KR20120099934A - Rigid polyurethane foams for automobile containing biopolyol - Google Patents

Abstract

PURPOSE: Hard polyurethane foam is provided to able to maintain physical properties like impact resistance, environment-friendliness, moldability, dimensional stability, flame retardance, etc by using bio-polyol having a specific number of functional groups, a specific value of hydroxy group, a specific viscosity, etc. CONSTITUTION: Hard polyurethane foam comprises polyol comprising bio polyol, and isocyanate. A core density of the hard polyurethane foam is 150 kg/m^3 or lower, a compressive strength is 2.0 kg/cm^2 or higher, a flexural strength is 3.0 kg/cm^2 or higher, an elongation is 40% or higher, a dimensional stability is -2.0% or less at 30 °C, 24 hr, and 3.0% or less at 70 °C, 24 hr. The biopolyol comprises 10-60 weight% of natural oil, 10-60 weight% of a polyfunctional active hydrogen-containing compound, 0.1-1.5 weight% of a catalyst, and 20-70 weight% of alkylene oxide. A number of functional groups is 3 or higher, a hydroxyl value of KOH/g is 200-600 mg, and a viscosity 25 25°C is 2,000-25,000.

Description

Rigid Polyurethane Foams for automobile Containing Biopolyol

The present invention relates to a rigid polyurethane foam containing bio polyols capable of maintaining physical properties as automotive materials.

Polyols, which are an essential component of polyurethanes, are usually prepared from petroleum-based raw materials, in particular polyether polyols, polyester polyols are known as the most common polyols. Such polyols have a significant effect on the properties of the polyurethane or polyurethane foam to be produced.

Generally, high molecular weight and low functional group polyols are used to make soft urethane foams, and small molecular weight and high functional group polyols are used to produce rigid urethane foams.

In particular, the molecular weight of the polyols used in the flexible polyurethane foam is greater than approximately 1,000. The molecular weight of the polyol used in the rigid polyurethane foam is approximately 200 to 4,000, the modulus of elasticity of about 100,000 psi or more (23 ℃), glass transition temperature of 20 ℃ or more, elongation not exceeding 10%, etc. Has the characteristics of.

On the other hand, in the urethane field, polyols produced from petroleum-based raw materials are recycled or environmentally friendly due to various reasons such as accelerated exhaustion of petroleum resources, reduction of greenhouse gases due to climate change, rising raw material prices, and increasing need for renewable raw materials. Has been proposed to replace the polyol.

Natural oils are generally composed of triglyceride molecules and have three fatty acids bonded to the glycerol junction.

Currently, the production of polyols using natural oils, in particular vegetable oils, involves the use of 1) incorporation of active oxygen into the molecular structure using an epoxidation-ring opening reaction (hydrogen peroxide, etc.), followed by alcohol or Method for performing ring-opening reaction with inorganic acid; Kandanarachchi et al ., J. Mol. Catal. A: Chem 2002, 184, 65), 2) Hydroformylation reaction (syngas and natural oil in the presence of rhodium or cobalt catalyst) Reaction method; Petrovic et al ., Polyurethanes from vegetable oils.Polymer Reviews 48: 1 109-155), 3) Ozone decomposition reaction (Ozone decomposition of natural oils directly to prepare polyols having hydroxyl groups at the terminal positions). How to perform; And Petrovic et al ., Biomacromolecules 2005, 6, 713), 4) esterification reactions (Vilar et al. , 2002) and the like.

It is reported that polyurethane foams using bio polyols prepared from natural oils can have properties comparable to polyurethane foams produced from petroleum oils. However, the actual bio polyol has a problem that the physical properties of the polyurethane foam is lowered due to low reactivity.

The low reactivity of biopolyols is attributed to the presence of secondary alcohols and the presence of multiple nonfunctional branches.

On the other hand, polyurethane foam (polyurethane foam), in particular rigid polyurethane foam is used in various fields, there is a difference in the physical properties required according to the application field. In particular, when used for automobiles, impact resistance, environmental friendliness, moldability, dimensional stability, and flame retardancy are required.

However, the rigid polyurethane foam to which the conventional bio polyol is applied may be deteriorated in physical properties such as impact resistance, compressive strength, bending strength and dimensional stability due to the low number of functional groups of the bio polyol, and the growth of cells in the production of rigid polyurethane foam Moldability may be degraded by the unreacted natural oils that hinder the application of the rigid polyurethane foam for automobiles.

In addition, the conventional bio polyol has a high risk of deterioration in storage stability due to the nature of natural oils, and a high viscosity without having a sufficiently high number of functional groups, which may cause problems such as reactivity and handleability during the manufacturing process of rigid polyurethane foam. There is a limit. This suggests the applicability of castor oil or soybean oil, which has an appropriate number of functional groups and is easy to manufacture with rigid polyurethane foam, but these are mainly used as food resources or relatively expensive, and thus have low economical limits.

Therefore, there is a need for a rigid polyurethane foam for automobiles using bio polyols that can provide equivalent or more physical properties compared to automotive polyurethane foams using petroleum-based polyols.

The present invention can maintain physical properties such as impact resistance, environmental friendliness, moldability, dimensional stability and flame retardancy as a rigid polyurethane foam for automobiles using a bio polyol having a specific functional group number, hydroxyl value (mgKOH / g) and viscosity, etc. To provide a rigid urethane foam.

The inventors of the present invention have found that a biopolyol containing a polyfunctional active hydrogen-containing compound and alkylene oxide in a natural oil to reduce the number of secondary alcohols and a plurality of nonfunctional branches present in the biopolyol is a component of the rigid polyurethane foam. By using it, it has been found that physical properties for automobiles such as impact resistance, environmental friendliness, moldability, dimensional stability, and flame retardancy can be maintained.

Accordingly, the present invention contains 10 to 60% by weight of natural oil, 10 to 60% by weight of polyfunctional active hydrogen-containing compound, 0.1 to 1.5% by weight of catalyst and 20 to 70% by weight of alkylene oxide, having 3 or more functional groups. A polyol comprising a bio polyol having a hydroxyl value of 200 to 600 mgKOH / g and a viscosity (25 ° C.) of 2,000 to 25,000 cps; And isocyanates,

The core density is 150 kg / m 3 or less; Compressive strength is at least 2.0 kg / cm ² ; Flexural strength is at least 1.5 kg / cm ² ; Tensile strength is at least 3.0 kg / cm ² ; Elongation is at least 40%; Dimensional stability is -2.0% or less at 30 ° C and 24hr, 3.0% or less at 70 ° C and 24hr; Flame retardancy provides a rigid polyurethane foam for automobiles that is self-extinguishing.

The polyfunctional active hydrogen compound is a polyfunctional alcohol, a polyfunctional amine or a mixture thereof, the polyfunctional alcohol is ethylene glycol, diethylene glycol, glycerin, trimethanol propane, pentaerythritol, dipentaerythritol, alphamethylglucoside , Xylitol, sorbitol, sugar or mixtures thereof, the multifunctional amine may be ethylenediamine, diethylenetriamine, triethanolamine, ortho-toluenediamine, diphenylmethanediamine, diethanol amine or mixtures thereof.

The catalyst may be potassium hydroxide, sodium hydroxide, cesium hydroxide, dimethyllaulamine, dimethylpalmitylamine, N, N-dimethyldodecane-1-amine, 1-octadecaneamine or mixtures thereof.

The alkylene oxide may be ethylene oxide, propylene oxide or a mixture thereof.

The bio polyol comprises the steps of: a) exchanging a natural oil with a polyfunctional active hydrogen-containing compound in the presence of a catalyst; And b) addition reaction of alkylene oxide to the product of the exchange reaction.

The bio polyol further comprises c) removing the catalyst from the addition reaction product of the alkylene oxide compound, wherein step c) may be carried out by adding a catalyst adsorbent and water, stirring and filtering have.

The bio polyol may include 10 to 60 parts by weight based on 100 parts by weight of polyol.

The isocyanate has a functional number ranging from 2.7 to 3.0, an NCO% value ranging from 25 to 35, an isocyanate index ranging from 90 to 180, and may include polymeric MDI (diphenylmethane diisocyanate).

0.1 to 7.0 parts by weight of the urethane catalyst, 0.1 to 15 parts by weight of the blowing agent, and 0.1 to 5.0 parts by weight of the surfactant based on 100 parts by weight of the polyol.

The rigid polyurethane foam has a viscosity (20 ° C.) of 200 to 2500 cps, a specific gravity (20 ° C.) of 1.00 to 1.30, a cream time of 5 to 65 sec, and a gel time of 40 To 200 sec, it may be made of a composition for producing a rigid polyurethane foam having a free density (FD) of 20 to 120 kg / ㎥.

The rigid polyurethane foam of the present invention has the advantage of maintaining physical properties such as impact resistance, environmental friendliness, moldability, dimensional stability, flame retardancy as a rigid polyurethane foam that is a vehicle material.

Therefore, it can be used not only for automobile under cover, package tray, sunshade board, impact absorption foam, head liner, etc. It can play a role of soundproofing material in dash panel, floor, roof, trunk, etc., which can introduce noise into some automobile interiors, which can be useful as various interior and exterior materials of automobiles. have.

In addition, the rigid polyurethane foam of the present invention has the advantage of eco-friendly and renewable by using a bio polyol.

The present invention relates to a rigid polyurethane foam containing bio polyols capable of maintaining physical properties as automotive materials.

Hereinafter, the present invention will be described in detail.

Terms used in the present specification 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 oils" is a concept involving animal and vegetable oils, and may preferably be vegetable oils. Examples of the animal oil may be one trillion or more selected from the group consisting of fish oil, bovine oil, pork oil, sheep oil and mixtures 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, sesame oil, It may be at least one selected from the group consisting of soybean oil, castor oil and mixtures thereof. The present invention is not limited to the types listed above.

Of these, 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 composed of about 90% of glycerin's triester or fatty acid with ricinoleic acid, with the remainder containing oleic acid, linoleic acid and the like.

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

division 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 the 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).

A "closed cell foam" is a foam in which a large percentage of cells are not connected by an open passage, preferably a non-open cell, an independent bubble ratio (the percentage of closed cells in a cell). May refer to a foam that is at least about 88%, preferably about 90%, although such figures are to be understood as illustrative.

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

"Isocyanate index" means the ratio of the number of equivalents of hydroxyl groups (-OH) and the number of equivalents of isocyanate (-NCO) present in the polyol in the urethane reactant, ie the amount of isocyanate used relative to the theoretical equivalent. Thus, if the isocyanate index is less than 100, it means that there is an excess of polyol, while if the isocyanate index is more than 100, it means that there is an excess of isocyanate.

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

The rigid polyurethane foam for automobiles of the present invention contains 10 to 60% by weight of natural oil, 10 to 60% by weight of polyfunctional active hydrogen-containing compound, 0.1 to 1.5% by weight of catalyst and 20 to 70% by weight of alkylene oxide, Polyols comprising a biopolyol having a functional number of 3 or more, a hydroxyl value of 200 to 600 mgKOH / g, and a viscosity (25 ° C) of 2,000 to 25,000 cps; And isocyanates.

The natural oil is as defined above and may be used in 10 to 60% by weight, preferably 15 to 40% by weight. When the content is less than 10% by weight, the amount of other components is relatively high, so the polyol prepared therefrom cannot be regarded as a bio polyol. When the content is more than 60% by weight, due to the low functional group number and low storage stability of the biopolyol, The physical properties of the rigid polyurethane foam to be produced may be lowered.

The bio polyol comprises the steps of: a) exchanging a natural oil with a polyfunctional active hydrogen-containing compound in the presence of a catalyst; And b) addition reaction of alkylene oxide to the product of the exchange reaction.

Examples of polyfunctional alcohols include ethylene glycol, diethylene glycol, glycerine, trimethanolpropane, pentaerythritol, dipentaerythritol, and alphamethylglucose. Seed (α-methylglucoside), xylitol (xylitol), sorbitol (sorbitol), sugar (sucrose) may be used one or more selected from the group consisting of. The functional group number of the polyfunctional alcohol is 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, diethylenetriamine, triethanolamine, ortho-toluenediamine (isomers), diphenylmethanediamine, and the like. One or more selected from the group consisting of diethanolamine may be used. The number of functional groups of the polyfunctional amine is shown in Table 3 below.

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

Such polyfunctional active hydrogen-containing compounds may be used at 10 to 60% by weight, preferably 15 to 40% by weight. When the content is less than 10% by weight, the number of functional groups is low, which does not indicate the physical properties of the target biopolyol, which affects the properties of the rigid urethane foam and the heat insulating material. Since the content of the lower polyol is a problem that can not be viewed as a bio polyol.

The catalyst uses a basic catalyst, for example potassium hydroxide (KOH), sodium hydroxide (NaOH), cesium hydroxide (CsOH), dimethyl lauramine, dimethyl palmityl amine, N, One or more selected from the group consisting of N-dimethyldodecan-1-amine and 1-octadecanamine may be used.

Such catalysts are used in an amount sufficient to carry out the exchange reaction, preferably 0.1 to 1.5% by weight, more preferably 0.2 to 1.0% by weight.

The exchange reaction adjusts the reaction conditions to be carried out in the range of about 10 to 90% by weight, preferably 20 to 70% by weight of the natural oil. For example, it may be carried out at 70 to 170 ° C, preferably 80 to 120 ° C while raising the temperature over 0.5 to 3 hours, preferably 1 to 2 hours.

The natural oil that has not been exchanged above causes the exchange reaction to occur with the addition reaction in the addition reaction step of the alkylene oxide. Natural oil is a lipophilic component having a long alkyl chain, and a polyfunctional active hydrogen-containing compound is a hydrophilic component. Therefore, when a part of natural oil is exchanged and alkylene oxide is added, the addition reaction with the alkylene oxide is easy. It can be carried out in a simple manner, it is possible to obtain a bio-polyol of a uniform structure to improve the storage stability of the composition for producing a rigid polyurethane foam (polyols and other additives containing biopolyol, etc.).

The present invention may perform a pretreatment step of purifying natural oil prior to the exchange reaction. In this pretreatment, gum components or other insoluble impurities (eg, phospholipids) can be settled and removed. The separated natural oil layer may also be treated with alkali or the like to remove free fatty acid components that may remain.

The exchange reaction is described in more detail as follows.

When a 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 glycerides can be obtained. And the polyhydric alcohol may form fatty acid esters with the separated fatty acids.

[Reaction Scheme 1]

In addition, in the case of a polyvalent amine containing a hydroxy group in a molecule such as diethanol amine in the polyvalent amine, an exchange reaction may be performed according to the reaction mechanism of 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 of Scheme 3 below (a kind of transamidation reaction).

Scheme 3

The exchange reaction can be carried out with a dehydration treatment, for example vacuum dehydration treatment, which contains a small amount or a small amount of water in the reactant natural oil, 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 may be determined in consideration of the extent of the alkylene oxide addition reaction in the future, the degree of expansion to be achieved in the process of preparing the final rigid polyurethane foam, the curing time, and the like. .

The present invention further reacts alkylene oxide with the product of the above exchange reaction (first stage reaction).

When the addition reaction of alkylene oxide to a specific content of the product obtained by the exchange reaction is carried out, it is possible not only to increase the storage stability while maintaining a high functional group, but also to maintain a low viscosity, which is required for a rigid polyurethane foam for building insulation It can improve the physical properties.

Alkylene oxide is a compound 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-epoxycyclohexane, amylene oxide oxide) and styrene oxide may be used. In consideration of commercialization, ethylene oxide, propylene oxide and butylene oxide may be preferably used, and in consideration of cost and physical properties, more preferably ethylene oxide and propylene oxide may be used.

In this case, when a plurality of alkylene oxides are used in combination, each of the alkylene oxides may be continuously added or simultaneously added, and the mixing ratio of the alkylene oxides may be variously adjusted to induce a change in physical properties.

It is also possible to promote alkylene oxide addition reactions using catalysts used in the exchange reaction, for example basic catalysts (particularly alkali hydroxide catalysts).

Increasing the amount of natural oil in the total amount of reactants reduces the amount of alkylene oxide used in the addition reaction. The present invention can reduce the emission of carbon dioxide by reducing the amount of energy input in the process of producing a bio polyol by increasing the amount of use of natural oil relative to the prior art.

On the other hand, when the alkylene oxide is added below a certain amount, the viscosity of the bio polyol may rather increase, resulting in decreased handleability and reduced storage stability.

In addition, when the amount of natural oil is reduced and the amount of alkylene oxide added is increased, the energy input amount required for the addition reaction is increased, and excessively lowering the amount of natural oil is a recent pursuit of green chemical processes. There is also a problem that is not consistent with the technology trends.

It is also possible to promote alkylene oxide addition reactions using catalysts used in the exchange reaction, for example basic catalysts (particularly alkali hydroxide catalysts).

As such, there is a need to properly adjust the composition of the reactants for preparing the biopolyol, in particular the addition amount of the alkylene oxide compound, in order to maximize the advantages of using natural oil and to alleviate the problems resulting from the use of natural oil.

In this regard, the alkylene oxide added to the exchange reaction product between the natural oil and the polyfunctional active hydrogen-containing compound contains 20% by weight or less, preferably 20 to 70% by weight, more preferably 30 to 60% by weight. can do.

The alkylene oxide addition reaction may be performed under temperature conditions of 80 to 140 ° C., preferably 100 to 120 ° C. over 1 to 40 hours, preferably 5 to 15 hours. The pressure may also be carried out at 5.0 kgf / cm 2 or less, preferably 3 to 4 kgf / cm 2.

The present invention may further comprise the step of optionally removing the catalyst component present in the product after the addition reaction step of the alkylene oxide. When remaining in the bio polyol, it is preferable to carry out the above steps, since the formability of the foam and the crosslinking reaction may be caused in the polyurethane synthesis process.

Removal of the catalyst component may be performed using a catalyst adsorbent. Specifically, a catalyst adsorbent and water may be introduced into the alkylene oxide addition reaction product, and then the method may be filtered. At this time, the catalyst removal step may be preferably performed under stirring.

The catalyst adsorbent may be, for example, silicates such as aluminum silicate and magnesium silicate, and these may be used alone or in combination. In addition, the catalyst adsorbent may be used in the range of 0.1 to 5.0% by weight, preferably 0.2 to 2.0% by weight.

In addition, the catalyst removal step (catalyst adsorbent injection and adsorption treatment) may be performed for 1 to 15 hours, preferably 2 to 10 hours for 50 to 140 ℃, preferably 70 to 100 ℃.

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

As described above, the bio polyol prepared according to the present invention exhibits excellent physical properties by increasing the number of functional groups and decreasing the amount of remaining natural oil, and in particular, by adding a considerable amount of alkylene oxide into the molecular structure, the viscosity is relatively high. It is lowered, and the storage stability is improved. 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 even during long-term storage. In addition, it is possible to easily change the properties of the rigid polyurethane foam to be prepared by controlling the selection of reactants, the ratio between the reactants, density, reactivity, and the like.

Due to these improvements, rigid polyurethane foams made using the biopolyols are particularly suitable for automotive materials.

On the other hand, a rigid polyurethane foam can be prepared by urethane-reacting a polyol including the bio polyol prepared above and an isocyanate.

The mechanism of such a urethane reaction is known in the art, by mixing a variety of additives (for example, catalysts, blowing agents, surfactants, flame retardants, etc.) so that the rigid polyurethane foam to be produced exhibits suitable properties for automotive materials Can be prepared.

The manufacturing method of the rigid polyurethane foam is not specifically limited, The urethane reaction may be performed by simultaneously mixing an additive, a polyol, and an isocyanate, or an additive may be first added to a polyol, and the polyol and the isocyanate containing an additive may be urethane-reacted. When the additive, polyol and isocyanate are mixed at the same time, the formation of uniform urethane foam is not easy due to the local nonuniformity of the concentration, and the latter may not be easy in terms of the handleability of the polyol and the moldability of the urethane foam. The method is preferred.

The polyol and the isocyanate are reacted at a stoichiometric ratio, but considering the efficiency of the reaction, the isocyanate may be used in an amount of 80 to 180 parts by weight, preferably 90 to 150 parts by weight, based on 100 parts by weight of the polyol.

In addition, considering the properties of the rigid polyurethane foam to be prepared, the isocyanate index may be in the range of 60 to 400, preferably 90 to 200, more preferably 90 to 180 in consideration of automotive applications.

Hereinafter, the reactants (polyols, isocyanates and additives) for preparing the rigid polyurethane foam will be described in detail.

The polyols of the present invention necessarily include bio polyols and may additionally comprise ether polyols, ester polyols or mixtures thereof.

Examples of the ether polyols include glycerin, trimethanolpropane, pentaerythritol, dipentaerythritol, alphapentylerythritol, alpha-methylglucoside, xylitol, and sorbitol. ) And polyfunctional alcohols such as sugar (sucrose); And / or alkylene oxides (eg, ethylene oxide, propylene) starting from polyfunctional amines such as ortho-toluene diamine, ethylene diamine, triethanol amine, etc. as starting materials. Oxides, butylene oxides or mixtures thereof) may be added. Methods of synthesizing such optionally containing ether polyols are known in the art, and the basic reaction mechanism is shown in Scheme 4 below.

Scheme 4

Examples of ester polyols include reaction products of polyhydric alcohols and polyhydric acids (particularly polyhydric carboxylic acids). At this time, instead of the polyacid, anhydrides thereof, ester compounds with lower alcohols, or mixtures thereof may be used. More specifically, diacid (e.g., phthalic anhydride, terephthalic acid, suberic acid, sebacic acid, isophthalic acid, trimellitic acid, succinic acid, adipic acid, fumaric acid, etc.) and polyhydric alcohols (e.g., ethylene glycol , Polyethylene synthesized by polymerizing diethylene glycol, 1,4-butanediol, glycerin, trimethylolpropane, propylene glycol and the like). In addition, a single ester polyol may be used, or two or more ester polyols may be used in combination. The reaction mechanism for the synthesis of such ester polyols is shown in Scheme 5 below.

Scheme 5

The hydroxyl value of the polyols (ether polyols and / or ester polyols) that can be used with bio polyols in order to satisfy the various physical properties required for automotive materials such as thermal conductivity, compressive strength and the like can range from 50 to 600 mgKOH / g. It is also possible to adjust the properties of the rigid polyurethane foam (eg, thermal conductivity and strength properties (compressive strength, flexural strength, etc.)) through appropriate selection of the hydroxyl value.

The polyol may comprise 10 wt% or more, preferably 10 to 60 wt% of the bio polyol. In addition, ether polyols which may be added may be used in an amount of 80 wt% or less (preferably 20 to 70 wt%), and ester polyols in 40 wt% or less (preferably 20 wt% or less).

In one example, the ether polyol comprises (i) 60 to 100% by weight of ether polyol having a hydroxyl value of about 5.5 to 7, a hydroxyl value of 350 to 500 mgKOH / g, and (ii) a number of functional groups of 2 to 5, 100 to 500 mg It may consist of a mixture comprising 0 to 40% by weight of ether polyols having a hydroxyl value of KOH / g. Moreover, ester polyol can use what has a functional group number of 2-4, and a hydroxyl value of 50-400 mgKOH / g.

In another example, the ether polyol may comprise (i) 60 to 100% by weight of ether polyol having a functional group number of 5 to 6.5, a hydroxyl value of 300 to 550 mgKOH / g, and (ii) a functional group number of 2 to 5, 30 to 450 It may consist of a mixture comprising 0 to 40% by weight of an ether polyol having a hydroxyl value of mgKOH / g. Moreover, the ester polyol can use what has a functional group number of 2-3 and a hydroxyl group value of 50-400 mgKOH / g.

Isocyanates of the present invention react with polyols to form urethane bonds in the foam, and include compounds in which aromatic, cycloaliphatic and / or aliphatic groups are linked to isocyanate groups.

Isocyanate compounds are known in the art, for example ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3 -Diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane ( Isophorone diisocyanate), 2,4-hexahydrotoluene diisocyanate, 2,6-hexahydrotoluene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI, or HMDI), 1,3- Phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate (TDI), diphenylmethane-2,4'- diisocyanate, diphenylmethane-4,4 ' Diisocyanate (MDI), naphthylene-1,5-diisocyanate , Triphenyl-methane-4,4 ', 4 "-triisocyanate, polyphenyl-polymethylene-polyisocyanate (crude MDI), norbornane diisocyanate, m-isocyanatophenyl sulfonyl isocyanate, p-iso Cyanatophenyl 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.

The isocyanate may be a functional group number of 2.5 to 3.5, NCO% of 25 to 35. Suitable isocyanates are MDI, polymeric MDI or crude having functional groups ranging from 2.6 to 3.0 (preferably around 2.7), NCO% values ranging from 25 to 35 (preferably NCO% values from 27 to 32). MDI (p-MDI, typically a weight average molecular weight (M _w ): about 350 to 420). p-MDI typically has a brown liquid at room temperature and a viscosity range may range from 100 to 3,000 cps (more specifically, 100 to 300 cps).

The reaction between the polyol and the isocyanate may be carried out in the presence of a catalyst for preparing urethane in order to shorten the curing time. The catalyst is not particularly limited, and at least one selected from the group consisting of an amine catalyst such as a secondary or tertiary amine compound and a metal catalyst such as an organic metal may be used.

Examples of the amine catalyst include triethylenediamine, triethylamine, tripropylamine, triisopropanolamine, tributylamine, trioctylamine, hexadecyldimethylamine, tetramethylethylenediamine, 3-methoxy-N-dimethyl -Propylamine, diethylethanol-amine, N-cocomorpholine, N, N-diethyl-3-diethylaminopropyl amine, tris (3-dimethylamino) propylhexahydrotriamine, N-methylmorpholine, N-ethylmorpholine, monoethanolamine, diethanolamine, dimethylethanolamine, triethanolamine, N-methyldiethanolamine, N, N-dimethylethanolamine, diethylenetriamine, N, N, N ', N' Tetramethylbutanediamine, N, N, N ', N'-tetraethylhexamethylenediamine, pentamethylenediethylenediamine, N, N'-dimethylbenzylamine, N, N-dimethylcyclohexylamine, N, N, At least one member selected from the group consisting of N ', N', n'-pentamethyldiethylenetriamine and triethylenediamine Can be used. In this case, N, N-dimethylcyclohexylamine is a brand name Polyact8, N, N, N ', N', n'-pentamethyldiethylenetriamine is a brand name Polyact5, and in the case of triethylenediamine, a brand name TEDA-33P Can be.

In addition, the metal catalyst is selected from the group consisting of, for example, potassium octoate, potassium acetate, bismuth-based gel catalyst, and tin type catalyst. More than one species may be used.

The gel catalyst mainly serves to promote the gel reaction to form a urethane chain in the urethane foam. In addition, the tin-based catalyst is, for example, tin salt of carboxylic acid, tin acrylate, trialkyl tin oxide, dialkyl tin dihalide, dialkyl tin oxide (dibutyltin (IV) oxide, etc.), dibutyltin diaurate, One or more selected from the group consisting of dibutyltin diacetate, diethyltin diacetate, dihexyltin diacetate, di-2-ethylhexyltin oxide, dioctyltin dioxide and tin octoate may be used.

The urethane catalyst may be used in the range of 0.1 to 7.0 parts by weight, preferably 0.2 to 5.0 parts by weight based on 100 parts by weight of the polyol. In general, as the amount of the catalyst increases, the reaction rate for forming the polyurethane foam increases, but when the reaction rate is too fast, the polyol and the isocyanate may change into solid phase before filling the molding space, and the problem of poor workability It may be caused, it is preferable to adjust appropriately.

The foaming agent plays a role of generating bubbles during the urethane reaction. As the foaming agent does not participate in the urethane reaction, it is vaporized (sublimed) by the heat of reaction and water (chemical reaction agent which generates carbon dioxide by reacting with isocyanate) which forms bubbles. As can be distinguished, the two types may be used alone or in combination.

The physical blowing agent vaporizes (sublimates) the heat of the reaction, and the resulting gas may accumulate by the enclosed cells of the foam so that the foam produced may exhibit low thermal conductivity. In addition, the physical blowing agent can adjust the required properties (density, etc.) of the polyurethane foam.

At this time, hydrocarbon-based C-pentane, hydrochlorofluorocarbon based HCFC-141b (1,1-dichloro-1-fluoroethane), hydrofluorocarbon (HFC) based HFC-245fa (1,1,1,3,3 -Pentafluoropropane), HFC-365mfc, mixed HFC-365mfc / 227ea, mixtures thereof and the like may be preferably used as blowing agent. Although it does not exclude the use of CFC-based blowing agents that have been used in the past, it may be preferable to exclude the use as possible because it may cause environmental problems. Preferably, more environmentally friendly components such as C-Pentane, HFC-based, and the like may be used. In particular, HFC-245fa can be used as the HFC-based blowing agent used in the manufacture of closed cell insulation foam.

The blowing agent may include 0.1 to 15 parts by weight based on 100 parts by weight of the polyol, and specifically, the physical blowing agent may range from 0.1 to 15 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the polyol. In addition, the chemical blowing agent may range from 0.1 to 10 parts by weight, more preferably from 0.5 to 6.0 parts by weight, based on 100 parts by weight of the polyol.

The present invention can use surfactants that affect the cell structure in the polyurethane foam. The surfactant may act as a mixture stabilization of the reaction raw material, bubble generation, stabilization of the bubble. For example, it is possible to increase the surface area by reducing the surface tension to decrease the size of the cell, and increase the foam stability by increasing the surface elasticity to recover the critically expanding film before cell breakdown occurs. And it is possible to increase the surface viscosity to reduce the deformation of the cell structure.

As such, the type of the surfactant may be appropriately selected in consideration of the cell structure in the foamed polyurethane. Examples thereof include silicone-based surfactants or foam stabilizers, for example, product names B-8462, manufactured by Evonik Corporation, B-8871, B-8481, and B-8404. In this regard, polysiloxane ether systems having a molecular weight of 1,000 to 10,000 g / mol, more preferably 3,000 to 7,000 g / mol, may be used to favor closed cell formation. In particular, when water is used as the blowing agent, the use of silicone-based surfactants may be preferred.

The amount of the surfactant used may be in the range of 0.1 to 5.0 parts by weight, more preferably 0.5 to 3.0 parts by weight based on 100 parts by weight of the polyol.

In addition to the present invention, chain extenders, flame retardants, colorants, fillers, internal mold release agents, antistatic agents, antimicrobial agents, cell control agents, reaction inhibitors and the like may be appropriately added or reacted.

The chain extenders include low molecular weight polyhydric alcohols (e.g., ethylene glycol, 1,4-butanediol, glycerin, etc.), low molecular weight amine polyols (dieethanolamine, triethanolamine, etc.), polyamines (ethylenediamine, xylene Diamines, etc.) can be used.

The flame retardant is a component used to impart flame retardancy to the polyurethane foam to be produced finally, may be used in an appropriate amount in consideration of the required level if necessary. For example, phosphorus flame retardants (TCPP, TCEP, Phosphorus ester, etc.) may be used.

Other additive ingredients may also be selected by the type and amount used in the art.

The urethane reactions of the present invention may utilize conventional foam forming principles and related devices, and in particular, it may be desirable to form a closed cell foam to conform to automotive materials. In one example, the polyols, isocyanates and additives can be contacted and mixed and then expanded / cured in the form of cell-like polymers (specifically, the foaming step). As another example, the polyol and the additive may be mixed first, followed by mixing with an isocyanate for the reaction to perform an expansion / curing reaction.

It is also possible to use a foaming machine for foam formation, the foaming temperature can range from 15 to 30 ° C. (more preferably 18 to 28 ° C.) and the foaming pressure from 90 to 160 bar (more preferably 110 to 140 bar). have. Further, in one embodiment, the temperature of the mold is 25 to 65 ° C. (more preferably 35 to 60 ° C.) or room temperature (20 to 25 ° C.), and the demolding time is 4 to 60 so as to be particularly suitable for automobile rigid urethane foams. The minutes (more preferably 2 to 40 minutes) and the aging time can be adjusted to 10 to 72 hours (more preferably 10 to 48 hours).

The urethane foam for vehicle shock absorbing device, package tray and undercover manufactured according to the embodiment of the present invention injects a polyurethane raw material into a molding mold of a predetermined shape to produce a molding having a desired shape.

In addition, the urethane foam for the headliner is foamed in the form of a block (block), aged after a certain period of time to produce a molded article of the desired shape.

The composition for preparing the rigid polyurethane foam (polyol and other additives) has a viscosity (20 ° C) of 200 to 2500 cps, specific gravity (20 ° C) of 1.00 to 1.30, cream time of 5 to 65 sec, The gel time may be 40 to 200 sec, and the free density (FD) may be 20 to 120 kg / m 3. At this time, the viscosity and specific gravity of the composition for producing a rigid polyurethane foam according to the present invention is the physical property of the mixture isocyanate is excluded in the composition for producing a rigid polyurethane foam.

The composition for producing rigid polyurethane foam has different physical properties required according to the field applied to automobiles.

For example, the composition of the rigid polyurethane foam for a vehicle shock absorber has a viscosity (20 ℃) of 900 to 2500 cps, specific gravity (20 ℃) of 1.0 to 1.20, cream time (10 to 20 sec) and Gel time (gel time) is 40 to 70 sec, free density (F / D) may be 30 to 60 kg / ㎥.

For example, the composition of the rigid polyurethane foam for package tray and undercover has a viscosity (20 ° C.) of 800 to 2500 cps, a specific gravity (20 ° C.) of 1.0 to 1.20, and a cream time of 30 to 60 sec. Gel time (gel time) is 50 to 100 sec, free density (F / D) may be 70 to 100 kg / ㎥.

In one example, the composition of the rigid polyurethane foam for headliner has a viscosity (20 ℃) of 900 to 1500 cps, specific gravity (20 ℃) of 1.0 to 1.20, cream time (30 to 60 sec), gel Gel time is 150 to 200 sec, free density (F / D) may be 25 to 40 kg / ㎥.

Further, the rigid polyurethane foam of the present invention has a core density of 150 kg / m 3 or less; Compressive strength is at least 2.0 kg / cm ² ; Flexural strength is at least 1.5 kg / cm ² ; Tensile strength is at least 3.0 kg / cm ² ; Elongation is at least 40%; Dimensional stability is -2.0% or less at 30 ° C and 24hr, and 3.0% or less at 70 ° C and 24hr; Flame retardancy may indicate self-extinguishing.

Such rigid polyurethane foams have different required physical properties (specifications) according to the field of application to automobiles.

For example, the rigid polyurethane foam for a vehicle shock absorber has a core density of 70 kg / m 3 or less; Compressive strength is at least 4.0 kg / cm ² ; Flexural strength is at least 7.0 kg / cm ² ; Independent bubble ratio is 10% or less; Dimensional stability is -2.0% or less at 30 ° C and 24hr, 3.0% or less at 70 ° C and 24hr; Flame retardancy may indicate self-extinguishing.

In one example, the rigid polyurethane foam for package tray and undercover has a core density of 150 kg / m 3 or less; Compressive strength is at least 6.0 kg / cm ² ; Flexural strength is at least 10.0 kg / cm ² ; Independent bubble ratio of 90% or more; Dimensional stability is -2.0% or less at 30 ° C and 24hr, 3.0% or less at 70 ° C and 24hr; Flame retardancy may indicate self-extinguishing.

In one example, the rigid polyurethane foam for header liner has a core density of 40 kg / m 3 or less; Compressive strength is at least 1.0 kg / cm ² ; Flexural strength is at least 1.5 kg / cm ² ; Tensile strength is at least 3.0 kg / cm ² ; Elongation is at least 40%; Flame retardancy may indicate self-extinguishing.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it is apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. Naturally, such modifications and variations fall within the scope of the appended claims.

1) 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; about 968.7; Cas. No .: 8001-22-7

Castor oil: molecular weight (Mw) 946.7 from Sigma-Aldrich; Functional group: 2.7; Cas No .: 8001-79-4

2) polyfunctional active hydrogen-containing compounds

Sugar: molecular weight (Mw) 342.3 from Sigma-Aldrich; Functional group: 8; Cas No .: 57-50-1

Sorbitol: molecular weight (Mw) 178.1 from Sigma-Aldrich; Functional group: 6

Pentaerythritol: molecular weight (Mw) 136.2 from Sigma-Aldrich; Functional group: tetravalent

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

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

Triethanolamine: Molecular weight (Mw) of Sigma-Aldrich Co., Ltd. 149.2

Ethylenediamine: Molecular weight (Mw) of Sigma-Aldrich 60.1

3) Exchange catalyst in the production of polyols

KOH catalyst: KOH solution of Sigma-Aldrich (concentration: 45% solution, Cas.No .: 1310-58-3) Molecular weight (Mw) 56.1

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

4) alkylene oxide

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

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

5) isocyanate

Cosmonate M-200 (compound name: p-MDI, functional group: 2.7, NCO%: 31) manufactured by KUMHO MITSUI CHEMICAL Co.,

6) urethane catalyst

Amine catalysts: Polyact5 (Pentamethyldiethylenetriamine), Polyact8 (Dimethylcyclohexylamine) and KPX Chemical Co., Ltd. TEDA-33P (Triethylenediamine / DPG)

7) surfactants

Silicone surfactants: product names B-8462, B-8871, B-8481 and B-8404 from Evonik

8) foaming agent

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

9) Flame Retardant

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

Polyol manufacturers

Example 1

Sugar, palm oil and KOH (45 wt%) 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.

The catalyst adsorbent and water were added to the reaction product thus obtained, stirred at about 80 캜 for about 1 hour, and then filtered to synthesize a bio-polyol. The composition ratio of the reactants is shown in Table 4 below.

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.

Classification (parts by weight) Example 1 Example 2 Example 3 Natural oil palm oil 200 - - Soybean oil - 200 - Castor oil - - 200 Polyfunctional active hydrogen-containing compounds Sugar 300 300 300 Sorbitol - - - Pentaerythritol - - - glycerin - - - o-TDA - - - Triethanolamine - - - Ethylenediamine - - - Water (reaction) 10 10 - catalyst KOH (45%) 3.5 3.5 3.5 Alkylene oxide PO 488 488 498 Water (treatment) handful handful handful Catalyst adsorbent Magnesium silicate handful handful handful Sum 1001.5 1001.5 1001.5

Examples 4-9

In this embodiment, palm oil was used as a natural oil, and the biopolyol was synthesized in substantially the same manner as in Example 1 according to the composition ratios shown in Table 5 by changing the type of the polyfunctional active hydrogen-containing compound.

Classification (parts by weight) Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Natural oil palm oil 200 200 200 200 200 200 Polyfunctional active hydrogen-containing compounds Sugar 300 - - - - - Sorbitol - 240 - - - - Pentaerythritol - - 280 - - - glycerin - - - - - - o-TDA - - - 275 - - Triethanolamine - - - - 300 - Ethylenediamine - - - - - 150 Water (reaction) 10 - - - 20 - catalyst KOH (45%) 3.5 3.5 3.5 3.5 3.5 3.5 Alkylene oxide PO 488 560 520 520 480 650 Water (treatment) handful handful handful handful handful handful Catalyst adsorbent Magnesium silicate handful handful handful handful handful handful Sum 1001.5 1003.5 1003.5 998.5 1003.5 1003.5

Examples 10 to 13

In this example, castor oil was used as a natural oil, and the biopolyol was synthesized in substantially the same manner as in Example 1 according to the composition ratio shown in Table 6 by changing the type of the polyfunctional active hydrogen-containing compound.

Classification (parts by weight) Example 10 Example 11 Example 12 Example 13 Natural oil Castor oil 200 200 200 200 Polyfunctional active hydrogen-containing compounds Sugar 300 - - - Sorbitol - 230 - - Pentaerythritol - - 260 - glycerin - - - 230 Water (reaction) - - - - catalyst KOH (45%) 3.5 3.5 3.5 3.5 Alkylene oxide PO 498 570 540 570 Water (treatment) handful handful handful handful Catalyst Absorber Magnesium silicate handful handful handful handful Sum 1001.5 1003.5 1003.5 1003.5

Examples 14-16

In this example, palm oil was used as a natural oil, and biopolyols were synthesized in substantially the same manner as in Example 1 according to the composition ratios shown in Table 7 by changing the ratio between the plurality of multifunctional active hydrogen-containing compounds.

Classification (parts by weight) Example 14 Example 15 Example 16 Natural oil palm oil 200 250 300 Polyfunctional active hydrogen-containing compounds Sugar 300 200 150 glycerin - 100 100 Water (reaction) 10 - 10 catalyst KOH (45%) 3.5 3.5 3.5 Alkylene oxide PO 488 450 440 Water (treatment) handful handful handful Catalyst Absorber Magnesium silicate handful handful handful Sum 1001.5 1003.5 1003.5

Examples 17-20

In this example, the biopolyol was synthesized in substantially the same manner as in Example 1 according to the composition ratios shown in Table 8 by changing the type and ratio of alkylene oxide and the type of catalyst.

Classification (parts by weight) Example 17 Example 18 Example 19 Example 20 Natural oil palm oil 200 200 200 200 Polyfunctional active hydrogen-containing compounds Sugar 300 300 300 300 Water (reaction) 10 10 10 10 catalyst KOH (45%) 3.5 3.5 - - Dimethyllaulamine - - 10.0 - Dimethylpalmitylamine - - - 10.0 Alkylene oxide PO 488 300 480 480 EO - 190 - - Water (treatment) handful handful - - Catalyst Absorber Magnesium silicate handful handful - - Sum 1001.5 1003.5 1000 1000

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, 176.7 parts by weight of phthalic anhydride and 0.1 parts by weight of TPT (tetraisopropyltitanate) were added for the ester reaction, and the reaction was carried out 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 while varying the addition amount of alkylene oxide, and the respective reactant compositions are shown in Table 9 below.

Classification (parts by weight) Example 21 Comparative Example 2 Natural oil palm oil 105 550 Polyfunctional active hydrogen-containing compounds Sugar 150 150 glycerin 100 100 (reaction) 10 10 catalyst KOH (45%) 3.5 3.5 Alkylene oxide PO 635 190 Water (treatment) handful handful Catalyst Absorber Magnesium silicate handful handful Sum 1003.5 1003.5

Test Example

The physical properties of the polyol prepared in the above Examples are measured in the following manners and are shown in Tables 10 to 15.

1) Color : Measured by Gardner Color test method.

2) 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 (200 mL), air cooling tube (30 cm), pipette (5 mL, 10 mL), burette (50 mL) and oil bath

<Measurement method>

(1) In the Erlenmeyer flask, the polyol synthesized in Examples 1 to 20 and 5 mL of acetic anhydride-pyridine mixed solution were added and shaken five times or more, followed by reaction with an oil bath for 1 hour and 30 minutes.

(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 0.5 N KOH standard solution by adding 3 to 4 drops of phenolphthalein indicator.

The hydroxyl value was calculated by Equation 1 below.

S: amount of sample

B: 0.5 N 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

3) viscosity

The measurement was carried out at 25 ° C. using DV-III from Brookfield.

4) functional group

The functional group of the prepared bio polyol was calculated by the method of Equation 2 using the number of moles and functional groups of the polyfunctional active hydrogen-containing compound and natural oil.

-A (a ₁ + a ₂ + a ₃ + a ₄ + ... + a _n ): sum of the polyfunctional active hydrogen-containing compound and the number of moles of natural oil

-a _n : moles of each of the polyfunctional active hydrogen-containing compound and natural oil

f _n : number of functional groups of each compound containing polyfunctional active hydrogen and natural oil

5) storage stability

The synthesized polyol was put into a 500 ml sample bottle and evaluated by checking the presence of layer separation for 100 days in an oven at 30 ° C.

(Layer separation: ○, no layer separation: ×, slight turbidity and instability: △)

division Example 1 Example 2 Example 3 color Yellow liquid Yellow liquid 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 Yellow liquid Yellow liquid Red 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 Yellow liquid Yellow liquid 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 Yellow liquid 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 Yellow liquid Yellow liquid Yellow liquid Hydroxyl value
(mg KOH / g) 440 420 435 430 Viscosity (25 ℃) 6,500 6,380 6,350 6,350 Functional group About 6.5 About 6.5 About 6.5 About 6.5 Storage stability × × × ×

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 4.2 Storage stability × × △ △

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.

Rigid Polyurethane Foam Manufacturing

Examples 22-23

While varying the amount of the bio polyol synthesized in Example 15, according to the composition shown in Table 16 and the manufacturing method of a conventional automotive foam was prepared a rigid polyurethane foam for impact absorption (Impact absorption).

In this case, a mechanical foaming machine was used for foaming to form a foam. In manufacturing foam, the urethane foaming temperature between polyol and isocyanate is about 20 ° C., foaming pressure is about 120 bar, mold temperature is about 50 ° C., and demolding time is about 5 Adjusted to minutes.

Comparative Examples 3 to 4

Using a conventional polyol and a bio polyol synthesized from Comparative Example 1, a rigid polyurethane foam for impact absorption was prepared in the same manner as in Example 22 according to the composition shown in Table 16 below.

Classification (parts by weight) Example 22 Example 23 Comparative Example 3 Comparative Example 4 Polyol A 40.0 27.0 53.0 40.0 Polyol B 35.0 23.0 47.0 35.0 Biopolyols according to Comparative Example 1 - - - 25.0 Biopolyols according to Example 15 25.0 50.0 - - Flame Retardant (TCPP) 15.0 15.0 15.0 15.0 water 3.0 3.0 3.0 3.0 Surfactants 2.0 2.0 2.0 2.0 Amine Catalyst A 2.0 1.9 2.15 About 2.1 Amine Catalyst B 0.30 0.25 0.30 0.35 approx. Sum 122.3 122.2 122.5 122.5 Viscosity (20 ℃) 1450 1350 1550 2400 Specific gravity (20 ℃) 1.091 1.091 1.090 1.092 p-MDI 182.5 184.3 180.6 180.6 -Polyol A: Polyol, Sucrose base ether polyol for vehicle shock absorber of KPX Chemical Co., Ltd.
-Polyol B: Polyol, Glycerine base ether polyol for vehicle shock absorber of KPX Chemical Co., Ltd.
Amine catalyst A: Polycat8
Amine catalyst B: Polycat5

Examples 24-25

While varying the amount of the bio polyol synthesized in Example 15, the rigid polyurethane foam for a vehicle package tray and under cover according to the composition shown in Table 17 and the manufacturing method of a typical automotive foam Prepared.

In this case, a mechanical foaming machine was used for foaming to form a foam. In the manufacture of foam, the urethane foaming temperature between polyol and isocyanate is about 20 ° C, foaming pressure is about 120bar, mold temperature is about 40 ° C, and demolding time is about 5 Adjusted to minutes.

Comparative Examples 5 to 6

Using a conventional polyol and a bio polyol synthesized from Comparative Example 1, a rigid polyurethane foam for a vehicle package tray and under cover was prepared in the same manner as in Example 22 according to the composition shown in Table 17 below. Prepared.

Classification (parts by weight) Example 24 Example 25 Comparative Example 5 Comparative Example 6 Polyol C 35.0 20.0 50.0 35.0 Polyol D 35.0 20.0 50.0 35.0 Biopolyols according to Comparative Example 1 30.0 Biopolyols according to Example 15 30.0 60.0 Flame Retardant (TCPP) 15.0 15.0 15.0 15.0 water 1.5 1.5 1.5 1.5 Surfactants 1.0 1.0 1.0 1.0 Amine Catalyst A 0.20 0.15 0.20 0.23 approx. Amine Catalyst C 2.00 1.95 2.10 About 2.20 Sum 119.7 119.6 119.7 119.9 Viscosity (20 ℃) 1020 950 1100 2200 Specific gravity (20 ℃) 1.098 1.099 1.098 1.11 p-MDI 167.3 165.6 170.0 163.3 -Polyol C: KPX Chemical's vehicle package tray and underbucker polyol, Sorbitol base ether polyol
-Polyol D: KPX Chemical's vehicle package tray and underbucker polyol, Glycerine base ether polyol
Amine catalyst A: Polycat8
-Amine Catalyst C: TEDA-33P, a catalyst for KPX Chemical Co., Ltd.

Examples 26-27

While varying the amount of the biopolyol synthesized in Example 15, according to the composition shown in Table 18 and the manufacturing method of a conventional automotive foam was prepared a head liner (hard liner) rigid polyurethane foam.

In this case, a mechanical foaming machine was used for foaming to form a foam. In the manufacture of foam, the urethane foaming temperature between polyol and isocyanate is about 20 ° C., the foaming pressure is about 120 bar, and it is manufactured in the form of block foam at room temperature, and Aging time was adjusted to about 24 hours.

Comparative Examples 7 to 8

A head liner rigid polyurethane foam was prepared in the same manner as in Example 22 using the conventional polyol and the bio polyol synthesized from Comparative Example 1.

division Example 26 Example 27 Comparative Example 7 Comparative Example 8 Polyol E 22.5 15.0 30.0 22.5 Polyol F 30.0 20.0 40.0 30.0 Polyol G 22.5 15.0 30.0 22.5 Biopolyols according to Comparative Example 1 - - - 25.0 Biopolyols according to Example 15 25.0 50.0 - - water 4.0 4.15 4.0 4.0 Surfactants 0.50 0.6 0.50 0.50 Amine Catalyst D 0.55 0.55 0.45 0.50 Sum 105.0 105.1 104.95 105.0 p-MDI 174.3 188.2 168.0 168.0 Viscosity (20 ℃) 880 865 895 1450 Specific gravity (20 ℃) 1.06 1.06 1.06 1.06 -Polyol E: Polyol for headliner, DPG base ether polyol of KPX Chemical Co., Ltd.
-Polyol F: Polyol for headliner, Glycerine base ether polyol of KPX Chemical Co., Ltd.
-Polyol G: Polyol for headliner, TPA + DEG base ester polyol of KPX Chemical Co., Ltd.
-Amine Catalyst D: Head Liner Catalyst of KPX Chemical Co., Ltd., DABCO T-12

Test Example

The physical properties of the prepared rigid polyurethane foam was measured in the following manner, and the results are shown in Tables 19 to 21.

1. Viscosity : measured at 20 ° C using DV-III of Brookfield.

2. Specific gravity : It was measured at 20 ℃ using Anton Paar's DMA4500.

3. Cream time (CT) : After foaming, bubbles were generated and the color of the mixed solution changed from dark brown to cream color, and the time when the mixed solution began to rise was measured.

4. Gel time (GT) : The time at which the fibers were formed was measured at the time when the urethane, urea, and allophanate reactions occurred.

5. Tack free time (TFT) : The time taken for the surface of the foam to lose viscosity after foaming was measured.

6. Free density (F / D) : measured according to ASTM D-3574.

7. Core density : measured according to ASTM 1622.

8. Independent bubble ratio was measured using ASTM D28566.

9. Flexural strength : measured according to ASTM C 203.

10. Flame retardancy : measured according to ASTM D 1692.

11. Compressive strength : measured according to ASTM D 1621.

12. Dimensional stability : measured according to ASTM D 2126.

13. Moldability : The surface of the manufactured rigid polyurethane foam was visually confirmed and evaluated by the following method.

[Assessment Methods]

1 5 10

Excellent <---------------- Normal -------------------> Bad

Item Example 22 Example 23 Comparative Example 3 Comparative Example 4 Bio polyol content%
(Based on polyols) 25 50 0 25 Isocyanate Index 130.0 128.0 132.0 135.0 Reactivity (CT / GT, sec) 16/52 16/53 15/52 16 / 52.5 Core density (kg / m ³ ) 65.7 65.3 65.1 65.9 Free density (kg / m ³ ) 55.2 55.5 55.3 56.1 Independent Bubble Rate (%) 7.2 7.0 6.9 7.3 Compressive strength (horizontal / vertical, kg / cm ² ) 5.39 / 4.41 5.31 / 4.30 5.41 / 4.48 4.65 / 3.83 Flexural Strength (kg / cm ² ) 8.27 8.12 8.22 6.89 Dimensional stability (△ V%) -30 ℃, 24hr -1.08 -1.00 -1.21 -1.30 70 ℃, 95% RH, 24hr 2.38 2.33 2.35 4.36 Flammability Self-esteem Self-esteem Self-esteem Self-esteem Formability 3 4 2 9

Item Example 24 Example 25 Comparative Example 5 Comparative Example 6 Bio polyol content%
(Based on polyols) 25 50 0 25 Isocyanate Index 120.0 123.0 118.0 125.0 Reactivity (CT / GT, sec) 55/82 54/83 55/80 53/86 Core density (kg / m ³ ) 110.1 111.0 110.5 112.0 Free density (kg / m ³ ) 89.5 89.1 88.9 89.5 Independent Bubble Rate (%) 92.1 93.0 92.5 89.8 Compressive strength (horizontal / vertical, kg / cm ² ) 7.01 / 5.31 6.90 / 5.20 6.98 / 5.32 6.55 / 4.93 Flexural Strength (kg / cm ² ) 12.12 12.04 12.10 11.85 Dimensional stability (△ V%) -30 ℃, 24hr -0.85 -0.90 -0.98 -1.20 70 ℃, 95% RH, 24hr 1.69 1.63 1.74 1.88 Flammability Self-esteem Self-esteem Self-esteem Self-esteem Formability 2 3 2 9

Item Example 26 Example 27 Comparative Example 7 Comparative Example 8 Bio polyol content%
(Based on polyols) 25 50 0 25 Isocyanate Index 110.0 108.3 115.1 111.7 Reactivity (CT / GT, sec) 45/175 43/177 45/172 45/173 Core density (kg / m ³ ) 33.0 32.9 33.5 33.3 Free density (kg / m ³ ) 31.5 32.1 31.6 31.8 Tensile Strength (kg / cm ² ) 3.65 3.30 3.55 2.25 Elongation (%) 45.0 40.2 47.0 33.1 Compressive strength (kg / cm ² ) 1.31 1.35 1.20 1.11 Flexural Strength (kg / cm ² ) 1.97 1.95 1.90 1.55 Flammability Self-esteem Self-esteem Self-esteem Self-esteem Formability 4 5 2 10

Claims (10)

10 to 60% by weight of natural oil, 10 to 60% by weight of polyfunctional active hydrogen-containing compound, 0.1 to 1.5% by weight of catalyst and 20 to 70% by weight of alkylene oxide,
Polyols comprising a biopolyol having a functional number of 3 or more, a KOH / g hydroxyl value of 200 to 600 mg, and a viscosity (25 ° C.) of 2,000 to 25,000 cps; And isocyanates,
The core density is 150 kg / m 3 or less; Compressive strength is at least 2.0 kg / cm ² ; Flexural strength is at least 1.5 kg / cm ² ; Tensile strength is at least 3.0 kg / cm ² ; Elongation is at least 40%; Dimensional stability is -2.0% or less at 30 ° C and 24hr, 3.0% or less at 70 ° C and 24hr; Rigid plastic foam for automobiles with flame retardancy.
The method according to claim 1, wherein the polyfunctional active hydrogen compound is a polyfunctional alcohol, polyfunctional amine or a mixture thereof,
The polyfunctional alcohol is ethylene glycol, diethylene glycol, glycerin, trimethanol propane, pentaerythritol, dipentaerythritol, alphamethylglucoside, xylitol, sorbitol, sugar or mixtures thereof,
Wherein said polyfunctional amine is ethylenediamine, diethylenetriamine, triethanolamine, ortho-toluenediamine, diphenylmethanediamine, diethanol amine or mixtures thereof.
The hard automobile according to 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. Polyurethane foam.
The rigid polyurethane foam for automobile according to claim 1, wherein the alkylene oxide is ethylene oxide, propylene oxide or a mixture thereof.
The method according to claim 1, wherein the bio polyol is
a) exchanging a natural oil with a polyfunctional active hydrogen-containing compound in the presence of a catalyst; And b) addition reaction of alkylene oxide to the product of the exchange reaction.
The method of claim 5, wherein the bio polyol further comprises c) removing the catalyst from the addition reaction product of the alkylene oxide compound,
Wherein step c) is carried out by adding a catalyst adsorbent and water and stirring, followed by filtration.
The rigid polyurethane foam for automobile according to claim 1, wherein the bio polyol is included in an amount of 10 to 60 parts by weight based on 100 parts by weight of the polyol.
The vehicle of claim 1, wherein the isocyanate has a functional number in the range of 2.7 to 3.0, an NCO% value in the range of 25 to 35, an isocyanate index in the range of 90 to 180, and includes polymeric MDI (diphenylmethane diisocyanate). Rigid polyurethane foam.
The rigid polyurethane foam for automobile according to claim 1, comprising 0.1 to 7.0 parts by weight of urethane catalyst, 0.1 to 15 parts by weight of blowing agent and 0.1 to 5.0 parts by weight of surfactant.
The method of claim 1, wherein the rigid polyurethane foam has a viscosity (20 ℃) of 200 to 2500 cps, specific gravity (20 ℃) of 1.00 to 1.30, cream time (5 to 65 sec), gel time ( Gel time) is 40 to 200 sec, the rigid polyurethane foam for automobiles made of a composition for producing a rigid polyurethane foam having a free density (FD) of 20 to 120 kg / ㎥.