KR20180056927A - Nonflammable bio-polyurethane resin composition prepared by biopolyol - Google Patents

Abstract

The present invention relates to a resin composition for producing nonflammable bio-polyurethane with excellent flame retardancy which can be utilized for various fields as an eco-friendly product. The resin composition can be applied to various industrial fields by solving the problems of coloring, weak durability and unpleasant malodor of conventional bio-polyurethane products by using bio-polyol.

Description

TECHNICAL FIELD [0001] The present invention relates to a flame retardant bio-polyurethane resin composition using a bio-polyol,

The present invention relates to a flame retardant bio-polyurethane resin composition produced using a bio-polyol.

Polyurethane is one of the six major synthetic polymers and has been actively developed for the production of bio-polyurethane using biomass as a plastic product group with excellent properties and wide range of applications. The polyurethane generally refers to a polymer compound containing a urethane (-NHCOO-) bond produced by a polymerization reaction of a polyol (-OH compound) and an isocyanate (-NCO compound).

Polyurethane is mainly used as a flexible foam and a hard foam, and is used as a material for a variety of products ranging from industrial products such as automobiles, architectural built-in goods, electronic products, packaging materials, furniture and clothes to daily necessities. Especially, it has advantages over other polymer materials in terms of utilization of various cushioning materials, sound absorption, heat insulation and adhesives.

In the conventional polyurethane manufacturing process, a polyester-polyol made by reacting petroleum purified adipic acid with glycol was used. However, not only environmental pollution is caused in various forms in their manufacturing process, but various problems have arisen in terms of environmental pollution such that a large amount of carbon dioxide is emitted during the combustion reaction in the post-use treatment process.

Therefore, there is an increasing need to develop bio-polyols and bioisocyanates using more environmentally friendly and sustainable biomass resources

Recently, in order to solve these problems, various biomolecules, including vegetable natural oils, have been developed to produce bio-polyols and bioisocyanate monomers, and bio-polyurethane synthesis technologies using these bio-poly-isomers have been developed.

The bio-polyol is obtained by using vegetable natural oils such as castor oil, soy bean oil and rapeseed oil, woody biomass such as cellulose and lignin, waste glycerol and the like Can be manufactured. In addition, succinic acid (succinic acid) and ODDA (C18, octadecanedioic acid) having a larger molecular weight than those of natural vegetable oil and sugar are used. not only. Polyols made from 1,3-propanediol PDO, 1,4-butanediol BDO, and diacid diacids are also used.

Bio-polyols have the same chemical structure as existing polyols, but they are advantageous not as chemical products but as renewable natural materials. In addition, polyurethanes made from bio-polyols have been limited in their use due to their coloration, poor durability such as bending strength and compressive strength, unpleasant odor, and the like, lagging behind conventional polyurethanes . In addition, the reactivity of the bio-polyol was so low that the reaction for preparing the polyurethane was not performed well, and the physical properties of the polyurethane produced therefrom were not good.

Due to recent environmental problems and depletion of petroleum resources, utilization of bio-polyurethane that can replace petroleum-derived polyurethane is becoming more and more important. Especially, in the case of the automobile industry, as the international environmental regulations are strengthened, the demand for bioplastics is increasing. In addition, eco-friendly bio-polyurethane applications can be extended to cushioning materials for seats, soundproofing pads, skin materials for internal parts, and sound absorbing pads for various internal and external parts.

Accordingly, if the problem of low reactivity of the bio-polyol is solved, the bio-polyurethane produced from the raw material thereof will continue to grow as an eco-friendly product.

Korean Patent No. 10-16316060000 (Jun. 16, 201), a method for producing a biopolyol from an epoxidized vegetable oil Korean Patent Laid-Open No. 10-2011-0131980 (2011.12.07), polyurethane foam for sound-absorbing materials including bio-polyols and a method for producing the same

Accordingly, the present inventors have found that, by reacting a bio-derived dicarboxylic acid compound with a specific divalent alcohol to prepare a bio-polyol and reacting it with isocyanate to produce a bio-polyurethane, it is possible to improve the physical properties of the flame- The present invention has been completed.

Accordingly, an object of the present invention is to provide a flame retardant bio-polyurethane resin composition.

To achieve the above object, the present invention provides a biopolyol prepared by esterifying a divalent alcohol containing diethylene glycol and triethylene glycol to a bio-derived dicarboxylic acid compound; And

The present invention also provides a flame retardant bio-polyurethane resin composition comprising an isocyanate-based compound.

The flame-retardant bio-polyurethane according to the present invention can be applied to various fields as an eco-friendly product by using a bio-polyol as a raw material, and has an advantage of excellent flame retardancy.

In particular, the biopolyols proposed in the present invention are produced in a specific composition, and the problems of coloration, low bending sensitivity and weak durability such as compressive strength and unpleasant odor of a polyurethane product using a conventional biopolyol have been solved.

Hereinafter, the present invention will be described in more detail.

Bio polyol

Polyurethanes are prepared by reaction of a polyol with an isocyanate compound. In the present invention, a bio-polyol made from the polyol-bio-derived material is used.

The polyol is synthesized through the esterification reaction of a dicarboxylic acid compound and a dihydric alcohol such as a diol. In the present invention, a 'bio-polyol' obtained by using a bio-derived dicarboxylic acid compound as the dicarboxylic acid and a diethylene glycol and triethylene glycol as a dihydric alcohol is used.

 The bio-derived dicarboxylic acid compound is not particularly limited in the present invention, and those obtained by the methods known in the art may be used or purchased commercially.

In one example, the Republic of Korea Patent Publication No. 1999-0067095 and, Lactobacillus bacteria (Lactobacillus) and E. coli in the medium glucose concentration as described in claim No. 2010-0109902 (Escherichia Coli ) may be added to prepare a dicarboxylic acid compound (e.g., succinic acid). In addition, as described in Korean Patent Laid-Open Publication No. 2013-0099475, (a) saccharifying a bird and a Family Hydrodictyceae to obtain a saccharified liquid containing a monosaccharide; And (b) culturing the microorganism using the saccharified liquid as a carbon source to produce an organic acid, the dicarboxylic acid compound can be obtained from a family of horses and (Family Hydrodictyaceae). It can also be obtained through fermentation of sugars such as sugarcane or corn sugar. Commercially available products are available from Cosun, Avebe, Reverdia and Succinity.

The bio-derived dicarboxylic acid compounds proposed in the present invention can be one kind selected from the group consisting of Azelaic Acid, Adipic Acid, Glutamic acid and succinic acid, Succinic acid is used as follows.

The dicarboxylic acid compound containing succinic acid reacts with a dihydric alcohol. As the dihydric alcohol, a mixture of diethylene glycol and triethylene glycol is used.

(2-hydroxyethoxy) ethan-2-ol, IUPAC name) and has a molecular weight of 106.123 g / mol and a CAS No. of 111-46-6 Lt; / RTI > The diethylene glycol is a colorless, sticky, sweet liquid

[Chemical Formula 1]

Triethylene glycol is a substance represented by the following formula (2) and having a molecular weight of 106.123 g / mol and a CAS number of 112-27-6. It is used as a raw material for plasticizers, synthetic resins, emulsifiers, and wetting agents for glue, gelatin, cork, tobacco, and cosmetics.

(2)

The diethylene glycol and triethylene glycol have hydroxyl groups (OH) at both ends, and the esterification reaction can be performed with the above-mentioned dicarboxylic acid compound. However, when they are used in combination, the esterification reaction with the dicarboxylic acid compound proceeds actively, and the physical properties of the finally obtained flame-retardant bio-polyurethane are improved.

Particularly, in the present invention, diethylene glycol and triethylene glycol are mixed in a weight ratio of 1: 0.2 to 1: 0.7, preferably 1: 0.2 to 1: 0.7, respectively. Through such mixed use, the physical properties of the flame-retardant bio-polyurethane produced in the subsequent step can be improved.

The diethylene glycol and triethylene glycol mentioned above are already known divalent alcohols, and there are various polyols for producing other polyols. For example, there may be mentioned ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- hexanediol, neopentyl glycol, Glycol, tetraethylene glycol, dibutylene glycol, 2-methyl-1,3-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol and the like. When diethylene glycol and triethylene glycol are combined with each other in dihydric alcohols having various compositions, it is possible to produce a flame-retardant bio-polyurethane having optimum physical properties.

The production of the bio-polyol having the above-mentioned composition is not particularly limited in the present invention, and follows the known production method of the bio-polyol.

For example, 1.5 to 3.0 moles, preferably 1.7 to 2.7 moles of diethylene glycol and triethylene glycol are added to 1 mole of the dicarboxylic acid compound to perform an ester reaction or an ester exchange reaction. If the content of the diethylene glycol and the triethylene glycol is less than the above range, unreacted dicarboxylic acid compound is generated, and if it exceeds this amount, the amount of the byproduct may be increased or the reaction rate may be slowed down.

The reaction is carried out at 100 to 250 ° C, preferably 160 to 220 ° C for 1 to 10 hours. If the reaction is carried out under the above-mentioned temperature and time, a slow reaction rate or unreacted material occurs, and if the reaction rate is too high, the pyrolysis of the biopolyol or the material used may occur.

Various additives are added to accelerate the polymerization reaction during the esterification reaction, transesterification reaction or condensation polymerization in the early stage of the polymerization. Examples of the catalyst include tetrabutyltin titanate, dioctyltin dilaurate, zinc acetate, calcium acetate, Magnesium acetate, trimethyl phosphate, triphenyl phosphate, cobalt acetate, and preferably dioctyltin dilaurate is used. The dioctyltin dilaurate is significantly less toxic than other catalysts, especially butyltin catalysts, and has a better reaction rate than other catalysts such as acids and alkalis. Particularly, it is most preferable to use dioctyltin dilaurate when considering that the biopolyol proposed in the present invention is used in products of environmentally friendly flame retardant bio-polyurethane.

In this case, the amount of the catalyst is preferably 0.03 to 0.5 mol% based on 1 mol of the dicarboxylic acid compound. If it is less than 0.03 mol%, the reaction rate becomes slow. On the other hand, if it is more than 0.5 mol%, the reaction rate is fast, but color contamination may occur due to the residual catalyst.

The bio-polyol according to the present invention produced through these steps has the following properties.

- Hydroxyl number: 360-420

- Acid value: 0.79-0.83

- Viscosity (mPa S): Not more than 500

- Color (Gardner index): 20 or less

Flame retardant bio polyurethane

The above-mentioned bio-polyols can be used in the production of flame-retardant bio-polyurethanes by reacting with isocyanate-based compounds and using bio-polyurethanes, especially flame retardants.

Specifically, the flame-retardant bio-polyurethane resin composition according to the present invention can be produced by including a bio-polyol, an isocyanate-based compound, and a flame retardant.

As the bio polyol, the one described above is used.

The isocyanate compound may be any compound used in the production of polyurethane. Preferably an average of 2 to 5, preferably 4 or less NCO groups. Examples of suitable isocyanates include aromatic isocyanates such as 2,4- or 4,4'-methylene diphenyl diisocyanate (MDI), xylylene diisocyanate (XDI), m- or p-tetramethyl xylylene diisocyanate (TMXDI ), Toluylene diisocyanate (TDI), di- or tetra-alkyldiphenylmethane diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate (TODI), 1,3-phenylene diisocyanate , 1,4-phenylene diisocyanate, naphthalene diisocyanate (NDI), 4,4'-dibenzyl diisocyanate, aliphatic isocyanates such as hydrogenated MDI (H12MDI), 1-methyl-2,4- 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, isophorone Isophorone diisocyanate (IPDI), tetramethoxybutane-1,4-di Butadiene-1,4-diisocyanate, hexane-1,6-diisocyanate (HDI), dimeric fatty acid diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate, ethylene diisocyanate Or a combination thereof.

The isocyanate compound may be used in a molar ratio of 1 to 1.8 based on 1 mole of the biopolyol. The molar ratio can be sufficiently used in a range outside the above range in consideration of the equivalence ratio of the isocyanate compound to NCO with respect to the number of OH of the biopolyol.

Particularly, the flame-retardant bio-polyurethane according to the present invention can be manufactured into various products through various molding processes, and in particular, it can be produced in foam form through foaming.

The production method of the flame-retardant bio-polyurethane foam is not particularly limited, and the urethane reaction may be carried out by mixing the additives, bio-polyol and isocyanate at the same time, or the additive may be added first to the bio-polyol and the bio- polyol containing the additive and the isocyanate compound may be mixed with urethane . When the additive, bio-polyol and isocyanate compound are mixed at the same time, it is not easy to form uniform urethane foam due to local nonuniformity of concentration, and handling of bio-polyol and moldability of flame-retardant bio-polyurethane foam are easy The latter method is preferable.

The additives for foaming can be carried out by using a foaming agent, a foaming agent, a catalyst and the like.

The foaming agent may be water as a chemical foaming agent; HCFC-based foaming agents such as HCFC-141b, HCFC-142b, HCFC-124 and HCFC-22; 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-pentafluoro Tetrafluoroethyldifluoromethyl ether (HFE-236pc), 1,1,2,2-tetrafluoroethyl methyl ether (HFE-254pc), 1,1,2,2- , And 1,1,1,2,2,3,3-heptafluoropropyl methyl ether (HFE-347mcc); Hydrocarbons such as pentane, n-pentane, isopentane and cyclopentane; A physical foaming agent such as carbon dioxide gas, liquefied carbon dioxide gas, or dichloromethane can also be used. Among these, water, carbon dioxide gas, and liquefied carbon dioxide gas are preferable from the viewpoint of the present invention. When added in the gaseous state, it may be any of liquid, supercritical, and subcritical. As the foaming agent according to the present invention, a physical foaming agent such as liquefied carbon dioxide gas can be used, but water can be most preferably used.

When water is used as the foaming agent, it is used in an amount of 1 to 10 parts by weight, preferably 1.2 to 8 parts by weight, more preferably 2 to 7 parts by weight, based on 100 parts by weight of the bio polyol. Particularly, when the amount of water in the foaming agent is in the above-mentioned range, foaming is stabilized and effectively performed.

Foam stabilizer, silicon foam stabilizer, fluorinated compound stabilizer and the like. However, the present invention is not limited to these, and any of them can be used as the foam stabilizer in the technical field. Specifically, a silicone foam stabilizer can be used to form a good foam. For example, FV-1013-16, SRX-274C, SF-2969, SF-2961, SF-2962, L-3601, SZ-1325, SZ-1328 and Momentive of Dow Corning Silicone Co., L-5309, L-3600, L-5366, L-580 and Y-10366 manufactured by Mitsubishi Chemical Corporation and DC-2525 and DC-6070 manufactured by Air Products, B-8715 and B- -8450 and the like can be preferably used. The amount of the foaming agent to be used may be 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the bio-polyol.

The catalyst is used to shorten the reaction time between the polyol and isocyanate, and is not particularly limited. Usually, it is possible to use an amine catalyst such as a gel catalyst, a secondary or tertiary amine compound, an amine catalyst and / have.

The gel catalyst mainly promotes the gel reaction to form a urethane chain in a urethane foam, and a tin catalyst is used. Examples of the tin catalyst include tin salts of carboxylic acid, tin acrylate, trialkyltin oxide, dialkyltin dihalide, dialkyltin oxide (dibutyltin (IV) oxide and the like), dibutyltin dilaurate, di At least one selected from the group consisting of butyltin diacetate, diethyltin diacetate, dihexyltin diacetate, di-2-ethylhexyltin oxide, dioctyltin dioxide and tin octoate may be used.

Examples of the amine-based catalyst include triethylenediamine, triethylamine, tripropylamine, triisopropanolamine, tributylamine, trioctylamine, hexadecyldimethylamine, tetramethylethylenediamine, 3-methoxy- N, N-diethylaminopropylamine, tris (3-dimethylamino) propylhexahydrotriamine, N-methylmorpholine, N N, N ', N'-tetramethylethylenediamine, diethylenetriamine, diethylenetriamine, diethylenetriamine, diethylenetriamine, diethylenetriamine, diethanolamine, N, N, N, N, N ', N'-tetramethylbutylamine, tetramethylbutylenediamine, tetramethylbutylenediamine, N, ', N', N'-pentamethyldiethylenetriamine, and triethylenediamine may be used. There. At this time, Polyact 8, N, N, N ', N', N'-pentamethyldiethylenetriamine, trade name Polyact 5 in the case of N, N-dimethylcyclohexylamine and trade name TEDA-33P in the case of triethylenediamine, .

Examples of the metal catalyst include at least one selected from the group consisting of potassium octoate, potassium acetate, bismuth-based gel catalyst, and tin type catalyst Can be used.

The catalyst may be contained in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the biopolyol. When the tin catalyst, the amine catalyst and the metal catalyst are contained simultaneously, the content may be 0.2 to 6 parts by weight.

The surface active agent controls the surface tension at the time of forming the foam cell to suppress the size of the foam cell from becoming excessively large, and stabilizes the formation of the foam cell. As the kind of the surfactant, it is possible to use various kinds known in the art.

In order to control the reactivity, 2 to 5 polyhydric alcohols may be added in an amount of 10 to 30 parts by weight based on 100 parts by weight of the biopolyol. Examples thereof include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, Dihydric alcohols such as diol, hexanediol, neopentyl glycol and cyclohexylene glycol; Trivalent alcohols such as trimethylol propane and glycerin; Pentaerythritol, sorbitol, methylglycoside, diglycerin, sorbitol, sucrose and the like may be used.

In addition to the above composition, a flame retardant is added to improve the flame retardancy.

The flame retardant is an additive added to improve the flammability of plastics and has the function of interfering with the combustion. By increasing the flame retardancy, the utilization of the biopolyurethane can be widened. The flame retardant may be in the form of a liquid or a powder, and may be at least one selected from the group consisting of a phosphorus flame retardant, a metal hydrate flame retardant, a halogen flame retardant, a flame retardant aid, and a mixture thereof.

The phosphorus flame retardant may be selected from the group consisting of triphenyl phosphate, cresyl diphenyl phosphate, isopropyl phenyl diphenyl phosphate, triethyl phosphate, tributyl phosphate, tris chloroethyl phosphate, tris chloropropyl phosphate (abbreviated as TCPP), triphenyl phosphate, tricresyl phosphate , Polyphosphoric acid, and mixtures thereof. The halogen-based flame retardant may include decabromodiphenyl oxide or octabromophenyl oxide, and the flame retarding auxiliary may include antimony trioxide.

The amount of the flame retardant to be used may be 10 to 60 parts by weight, preferably 20 to 40 parts by weight, based on 100 parts by weight of the mixture of polyol and isocyanate, in order to ensure both excellent mechanical properties and flame retardancy in the obtained rigid foam.

In addition to the above-mentioned composition, any additive may be additionally used. As a compounding agent, chain extenders, chain terminators, colorants, fillers, internal mold release agents, antistatic agents, antibacterial agents, cell control agents, reaction inhibitors, antioxidants, antioxidants, dispersants, antifading agents, antifungal agents, .

Examples of the chain extender include diamines such as ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, 5-diaminopentane, 1,6-hexamethylenediamine and 1,4-cyclohexanediamine, or a mixture of two or more thereof.

As the chain termination agent, an amine having one functional group such as diethylamine, monoethanolamine, dimethylamine and the like can be used.

The addition of the chain extender and the chain termination is generally used for the production of polyurethane, and the specific use method and the use amount thereof can be appropriately selected by those skilled in the art.

The curing accelerator may be a room temperature and high-temperature curing accelerator, and is not particularly limited in the present invention.

As the room temperature curing accelerator, metal salt compounds or metal-naphthenic acid compounds may be used. Examples of the metal salt compound include potassium oleate, tetra-2-ethyl-hexyltitanate, tin (IV) chloride, iron (III) Chloride (Iron (III) Chloride), dibutyltin dilaurate (DBTL) and the like. Examples of the metal-naphthenic acid compound include zinc naphthenate, lead naphthenate, cobalt naphthenate, calcium naphthenate, and the like. .

As the high-temperature hardening accelerator, an amine-based compound can be used. Examples of specific amine-based compounds include triethylamine (TEA), N, N-diethylcyclohexylamine, 2,6-dimethylmorpholine, triethylenediamine (DABCO, triethylene diamine), dimethylaminoethyl adipate, diethylethanolamine, N, N-dimethylbenzyl amine, DBU (1,8-Diazabicyclo [ Undec-7-ene) and DBN (1,5-diazabicyclo [4.3.0] non-5-ene).

The colorant may be a color pigment or a dye and may be a metal oxide, a composite oxide, a metal sulfide or a metal carbonate including any one of iron, copper, manganese, cobalt, chromium, nickel, zinc, calcium and silver, Pigment components such as black, titanium black, organic black and graphite may be used. If necessary, the above-mentioned coloring materials may be used by mixing two or more kinds thereof.

The flame-retardant bio-polyurethane according to the present invention is an eco-friendly product and can be used variously throughout the industry.

For example, in the form of a foam, it is used in the manufacture of automobile parts, machine parts, industrial parts, electric wires, cables, rolls, hoses, tubes, belts, films, sheets, laminate articles, coatings, adhesives, sealing materials, sports articles, Parts, goods, nursing articles, housing goods, medical care, construction materials, civil engineering, waterproofing materials, packaging materials, insulating materials, insulation materials, and slush powders. In addition, a suitable face material may be provided on one or both sides of the polyurethane foam. The face plate can be, for example, paper, wood, gypsum board, resin, aluminum foil, steel plate, and the like.

It can be applied to applications such as elastomers, artificial leather, spandex, paints, inks, adhesives, sealing materials and the like when they are produced in the form of a resin composition other than a foam.

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 present invention. Such variations and modifications are intended to be within the scope of the appended claims.

[Example]

Manufacturing example  1: Preparation of bio-polyol

(1 mole, manufactured by Succinec Co., Ltd.) and diethylene glycol / triethylene glycol (2.2 mole, 0.7: 0.3 weight ratio) were put into 1 liter of a dried four-necked flask and mechanically stirred. And a DOP catalyst (dioctyltin dilaurate, 0.05 mole) was added thereto. When the solid was dissolved, the temperature was raised to 220 ° C under a reduced pressure, and the reaction was carried out for 6 hours. At this time, the reaction was terminated at the point of 2 mg KOH / g by checking the acid value of the reactant.

Manufacturing example  2: Preparation of bio-polyol

Except that diethylene glycol and triethylene glycol were used as a dihydric alcohol in a weight ratio of 0.6: 0.4, to prepare a bio-polyol.

Manufacturing example  3: Preparation of bio-polyol

Except that diethylene glycol and triethylene glycol were used as a dihydric alcohol in a weight ratio of 0.5: 0.5, to prepare a bio-polyol.

Manufacturing example  4: Preparation of bio-polyol

Except that diethylene glycol and triethylene glycol were used as a dihydric alcohol in a weight ratio of 0.4: 0.6, to prepare a bio-polyol.

Manufacturing example  5: Preparation of biopolyol

Except that diethylene glycol and triethylene glycol were used as a dihydric alcohol in a weight ratio of 0.3: 0.7, to prepare a bio-polyol.

Manufacturing example  6: Preparation of bio-polyol

A biopolyol was prepared in the same manner as in Preparation Example 1 except that diethylene glycol was used alone as a dihydric alcohol.

Manufacturing example  7: Preparation of bio-polyol

The preparation of the bio-polyol was carried out in the same manner as in Preparation Example 1, except that triethylene glycol was used alone as the divalent alcohol.

Manufacturing example  8: Preparation of bio-polyol

Except that diethylene glycol and 1,3-butylene glycol were mixed as a dihydric alcohol, to prepare a bio-polyol.

Manufacturing example  9: Preparation of polyol

A biopolyol was prepared in the same manner as in Preparation Example 1, except that Sigma-Aldrich, a non-bio-derived succinic acid, was used.

Experimental Example  One

The OH value, viscosity, specific gravity and moisture content of the bio-polyol prepared in the above Preparation Example were measured and the results are shown in Table 1 below.

- Specific gravity: KS M 004: 1997

- Viscosity (mPa s): KS A 0531: 2011

- Water (%): KS M 0010: 2011 (Karl Fischer method)

- Molecular weight: US EPA 3640A: 1994 (GPC)

Hydroxyl Number Acid Value
(mg KOH / g) Moisture (wt%) Viscosity (mPa.S) Functionality Color (GARDNER) Production Example 1 322.4 0.59 0.3 380 2.0 15 Production Example 2 311.6 0.68 0.2 365 2.0 15 Production Example 3 304 0.77 0.5 375 2.0 15 Production Example 4 295 0.89 0.4 380 2.0 18 Production Example 5 287 0.92 0.3 350 2.0 18 Production Example 6 384 0.79 0.3 340 2.0 11 Production Example 7 352 0.83 0.5 385 2.0 18 Production Example 8 374 0.88 0.3 365 2.0 11 Production Example 9 384 0.79 0.3 365 2.0 11

Example  1 to 5 and Comparative Example  1 to 3: Preparation of flame retardant bio-polyurethane foam

A flame-retardant bio-polyurethane foam was prepared using the bio-polyol prepared in Preparation Example 1.

A polyol, a catalyst, a foaming agent and a foaming agent shown in the following Table 2 were put into a preformed mold, stirred well at 5000 rpm at room temperature, and then an equivalent amount of MDI corresponding to the OH value of the polyol mixture was added. Urethane foam was prepared. After completion of the reaction, the reaction mixture was allowed to stand for about 20 minutes, demolded, and stored for 6 hours or more in a cool place, followed by cutting the foam.

Table 2 shows the blending ratio (when the MDI index is 1) of each of the examples used for the synthesis of the polyurethane foam. At this time, 100 parts by weight of biopolyol was used to show the respective weight parts of the foam stabilizer, the catalyst, the blowing agent and the isocyanate.

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

- Catalyst: Amine catalyst: Polyact5 (Pentamethyldiethylenetriamine) and Polyact8 (Dimethylcyclohexylamine) from Air Products, TEDA-33P (Triethylenediamine / DPG) from KPX Chemical Co.,

- Silicone surfactant: product name of B-8462, B-8404

- Foaming agent: Product name HCFC-141b (compound: 1,1-dichloro-1-fluoroethane; Cas No. 1717-00-6) manufactured by Zhejiang Juhua Calcium Carbide Co.,

Flame Retardant: Fyrol PCF (compound: Tris (2-chloroisopropyl) phosphate; Cas. No .: 13674-84-5)

Composition (parts by weight) Bio polyol water catalyst Foaming agent blowing agent Flame retardant Isocyanate compound Example 1 100 (Preparation Example 1) 1.3 2 1.5 24 15 100: 120 Example 2 100 (Preparation Example 2) 1.3 2 1.5 24 15 100: 120 Example 3 100 (Preparation Example 3) 1.3 2 1.5 24 15 100: 120 Example 4 100 (Preparation Example 4) 1.3 2 1.5 24 15 100: 130 Example 5 100 (Preparation Example 5) 1.3 2 1.5 24 15 100: 130 Comparative Example 1 100 (Preparation Example 6) 1.3 2 1.5 24 15 100: 100 Comparative Example 2 100 (Preparation Example 7) 1.3 2 1.5 24 15 100: 100 Comparative Example 3 100 (Preparation Example 8) 1.3 2 1.5 24 15 100: 100 Comparative Example 4 100 (Preparation Example 9) 1.3 2 1.5 24 15 100: 120

Experimental Example  2: Evaluation of physical properties -1

The properties of the flame-retardant polyurethane foam prepared in the above Examples and Comparative Examples were measured according to the following, and the results are shown in Table 3 below.

(One) Heat output :

The heat release test was carried out in accordance with KS F ISO 5660-1: 2008. The items and judgment criteria are as follows.

<Criteria>

- Total emission heat for 5 minutes: 8 MJ / m ² or less

- 5 minutes continuous heat release rate over 200KW / M2: 10 seconds or less

- Inspection of test specimens after test: Burning through the specimen. Harmful cracks, pitting and melting: None

(2) Gas hazard test

The gas toxicity test was applied to KS F 2771: 2006 and the combustion gas was assessed by measuring the behavior time by exposure to rodents (experimental white rats).

<Criteria>

- Average duration of downtime for experimental rats: 9 minutes or longer

(3) Evaluation of flame retardancy

ISO 3795 flammability test method.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Heat release test Total heat released for 5 minutes 0.9 0.7 0.5 1.7 1.9 5.9 3.3 3.1 0.8 Overtime 0 0 0 0 0 0 0 0 0 Inspection none none none none none none none none none Gas hazard test Time (minutes: seconds) 12:50 12:30 12:25 9:45 9:01 6:30 7:56 8:30 11:55 Flammability Self-baking Self-baking Self-baking Self-baking Self-baking Self-baking Self-baking Self-baking Self-baking Self-baking

From the results of Table 3, it was confirmed that the polyurethane of Examples 1 to 5 according to the present invention had a physical property equal to or higher than that of the polyurethane (Comparative Example 4) using non-bio derived succinic acid.

In comparison, Comparative Examples 1 to 3 using the compositions not shown in the present invention, even when the dihydric alcohols were used individually or in combination, showed a significant decrease in physical properties as compared with the polyurethane of the examples.

Experimental Example  3: Property evaluation -2

The properties of the polyurethane foam samples prepared in the above Examples and Comparative Examples were measured according to the following methods, and the results are shown in Table 4 below.

(1) Accelerated weatherability: The degree of discoloration was measured by KSM 5982 method to obtain ΔE value. : 4 cycle progress [1 cycle: 8 hours (fluorescent UV irradiation 4 hours, condensation 4 hours)]

(2) Yellow Index: Measured by the KSM 3026 method.

(3) Bending strength and compressive strength (N / cm ² ): Measured according to KS M 3809: 2002.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 ΔE 3.1 3.5 3.1 3.7 3.8 4.1 4.3 4.0 5.0 Yellow Index 13.8 13.2 13.1 15.5 15.9 24.5 26.7 26.7 43.1 Bending strength (N / cm ² ) 340 365 374 315 301 287 255 288 251 Compressive strength (N / cm ² ) 65 63 66 59 58 51 52 53 52

The results of Table 4 show that the polyurethane of Examples 1 to 5 according to the present invention overcomes the discoloration problem caused by the use of the conventional bio-polyol and has excellent bending strength and compressive strength, .

The bio-polyurethane according to the present invention is excellent in flame retardancy and is environment-friendly and applicable to various fields.

Claims (7)

A biopolyol prepared by esterifying a bio-derived dicarboxylic acid compound with a dihydric alcohol containing diethylene glycol and triethylene glycol;
Isocyanate compounds; And
A flame retardant bio-polyurethane resin composition comprising a flame retardant.
The method according to claim 1,
Wherein the bio-derived dicarboxylic acid compound is at least one selected from the group consisting of Azelaic Acid, Adipic Acid, Glutamic acid and succinic acid. Urethane resin composition.
The method according to claim 1,
Wherein the dihydric alcohol is a mixture of diethylene glycol and triethylene glycol in a weight ratio of 1: 0.2 to 1: 0.7.
The method according to claim 1,
Wherein the bio polyol is a flame retardant flame retardant which is produced under one kind of catalyst selected from the group consisting of tetrabutyl tin titanate, dioctyltin dilaurate, zinc acetate, calcium acetate, magnesium acetate, trimethyl phosphate, triphenyl phosphate and cobalt acetate. Polyurethane resin composition.
The method according to claim 1,
Wherein the bio polyol is reacted with 1.5 to 3.0 mols of a dihydric alcohol per mole of the dicarboxylic acid compound derived from sugar fermentation.
The method according to claim 1,
Wherein the flame-retardant bio-polyurethane resin composition is contained in an amount of 1 to 1.8 moles of an isocyanate-based compound per mole of the bio-polyol.
The method according to claim 1,
The flame retardant bio-polyurethane resin composition is used as a blowing agent, a foaming agent, a catalyst, a chain extender, a chain terminator, a flame retardant, a colorant, a filler, an internal mold release agent, an antistatic agent, an antibacterial agent, a cell regulator, a reaction inhibitor, , At least one additive selected from the group consisting of an anti-fading agent, an anti-fungal agent, and a plasticizer.