KR20140070695A - Rigid Polyurethane Foams for LNG Ship-Insulator Containing Biopolyol - Google Patents

Abstract

The present invention relates to hard polyurethane foam for an LNG carrier insulator containing biopolyol, and more specifically, to hard polyurethane foam for an LNG insulator which contains polyol comprising biopolyol containing natural oil, a multifunctional active hydrogen-containing compound, a catalyst, and oxidized alkylene, and having three or more functional groups, 200-600 mg of hydroxyl value of KOH/g, and 2,000-25,000 cps of viscosity (25°C), thereby maintaining physical properties as an LNG carrier insulator, such as excellent compressive strength, room/low temperature tensile strength, heat conductivity, impregnation and impact resistance of glass fibers, etc. and being environmentally friendly and recyclable.

Description

TECHNICAL FIELD [0001] The present invention relates to a rigid polyurethane foam for an LNG insulator containing a bio-polyol,

The present invention relates to a rigid polyurethane foam containing a biopolyol and capable of maintaining physical properties as an LNG insulator.

Polyols, which are essential components of polyurethane, are usually produced from petroleum-based raw materials, and polyether polyols and polyester polyols are especially known as the most popular polyols. The components of such polyols have a significant effect on the properties of the polyurethane or polyurethane foam to be produced.

Generally, a polyol having a high molecular weight and a low functionality is used for producing a soft urethane foam, and a polyol having a small molecular weight and a high number of functional groups is used for producing a rigid urethane foam.

Specifically, the molecular weight of the polyol used in the flexible polyurethane foam is greater than about 1,000. The polyol used in the rigid polyurethane foam has a molecular weight of about 200 to 4,000 and has a modulus of elasticity of at least about 100,000 psi (23 DEG C), a glass transition temperature of 20 DEG C or higher, an elongation of not more than 10% .

On the other hand, due to various reasons such as accelerated depletion of petroleum resources, reduction of greenhouse gas due to climate change, increase of raw material price, increase in need for renewable raw materials, etc., in the urethane field, the regeneration of polyol produced from petroleum- Has been suggested as a substitute for polyol.

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

At present, the production of polyols from natural oils, in particular vegetable oils, is carried out by epoxidation-ring opening reactions (for example, by incorporating active oxygen into the molecular structure using hydrogen peroxide, Method for carrying out the ring opening reaction; Kandanarachchi et al ., J. Mol. Catal. A: Chem 2002, 184, 65), hydroformylation reaction (reaction of synthetic gas 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 (ozone decomposition of natural oil directly to prepare polyol having a hydroxyl group at the terminal position); And Petrovic et al ., Biomacromolecules 2005, 6, 713), esterification reactions (Vilar et al . , 2002), and the like are known.

Although it has been reported that the polyurethane foam using the bio-polyol obtained from such a natural oil can secure properties comparable to the polyurethane foam produced from petroleum-based products, the bio-polyol presents a problem such as lowered reactivity. One of the causes is the presence of secondary alcohols and the presence of a large number of nonfunctional branches.

On the other hand, polyurethane foam, especially rigid polyurethane foam, is used in various fields, and there is a difference in physical properties required depending on the application field.

When used as a thermal insulation material for LNG ships, it is known that compressive strength, room temperature and low temperature tensile strength, impact resistance and thermal conductivity are important factors.

However, since the rigid polyurethane foam to which the conventional bio-polyol is applied has low compressive strength, high and low temperature tensile strength, and low impact resistance due to low bio-polyol storage stability and functional groups, the rigid polyurethane foam used as an LNG insulator There was a limit to apply as raw material.

In addition, the bio-polyol has a high risk of degrading the storage stability due to the nature of the natural oil, so that there is a problem that problems such as reactivity and handling during hard polyurethane foam production may occur. That is, the conventional bio-polyol only shows the possibility of application of relatively expensive castor oil or soybean oil mainly used as a food resource.

Therefore, there is a need for a rigid polyurethane foam for LNG insulator using a bio-polyol that can provide equivalent or better physical properties as compared with a polyurethane foam of an LNG insulator using a petroleum-based polyol.

An object of the present invention is to provide a rigid polyurethane foam for an LNG insulator which can contain physical properties as a heat insulating material for LNG, such as compressive strength, room temperature and low temperature tensile strength, impact resistance and thermal conductivity.

The present inventors have found that the use of a bio-polyol containing a polyfunctional active hydrogen-containing compound and an alkylene oxide in a natural oil to lower the number of secondary alcohols and a large number of non-functional branches present in the bio- It was found that the physical properties of the LNG insulator such as compressive strength, room temperature and low temperature tensile strength, impact resistance, thermal conductivity and the like can be maintained.

Accordingly, the present invention relates to a process for the preparation of a polyurethane foam comprising 10 to 60% by weight of a natural oil, 10 to 60% by weight of a polyfunctional active hydrogen-containing compound, 0.1 to 1.5% by weight of a catalyst and 20 to 70% by weight of an alkylene oxide, A polyol having a hydroxyl value of KOH / g of 200 to 600 mg and a viscosity (25 ° C) of 2,000 to 25,000 cps; And an isocyanate-containing rigid polyurethane foam for an LNG insulator.

Wherein the polyfunctional active hydrogen compound is a polyfunctional alcohol, a polyfunctional amine or a mixture thereof, wherein the polyfunctional alcohol is at least one selected from the group consisting of ethylene glycol, diethylene glycol, glycerin, trimethanolpropane, pentaerythritol, dipentaerythritol, alphamethyl glucoside , Xylitol, sorbitol, sugar or a mixture thereof, and the polyfunctional amine may be ethylenediamine, diethylenetriamine, triethanolamine, ortho-toluenediamine, diphenylmethanediamine, diethanolamine or a mixture thereof.

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

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

The biopolyol may be prepared by a) exchanging a natural oil with a polyfunctional active hydrogen-containing compound in the presence of a catalyst; And b) subjecting the product of the exchange reaction to an addition reaction with alkylene oxide.

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

The biopolyol may be contained in an amount of 10 parts by weight or less based on 100 parts by weight of the polyol.

The isocyanate may include polymeric MDI (diphenylmethane diisocyanate), the number of functional groups being in the range of 2.7 to 3.0, the NCO% in the range of 25 to 35, and the isocyanate index in the range of 90 to 140.

5 to 50 parts by weight of a fiber reinforcing material, 0.05 to 4 parts by weight of a urethane catalyst, 0 to 20 parts by weight of a foaming agent, 0.1 to 5.0 parts by weight of a surfactant and 0 to 15 parts by weight of a flame retardant may be contained relative to 100 parts by weight of the polyol.

The rigid polyurethane foam has a closed cell content of 90% or more, a water flow density of 4.0 g / m 2 / h or less, a thermal conductivity of 0.0300 kcal / mh ° C or less, an apparent density of 100 to 140 kg / Lt; / RTI >

The rigid polyurethane foam has a compressive strength (Z) of 1.00 MPa or more and a modulus of 40 MPa or more; The tensile strength (X, Y) at 2.degree. C. is 2.00 MPa or more and 90 MPa <modulus <170 MPa, and the strength at -170 DEG C is 2.00 MPa or more and 150 MPa or less <modulus <250 MPa.

The rigid polyurethane foam of the present invention has an advantage that the physical properties of the LNG insulator such as compressive strength, normal temperature and low temperature tensile strength, impact resistance, and thermal conductivity can be maintained by using the bio polyol.

The hard polyurethane foam of the present invention is advantageous in that it is eco-friendly and can be regenerated by using a biopolyol.

In addition, the rigid polyurethane foam of the present invention can be usefully used as a heat insulating material for storing and liquefying low-temperature liquefied gas such as an LNG carrier.

The present invention relates to a rigid polyurethane foam containing a biopolyol and capable of maintaining physical properties as an LNG insulator.

Hereinafter, the present invention will be described in detail.

The terms used in this specification can be defined as follows.

"Polyol" means an organic molecule having a hydroxy group per molecule with an average greater than 1.0.

"Polyurethane foam" refers to a cellular foam product obtained by reacting a di- or polyisocyanate with an isocyanate-reactive hydrogen-containing compound (polyol, amino alcohol and / or polyamine) and a blowing agent . &Lt; / RTI &gt;

"Natural oil" is a concept involving animal and vegetable oils, preferably vegetable oils. Examples of animal oils may include fish oil, bovine oil, lard, sheep oil, and the like, and mixtures thereof. Examples of the vegetable oil include vegetable oils such as sunflower seed oil, canola oil, palm oil, corn oil, cottonseed oil, plain oil, flaxseed oil, safflower oil, oats oil, olive oil, palm oil, peanut oil, rape oil, , Soybean oil, castor oil and the like, more typically, soybean oil, castor oil, palm oil, etc., and mixtures thereof. However, the present invention is not limited to the above listed kinds.

For example, in the case of pizza hemp, it is the oil obtained by squeezing the seed of castor bean (Rucinus communis). The seed contains about 45% of this oil and has a higher oil content percentage than other seeds. The fat is made entirely of triester (triglyceride) structure of fatty acid and glycerin. Castor induction Similarly, it is characterized in that about 90% of the triesters or fatty acids of glycerin are composed of ricinoleic acid. The remainder contains oleic acid, linoleic acid, and the like.

The compositional characteristics of typical vegetable oils are shown in Table 1 below.

Olein Linoleine Linolenine Ricinoleine stearin Palmitin 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 oil 13.1 77.7 - - 2.4 6.5 0.3 Palm oil 45.2 7.9 - - 3.6 40.8 2.5

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

"Hydroxyl number" is an index indicating the amount of reactive hydroxyl groups capable of participating in the reaction, and means the number of mg of KOH necessary to neutralize the acetic acid bonded to the acetyl compound obtained from 1 g of polyol (unit: mg KOH / g).

The term "closed cell foam" refers to a foam in which cells that are not connected by open passages occupy a large proportion, preferably cells that are not open in the cell, independent cells (meaning the percentage of cells closed in the cell ) Is at least about 88%, preferably about 90%, but these figures should be understood by way of example.

"NCO%" means the wt% of NCO contained in the isocyanate sample.

"Isocyanate index" means the amount of isocyanate used relative to the ratio of the number of hydroxyl groups (-OH) present in the polyol to the number of equivalents of isocyanate (-NCO), ie, the theoretical equivalent. Thus, an isocyanate index of less than 100 implies the presence of an excess of polyol, while an isocyanate index of greater than 100 means that an excess of isocyanate is present.

"Acid number" means the number of mg of KOH required to neutralize the acid present in 1 g of the polyol sample (unit: mg KOH / g).

The rigid polyurethane foam for LNG insulator of the present invention comprises 10 to 60 wt% of natural oil, 10 to 60 wt% of polyfunctional active hydrogen-containing compound, 0.1 to 1.5 wt% of catalyst, and 20 to 70 wt% of alkylene oxide A polyol including a bio-polyol having a functional group number of 3 or more, a hydroxyl value of KOH / g of 200 to 600 mg and a viscosity (25 ° C) of 2,000 to 25,000 cps; And isocyanates.

The natural oils are as defined above and may be used in an amount of 10 to 60% by weight, preferably 15 to 40% by weight. If the content is less than 10% by weight, the amount of the other components is excessively large. Thus, the polyol thus prepared can not be regarded as a bio-polyol. When the content exceeds 60% by weight, the number of functional groups of the bio- Urethane foam may deteriorate physical properties such as storage stability.

The biopolyol may be prepared by a) exchanging a natural oil with a polyfunctional active hydrogen-containing compound in the presence of a catalyst; And b) subjecting the product of the exchange reaction to an addition reaction with alkylene oxide.

Examples of the polyfunctional alcohols include ethylene glycol, diethylene glycol, glycerine, trimethanolpropane, pentaerythritol, dipentaerythritol, Α-methylglucoside, xylitol, sorbitol, sucrose, and the like, which can be used singly or in combination. Specifically, the number of functional groups of the polyfunctional alcohol is shown in Table 2 below.

Polyfunctional alcohol Functionality Carbohydrate system Sugar 8 Sorbitol 6 Almamethylglycoside 4 Aliphatic system Glycols 2 glycerin 3 Trimethanolpropane 3 Pentaerythritol 4

Examples of the polyfunctional amine include ethylenediamine, diethylene triamine, triethanolamine, ortho-toluene diamine, diphenylmethanediamine (diphenylmethanediamine), diphenylmethanediamine ), Diethanol amine, and the like, which may be used alone or in combination. Specifically, 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 a polyfunctional active hydrogen-containing compound may be used in an amount of 10 to 60% by weight, preferably 15 to 40% by weight. If the content is less than 10% by weight, the number of functional groups is low and the physical properties of the desired bio-polyol can not be exhibited. Therefore, the physical properties of the hard urethane foam and the heat insulating material produced therefrom may be deteriorated. There is a problem that the produced polyol can not be regarded as a biopolyol because the content of natural oil is lowered.

The catalyst used is a basic catalyst such as KOH, NaOH, CsOH, dimethyl lauramine, dimethyl palmityl amine, At least one selected from the group consisting of N, N-dimethyldodecan-1-amine and 1-octadecanamine can be used.

Such a catalyst is 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 reaction conditions are adjusted so that the exchange reaction is carried out in the range of about 10 to 90% by weight, preferably 20 to 70% by weight, of the natural oil. For example, from 70 to 170 DEG C, preferably from 80 to 120 DEG C, while raising the temperature over a period of from 0.5 to 3 hours, preferably from 1 to 2 hours.

In the above-mentioned natural oil which has not been subjected to exchange reaction, an addition reaction and an exchange reaction are caused in the addition reaction step of alkylene oxide. Since the natural oil is a lipophilic component having a long alkyl chain and the polyfunctional active hydrogen-containing compound is a hydrophilic component, when the alkylene oxide is added after a part of the natural oil is exchanged, the addition reaction with the alkylene oxide And a homogeneous bio-polyol can be obtained. As a result, the storage stability of a composition for producing a rigid polyurethane foam (polyol containing a bio-polyol and other additives, etc.) can be enhanced.

The present invention can perform a pretreatment step of purifying natural oil prior to the exchange reaction. During this pretreatment, gums or other non-sparing impurities (such as phospholipids) can be removed by submersion. In addition, the separated natural oil layer may be treated with an alkali or the like to remove the remaining free fatty acid component.

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

When polyhydric alcohols are used as polyfunctional active hydrogen-containing compounds, triglycerides present in natural oils as shown in the following Reaction Scheme 1 react with dihydric alcohols in the presence of di- and mono-substituted hydroxy While polyhydric alcohols can form fatty acid esters with the separated fatty acid groups.

[Reaction Scheme 1]

On the other hand, in the case of a polyhydric amine containing a hydroxyl group in a molecule such as diethanolamine in the polyhydric amine, the exchange reaction can be carried out according to the reaction mechanism of the following reaction formula (2).

[Reaction Scheme 2]

Further, in the case of a polyhydric amine which does not contain a hydroxyl group in the molecule, an exchange reaction can be carried out according to the reaction mechanism of the following reaction formula 3 (a kind of transamidation reaction).

[Reaction Scheme 3]

The exchange reaction can be carried out with a dehydration process, for example a vacuum dehydration process, in which a trace or small amount of water is contained in the natural oil as the reactant, or the catalyst is in the form of an aqueous solution (for example an aqueous solution of an alkali hydroxide) It is also possible to use it as.

The reaction conditions and the selection of the polyfunctional active hydrogen-containing compound can be determined in consideration of the degree of the alkylene oxide addition reaction, the degree of expansion to be achieved in the final hard polyurethane foam, and the curing time .

The present invention causes addition reaction of alkylene oxide to the product of the exchange reaction (first step reaction).

Addition reaction of the alkylene oxide to the product obtained by the exchange reaction in a specific amount can increase the storage stability while maintaining high functional groups and can keep the viscosity low. It is also possible to maintain the viscosity of the polyurethane, especially the hard poly The physical properties required for the urethane foam can be improved.

The alkylene oxide is a compound having at least one alkylene oxide group such as ethylene oxide, propylene oxide (1,2-epoxypropane), butylene oxide (1,4-epoxybutane), 1,2- , 2,3-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, amylene oxide, styrene oxide, and the like can be used. It is preferable to use ethylene oxide, propylene oxide and butylene oxide in view of double commercialization, and it is more preferable to use ethylene oxide and propylene oxide in consideration of price competitiveness and physical property.

At this time, the alkylene oxide compound may be used singly or in combination of two or more (mixed). When a plurality of alkylene oxides are used in combination, each of the alkylene oxides may be continuously or simultaneously introduced. Further, if the mixing ratio of the alkylene oxide components used is controlled, physical properties can be variously realized.

In addition, a catalyst used in the exchange reaction, such as a basic catalyst (especially an alkali hydroxide catalyst), can be used to promote the alkylene oxide addition reaction.

Increasing the amount of natural oil used in a given amount of total reactant reduces the amount of alkylene oxide used in the addition reaction. The present invention can reduce carbon dioxide emissions by reducing the amount of energy input in the course of manufacturing biopolyols by increasing the amount of natural oil used relative to conventional ones.

On the other hand, when the amount of natural oil used is decreased and the amount of alkylene oxide added is increased, the amount of energy required for the addition reaction is increased. Further, And does not meet the latest technology trends.

Thus, there is a need to appropriately control the composition of the reactants for production of bio polyols, particularly the addition amount of the alkylene oxide compound, in order to maximize the advantage of using natural oil and alleviate the problems caused by the use of natural oil.

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

The alkylene oxide addition reaction may be carried out at a temperature of from 80 to 140 DEG C, preferably from 100 to 120 DEG C over a period of from 1 to 40 hours, preferably from 5 to 15 hours. Also, the pressure can be performed at 5.0 kgf / cm 2 or less, preferably 3 to 4 kgf / cm 2.

The present invention may further comprise, after the addition reaction step of the alkylene oxide, selectively removing the catalyst component present in the product. In the case of remaining in the bio-polyol, it is preferable to carry out the above step since the foam may be degraded in the formability and cross-linking reaction of the foam during the polyurethane synthesis process.

The removal of the catalyst component can be carried out using a catalyst adsorbent. Specifically, a catalyst adsorbent and water may be introduced into the alkylene oxide addition reaction product and then filtered. At this time, it is preferable that the catalyst removal step is carried out under stirring.

As the catalyst adsorbent, for example, silicates such as aluminum silicate and magnesium silicate may be used, and these catalysts may be used singly or in combination. The catalyst adsorbent may be used in an amount 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 carried out at 50 to 140 ° C, preferably at 70 to 100 ° C over 1 to 15 hours, preferably 2 to 10 hours.

The bio-polyol prepared by the above process (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 mg KOH / g (preferably 300 to 500 Mg KOH / g), and the viscosity (25 DEG 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 embodiment of the present invention exhibits excellent physical properties due to an increase in the number of functional groups and the like. Especially, by adding a considerable amount of alkylene oxide into the molecular structure, And the storage stability is improved. Such properties are unexpected in the prior art, and are easy to handle and have the advantage of being able to inhibit changes in the physical properties of the polyol even during long-term storage. In addition, the properties of the rigid polyurethane foam to be produced can be easily changed by selecting the reactants, controlling the ratio, density, reactivity, etc. between the reactants.

Due to these improvements, the rigid polyurethane foam produced using the bio-polyol is particularly suitable for use as an LNG insulator.

The rigid polyurethane foam can be produced by reacting isocyanate and urethane with the bio-polyol prepared as described above.

The mechanism of such urethane reaction is well known in the art and various kinds of additives (for example, glass fiber, catalyst, blowing agent, surfactant, flame retardant, etc.) may be added so that the rigid polyurethane foam to be produced exhibits properties suitable for LNG insulator use ). &Lt; / RTI &gt;

The method of producing the rigid polyurethane foam is not particularly limited, and the urethane reaction may be performed by mixing the additives, polyol, and isocyanate at the same time, or the additive may be first added to the polyol, and the polyol containing the additive and the isocyanate may be urethane-reacted. When the additive, polyol and isocyanate are mixed at the same time, it is difficult to form uniform urethane foam due to the local unevenness of the concentration, and handling properties of the polyol and moldability of the urethane foam may not be easy. Method is preferable.

The polyol and isocyanate are reacted at a stoichiometric ratio, but 80 to 180 parts by weight, preferably 90 to 150 parts by weight of isocyanate may be used relative to 100 parts by weight of the polyol in consideration of the reaction efficiency and the like.

Also, considering the characteristics of the rigid polyurethane foam to be produced, the isocyanate index may be in the range of 60 to 400, preferably 90 to 200, and more preferably 90 to 160.

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

The polyol of the present invention necessarily comprises a biopolyol and may additionally comprise an ether polyol, an ester polyol or a mixture thereof.

Examples of the ether polyols include glycerine, trimethanolpropane, pentaerythritol, dipentaerythritol, alpha-methylglucoside, xylitol, sorbitol, Polyfunctional alcohols such as sucrose and the like; (For example, ethylene oxide, propylene oxide, and the like) with a polyfunctional amine, such as ethylene oxide and / or o-toluene diamine, ethylene diamine, triethanol amine, Oxides, butylene oxides, or mixtures thereof). The method of synthesizing such an optionally containing ether polyol is known in the art, and the basic reaction mechanism is shown in the following reaction formula (4).

[Reaction Scheme 4]

Examples of ester polyols include reaction products of polyhydric alcohols with polyhydric acids (especially polyhydric carboxylic acids). At this time, an anhydride thereof, an ester compound with a lower alcohol or a mixture thereof may be used instead of the polyvalent acid. More specifically, it is possible to use a polyhydric alcohol such as dicarboxylic acid (e.g., phthalic anhydride, terephthalic acid, suberic acid, sebacic acid, isophthalic acid, trimellitic acid, succinic acid, adipic acid, fumaric acid, , Diethylene glycol, 1,4-butanediol, glycerin, trimethylol propane, propylene glycol, etc.) can be used. Further, a single ester polyol may be used, or two or more ester polyols may be used in combination. The reaction mechanism for synthesizing such an ester polyol is shown in the following reaction formula (5).

[Reaction Scheme 5]

The hydroxyl value of the polyol (ether polyol and / or ester polyol) usable in combination with the biopolyol is preferably 50 to 100, more preferably 50 to 100, in order to satisfy various physical properties required as an LNG insulator such as compressive strength, normal temperature and low temperature tensile strength, impact resistance, 600 mg KOH / g. The physical properties (e.g., thermal conductivity and strength properties (compressive strength, flexural strength, etc.) of the rigid polyurethane foam can be controlled through appropriate selection of the hydroxyl value.

The polyol may contain 10% by weight or more, preferably 15 to 40% by weight of the bio-polyol. The ether polyol which can be added may be used in an amount of 90% by weight or less (preferably 30 to 90% by weight) and the ester polyol may be used in an amount of 60% by weight or less (preferably 50% by weight or less).

For example, the ether polyol may be selected from the group consisting of (i) 20 to 80% by weight of an ether polyol having a hydroxyl number of from 350 to 500 mg KOH / g, and (ii) a number of functional groups of from 2 to 5.5, And 20 to 80% by weight of an ether polyol having a hydroxyl value of KOH / g. The ester polyol having a functional group number of 2 to 3 and a hydroxyl value of 50 to 400 mg KOH / g can be used.

As another example, the ether polyol may be selected from the group consisting of (i) 20 to 80% by weight of an ether polyol having a hydroxyl number of from 300 to 550 mg KOH / g, and (ii) a number of functional groups of from 2 to 5, And 20 to 80% by weight of an ether polyol having a hydroxyl value of mg KOH / g. The ester polyol having a functional group number of 2 to 3 and a hydroxyl value of 50 to 400 mg KOH / g can be used.

The isocyanate of the present invention reacts with a polyol to form a urethane bond in the foam, and includes a compound in which an isocyanate group is bonded with an aromatic, cycloaliphatic, and / or aliphatic group.

The isocyanate compounds are known in the art and include, for example, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, 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) Modified polyisocyanate, isocyanate-modified polyisocyanate, isocyanurate-modified polyisocyanate, isocyanurate-modified polyisocyanate, isocyanate-modified polyisocyanate, isocyanate-modified polyisocyanate, Modified polyisocyanates, urea-modified polyisocyanates, buret-containing polyisocyanates, isocyanate-terminated prepolymers, or mixtures thereof.

The isocyanate may have a number of functional groups of 2.5 to 3.5 and an NCO% of 25 to 35. Suitable isocyanates for LNG insulations are MDI, polymeric MDI or crude MDI (p-MDI, typically having a weight average of from about 2.6 to about 3.0 (preferably about 2.7) It may be from about 350 to 420): The molecular weight (M _w). The p-MDI is typically in the form of a brown liquid at room temperature, and the viscosity range may range from 100 to 3,000 cps (more specifically, from 100 to 300 cps).

The reaction between the polyol and the isocyanate can be carried out in the presence of a catalyst for urethane production in order to shorten the curing time and the like. The catalyst is not particularly limited and is generally used in the art. Specifically, an amine catalyst such as a secondary or tertiary amine compound, a metal catalyst such as an organic metal, or the like can be used. Further, two or more kinds of catalysts may be used in combination for the purpose of realizing the desired physical properties.

Examples of the amine catalyst include triethylenediamine, triethylamine, tripropylamine, triisopropanolamine, tributylamine, trioctylamine, hexadecyldimethylamine, tetramethylethylenediamine, 3-methoxy- N-dimethylaminopropylamine, diethylethanolamine, N-cocomorpholine, N, N-diethyl-3-diethylaminopropylamine, tris (3-dimethylamino) propylhexahydrotriamine, N- N, N ', N', N'-tetramethylethylenediamine, diethylenetriamine, diethylenetriamine, diethylenetriamine, diethylenetriamine, diethanolamine, N, N'-dimethylbenzylamine, N, N-dimethylcyclohexylamine, N, N ', N'-tetramethylbutylenediamine, , N ', N', n'-pentamethyldiethylenetriamine, and triethylenediamine.

Examples of the metal catalyst include potassium octoate, potassium acetate, bismuth-based gel catalyst, and tin type catalyst. In the case of the above-mentioned bismuth-based gel catalyst, it typically plays a role of promoting a gel reaction mainly forming a urethane chain in a urethane foam. The tin-based catalyst may be selected from, for example, tin salts of carboxylic acids, tin acrylates, trialkyltin oxides, dialkyltin dihalides, dialkyltin oxides (dibutyltin (IV) oxides and the like), dibutyltin diaurate, Dibutyltin diacetate, diethyltin diacetate, dihexyltin diacetate, di-2-ethylhexyltin oxide, dioctyltin dioxide, tin octoate, or combinations thereof.

In the case of N, N-dimethylcyclohexylamine, N, N, N ', N', N'-pentamethyldiethylenetriamine is commercially available under the trade name Polyact® 5, have.

The urethane catalyst may be used in an amount of 0.05 to 4 parts by weight, preferably 0.05 to 1 part by weight, based on 100 parts by weight of the polyol. Generally, as the content of the catalyst component increases, the polyurethane foam forming reaction rate will be accelerated. However, when the reactivity is excessively high, there is a problem that the polyol and isocyanate may be changed into a solid phase before the polyurethane foam has a proper shape. It is preferable to use it by adjusting it appropriately.

The blowing agent acts to generate bubbles during the urethane reaction. Such a blowing agent may be divided into a physical blowing agent which does not participate in the urethane reaction but is vaporized (sublimed) by the reaction heat to form bubbles, and water which is a chemical blowing agent (which reacts with isocyanate to generate carbon dioxide) Can be used.

In the physical blowing agent, the foaming agent is vaporized (sublimated) by the heat of reaction, and the resulting gas is accumulated by the cells surrounded by the foam, so that the foam produced can exhibit a low thermal conductivity. HFC-245fa (1,1,1,3,3,3-pentafluoropropane), which is a hydrocarbonsystem, CFC-pentane, hydrofluorocarbon-based HCFC-141b (1,1-dichloro-1-fluoroethane) and hydrofluorocarbon - pentafluoropropane), HFC-365mfc (1,1,1,3,3-pentafluorobutane), mixed HFC-365mfc / 227ea (1,1,1,3,3-pentafluorobutane / 1,1,1,3,3- , 1,2,3,3,3-heptafluoropropane), a mixture thereof, and the like may be preferably used as a foaming agent. The use of the CFC foaming agent conventionally used is not excluded, but it may cause an environmental problem and it may be preferable to exclude the use as much as possible. Preferably, a more environmentally friendly component such as C-Pentane, HFC, or the like can be used. In particular, it is preferable to use HFC-245fa as the HFC-based foaming agent used in the production of the closed cell insulating foam.

The amount of the physical foaming agent to be used can be determined according to the required characteristics such as the density of the polyurethane foam to be produced, for example, 30 parts by weight or less, preferably 3 to 25 parts by weight, And may be in the range of 4 to 20 parts by weight.

In addition, water as a chemical blowing agent reacts with isocyanate to generate carbon dioxide gas. The amount of water used may be in the range of 0 to 10 parts by weight, more preferably 0 to 5 parts by weight, based on 100 parts by weight of the polyol.

The present invention can use a surfactant that affects the cell structure in the polyurethane foam. The surfactant may act to stabilize the mixing of the reaction raw materials, to generate bubbles, and to stabilize the bubbles. For example, it is possible to increase the surface area by reducing the surface tension by decreasing the cell size, and by increasing the surface elasticity, it is possible to restore the critical expanding film before cell destruction occurs, And increase the surface viscosity which reduces deformation of the cell structure.

As such, the kind of the surfactant can be appropriately selected in consideration of the cell structure in the foamed polyurethane, and specific examples thereof include a silicone surfactant or a foam stabilizer. Examples thereof include B-8404, product name of Evonik, B-8462 and the like. Such a surfactant may be a polysiloxane ether having a molecular weight of 1,000 to 10,000 g / mol, more preferably 3,000 to 7,000 g / mol, in order to facilitate the formation of a closed cell. Particularly, when water is used as the foaming agent, it is preferable to use a silicone surfactant.

The amount of the surfactant to be used may range from 0.1 to 5.0 parts by weight, more preferably from 0.5 to 4.0 parts by weight, based on 100 parts by weight of the polyol.

Since LNG insulation must not generate cracks or water even during shaking or vibration of ship during transportation, addition of fiber reinforcement is required to enhance mechanical strength.

Examples of the fiber reinforcing material include synthetic fibers such as glass fiber, polyamide and polyester, and inorganic fibers such as carbon fiber and ceramic fiber. As the fiber reinforcing material suitable for the present invention, glass fibers are exemplified. In particular, it is preferable to use a glass fiber mat laminate.

The fiber reinforcement is preferably 5 to 50 parts by weight, more preferably 5 to 40 parts by weight, based on 100 parts by weight of the polyol. At this time, if the content of the glass fiber is less than 5 parts by weight, the low temperature shrinkage stability and the effect of preventing cracks are lowered. If the amount is more than 50 parts by weight, abnormal foaming of the foam and cracking of the foam occur upon foaming of the polyurethane foam stock solution .

In addition, the present invention can be carried out by appropriately adding a flame retardant, a colorant, a filler, a cell regulator, etc., alone or in combination.

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

Other additives may be appropriately selected depending on the type and amount used in the art.

The urethane reaction of the present invention may utilize conventional foam forming principles and associated devices, and it may be desirable to form a closed cell foam specifically for use with LNG insulator applications. For example, the polyol, isocyanate and additives can be contacted and mixed and then expanded / cured in the form of a cellular polymer (foaming step). As another example, the polyol and the additive may be first mixed and then subjected to an expansion / cure reaction by mixing with the isocyanate for the reaction.

Further, a foaming machine may be used for foam formation, and the foaming temperature may be in the range of 15 to 30 DEG C (more preferably 18 to 28 DEG C) and the foaming pressure may be in the range of 90 to 200 bar (more preferably 110 to 180 bar) have.

The rigid polyurethane foam according to the present invention has an apparent density of 100 kg / m 3 to 140 kg / m 3, a closed cell content of 90% or more, a flow density of water vapor of 4.0 g / m 2 / h or less, a thermal conductivity Z of 0.0300 kcal / mh &lt; 0 &gt; C.

The rigid polyurethane foam has a compressive strength (Z) of 1.00 MPa or more and a modulus of 40 MPa or more; The tensile properties (X, Y) may have a strength of 2.00 to 90 MPa <modulus <170 MPa at 20 ° C and a strength of 2.00 MPa or more and 150 MPa <modulus <250 MPa at -170 ° C. For reference, X, Y and Z mean width (X), length (Y) and thickness (Z) of the rigid polyurethane foam block.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the inventions. , And it is natural that such variations and modifications fall within the scope of the appended claims.

1) Natural oil

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

Soybean oil: molecular weight (Mw) of Sigma-Aldrich of about 968.7; Cas. No .: 8001-22-7

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

2) Multifunctional  Active hydrogen-containing compound

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

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

Pentaerythritol: Molecular weight (Mw) of Sigma-Aldrich, 136.2; Functional group: 4

Glycerin: molecular weight (Mw) of Sigma-Aldrich 92.1; 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: 149.2, Functional group: 3

Ethylenediamine: molecular weight (Mw) of Sigma-Aldrich 60.1; Functional group: 2

3) Polyol  Exchange catalyst

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

Dimethyllauramine: 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-based catalysts: Product names Polyact®5 and Polyact®8 from Air Products (respectively: Pentamethyldiethylenetriamine and Dimethylcyclohexylamine)

7) Surfactants

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

8) Foaming agent

(Compound: HCFC-141b; 1,1-Dichloro-1-fluoroethane; Cas. No .: 1717-00-6)

Enovate 占 and HFC-245fa (compound: 1,1,1,3,3-Pentafluoropropane; Cas. No. 460-73-1)

9) Flame retardant

(Compound: Tris (2-chloroisopropyl) phosphate; Cas. No .: 13674-84-5), product name of Supresta Co. Fyrol PCF (TCPP)

Polyol  Produce

Example  One

The reaction was carried out by adding sugar, palm oil and KOH (45%) catalyst to a 20 L high-pressure vessel, stirring under nitrogen atmosphere (reduced pressure substitution), and vacuum dehydrating at about 120 ° C for about 1 hour. Then, propylene oxide was added at about 115 캜 and reacted 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 ratios of the reactants are shown in Table 6 below.

Example  2 and 3

A bio-polyol was synthesized in substantially the same manner as in Example 1, except that the kind of natural oil was changed in the reactants. The composition ratios of the reactants are shown in Table 6 below.

Classification (parts by weight) Example 1 Example 2 Example 3 Natural oil palm oil 200 - - Soybean oil - 200 - Castor oil - - 200 Multifunctional active hydrogen-containing compound 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 (disposal) handful handful handful Catalyst adsorbent Magnesium silicate handful handful handful Sum 1001.5 1001.5 1001.5

Examples 4 to 9

In this example, palm oil was used as the natural oil, the type of the polyfunctional active hydrogen-containing compound was changed, and a bio-polyol was synthesized in substantially the same manner as in Example 1 according to the composition ratio shown in Table 5 below.

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 Multifunctional active hydrogen-containing compound 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 (disposal) 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, the kind of the polyfunctional active hydrogen-containing compound was changed, and a bio-polyol was synthesized in substantially the same manner as in Example 1 according to the composition ratio shown in Table 6 below.

Classification (parts by weight) Example 10 Example 11 Example 12 Example 13 Natural oil Castor oil 200 200 200 200 Multifunctional active hydrogen-containing compound 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 (disposal) handful handful handful handful Catalyst absorbent Magnesium silicate handful handful handful handful Sum 1001.5 1003.5 1003.5 1003.5

Examples 14 to 16

In this Example, a bipolyol was synthesized in substantially the same manner as in Example 1 by using palm oil as a natural oil and varying the ratio between a plurality of polyfunctional active hydrogen-containing compounds according to the composition ratios shown in Table 7 below.

Classification (parts by weight) Example 14 Example 15 Example 16 Natural oil palm oil 200 250 300 Multifunctional active hydrogen-containing compound 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 (disposal) handful handful handful Catalyst absorbent Magnesium silicate handful handful handful Sum 1001.5 1003.5 1003.5

Examples 17 to 20

In this Example, the type and proportion of the alkylene oxide and the kind of the catalyst were changed, and a bio-polyol was synthesized in substantially the same manner as in Example 1 according to the composition ratios shown in Table 8 below.

Classification (parts by weight) Example 17 Example 18 Example 19 Example 20 Natural oil palm oil 200 200 200 200 Multifunctional active hydrogen-containing compound Sugar 300 300 300 300 Water (reaction) 10 10 10 10 catalyst KOH (45%) 3.5 3.5 Dimethyllauamine 10.0 Dimethylpalmitylamine 10.0 Alkylene oxide PO 488 300 480 480 EO 190 Water (disposal) handful handful Catalyst absorbent 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, stirred in a nitrogen atmosphere, and dehydrated in vacuo at 110 ° C. 565.3 parts by weight of castor oil was added to the mixture, and the mixture was reacted at 200 ° C for about 4 hours. Then, 127.2 parts by weight of glycerin and 49.5 parts by weight of diethylene glycol were added, followed by further reaction for 3 hours. Finally, 176.7 parts by weight of phthalic anhydride and 0.1 part by weight of tetraisopropyltitanate (TPT) were added for the ester reaction, and the reaction was carried out at 230 DEG C for about 15 hours.

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

Example  21 and Comparative Example  2

The biopolyol was synthesized in substantially the same manner as in Example 1 while varying the addition amount of alkylene oxide. The composition of each reactant is shown in Table 9 below.

division Example 21 Comparative Example 2 Natural oil palm oil 105 550 Multifunctional active hydrogen-containing compound Sugar 150 150 glycerin 100 100 Water (reaction) 10 10 catalyst KOH (45%) 3.5 3.5 Alkylene oxide PO 635 190 Water (disposal) handful handful Catalyst adsorbent Catalyst adsorbent (magnesium silicate) handful handful Sum 1003.5 1003.5

Test Example

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

1) Color : Measured by the Gardner Color test method.

2) Hydroxyl value  Measure

The hydroxyl value of the bio-polyol 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 Mechanism>

An Erlenmeyer flask (200 ml), air cooling tube (30 cm), pipette (5 ml, 10 ml), buret (50 ml)

<Measurement method>

(1) The polyol synthesized in Examples 1 to 20 and 5 ml of anhydrous acetic acid-pyridine solution were added to an Erlenmeyer flask, and the mixture was shaken 5 times or more. After cooling with a cooler, the reaction was conducted in a oil bath for 1 hour and 30 minutes.

(2) 1 ml of distilled water was added, and the mixture was shaken 5 times or more. Then, the mixture was allowed to stand in a oil bath for 10 minutes to promote hydrolysis.

(3) After taking out from the oil bath and keeping it at room temperature for 10 minutes, the inner wall of the cooler was washed with 10 ml of acetone and then shaken 5 times or more, 3 to 4 drops of phenolphthalein indicator were added and titrated with 0.5N KOH standard solution.

The hydroxyl value was calculated by the following equation.

S: Amount of sample

B: 0.5 N KOH (ml) required for blank

A: 0.5 N KOH (ml)

B: The acid value of the sample used in this test

3) Viscosity

Was measured at 25 캜 using DV-III from Brookfield.

(Layer separation:?, No layer separation: X, slight haziness and instability:?).

4) Functional group

The functional groups of the prepared bio-polyol were calculated by the following formula (2) using the molar number of the polyfunctional active hydrogen-containing compound and the natural oil and the number of functional groups.

- A (a1 + a2 + a3 + a4 + ... + an): Sum of polyfunctional active hydrogen-containing compounds and natural oils

- an: the number of moles of each of the polyfunctional active hydrogen-containing compound and the natural oil

- fn: polyfunctional active hydrogen-containing compound and natural oil Each functional group

5) Storage stability

The synthesized polyol was placed in a 500 ml sample bottle, and the presence or absence of the layer separation was evaluated in an oven at 30 ° C for 100 days.

(Layer separation:?, No layer separation:?, Slight haziness and unstable:?)

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 Approximately 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 phase Red liquid phase 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 About 5.2 About 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 Approximately 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 About 4.2 About 4.0 About 4.2 Storage stability × × △ △

As can be seen from the above table, when the addition reaction of the alkylene oxide was not carried out (Comparative Example 1), the storage stability and appearance characteristics were poorer than the biopolyol obtained according to the Example under the same conditions, It can be seen that the handling property is low.

In addition, when the amount of the alkylene oxide used was less than a certain amount (Comparative Example 2), the viscosity was so high that the handling property in the urethane reaction was lowered.

Rigid polyurethane foam manufacturing

Example  22 to 25

The amounts of the bio-polyols synthesized in Example 15 were varied, and the compositions were mixed in the compositions shown in Tables 16 and 17 to prepare rigid polyurethane foams.

At this time, a mechanical foaming machine was used for foaming for forming foam, and at the time of foam production, the foaming temperature of polyurethane and isocyanate was adjusted to about 20 ° C and the foaming pressure to about 130 bar.

Comparative Examples 3 to 6

The hard polyurethane foam was prepared in the same manner as in Example 22 except that the conventional polyol and the bio-polyol synthesized from Comparative Example 1 were mixed in the compositions shown in Tables 16 and 17 below.

Classification (parts by weight) Example 22 Example 23 Comparative Example 3 Comparative Example 4 Polyol A 25.0 10.0 40.0 10.0 Polyol B 30.0 30.0 30.0 30.0 Polyol C 10.0 10.0 10.0 10.0 Polyol D 20.0 20.0 20.0 20.0 The bio-polyol according to Comparative Example 1 30.0 The biopolyol of Example 15 15.0 30.0 Flame retardant (TCPP) 10.0 10.0 10.0 10.0 Water (foaming agent) 1.0 1.0 1.0 1.0 Silicone surfactant 3.0 3.0 3.0 3.0 Amine catalyst A 0.2 0.2 0.2 0.2 Sum 114.2 114.2 114.2 114.2 Viscosity (20 ℃) 1395 1310 1480 2015 p-MDI 130.0 130.0 130.0 130.0 Glass fiber 30.0 30.0 30.0 30.0 - Polyol A: Ether polyol of sorbitol base for thermal insulation of LNG produced by KPX Chemical
- Polyol B: LPG produced by KPX Chemical Co., Ltd. Ether / polyether of sugar / glycerin base for insulation
- Polyol C: ester polyol of phthalic anhydride base for LNG insulator produced by KPX Chemical Co., Ltd.
- Polyol D: Ether polyol of glycerine base for LNG insulator produced by KPX Chemical
- Amine catalyst A: Amine catalyst for thermal insulation of LNG used in KPX Chemicals
- Fiber reinforcing materials (glass fiber): WR580A, Korea Fibers

division
(Parts by weight) Example 24 Example 25 Example 26 Comparative Example 5 Comparative Example 6 Comparative Example 7 Polyol B 15.0 15.0 15.0 15.0 15.0 15.0 Polyol C 30.0 30.0 30.0 30.0 30.0 30.0 Polyol E 25.0 25.0 25.0 25.0 25.0 25.0 Polyol F 15.0 15.0 30.0 30.0 The bio-polyol according to Comparative Example 1 30.0 The biopolyol of Example 15 15.0 15.0 30.0 Flame retardant (TCPP) 10.0 10.0 10.0 10.0 10.0 10.0 Silicone surfactant 3.0 3.0 3.0 3.0 3.0 3.0 Water (foaming agent) 0.30 0.15 0.15 0.30 0.15 0.15 Amine catalyst A 0.2 0.2 0.2 0.2 0.2 0.2 HCFC-141b (foaming agent) 5.0 5.0 HFC-245fa (blowing agent) 7.0 7.0 7.0 7.0 Sum 118.5 120.35 120.35 118.5 120.35 120.35 Viscosity (20 ℃) 1830 1750 1550 2050 2000 2100 p-MDI 147.2 151.1 151.1 147.2 151.1 151.1 Glass fiber 29.0 30.0 30.0 29.0 30.0 30.0 - Polyol E: Ether polyol of glycerine base for LNG insulator produced by KPX Chemical
- Polyol F: Ether polyol of sorbitol base for thermal insulation of LNG produced by KPX Chemical

Test Example

The physical properties of the hard polyurethane foam thus prepared were measured by the following methods, and the results are shown in Tables 18 and 19. Table 18 shows the results of physical properties for Table 16, which is a water blowing agent, and Table 19, shows physical properties for Table 17, in which the blowing agent is hydrocarbon.

[Measurement of physical properties]

1. Apparent density: measured according to ISO 845

2. Closed cell content: measured according to ASTM D 2856

3. Flow density of water vapor: measured according to ISO 1663

4. Thermal conductivity coefficient: measured according to ASTM C 518

5. Compression characteristics (strength, modulus): measured according to ASTM D 1621

6. Tensile properties (strength, modulus at 20 ° C and -170 ° C): measured according to ASTM D 1623

Item Example 22 Example 23 Comparative Example 3 Comparative Example 4 Biopolyol content%
(Based on polyol) 15 30 0 30 Glass fiber content% 10.9 10.9 10.9 10.9 Isocyanate index 115 114 116 123 Reactivity (CT / GT, sec) 132/907 138/915 130/901 127/895 Apparent density (kg / m ³ ) 129.3 128.5 129.7 128.6 Percentage of closed cells (%) 95.1 94.2 94.3 90.1 Water absorption rate (g / m ² h) 2.6 2.9 3.0 2.9 Thermal conductivity (kcal / mh ° C) 0.0268 0.0272 0.0268 0.0291 Compression 20 ° C Strength (MPa) Z 1.30 1.36 1.38 0.98 Modulus (MPa) Z 50 57 59 37 Tensile 20 ℃ Strength (MPa) X 2.85 3.21 3.49 1.95 Y 2.75 3.07 3.35 2.03 Modulus (MPa) X 131 140 142 109 Y 140 147 149 114 Seal
-170 ° C Strength (MPa) X 2.95 3.05 3.60 2.00 Y 2.90 3.12 3.80 1.94 Modulus (MPa) X 197 198 200 190 Y 203 202 210 191

Item Example 24 Example 25 Example 26 Comparative Example 5 Comparative Example 6 Comparative Example 7 Biopolyol content%
(Based on polyol) 15 15 30 0 0 30 Glass fiber content% 9.8 10.0 10.0 9.8 10.0 10.0 Isocyanate index 125 132 132 129 126 142 Reactivity (CT / GT / TFT, sec) 173/719/1140 178/715/1180 185/722/1210 173/711/1140 170/702/1130 167/689/1110 Apparent density (kg / m ³ ) 129.5 129.1 129.4 128.5 128.8 128.7 Percentage of closed cells (%) 93.9 94.8 94.1 94.2 94.1 90.7 Water absorption rate (g / m ² / h) 2.7 2.7 2.8 2.7 2.9 3.2 Thermal conductivity (Kcal / mhr ° C) 0.0219 0.0210 0.0211 0.0218 0.0207 0.0220 Compression 20 ° C Strength (MPa) Z 1.30 1.31 1.35 1.41 1.40 0.94 Modulus
(MPa) Z 50 51 59 65 63 43 Tensile 20 ℃ Strength (MPa) X 2.88 2.87 3.18 3.29 3.30 2.01 Y 2.69 2.71 3.08 3.71 3.70 1.97 Modulus
(MPa) X 120 122 131 135 133 100 Y 131 133 145 149 148 101 Seal
-170 ° C Strength (MPa) X 2.91 2.98 3.52 3.78 3.81 2.10 Y 3.25 3.24 3.85 3.98 4.01 2.14 Modulus (MPa) X 183 182 187 190 188 175 Y 183 185 195 201 198 180

Claims (14)

10 to 60% by weight of a natural oil, 10 to 60% by weight of a polyfunctional active hydrogen-containing compound, 0.1 to 1.5% by weight of a catalyst and 20 to 70% by weight of an alkylene oxide,
A polyol comprising a bio-polyol having a functional group number of 3 or more, a hydroxyl value of KOH / g of 200 to 600 mg and a viscosity (25 ° C) of 2,000 to 25,000 cps; And
Rigid polyurethane foam for LNG insulator including isocyanate.
The method of claim 1, wherein the polyfunctional active hydrogen compound is a polyfunctional alcohol, a polyfunctional amine,
Wherein the polyfunctional alcohol is ethylene glycol, diethylene glycol, glycerin, trimethanolpropane, pentaerythritol, dipentaerythritol, alpha methyl glucoside, xylitol, sorbitol,
The polyfunctional amine is a hard polyurethane foam for LNG insulator, which is ethylenediamine, diethylenetriamine, triethanolamine, ortho-toluenediamine, diphenylmethanediamine, diethanolamine or a mixture thereof.
The catalyst according to claim 1, wherein the catalyst is at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, cesium hydroxide, dimethylarylamine, dimethylpalmityl amine, N, N-dimethyldodecane- Rigid polyurethane foam for use.
The rigid polyurethane foam according to claim 1, wherein the alkylene oxide is ethylene oxide, propylene oxide or a mixture thereof.
The bio-polyol according to claim 1,
a) exchanging a natural oil with a polyfunctional active hydrogen-containing compound in the presence of a catalyst; And b) subjecting the product of the exchange reaction to an addition reaction with alkylene oxide.
[7] 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 the step c) is carried out in such a manner that a catalyst adsorbent and water are added, stirred, and then filtered.
The rigid polyurethane foam for LNG insulator according to claim 1, wherein the biopolyol is at least 10 parts by weight based on 100 parts by weight of the polyol.
The isocyanate according to claim 1, wherein the isocyanate has a functional group 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 140, and an LNG carrier containing polymeric MDI (diphenylmethane diisocyanate) Rigid polyurethane foam for insulation.
The polyurethane foam according to claim 1, which comprises 5 to 50 parts by weight of a fiber reinforcing material, 0.05 to 4 parts by weight of a urethane catalyst, 25 parts by weight or less of a foaming agent, 0.1 to 5.0 parts by weight of a surfactant and 0 to 15 parts by weight of a flame retardant, Rigid Polyurethane Foam for LNG Insulation.
The rigid polyurethane foam according to claim 9, wherein the foaming agent is a chemical foaming agent, a physical foaming agent, or a mixture thereof.
The blowing agent according to claim 10, wherein the blowing agent is at least one selected from the group consisting of water, CFC-pentane, HFC-141b (1,1-dichloro-1-fluoroethane), hydrofluorocarbon (HFC) , 3,3-pentafluoropropane), HFC-365mfc (1,1,1,3,3-pentafluorobutane) and mixed HFC-365mfc / 227ea (1,1,1,3,3-pentafluorobutane / 1,1,1,2,3,3,3-heptafluoropropane). The rigid polyurethane foam for LNG insulator.
The rigid polyurethane foam according to claim 10, wherein the physical foaming agent is not more than 25 parts by weight and the chemical foaming agent is not more than 10 parts by weight based on 100 parts by weight of the polyol.
The rigid polyurethane foam according to claim 1, wherein the hard polyurethane foam has a closed cell content of 90% or more, a water flow density of 4.0 g / m 2 / h or less, a thermal conductivity of 0.0300 kcal / mh ° C or less, To 140 kg / m &lt; 3 &gt; for LNG insulators.
The rigid polyurethane foam according to claim 1, wherein the rigid polyurethane foam has a compressive strength (Z) of 1.00 MPa or more and a modulus of 40 MPa or more; A rigid polyurethane foam for LNG insulator having a tensile strength (X, Y) of 2.00 to 90 MPa at 20 캜 and a modulus of <170 MPa at 20 캜 and a strength of 2.00 MPa or more and 150 MPa <modulus <250 MPa at -170 캜.