KR20120038038A - Method for preparing natural oil-derived biopolyol and polyurethanes made therefrom - Google Patents

Abstract

PURPOSE: A manufacturing method of biopolyol is provided to embody environment-friendly properties, and to improve functional group, reactivity, storage stability, viscosity properties, and polyurethane, thereby suitable as raw material of polyurethane. CONSTITUTION: A manufacturing method of biopolyol comprises a step of exchange-reacting natural oils and a multifunctional active hydrogen containing compound under the presence of a catalyst; a step of addition-reacting alkylene oxide to the product of the exchange-reaction; and additionally a step of removing the catalyst from the product of the addition-reaction of the alkylene oxide compound. On the basis of the total weight of the biopolyol manufacturing reactant, at least 20 weight% of the oxide alkylene is addition-reacted.

Description

Method for preparing bio polyol using natural oil and polyurethane prepared therefrom {Method for Preparing Natural Oil-Derived Biopolyol and Polyurethanes Made Therefrom}

The present invention relates to the production of bio polyols using natural oils. More specifically, the present invention not only utilizes natural oils derived from various sources, but also improves functional groups, reactivity, storage stability, viscosity characteristics, and the like. It is about.

Polyols essentially used in the production of polyurethanes are usually produced from petroleum-based raw materials, in particular polyether polyols, polyester polyols are known as the most common polyols used in polyurethane production. These polyol components have a significant impact on the properties of the polyurethane or polyurethane foam to be produced.

Typically, polyols with high molecular weight and low functionality are used to produce soft urethane foams, while polyols with low molecular weight and high functionality are used to produce rigid urethane foams. For example, in the case of flexible polyurethane foams, the molecular weight of the polyols is greater than approximately 1,000. In the case of rigid polyurethane foams, on the other hand, the molecular weight of the polyols is approximately 200 to 4,000, and the modulus of elasticity is, for example, about 100,000 psi or more (23 ° C.), glass transition temperature of 20 ° C. or higher, and 10 It has elongation properties that do not exceed%.

Meanwhile, in the urethane field, polyether polyols, polyester polyols, etc., manufactured from petroleum-based raw materials, are being used for various reasons, such as accelerated exhaustion of petroleum resources, reduction of greenhouse gases due to climate change, rising raw material prices, and increased need for renewable raw materials. It has been suggested to replace partially or completely with not only renewable but more environmentally friendly ingredients.

In this regard, various studies have been made for producing bio polyols using natural ingredients (animal, vegetable oils, etc.). Some of them have been commercialized. Typically, urethane Soy Systems Company, which is made by modifying soybean oil, has a value of about 50 to 60 mg KOH / g hydroxyl value under the trade name solyol. And bi- or tri-functional polyols having a value of about 160 to 180 mg KOH / g hydroxyl group, such bio polyols have been applied to soft and rigid foams, coatings, adhesives, sealants and the like.

Natural oils, especially vegetable oils, are generally composed of triglyceride molecules, as illustrated in Formula 1 below, and have a structure in which three fatty acids are bonded to a glycerol junction.

[Formula 1]

In the case of animal oils, fish oils and pork oils are generally known, while vegetable oils include soybean oil, castor oil, palm oil and rapeseed oil. And sunflower oils are known. Among these natural oils, soybean oil, castor oil, palm oil and the like are currently produced in large quantities.

Currently, epoxidation-ring opening reactions (incorporation of active oxygen into molecular structures using hydrogen peroxide and the like, followed by ring-opening reactions with alcohols or inorganic acids, etc .; Kandanarachchi et al ., J. Mol. Catal. A: Chem 2002, 184, 65), hydroformylation reaction (reaction of syngas with natural oil in the presence of rhodium or cobalt catalyst; Petrovic et al ., Polyurethanes from vegetable oils.Polymer Reviews 48: 1 109-155) , Ozonolysis reaction (directly ozonation of natural oils to produce polyols having hydroxyl groups at the terminal positions; Petrovic et al ., Biomacromolecules 2005, 6, 713), esterification reactions (Vilar et al. , 2002) Methods of preparing polyols from natural oils, particularly vegetable oils, in particular vegetable oils, are known using a variety of routes.

In the case of oils that do not contain a hydroxyl group in fatty acids, such as soybean oil, which are produced in a large amount, vegetable oil is epoxidized and then ring-opened.

Although it has been reported that polyurethane foams made from natural oils can have properties comparable to polyurethane foams made from petroleum oils, natural oil-based polyols exhibit problems such as reduced reactivity. One of the causes is the presence of secondary alcohols and the presence of a large number of non-functional branches. For example, secondary hydroxy groups (-OH) are known to be at least about three times lower than primary hydroxy groups.

Meanwhile, polyurethane insulating foams are widely used in various fields such as refrigerators, roofing panels, packaging, and building structural materials. Conventional polystyrene foam has been used in several fields, but in most cases rigid polyurethane foams are used, and in recent years, attempts to apply natural oils to rigid polyurethane foams have been made in response to the demands of green technology. (US Pat. Nos. 6,624,244, 6,649,667, etc.).

However, conventional bio polyols are mainly used for the production of flexible urethane foams due to low functional group numbers, and have limitations in securing reactivity and physical properties that can be used in various fields as raw materials for rigid urethane foams. In addition, biopolyols have a high risk of deterioration in storage stability due to the nature of natural oils. Furthermore, some of the conventionally known biopolyols for hard polyurethanes have a high viscosity without having a sufficiently high functional group and often have high viscosity during the polyurethane foam manufacturing process. It may cause problems in reactivity, handleability and the like. In addition, the conventional bio-polyol-related technology only shows the applicability mainly based on relatively expensive castor oil or soybean oil mainly used as food resources.

Therefore, while overcoming the problems of the conventional biopolyol described above, there is a need for a method for producing a high quality biopolyol, which can be widely applied to other natural oils such as palm oil.

In order to overcome the limitations of the prior art, the present invention not only can utilize a natural oil derived from a variety of sources in the production of various polyurethane, but also a method for producing a bio polyol with improved functional groups, reactivity, storage stability, viscosity characteristics, etc. To provide.

In particular, the present invention is to provide a method for producing a bio polyol suitable as a raw material of polyurethane that can be applied to various fields.

According to one embodiment of the invention,

As a method for producing bio polyol using natural oil,

a) exchanging a natural oil with a multifunctional active hydrogen-containing compound in the presence of a catalyst; And

b) addition reaction of alkylene oxide to the product of said exchange reaction;

Including;

On the basis of the total weight of the reactants for producing the bio polyol, there is provided a production method characterized in that the alkylene oxide addition reaction at least 20% by weight.

In the above-described embodiment, c) may further comprise the step of removing the catalyst from the addition reaction product of the alkylene oxide.

According to another embodiment of the present invention,

There is provided a polyurethane produced by reacting a polyol component and an isocyanate component containing a bio polyol prepared by the method described above.

In the above embodiment, the polyurethane produced using the biopolyol described above may be a polyurethane foam, and moreover, a rigid polyurethane foam.

Bio-polyol according to the embodiment of the present invention can be implemented as a raw material of polyurethane that can be applied to various fields by improving the functional group, reactivity, storage stability, viscosity characteristics, as well as the eco-friendly characteristics according to the utilization of natural oils Has a suitable advantage. Therefore, broad commercialization is expected in the future.

The present invention can all be achieved by the following description. The following description is to be understood as describing preferred embodiments of the invention, but the invention is not necessarily limited thereto.

The terminology used herein may be defined as follows:

"Polyol" means an organic molecule having hydroxy groups per molecule greater than 1.0 on average.

"Polyurethane foam" is a cellular foam product obtained by reacting di- or polyisocyanates with isocyanate-reactive hydrogen-containing compounds (polyols, aminoalcohols and / or polyamines) and blowing agents. It may mean.

"Natural oil" is a concept involving animal and vegetable oils, and may preferably mean vegetable oils. Examples of the animal oil may mean fish oil, cow oil, pork oil, sheep oil, and the like, and may also include a mixture thereof. Examples of vegetable oils include sunflower seed oil, canola oil, palm oil, corn oil, cottonseed oil, rapeseed oil, linseed oil, safflower oil, oat oil, olive oil, palm oil, peanut oil, rapeseed oil, rice bran oil, flaxseed oil, and sesame oil. , Soybean oil, castor oil, and the like, and more typically, soybean oil, castor oil, palm oil, and the like, may also include a mixture thereof. However, the present invention is not limited to the types listed above.

For example, pizza horse oil is an oil obtained by compressing the seed of castor bean (Rucinus communis). Seeds contain about 45% of this oil and have a higher oil content percentage than other seeds. The fats and oils have a triester (triglyceride) structure of fatty acid and glycerin as a whole. Castor oil is similarly characterized by about 90% of glycerin's triester or fatty acid being made up of ricinoleic acid. The rest contains oleic acid and linoleic acid.

The compositional properties of representative vegetable oils are shown in Table 1 below.

Olein Linoleine Linolenin Ricinoleine stearin Palmitine Etc Soybean oil 24 54.5 6.8 - 3.2 10.9 0.6 Castor oil 6.0 1.0 89.5 1.0 2.0 0.5 Safflower seed oil 13.1 77.7 2.4 6.5 0.3 Palm oil 45.2 7.9 3.6 40.8 2.5

"Polyol functionality" means the average number of hydroxy groups per molecule of polyol.

The “hydroxyl number” is an indicator of the amount of reactive hydroxyl groups that can participate in a reaction, and refers to the number of mg of KOH required to neutralize acetic acid bound to an acetyl compound obtained from 1 g of polyol (unit: mg). KOH / g).

"NCO%" means the weight percent of NCO contained in an isocyanate sample.

"Isocyanate index" means the ratio of the number of equivalents of hydroxy group (-OH) and the number of equivalents of isocyanate (-NCO) present in the polyol component in the urethane reactant, ie the amount of isocyanate used relative to the theoretical equivalent .

"Acid number" means the number of mg of KOH needed to neutralize the acid present in 1 g of polyol sample in mg KOH / g.

Exchange reaction between polyfunctional active hydrogen-containing compound and natural oil (first stage)

According to an embodiment of the invention, it is possible to use polyfunctional active hydrogen-containing compounds as initiators. The polyfunctional active hydrogen compound may specifically be a polyfunctional alcohol, a polyfunctional amine or a mixture thereof.

Examples of the polyfunctional alcohols include ethylene glycol, ethylene glycol, diethylene glycol, glycerin, trimethanolpropane, pentaerythritol, pentaerythritol, dipentaerythritol, and alphamethyl. Glucoside (α-methylglucoside), xylitol, xylitol, sorbitol, sugar, and the like, and the like, and these may be used alone or in combination. In this regard, the functional group numbers of exemplary polyfunctional alcohols are shown in Table 2 below.

Polyfunctional alcohol Functionality
Carbohydrate Sugar 8 Sorbitol 6 Almarketyl Glucoside 4
Aliphatic Glycols 2 glycerin 3 Trimethanol Propane 3 Pentaerythritol 4

Further, examples of the multifunctional amine include ethylenediamine, diethylene triamine, triethanolamine, ortho-toluene diamine (isomers), diphenylmethanediamine ), Diethanol amine, and the like, and these may be used alone or in combination.

In this regard, the functional group numbers of exemplary polyfunctional amines are shown in Table 3 below.

Polyfunctional amine Functionality Ethylenediamine 4 Diethylenetriamine 5 Toluene diamine 4 Triethanolamine 3

According to an embodiment of the invention, the multifunctional active hydrogen-containing compound, based on the total weight of the reactants (including the weight of the component introduced in the subsequent step, including the exchange reaction) for producing a bio polyol, about 10 To 50% by weight, more specifically, about 15 to 40% by weight. Although the present invention is not limited to the above content range, when the amount of the polyfunctional active hydrogen-containing compound is too low, it may be difficult to secure desired levels of physical properties because the functionality of the biopolyol cannot be enhanced. Therefore, it is desirable to adjust appropriately in consideration of the required properties of the polyurethane to be finally produced.

On the other hand, the natural oil may be used in about 10 to 60% by weight, more specifically, about 15 to 40% by weight based on the total weight of the reactants for producing the bio polyol.

According to an embodiment of the present invention, it may be desirable to perform some exchange reaction between the polyfunctional active hydrogen-containing compound and the natural oil during the first step, about 10 to 90% by weight of the natural oil, more specifically The reaction conditions may be adjusted to effect exchange reactions in the range of about 20 to 70 wt%. In addition, the natural oil that is not exchange-reacted in the above step may cause the exchange reaction to occur together with the addition reaction in the addition reaction step of the alkylene oxide. The reason is that natural oils are lipophilic components with long alkyl chains, whereas polyfunctional active hydrogen-containing compounds are hydrophilic components. This is because the addition reaction with can be facilitated and a biopolyol having a uniform structure can be obtained, and thus the storage stability can be improved.

According to an embodiment of the present invention, the above-mentioned multifunctional active hydrogen-containing compound and natural oil can be exchanged in the presence of a catalyst. The catalyst may preferably be a basic catalyst, for example potassium hydroxide (KOH), sodium hydroxide (NaOH), cesium hydroxide (CsOH), dimethyl lauramine, dimethyl palmityl amine ), N, N-dimethyldodecan-1-amine, and 1-octadecanamine. The catalyst components may be used alone or in combination. In this embodiment, the catalyst may be included in about 0.1 to 1.5% by weight, more specifically, about 0.2 to 1.0% by weight based on the total weight of the reactants for producing the biopolyol. In addition, the exchange reaction is preferably carried out under stirring.

According to an embodiment of the present invention, a pretreatment step may optionally be carried out prior to the exchange reaction to purify the natural oil, during which the gum component or other insoluble impurities (eg, phospholipids) Can be removed by sinking. Furthermore, the separated natural oil layer may be treated with alkali or the like to remove free fatty acid components and the like that may remain.

The exchange reaction will be described in more detail as follows.

When polyhydric alcohol is used as the polyfunctional active hydrogen-containing compound, triglycerides present in natural oils lose fatty acid groups through transesterification with polyhydric alcohols and di- and mono-substituted hydroxy as shown in Scheme 1 below. While forming glycerides, polyhydric alcohols can form fatty acid esters with the isolated fatty acids.

Scheme 1

On the other hand, in the case of a polyvalent amine containing a hydroxyl group in a molecule such as diethanol amine in the polyamine, the exchange reaction may be performed according to the reaction mechanism illustrated in Scheme 2 below.

Scheme 2

In addition, in the case of a polyvalent amine that does not contain a hydroxyl group in the molecule, an exchange reaction may be performed according to the reaction mechanism illustrated in Scheme 3 below (a kind of transamidation reaction).

Scheme 3

The reaction of the multifunctional active hydrogen-containing compound with the natural oil may be performed under elevated temperature, for example, about 70 to 170 ° C. over about 0.5 to 3 hours (more specifically, about 1 to 2 hours), More specifically, it may be performed at about 80 to 120 ℃.

The exchange reaction can be carried out in conjunction with dehydration, for example vacuum dehydration, which contains traces or small amounts of water in the reactant natural oils, or the catalyst is in the form of an aqueous solution (eg an aqueous solution of alkali hydroxide). It can also be used as.

The above-mentioned reaction conditions and the selection of the polyfunctional active hydrogen-containing compound can be determined in consideration of the extent of the alkylene oxide addition reaction later, the degree of expansion to be achieved in the synthesis reaction of the final polyurethane, the curing time and the like.

Alkylene oxide addition reaction step (second step)

According to an embodiment of the invention, the alkylene oxide addition reaction is carried out on the first stage reaction product.

In the case of addition reaction of the alkylene oxide to the above-mentioned exchange reaction product according to the present embodiment, it is possible not only to have a high functional group, but also to increase the storage stability, to keep the viscosity low, and to further improve the polyurethane, in particular When manufacturing a polyurethane foam it is possible to secure improved mechanical properties.

In this connection, usable alkylene oxide compounds are compounds having at least one alkylene oxide group, for example ethylene oxide, propylene oxide (1,2-epoxypropane), butylene oxide (1,4-epoxybutane) , 1,2-epoxybutane, 2,3-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxycyclopentane, 1,2-epoxycyclo Hexane, amylene oxide, styrene oxide and the like. Preferred examples include ethylene oxide, propylene oxide and butylene oxide, and more preferably ethylene oxide and propylene oxide. Under the present circumstances, an alkylene oxide compound can be used individually or in combination (mixing) of 2 or more.

When a plurality of alkylene oxides are used in combination, for example, individual alkylene oxides may be added continuously or simultaneously, and the ratio (the ratio between the respective alkylene oxides) may be changed during the addition reaction. It may be.

It is also possible to promote the alkylene oxide addition reaction using the catalyst used in the first step, for example a basic catalyst (particularly an alkali hydroxide catalyst).

Increasing the amount of natural oil used in a certain amount of the total reactant reduces the amount of alkylene oxide added, which may mean that energy input required for the addition reaction is reduced. However, when the alkylene oxide is added below a certain content, the viscosity of the bio polyol may rather increase, leading to lower handleability and lower storage stability. On the other hand, if the amount of natural oil used is reduced and the amount of alkylene oxide added is increased, it acts as a factor to increase the energy input required for the addition reaction. This is not in line with recent technological trends.

As such, in order to maximize the advantages of using natural oils and to alleviate the problems resulting from the use of natural oils, it is necessary to appropriately adjust the composition of the reactants for preparing the biopolyol, in particular the addition amount of the alkylene oxide compound.

In this regard, the amount of alkylene oxide added to the exchange reaction product between the natural oil and the polyfunctional active hydrogen-containing compound is at least about 20% by weight, preferably about about based on the total weight of the reactants for producing the biopolyol. 20 to 70% by weight, more preferably about 30 to 60% by weight.

On the other hand, the alkylene oxide addition reaction is, for example, under a temperature condition of about 80 to 140 ° C (more specifically, about 100 to 120 ° C) over about 1 to 40 hours (more specifically, about 5 to 15 hours). Can be performed. In addition, the pressure may be set at, for example, about 5.0 kgf / cm 2 or less (more specifically, about 3 to 4 kgf / cm 2).

According to a preferred embodiment of the present invention, it may be desirable to optionally remove the catalyst component present in the product after the aforementioned alkylene oxide addition reaction step. The reason for this is that if remaining in the bio polyol, the foamability and crosslinking reaction of the foam may be caused later in the polyurethane synthesis process.

To this end, a catalyst adsorbent may be used, and according to an exemplary embodiment, a catalyst adsorbent and water may be introduced into the alkylene oxide addition reaction product, and then a method of filtering the adsorbent may be used. At this time, the catalyst removal step may be preferably performed under stirring.

As the catalyst adsorbent, for example, silicates such as aluminum silicate and magnesium silicate may be used, and these may be used alone or in combination. In addition, the amount of the catalyst adsorbent may range from about 0.1 to 5.0 wt%, more specifically from about 0.2 to 2.0 wt%, based on the total weight of the reactants for producing the bio polyol.

In addition, the catalyst removal step (catalyst adsorbent injection and adsorption treatment) is performed for about 50 to 140 ° C. (more specifically, about 70 to 100 ° C.) over about 1 to 15 hours (more specifically, about 2 to 10 hours). Can be performed.

The biopolyol prepared by the above-described process (exchange reaction and addition reaction of alkylene oxide) has a functional group number of about 3 or more (more specifically, about 4 to 7), and a hydroxyl value of about 200 to 600 mg KOH / g ( More specifically about 300 to 500 mg KOH / g), and the viscosity (25 ° C) may range from about 2,000 to 25,000 cps (more specifically about 3,000 to 15,000 cps).

As described above, the bio polyol prepared according to the embodiment of the present invention exhibits excellent physical properties due to an increase in the number of functional groups, and the like, and in particular, by adding a considerable amount of alkylene oxide into the molecular structure, the viscosity is relatively low and stored. It has the property of improving stability. Such a characteristic is unexpected in the prior art, and has the advantage of being easy to handle and suppressing a change in physical properties of the polyol component even during long-term storage. In addition, it is possible to easily change the properties of the final polyurethane by controlling the selection of reactants, the ratio between reactants, density, reactivity, and the like.

Due to these improvements, the biopolyols according to this embodiment do not exclude the use in the production of flexible polyurethanes, but are used in the production of rigid polyurethane foams, in particular in the fields of various insulations, building materials and the like. It can expand the scope of the application more.

According to another embodiment of the present invention, polyurethane may be prepared by urethane-reacting an isocyanate component by including the bio polyol obtained as described above in the polyol component.

In the case of the urethane reaction, it may be carried out by blending with a component (for example, a catalyst, a blowing agent surfactant, etc.) suitable for the field of application or required performance of the polyurethane to be prepared.

Such urethane reaction mechanisms are well known in the art, and biopolyols prepared in embodiments of the present invention may be used alone or in combination with other polyols (eg, ether polyols, ester polyols or mixtures thereof) for polyols for urethane reactions. Can be used as a component.

On the other hand, the isocyanate component includes a compound in which an isocyanate group is linked with an aromatic, cycloaliphatic and / or aliphatic group, and in the above embodiments, these isocyanate compounds may be used alone or in combination.

As such isocyanate compound, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1, 3- and -1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate), 2,4- and 2, 6-hexahydrotoluene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI, or HMDI), 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6 -Toluene diisocyanate (TDI), diphenylmethane-2,4'- and / or -4,4'-diisocyanate (MDI), naphthylene-1,5-diisocyanate, triphenyl-methane-4,4 ', 4 "-triisocyanate, polyphenyl-polymethylene-polyisocyanate (crude MDI), norbornane diisocyanate, m- and p-iso Anatotophenyl sulfonyl isocyanate, perchlorinated aryl polyisocyanate, carbodiimide-modified polyisocyanate, urethane-modified polyisocyanate, allophanate-modified polyisocyanate, isocyanurate-modified polyisocyanate, urea-modified polyisocyanate, Biuret-containing polyisocyanates, isocyanate-terminated prepolymers or mixtures thereof, etc. may be used and may be appropriately selected depending on the required properties of the polyurethanes to be finally prepared. To 35.

As the urethane reaction catalyst, for example, amine-based catalysts such as, for example, secondary or tertiary amine compounds known in the art (eg, DMEA, TEDA, DMCHA, TMCHA, etc.), organic metals (eg, Metal catalysts such as organotin) and the like. In particular, two or more catalysts may be used in combination according to the required properties.

The blowing agent may be a chemical foaming agent (water reacting with isocyanate to generate carbon dioxide) as a component that generates bubbles during the resin reaction, and together with this, or alternatively, it does not participate in the resin reaction and is vaporized by the heat of reaction to form bubbles. Components to be formed, for example, HCFC-141b (1,1-dichloro-1-fluoroethane), HFC-245fa (1,1,1,3,3-pentafluoropropane) which is a hydrofluorocarbon (HFC) system , HFC-365mfc, mixed HFC-365mfc / 227ea, C-Pentane and the like can be used, preferably more environmentally friendly components such as C-Pentane, HFC system can be used.

In the case of the surfactant, it may be appropriately selected in consideration of the structure of the polyurethane (particularly, the cell structure in the polyurethane foam), and specific examples thereof include silicone-based surfactants (for example, product names B-8404, B- 8462).

In addition, a flame retardant (for example, a phosphorus flame retardant such as TCPP, TCEP, Phosphorus ester, etc.), a colorant, a filler, an internal mold release agent, an antistatic agent, an antimicrobial agent, and the like may be appropriately added and reacted.

In an embodiment of the present invention, the polyurethanes described above may be polyurethane foams (soft, semi-rigid or rigid), more specifically rigid polyurethane foams. To this end, conventional foaming principles and related devices can be used, in particular, the physical properties (density, etc.) of the foam can be controlled by changing the reactants, reaction conditions, etc. for the production of polyurethane foam. For example, in applications where a thermal insulation effect is required, the size of the cell may be relatively small.

The present invention can be more clearly understood by the following examples, which are only intended to illustrate the present invention and are not intended to limit the scope of the invention.

The reactants used in this example are as follows.

Natural oil

Palm oil: molecular weight (Mw) from Sigma-Aldrich; about 950; Cas. No: 8002-75-3

Soybean oil: molecular weight (Mw) from Sigma-Aldrich; Cas. No: 8001-22-7

Castor oil: molecular weight (Mw) 946.7 from Sigma-Aldrich; Functional group: 2.7; Cas: 8001-79-4

Polyfunctional active hydrogen-containing compounds

Sugar: molecular weight (Mw) 342.3 from Sigma-Aldrich; Functional group: 8; Cas: 57-50-1

Glycerin: molecular weight (Mw) 92.1 from Sigma-Aldrich; Functional group: 3; Cas. No .: 56-81-5

o-TDA: Molecular weight (Mw) of KPX Fine Chemical Co., Ltd. 122.2; Functional group: 4

Exchange catalyst in the production of polyols

KOH catalyst: KOH solution of Sigma-Aldrich (concentration: 45% solution, Cas.No .: 1310-58-3)

Dimethyllaulamine: the product name of Kao Corporation: DM-2098; Cas. No: 112-18-5

Alkylene oxide

Propylene oxide: molecular weight (Mw) of SKC Co., Ltd. 58.08; Cas. No: 75-56-9

Ethylene oxide: molecular weight (Mw) of Honam Petrochemical Co., Ltd. 44.05; Cas. No75-21-8

Isocyanate

Kumho Mitsui Chemicals Cosmonate M-200 (Compound name: p-MDI, Functional group: 2.7, NCO%: 31)

Urethane catalyst

Amine catalysts: Polyact® 5, Polyact® 8, (Products: Pentamethyldiethylenetriamine, Dimethylcyclohexylamine ...)

Surfactants

Silicone surfactant: Product name B-8404 by Evonik

blowing agent

Product Name HCFC-141b (Compound: 1,1-dichloro-1-fluoroethane; Cas.No .: 1717-00-6) of Zhejiang Juhua Calcium Carbide Co., Ltd.

Flame retardant

Product name Fyrol PCF (Compound: Tris (2-chloroisopropyl) phosphate; Cas. No .: 13674-84-5)

Example 1

First, sugar, palm oil and KOH (45%) catalyst were added to a 20 L high-pressure container, stirred under a nitrogen atmosphere (reduced pressure reduction), and the reaction was performed while vacuum dehydrating at about 120 ° C. for about 1 hour. Then, propylene oxide was added at about 115 ° C. for 15 hours.

A catalyst adsorbent and water were added to the reaction product obtained as described above, stirred at about 80 ° C. for about 1 hour, and then filtered to synthesize biopolyol. The composition ratio of the reactants is shown in Table 4 (unit: parts by weight).

Examples 2 and 3

Biopolyol was synthesized in substantially the same manner as in Example 1 except for changing the type of natural oil in the reactants, and the composition ratio of the reactants is shown in Table 4 below.

division Molecular Weight Example 1 Example 2 Example 3 palm oil 950 200 Soybean oil 968.7 200 Castor oil 946.7 200 Sugar 342.3 300 300 300 Sorbitol 178.1 Pentaerythritol 136.2 glycerin 92.1 o-TDA 122.2 Triethanolamine 149.2 Ethylenediamine 60.1 Water (reaction) 19 10 10 KOH (45%) 56.1 3.5 3.5 3.5 PO 58.1 488 488 498 Water (treatment) 19 handful → → Magnesium silicate handful → → Sum 1001.5 1001.5 1001.5

Examples 4-9

In this embodiment, palm oil is used as a natural oil, and the biopolyol is prepared in substantially the same manner as in Example 1 according to the composition ratio (unit: parts by weight) shown in Table 5 by changing the type of the polyfunctional active hydrogen-containing compound. Synthesized.

division Molecular Weight Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 palm oil 950 200 200 200 200 200 200 Sugar 342.3 300 Sorbitol 178.1 240 Pentaerythritol 136.2 280 glycerin 92.1 o-TDA 122.2 275 Triethanolamine 149.2 300 Ethylenediamine 60.1 150 Water (reaction) 19 10 20 KOH (45%) 56.1 3.5 3.5 3.5 3.5 3.5 3.5 PO 58.1 488 560 520 520 480 650 Water (treatment) 19 handful → → → → → Magnesium silicate handful → → → → → Sum 1001.5 1003.5 1003.5 998.5 1003.5 1003.5

Examples 10 to 13

In this embodiment, castor oil is used as a natural oil, and the ratio between the plurality of multifunctional active hydrogen-containing compounds is changed to substantially the same method as in Example 1 according to the composition ratio (unit: parts by weight) shown in Table 6 below. Bio polyols were synthesized.

division Molecular Weight Example 10 Example 11 Example 12 Example 13 Castor oil 946.7 200 200 200 200 Sugar 342.3 300 Sorbitol 178.1 230 Pentaerythritol 136.2 260 glycerin 92.1 230 Water (reaction) 19 KOH (45%) 56.1 3.5 3.5 3.5 3.5 PO 58.1 498 570 540 570 Water (treatment) 19 handful → → → Magnesium silicate handful → → handful Sum 1001.5 1003.5 1003.5 1003.5

Examples 14-16

In this embodiment, castor oil is used as a natural oil, and the ratio between the plurality of multifunctional active hydrogen-containing compounds is changed to substantially the same method as in Example 1 according to the composition ratio (unit: parts by weight) shown in Table 7 below. Bio polyols were synthesized.

division Molecular Weight Example 14 Example 15 Example 16 palm oil 950 200 250 300 Sugar 342.3 300 200 150 glycerin 92.1 100 100 Water (reaction) 19 10 10 KOH (45%) 56.1 3.5 3.5 3.5 PO 58.1 488 450 440 Water (treatment) 19 handful → → Magnesium silicate handful → → Sum 1001.5 1003.5 1003.5

Examples 17-20

In this embodiment, the biopolyol was synthesized in substantially the same manner as in Example 1 according to the composition ratio (unit: parts by weight) of the alkylene oxide and the type of catalyst and catalyst type.

division Molecular Weight Example 17 Example 18 Example 19 Example 20 palm oil 950 200 200 200 200 Sugar 342.3 300 300 300 300 Water (reaction) 19 10 10 10 10 KOH (45%) 56.1 3.5 3.5 Dimethyllaulamine 10.0 Dimethylpalmitylamine 10.0 PO 58.1 488 300 450 440 EO 44.1 190 Water (treatment) 19 handful → Magnesium silicate handful → → → Sum 1001.5 1003.5 1062 1062

Measurement of hydroxyl value

The hydroxyl value of the biopolyol synthesized in Examples 1 to 20 was measured according to the acetic anhydride-pyridine method (JISK 8004-1961, JISK 3342-1961, JISK 3361-1963).

<Measuring device>

Erlenmeyer flask (200ml), air cooling tube (30cm), pipette (5ml, 10ml), burette (50ml) and oil bath

<Measurement method>

(1) In the Erlenmeyer flask, the polyol synthesized in Examples 1 to 20 and 5 ml of anhydrous acetic acid-pyridine method were mixed and shaken five times or more, followed by attaching a cooler and reacting for 1 hour and 30 minutes in an oil bath.

(2) 1 ml of distilled water was added and shaken 5 times or more, and then left in an oil bath for 10 minutes to promote hydrolysis.

(3) After removing from the oil bath and left at room temperature for 10 minutes, the inner wall of the cooler was washed with 10 ml of acetone, shaken five times or more, and then titrated with 0.5N KOH standard solution by adding 3 to 4 drops of phenolphthalein indicator.

The hydroxyl value was calculated by the following equation.

[Equation 1]

Hydroxyl value = [(B-A) × F × 28.05 / S] + acid value

S: amount of sample

B: 0.5N KOH (ml) required for the blank

A: 0.5N KOH (ml) required for this test

B: Acid value of the sample used for this test

The hydroxyl value of the biopolyol synthesized in Examples 1 to 20 according to the above-described method is shown in Tables 9 to 13 below.

division Example 1 Example 2 Example 3 color Yellow liquid → → Hydroxyl value
(mg KOH / g) 440 445 420 Viscosity (25 ℃) 6,500 6,320 6,720 Functional group About 6.5 About 6.5 About 6.9 Storage stability × × ×

division Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 color Yellow liquid → → Red liquid → Yellow liquid Hydroxyl value
(mg KOH / g) 440 450 455 460 440 520 Viscosity (25 ℃) 6,500 5,210 3,890 - - - Functional group About 6.5 5.2 Approximately 3.6 About 3.7 About 3.0 About 3.0 Storage stability × × × × × ×

division Example 10 Example 11 Example 12 Example 13 color Yellow liquid → → → Hydroxyl value
(mg KOH / g) 420 455 450 445 Viscosity (25 ℃) 6,720 5,750 - - Functional group About 6.9 About 5.6 About 4.3 About 3.4 Storage stability × × × ×

division Example 14 Example 15 Example 16 color Yellow liquid → → Hydroxyl value
(mg KOH / g) 440 435 430 Viscosity (25 ℃)  6,500 5,920 5,330 Functional group About 6.5 About 6.5 About 6.5 Storage stability × × ×

division Example 17 Example 18 Example 19 Example 20 color Yellow liquid → → → Hydroxyl value
(mg KOH / g) 440 420 435 430 Viscosity (25 ℃) 6,500 6,380 6,350 6,290 Functional group About 6.5 About 6.5 About 6.5 About 6.5 Storage stability × × × ×

Storage stability was evaluated by placing the synthesized polyol in a 500 ml sample bottle and checking the presence of delamination for 100 days in a 30 ° C. oven (layer separation: ○, no layer separation: ×, slight turbidity and instability: Δ).

Comparative Example 1

563.3 parts by weight of sorbitol and 2 parts by weight of KOH were added to a 2000 ml round bottom flask, followed by stirring under nitrogen atmosphere, followed by vacuum dehydration at 110 ° C. 565.3 parts by weight of castor oil was added to the mixture and reacted at 200 ° C. for about 4 hours, and then 127.2 parts by weight of glycerin and 49.5 parts by weight of diethylene glycol were further reacted for 3 hours. Finally, for the ester reaction, 176.7 parts by weight of phthalic anhydride and 0.1 part by weight of TPT (tetraisopropyltitanate) were added and reacted at 230 ° C. for about 15 hours.

A small amount of magnesium silicate and water were added to the reaction product as a catalyst adsorbent, stirred at 80 ° C. for 1 hour, and then filtered to synthesize biopolyol.

Example 21 and Comparative Example 2

Biopolyols were synthesized in substantially the same manner as in Example 1 with varying addition amounts of alkylene oxide, and the respective reactant compositions are shown in Table 14 below.

division Example 21 Comparative Example 2  palm oil 105 550 Sugar 150 150 glycerin 100 100  Water (reaction) 10 10 KOH (45%) 3.5 3.5 PO 635 190 Water (treatment) handful → Catalytic Adsorbent (Magnesium Silicate) handful → Sum 1003.5 1003.5

Property contrast test

The color, hydroxyl value, viscosity and storage stability of Example 21 and Comparative Examples 1 and 2 were evaluated, respectively, and are shown in Table 15 together with the results measured in Example 16.

division Example 16 Example 21 Comparative Example 1 Comparative Example 2 color Yellow liquid Yellow liquid bitumen Yellow liquid Hydroxyl value
(mg KOH / g) 430 427 325 425 Viscosity (25 ℃) 5,330 3,620 29,000 32,000 Functional group About 6.5 4.2 About 4.0 About 3.2 Storage stability × × △ △

* Viscosity was measured using DV-III from Brookfield.

Storage stability was evaluated by placing the synthesized polyol in a 500 ml sample bottle and checking the presence of delamination for 100 days in a 30 ° C. oven (layer separation: ○, no layer separation: ×, slight turbidity and instability: Δ).

As can be seen from the above table, when the addition reaction of the alkylene oxide is not performed (Comparative Example 1), under the same conditions, the storage stability and appearance characteristics are not as good as compared to the biopolyol obtained according to the Examples, due to the high viscosity. It can be seen that the handleability is low.

In addition, when the alkylene oxide is used in less than a certain amount (Comparative Example 2), it was confirmed that there is a problem in long-term storage because the viscosity is high, the handleability is lowered in the urethane reaction later, especially the storage stability is low.

Examples 22-23 and Comparative Example 3

Polyurethane foams were prepared using biopolyols synthesized from Examples 16 and 21, and Comparative Example 1. Polyurethane foam was prepared using a foaming machine (Hnnecke product name: HK-270), the foaming temperature was 20 ℃, foaming pressure was 120 bar.

The composition of the urethane reactant is shown in Table 16 below.

division Example 22 Example 23 Comparative Example 3 Polyol according to Example 16 100 Polyol according to Example 21 100 Polyol according to Comparative Example 1 100 Flame Retardant (TCPP) 10 10 10 water 2.0 2.0 2.0 Urethane catalyst 1.5 1.2 1.8 Surfactants 1.5 1.5 1.5 Foaming Agent (HFCF-141b) 20.0 20.0 17.0 p-MDI 148.0 148.0 120.0 Isocyanate Index 110 110 110

Physical property test for polyurethane foam

The apparent shrinkage phenomenon, density, independent bubble ratio, compressive strength, and flexural strength of the polyurethane foams prepared in Examples 22 and 23, and Comparative Example 3, respectively, were measured and shown in Table 17 below.

division Example 22 Example 23 Comparative Example 3  Apparent shrinkage No shrink Slightly shrink Shrink Density (kg / m ³ )  28.5 28.6 28.8 Independent bubble ratio content (%)  90.3 90.4 90.2 Compressive strength (kg / cm ² )  1.83 1.72 1.55 Flexural strength (kg / cm ² )  2.63 2.55 2.41

* Apparent shrinkage: After foaming, it was left at room temperature and the relative shrinkage was confirmed.

* Density: After foaming, the foam was cut into 140 × 140 × 150 mm and calculated by measuring the weight and volume.

* Independent bubble ratio: Measured by using an air pycnometer by the ASTM D-2856 test method.

* Compressive strength: A specimen of 50 × 50 × 50mm size was measured horizontally and vertically using a universal test machine (UTM) according to ASTM D-1621 test method.

* Flexural strength: measured using a universal test machine (UTM) according to ASTM D-790 test method.

From the above table, polyurethane foams prepared using biopolyols having a considerable amount of alkylene oxide addition reactions according to embodiments of the present invention are in particular compared to polyurethane foams prepared using biopolyols according to Comparative Examples under the same conditions. It was confirmed that the strength characteristics were significantly improved.

Simple modifications and variations of the present invention can be readily used by those skilled in the art, and all such variations or modifications can be considered to be included within the scope of the present invention.

Claims (19)

As a method for producing bio polyol using natural oil,
a) exchanging a natural oil with a multifunctional active hydrogen-containing compound in the presence of a catalyst; And
b) addition reaction of alkylene oxide to the product of said exchange reaction;
Including;
On the basis of the total weight of the reactants for preparing the bio polyol, the alkylene oxide is added at least 20% by weight. The process according to claim 1, further comprising c) removing the catalyst from the addition reaction product of the alkylene oxide compound. The method according to claim 1, wherein the polyfunctional active hydrogen compound is a polyfunctional alcohol, a polyfunctional amine or a mixture thereof. The method of claim 3, wherein the polyfunctional alcohol is ethylene glycol, diethylene glycol, glycerin, trimethanol propane, pentaerythritol, dipentaerythritol, alpha methyl glucoside, xylitol, sorbitol, sugar or a mixture thereof Manufacturing method. The method of claim 3, wherein the multifunctional amine is ethylenediamine, diethylenetriamine, triethanolamine, ortho-toluenediamine, diphenylmethanediamine, diethanol amine or a mixture thereof. The method of claim 1, wherein the catalyst is potassium hydroxide, sodium hydroxide, cesium hydroxide, dimethyllaulamine, dimethylpalmitylamine, N, N-dimethyldodecane-1-amine, 1-octadecaneamine, or a mixture thereof. Manufacturing method. The method of claim 1, wherein the alkylene oxide is added in an amount of 20 to 70% by weight based on the total weight of the reactants for preparing the biopolyol. The method of claim 1, wherein the alkylene oxide is ethylene oxide, propylene oxide (1,2-epoxy propane), butylene oxide (1,4-epoxy butane), 1,2-epoxy butane, 2,3- epoxy butane , 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, amylene oxide, styrene oxide or mixtures thereof The manufacturing method to make. The method of claim 8, wherein the alkylene oxide is ethylene oxide, propylene oxide or a mixture thereof. The method according to claim 1, wherein the reaction is carried out to 10 to 90% by weight of the natural oil in step a). The process according to claim 2, wherein step c) is carried out by adding a catalyst adsorbent and water, stirring and filtering. The method of claim 7, wherein the reactant of step a) is based on the total weight of the reactants for preparing the biopolyol, 10 to 50% by weight of the multifunctional active hydrogen-containing compound, 10 to 60% by weight of the natural oil and 0.1 to 1.5 of the catalyst. A manufacturing method comprising a weight percent. The method of claim 11, wherein the catalytic adsorbent is aluminum silicate, magnesium silicate or mixtures thereof. The method of claim 11, wherein the catalyst adsorbent is added in an amount of 0.1 to 5 wt% based on the total weight of the reactants for preparing the biopolyol. The process of claim 1, wherein step a) is performed at 70 to 170 ° C. for 0.5 to 3 hours; And
The step b) is characterized in that it is carried out at 80 to 140 ℃ for 1 to 40 hours. Biopolyol prepared according to any one of claims 1 to 15. The biopolyol of claim 16, wherein the biopolyol exhibits at least three functional groups, a hydroxyl value of 200 to 600 mg KOH / g, and a viscosity of 25 to 25,000 cps (25 ° C.). A polyurethane prepared by reacting a polyol component and an isocyanate component containing the bio polyol according to claim 16. 19. The polyurethane of claim 18, wherein the polyurethane is a rigid polyurethane foam.