure to obtain 20 to 90% by weight, preferably 50 to 90% by weight, of polymerized acid of dimeric acid.

At this time, the free fatty acid is polymerized by adding 2 to 15% by weight of a polymerization catalyst such as clay and zeolite at a temperature of 100 to 300 ° C under a pressure of 5 to 40 kg / cm ₂ to polymerize to obtain dimeric acid.

Here, the polymerization process of the unsaturated fatty acid is as follows.

&Lt; Polymerization step of unsaturated fatty acid &

The dimer acid prepared from animal and vegetable oils present in nature as a raw material has a weight average molecular weight of 560 and is very high in molecular weight as compared with the molecular weight 62 of ethylene glycol used conventionally as a reaction initiator for the synthesis of polypropylene glycol. Therefore, when such a dimer acid is used as a reaction initiator for the synthesis of polypropylene glycol, it is easier to polymerize polypropylene glycol and shorten the synthesis time.

(C) reacting the dimeric acid with propylene oxide to prepare polypropylene glycol

This is a step for the (B) adding 10 to 90% by weight of propylene oxide in the production of dimer acid in step and, KOH, NaOH, Ba (OH ) 2, Fe (OH) 3 or Na ₂ CO ₃ · 10H ₂ 0 The catalyst To 1 to 20% by weight, and the mixture is reacted at a temperature of 50 to 200 캜 for 30 minutes to 7 hours to obtain polypropylene glycol.

Here, the reaction between dimer acid and propylene oxide is as follows, whereby a polypropylene glycol having a weight average molecular weight of 800 or more can be obtained.

&Lt; Reaction of dimer acid with propylene oxide >

The dimer acid has two carboxyl groups (-COOH) at the terminal. When the reaction is carried out with propylene oxide, a reaction process is performed in which the molecular weight is increased while reacting at the terminal of the carboxyl group as described above. In addition, in the step of polymerizing the vegetable oil in the previous step, trimeric acid and the like may be produced in addition to dimeric acid. In the case of trimeric acid, three carboxyl groups (-COOH) are contained. When reacting with propylene oxide, A reaction process in which the molecular weight is increased while reacting in the same manner may occur.

As described above, the present invention provides a polyol (polypropylene glycol) having a weight average molecular weight of 800 or more after making the weight average molecular weight of dimer acid to 560 or more by dimer oxidation using animal or vegetable oil, It is advantageous.

Further, the present invention is suitable for the production of linear polyols because the reaction takes place at the carboxyl groups located at the terminal of dimer acid. When the urethane resin is synthesized by using the linear polyol, the urethane resin is very excellent in the properties of the urethane resin because the urethane is not produced in the form of a ring and other forms, and is also very advantageous in the synthesis of a single kind of urethane resin. In addition, since the dimer acid contains 100% of carboxyl groups in the present invention, the yield of the reaction is very high.

On the other hand, in the case of a conventional technique of epoxidizing soybean oil with a double bond and using an epoxidizer to produce a polyol, it is not suitable for the production of a linear polyol because a polyol is prepared from an epoxy located in the middle of soybean oil. When the epoxidized soybean oil is used as a raw material, the yield of the reaction is also very low because the functional group is less than 80%.

(D) reacting the polypropylene glycol with a diisocyanate to prepare a polyurethane

In this step, about 1 to 50% by weight of diisocyanate is added to the polypropylene glycol prepared in the step (C), and the reaction is performed at 50 to 300 ° C to obtain a urethane resin.

The diisocyanate may be selected from the group consisting of methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), naphthalene diisocyanate (NDI), and p-phenylene diisocynate PPDI). &Lt; / RTI &gt;

Preferably, polypropylene glycol: diisocyanate is mixed at a ratio of 1: 1 to 1: 1.5 at an equivalent ratio to prepare a prepolymer, which is then dried in a vacuum oven to obtain a desired urethane resin. At this time, ethylene glycol, glycerin and the like may be added thereto as an extender.

The quality standards of the urethane resin thus produced are as follows.

Product Name OH value Acid value moisture Viscosity mn TS
(kgf / cm ² ) Elong
(%) 50% Modulus
(kgf / cm ² ) Dimer
Urethane resin 91.28 1.215 0.0166 277 1213 1030 95 582

The eco-friendly urethane resin of the present invention thus produced can be used as a chemical resistant material and various coating materials in a waterproof antiperspirant. In particular, the eco-friendly urethane resin can be used in products that are more closely related to human body such as fibers.

The present invention synthesizes a bio-polyol (polypropylene glycol) as a raw material that is environment-friendly and does not contain toxicity, and synthesizes polyurethane using such a bio-polyol, so that an environment-friendly polyurethane can be obtained. That is, the present invention can secure the stability of synthesis on the basis of environment-friendly non-toxicity, and can also ensure eco-friendliness in the final coating and fiber products.

In addition, since dimer acid oxidized by dimerization using an animal or vegetable oil and having a weight average molecular weight of 560 or more is used in the production of a polyol, a polyol (polypropylene glycol) having a weight average molecular weight of 800 or more can be easily produced, It is also very advantageous to increase the amount.

In addition, since dimer acid is used in the production of a polyol, the present invention can produce a linear polyol. By synthesizing a urethane resin by using such a linear polyol, the urethane resin has excellent properties and a single kind of urethane resin can be synthesized , The yield of the reaction is very high.

Hereinafter, the structure of the present invention will be described in detail with reference to the following examples, but the scope of the present invention is not limited to the following examples, but includes modifications of equivalent technical ideas.

Example  1: Manufacture of environmentally friendly urethane resin

10 to 30% by weight of water was added to 1 kg of soybean oil and hydrolyzed at a temperature of 200 ° C and a pressure of 15 kg / cm ² for 15 hours, followed by distillation at 200 ° C under a vacuum of 5 torr to obtain a free fatty acid having an unsaturated fatty acid content of 50% . The obtained free fatty acid was polymerized under the conditions of a temperature of 150 캜, a pressure of 3 kg / cm ² , and an acidic clay soil of 0.1 kg to obtain a dimer acid. At this time, the amount of dimeric acid produced after polymerization was 0.5 kg. 0.0009375 kg of KOH and 0.219 kg of propylene oxide were added to the obtained dimer acid, and the reaction was carried out at 100 占 폚 for 5 hours to obtain PPG. The acidic white clay was added thereto, followed by filtration. 1.62494 kg of MDI was added, and the reaction was allowed to proceed while stirring at 50 캜 to obtain a urethane resin. The quality of the obtained urethane resin is shown in Table 3 below.

Example 2 : Preparation of eco-friendly urethane resin

10 to 30% by weight of water is added to 1 kg of waste cooking oil and hydrolyzed at a temperature of 180 ° C. under a pressure of 30 kg / cm ² for 7 hours. Thereafter, distilled at 200 ° C. under a vacuum of 6 torr, . The obtained free fatty acid was polymerized under the conditions of a temperature of 150 캜, a pressure of 5 kg / cm ² and an acidic clay soil of 0.1 kg to obtain a dimer acid. At this time, the amount of dimeric acid produced after polymerization was 0.5 kg. 0.0009375 kg of NaOH and 0.219 kg of propylene oxide were added to the obtained dimer acid, and the reaction was carried out at 100 DEG C for 5 hours to obtain PPG. The acidic white clay was added thereto, followed by filtration. 1.62494 kg of MDI was added, and the reaction was allowed to proceed while stirring at 50 캜 to obtain a urethane resin. The quality of the obtained urethane resin is shown in Table 3 below.

Example 3: Preparation of eco-friendly urethane resin

After 10 to 30% by weight of water was added to 1 kg of the seed oil and hydrolyzed at a temperature of 200 ° C and a pressure of 10 kg / cm ² for 20 hours, distillation was carried out at 200 ° C under a vacuum of 7 torr to obtain a free fatty acid having an unsaturated fatty acid content of 50% . The obtained free fatty acid was polymerized under the conditions of a temperature of 200 캜, a pressure of 10 kg / cm ² , and 0.1 kg of an acidic white clay to obtain a dimer acid. At this time, the amount of dimeric acid produced after polymerization was 0.6 kg. 0.001125 kg of Ba (OH) _{2 and} 0.2628 kg of propylene oxide were added to the obtained dimer acid, and the reaction was carried out at 120 ° C for 5 hours to obtain PPG. The acidic white clay was added thereto and filtered. Then, 1.949928 kg of MDI was added, and the reaction was allowed to proceed while stirring at 50 캜 to obtain a urethane resin. The quality of the obtained urethane resin is shown in Table 3 below.

Example 4: Preparation of eco-friendly urethane resin

1 kg of oleic acid was polymerized under the conditions of a temperature of 200 캜, a pressure of 10 kg / cm ² , and an acidic clay soil of 0.1 kg to obtain a dimer acid. At this time, the amount of dimeric acid produced after polymerization was 0.7 kg. 0.0013125 kg of NaOH and 0.3066 kg of propylene oxide were added to the obtained dimer acid, and the reaction was carried out at 120 DEG C for 5 hours to obtain PPG. The acidic white clay was added thereto, followed by filtration. 2.274916 kg of MDI was added, and the reaction was allowed to proceed while stirring at 50 캜 to obtain a urethane resin. The quality of the obtained urethane resin is shown in Table 3 below.

Example 5: Preparation of eco-friendly urethane resin

10 to 30% by weight of water is added to 1 kg of linseed oil and hydrolyzed at a temperature of 200 ° C. and a pressure of 10 kg / cm ² for 17 hours, followed by distillation at 200 ° C. under a vacuum of 9 torr to obtain a free fatty acid having an unsaturated fatty acid content of 50% . The obtained free fatty acid was polymerized under the conditions of a temperature of 150 ° C, a pressure of 15 kg / cm ² , and an acidic clay soil of 0.1 kg to obtain dimeric acid. At this time, the amount of dimeric acid produced after polymerization was 0.7 kg. 0.0013125 kg of KOH and 0.3066 kg of propylene oxide were added to the obtained dimer acid, and the reaction was carried out at 110 DEG C for 5 hours to obtain PPG. The acidic white clay was added thereto, followed by filtration. 2.274916 kg of MDI was added, and the reaction was allowed to proceed while stirring at 50 캜 to obtain a urethane resin. The quality of the obtained urethane resin is shown in Table 3 below.

Claims (9)

A method for producing a polyurethane from a bio polyol,
(A) hydrolyzing animal and plant oil to produce a free fatty acid;
(B) polymerizing the free fatty acid under high temperature and high pressure to prepare dimeric acid;
(C) reacting the dimer acid with propylene oxide to produce polypropylene glycol; And
(D) reacting the polypropylene glycol with a diisocyanate to prepare a polyurethane.
The method according to claim 1,
In the step (A)
Wherein the animal or vegetable oil is at least one vegetable oil selected from the group consisting of soybean oil, seed oil, palm oil, linseed oil, castor oil, sunflower oil, grape seed oil, and waste cooking oil.
The method according to claim 1,
In the step (A)
Wherein the animal and vegetable oil is hydrolyzed at a temperature of 100 to 200 DEG C and a pressure of 5 to 40 kg / cm &lt; ² &gt; for 5 to 20 hours.
The method according to claim 1,
In the step (A)
Wherein the free fatty acid is at least 50% by weight of an unsaturated fatty acid fatty acid.
The method according to claim 1,
In the step (B)
Wherein said free fatty acid is polymerized at a temperature of 100 to 300 DEG C under a pressure of 5 to 40 kg / cm &lt; ² &gt;.
The method according to claim 1,
In the step (C)
A polypropylene glycol having a weight average molecular weight of 800 or more is prepared.
The method according to claim 1,
In the step (C)
A catalyst selected from the group consisting of KOH, NaOH, Ba (OH) ₂ , Fe (OH) ₃ and Na ₂ CO ₃ .10H ₂ O is added and reacted at a temperature of 50-200 ° C for 30 minutes to 7 hours &Lt; / RTI &gt;
The method according to claim 1,
In the step (D)
Polypropylene glycol and diisocyanate are mixed at an equivalent ratio of 1: 1 to 1: 1.5, and then reacted at 50 to 300 占 폚.
The method according to claim 1,
In the step (D)
The diisocyanate may be selected from the group consisting of methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), naphthalene diisocyanate (NDI), and p-phenylene diisocynate ). &Lt; / RTI &gt;