KR100867156B1 - Polyester-based polymer polyol with an excellent anti-flame property and a manufacturing method thereof - Google Patents

Abstract

The present invention relates to the production of polyester-based polymer polyols having excellent dispersion stability and excellent flame retardancy. The polymer polyols used ester polyols containing aromatic compounds instead of ester polyols using conventional adipic acid, and improved flame retardancy by adding bromostyrene derivatives having excellent flame retardancy, and dispersion stability by introducing a small amount of dispersion stabilizer. A polymer polyol was obtained which was good and also had good mechanical strength. This product is applicable to the field of floor waterproofing material which requires flame retardancy.

Polymer polyols

Description

Polyester-based polymer polyol excellent in flame retardancy and its manufacturing method {POLYESTER-BASED POLYMER POLYOL WITH AN EXCELLENT ANTI-FLAME PROPERTY AND A MANUFACTURING METHOD THEREOF}

Polymer polyols suitable for the production of polyurethane foams and elastomers are well known in the art, and when introduced into the polyurethane foams of the polymer polyols, it is possible to obtain an effect of promoting cell communication and improving foam hardness. Polymer polyols are prepared by polymerizing one or more vinyl monomers (styrene, acrylonitrile, etc.) dissolved in a polyol with a free radical polymerization initiator, which results in stable dispersion of the polymer particles in the polyol liquid phase. It has higher hardness and physical properties than that produced by ordinary polyols made from this kind of polymer polyols.

Such polymer polyols are usually prepared using polyether polyols having a molecular weight of about 1000 to 10000. In particular applications such as shoes, they are prepared using adipic acid polyester polyols.

The method for producing polymer polyols using polyester polyols as base polyols was studied by Hoockers in 1986. Previously, polyester polyols have been used to produce polyols for special applications, called polyether-ester polyols, which have better mechanical properties than polyether-based polyols when used in footwear. When manufacturing a polymer polyol using the base polyol can be expected a lightweight polyol system with excellent physical properties for footwear. As a result of Hoockers' research, a patent for a polymer polyol using adipic acid, a polyester polyol having a molecular weight of 2000 and having a solid content of 25% and purely PS particles dispersed in the base polyol is EP 0 250 351 A2. Was registered as. In this patent, maleic anhydride was added to prepare an unsaturated polyester polyol having an unsaturated group having an OH average hydroxyl value of 53 to 60, and used as a dispersion stabilizer. The polymer polyol prepared using the same had a viscosity value of 16000-18000 cps / 25 ° C. in a solid content of 25-30%. However, since polyester polyols are more hydrophilic than ether polyols, they are less compatible with hydrophobic monomers. Thus, when polyester polyols are used as base polyols, the viscosity is higher than that of polyether polyols.

In addition, in Korean Patent Application No. 2003-0002689, adipic acid and maleic anhydride (0.01 to 0.50% by weight), or isophthalic acid were also used as a diacid to prepare an unsaturated polyester polyol, and a polymer polyol was prepared using the same. Anionic interfaces such as lauryl sulfate, ammonium lauryl sulfate, distearyldimethyl ammonium chloride, cocoamidopropyl betaine, coco ampocarboxy glycinate, coco patioacid monoethanol amide, copolymers of polydimethyl siloxane and polyethylene glycol, etc. It is characteristic that the active agent was used together as an auxiliary dispersion stabilizer. The average hydroxyl value of the obtained polymer polyol was the range of 65-75, and the size of PS particle which is solid content was 400-550 nm.

Polyurethane foams have been used in a wide range of applications, but have the drawback of being easy to burn. Therefore, the flame retardancy of polyurethane foam has emerged as an important issue, especially in the automotive, railroad car, aircraft applications, such a trend is appearing larger.

Conventionally, in flame retardation of polyurethane, a method of dispersing melamine as a flame retardant in a polyol, a method of adding a halogen-based flame retardant containing phosphorus such as tris (2-chloroethyl) phosphate, tris (β-chloropropyl) phosphate, or the like It is known, special forces 38-1850, special forces 45-9197, special forces 39-249, special forces 39-4846, special forces 39-8696, special forces 46-26335, special forces 41-13037, special forces 46- 2269 and the like are known.

However, when the phosphorus- or halogen-based flame retardant is used in a large amount, the physical properties of the foam are deteriorated, and it is easy to cause smearing or sticking. In addition, when using a mixed polyisocyanate, it becomes high density and it is economically disadvantageous. For example, an example of using a phosphorus-containing or halogen-containing compound as a flame retardant is known from Special Offices 38-1750 and Special Offices 45-9197, where a phosphorus-containing compound is added so that the phosphorus content in the polyurethane foam is 1% or more. Or a flame retardant should be blended in an amount of 5 to 30% by weight with respect to the polyurethane foam, and as a result of the addition of the flame retardant in large quantities, problems such as a decrease in the physical properties and hardness of the foam, an increase in permanent deformation, and a decrease in strength In the case of foaming in large quantities, it may be smeared or crushed. In addition, since the content of the flame retardant is large, it tends to be volatilized and lost due to heat and time, and the flame retardant effect tends to be lowered.

Moreover, as a polymer polyol which exhibits a flame retardant effect to a polyurethane conventionally, the polymer condensation polyol which superposed | polymerized the aldehyde condensed-system resin fine particle dispersion described in Unexamined-Japanese-Patent No. 2527006, the halogen-containing monomer in a polyol, etc. is known. .

However, according to Korean Patent No. 1998-0071784, in the case of the aldehyde-based resin fine particle dispersed polyol, physical properties such as wet heat compression permanent deformation regarding durability are deteriorated, and in the case of the halogen-containing monomer, since it contains halogen, It was not desirable.

In Japanese Patent Laid-Open No. 51-73588, a polymer polyol is prepared by copolymerizing at least one of acrylonitrile and methacrylonitrile and at least one of acrylamide and methacrylamide. Publication -997 discloses that polymer polyol is prepared by radical copolymerization of acrylonitrile and acrylamide in the presence of water, in which case the polymer polyol can be made low viscosity.

In addition, US Patent Nos. 4,503,207 and 4,555,527, which prepare polymer polyols and radically polymerize acrylamide or methacrylamide in polyols in the presence of a dispersion stabilizer and water. Suggesting. These patents mention that polymer polyols using acrylamide in the presence of dispersion stabilizers can be made low viscosity by micronization of the dispersed polymer. However, the effect of this polymer polyol on the flame retardant of polyurethane is not mentioned.

However, polymer polyols obtained from acrylamide or (meth) acrylamide and (meth) acrylonitrile as monomers have some effect on flame retardancy, but the polyurethanes obtained by using them have a great durability, particularly wet heat permanent compression deformation. It is weakened to, and has a disadvantage in that the storage stability of a mixed solution of water, a catalyst, a foaming agent and the like as these polymer polyols, blowing agents.

Accordingly, there is a continuing need for polymer polyols that exhibit flame retardancy and are excellent in dispersion stability of dispersed polymer particles and capable of producing a flame retardant polyurethane.

It is an object of the present invention to provide polymer polyols for the production of novel flame retardant polyurethanes.

Another object of the present invention is to provide a novel process for the preparation of polymer polyols for producing flame retardant polyurethanes.

Still another object of the present invention is to provide a polyurethane having excellent flame retardancy and stability.

In order to achieve the above object, the flame-retardant polymer polyol production method of the present invention is characterized in that a mixture of 1-10% by weight of styrene halide and 90-99% by weight of ethylenically unsaturated monomer to the aromatic polyester polyol is polymerized. It is done.

In the present invention, a polyester polyol is mainly used as the base polyol constituting the polymer polyol, and an aromatic polyester polyol is suitable for showing flame retardancy.

In the practice of the present invention, the aromatic polyester polyol may be prepared by reacting a polyhydric acid which is an aromatic compound with a polyhydric alcohol of two or more.

In the practice of the present invention, adipic acid, succinic acid, oxalic acid, malonic acid, trimethyl adipic acid, terephthalic acid, phthalic anhydride, isophthalic anhydride and the like can be used as the type of the polyacid, and in order to exhibit flame retardancy, terephthalic acid, anhydrous Preference is given to using phthalic acid or mixtures thereof.

In the practice of the present invention, dihydric alcohols such as ethylene glycol, diethylene glycol, and polyethylene glycol are generally used as the type of the polyhydric alcohol. In addition, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,4- Dihydric alcohols, such as cyclohexane dimethanol, are used. In addition, in order to increase the functional group of the ester polyol to 2 or more, a trihydric or higher polyhydric alcohol such as trimethylol propane or pentaerythritol may be used.

In the present invention, the aromatic polyester polyol has a functional group of 2-3, an OH value of 50-700, and more preferably 100-400. If the polyol functional group is low, the dispersion of the polymer particles is poor, the particles are entangled, if high, the viscosity of the base polyol may be too high. When the OH value is low, the viscosity of the base polyol is too high, and when the OH value is high, the amount of the dispersion stabilizer added during polymer polyol polymerization increases.

In the present invention, the ethylenically unsaturated monomer polymerized in the polyol is styrene, acrylonitrile, acrylate, methacrylonitrile, acryloin, methyl methacrylate, vinyl acetate art, vinyl chloride, vinylidene Chloride, acrylamide, methacrylamide or mixtures thereof can be used, preferably a mixture of styrene, styrene and acrylonitrile.

In the present invention, the halogenated styrene is monobromo styrene, dibro styrene, tribromo styrene, tetrabromo styrene, pentabromo styrene, monochloro styrene, dichloro styrene, trichloro styrene, tetrachlorostyrene, penta Chlorostyrene or mixtures thereof, preferably tribromostyrene.

In the present invention, the mixture is preferably composed of 1 to 10% by weight of halogenated styrene and 90 to 99% by weight of ethylenically unsaturated monomer, more preferably 3 to 7% by weight of halogenated styrene and ethylenically. It is preferably made up of 93 to 97% by weight of unsaturated monomers. When the amount of the styrene halide increases, the flame retardancy is good, but the price is high, and when the amount is less, the flame retardancy is lowered.

In the present invention, the polymerized and dispersed mixture preferably contains 5 to 60 parts by weight based on 100 parts by weight of the aromatic polyester polyol. The larger the amount of particles dispersed, the higher the hardness reinforcement effect, but the higher the viscosity of the polymer polyol, resulting in poor fluidity.

In the invention, the polymerization step is preferably carried out in the presence of a dispersant for the stability of the polymer polyol to be produced of the dispersant. More preferably, the dispersant includes a dispersant containing an unsaturated group. Preferably, the dispersant containing the unsaturated group is preferably an unsaturated polyester polyol containing unsaturated polyacid. The unsaturated polyesters containing unsaturated polyacids can use conventional products and are also commercially available.

In the practice of the present invention, the dispersion stabilizer used in the preparation of the polymer polyol contains a double bond which can cause a chemical bond in the molecule, for which a small amount of unsaturated polyacid having a double bond is used. As the type of unsaturated polyacid, maleic acid, fumaric acid itaconic acid, esters of the compounds, chloride derivatives and the like are used, and mainly maleic anhydride is suitable.

In the present invention, the polymerization of ethylenically unsaturated monomers, such as vinyl monomers, is carried out by free radical polymerization initiators. Such initiators are typically used in amounts of 0.01 to 1% by weight relative to the total weight of the monomers. Suitable polymerization initiators include peroxide compounds and azo compounds.

In the practice of the present invention, the polymerization temperature of the polymer polyol is determined according to the type of initiator added, and the yield and efficiency of the polymerization of the reactive monomer can be increased only when the resolution of the initiator is maintained at an appropriate temperature. In other words, it is desirable to maintain a temperature at which the half life of the initiator is about 30 to 120 minutes, and usually a temperature of 100 to 130 ^° C. is appropriate.

In the practice of the present invention, the method of administering the vinyl monomer to the polyol may be a method in which all of the vinyl monomers are administered or slowly added dropwise. However, in terms of yield and efficiency of the polymer polymerization reaction, the method of dropping slowly rather than administering the polymer monomer at once is easy to control the reaction temperature, and the reaction yield can also be improved. Usually, 3-5 hours is appropriate for the continuous addition time of the monomer.

Also in the step of removing the unreacted monomer after polymer polymerization; The presence of the remaining unreacted monomers must be removed completely as they finally cause irritating odors to the polyols in which the polymers are dispersed and have a very detrimental effect on the human body. The removal process of the unreacted monomers varies slightly depending on the type and pressure of the monomers, but it is removed by the distillation under reduced pressure at a temperature above the boiling point of the monomers used in the polymerization of the polymer, generally at a temperature of 100 to 140 ^o C and a pressure of 10 to 15 torr. Remove by distillation under reduced pressure for 5-7 hours.

In the present invention, the polymer polymer which is a dispersed phase of the polymer polyol in which the monomer is dispersed and polymerized by the above step has a particle size (diameter) of 0.1 to 0.7 μm and the particle size is the double bond content, composition, molecular weight and content in the dispersion stabilizer. It can be adjusted by the type and content of the initiator, the solid content and the like. That is, the larger the content of the unsaturated polyacid in the dispersion stabilizer, and the larger the molecular weight, the smaller the size of the polymer fine particles obtained when the same amount of the dispersion stabilizer is added, the lower the viscosity of the polymer polyol. In addition, in the case of the content of the dispersion stabilizer 3 ~ 5pt addition can have a low viscosity polymer polyol having an appropriate particle size and distribution. In addition, the larger the content of the solid content, the greater the viscosity of the polymer polyol obtained by agglomeration of particles between the larger the amount of dispersion stabilizer must be increased.

In one aspect, the flame retardant polymer polyol of the present invention has 1-10% by weight of styrene halide and 90-99% by weight of ethylenically unsaturated monomer in 100 parts by weight of an aromatic polyester polyol having a functional group of 2-3 and an OH value of 50-700. The copolymer consisting of% is dispersed 5 to 60 parts by weight.

In the present invention, the flame retardant polymer polyol may be dispersed using a dispersion stabilizer for preparing a conventional polymer polyol, and preferably, is dispersed in an unsaturated polyester polyol dispersant containing unsaturated polyacid.

The present invention, in one aspect, consists of a flame retardant polyurethane prepared using a flame retardant polymer polyol according to the invention.

In general, the standards for flame retardancy of polyurethane foams include the FMVSS 302 (American Automobile Safety Standards) test method (horizontal method, automobile interior materials), and the Japanese A-A standard (railcar cushions), California No. 117 (Vertical Law, Furniture Chair Bedding), BS-5852 Part 2 (Furniture Chair Bedding) in the UK, UL-94HF-1 (Continuous Ignition Leveling, Electric / Electronic), USA, FAR 25-853 (b) (Aviation Sex screening methods, aircraft cushions), and KSF 2271 (Building Interior, Flame Retardant Class 3) in Korea. In the FMVSS-302 test, the acceptance criteria are to ignite a 1/2 "x4" x4 "specimen for 15 seconds using a Bunsen burner and have a burning rate of 4" / min or self-firing. The CAL 117 open flame method is a vertical test on 10 1/2 "x3" x12 "specimens with an ignition time of 12 seconds and heat treatment for 24 hours at 104 ° C. Combustion lengths up to an average of 4" (up to 8 ", Passed within an average of 5 seconds of burning time (maximum 10 seconds). KSF 2271 (Building Materials Flame Retardant Test Method-Flame Retardant Class 3) for three test pieces has a residual flame that remains on the surface for at least 30 seconds after completion of heating. There should be no deformation, no cracking, more than 1/10 of the melting and specimen thickness, etc. In addition, the gas hazard test method should have a mean duration of at least 9 minutes in white rats.

The polyisocyanate can use all the well-known thing normally used in manufacture of a polyurethane. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, an 80/20 weight ratio mixture of these organic polyisocyanates (TDI-80 / 20, any isomeric mixture of diphenylmethane diisocyanate, Polymer MDI, toluidine diisocyanate, hexamethylene diisocyanate, or a prepolymer modified by reacting these with a polyol, etc. Said polyisocyanate can also be mixed and used in arbitrary ratios.

The equivalent ratio of polyisocyanate to polyol is preferably in the range of NCO / H (active hydrogen) of 0.5-3.0 based on NCO in the polyisocyanate and active hydrogen such as polymer polyol, water and crosslinking agents.

As the blowing agent, a blowing agent usually used in the production of polyurethane foams such as low boiling point hydrocarbons such as water, carbon dioxide, cyclopentane, and hydrofluorocarbons such as HFC-245fa is used.

In addition, polyurethane foams are prepared using commonly used additives such as amine catalysts, organometallic catalysts, silicon foam stabilizers, and crosslinking agents.

Hereinafter, the present invention will be described in detail through examples. The following examples are intended to illustrate the invention and are not to be understood or interpreted as limiting the invention in any form.

Example

Measurements were made according to the following test methods to test the properties of the polymer polyols set forth in the Examples below.

Average hydroxyl value: The value of the equivalent of OH group in grams of polyol in terms of mg of KOH (esterified with excess phthalic anhydride / pyridine solution, and the titration of remaining phthalic anhydride with KOH solution. ASTM D 4274-94 Measured according to the method)

Flame retardant: measured by burning rate of specimen by FMVSS 302 method (mm / min)

Viscosity: Measured using a Brookfield viscometer at room temperature (Spindle No. 4, rpm 5 ~ 10) (cps / 25 ℃)

Example 1 (aromatic polyester polyol synthesis Es. 1)

Into a 1 liter reactor equipped with a stirrer, a thermometer, a condenser, and an N ₂ bubble generator, 269 g of diacid and diethylene glycol composed of 126 g of terephthalic acid and 112 g of phthalic anhydride were added, and the temperature was raised to 220 ° C. The reaction was continued until the acid value was less than 0.8 mg / g KOH while removing the reaction water. The average hydroxyl value of the prepared polyol was 285 and the viscosity was 13000 cps / 25 ° C.

Example 2 (Es. 2)

To prepare a polyester polyol in the same manner as in Example 1. As shown in Table 1, a polyester polyol was prepared by varying the composition of terephthalic acid, phthalic anhydride, and diethylene glycol.

TABLE 1 Aromatic Polyester Polyol Synthesis Examples 1-2

Terephthalic acid (g) Phthalic anhydride (g) Diethylene glycol (g) Average hydroxyl value (mg KOH / g) Viscosity (cps / 25 ℃) 1 Es.1 126 112 269 285 13000 2 Es.2 151 135 264 132 27000

Example 3 (Dispersion Stabilizer Synthesis M. 1)

Into a 1 liter reactor equipped with a stirrer, a thermometer, a condenser, and an N ₂ bubble generator, diacid and diethylene glycol 144 g / ethylene glycol 84g composed of adipic acid 347g / maleic anhydride 12g were added and the temperature was raised to 220 ° C. The reaction was continued until the acid value was less than 0.8 mg / g KOH while removing the reaction water. The average hydroxyl value of the prepared polyol was 42 and the viscosity was 26000 cps / 25 ℃.

Examples 4-6 (M. 2-4)

To prepare a dispersion stabilizer in the same manner as in Example 3. As shown in the following [Table 2], the dispersion stabilizer was prepared by changing the composition of adipic acid, maleic anhydride, and the composition of diethylene glycol / ethylene glycol.

TABLE 2 Dispersion Stabilizer Synthesis Example 3-6

Adipic acid (g) Maleic Anhydride (g) Diethylene glycol (g) Ethylene glycol (g) Average hydroxyl value (mgKOH / g) Viscosity (cps / 25 ^o C) 3 M.1 347 12 144 84 42 26000 4 M.2 339 12 148 87 75 17000 5 M.3 354 6 144 84 46 19000 6. M.4 346 6 148 86 77 10000

Example 5 Preparation of Polymer Polyols (POP 1)

Polyol (450 g) is charged into a three-liter reactor with a volume of 3 liters with a stirrer, condenser, thermometer, and addition tube. As the polyol, Es. 1 (Example 1), which is an aromatic polyester polyol, was used. Also, styrene (285 g), 2,4,5-tribromostyrene (TBS) (15 g), and the remainder of the aromatic polyester polyol (Es. 1) (690 g), dispersion stabilizer (M. 1, 60 g), Vazo- 67 (9 g) were mixed to prepare the inject composition. The supernatant polyol was heated to 120 ° C. and then the feed was fed into the reactor for 4 hours continuously while maintaining 115-125 ° C. After the addition is complete, hold for 0.5 to 1 hour, then remove the unreacted monomer for 7 hours at <5 mmHg and 120 ° C. Solid content: 20%, Viscosity: 27,000 cps / 25 ℃

Examples 6-19 Polymer Polyol Polymerization (POP 2-15)

In the same manner as in Example 5, a polymer polyol was prepared by adding a reactant according to the type and amount of aromatic polyester polyol set as illustrated in Table 2 below, the type and amount of dispersion stabilizer, the amount of monomer added, and the amount of initiator added. . The component ratios of Table 2 are expressed in weight (g).

Table 2 Preparation Examples of Polymer Polyols

POP.1 POP.2 POP.3 POP.4 POP.5 Polyol Type Es.1 Es.1 Es.1 Es.1 Es.1 Additive amount (g) 450 450 450 450 450 Addition amount (g) 690 705 690 705 690 Dispersion Stabilizer Type M.1 M.1 M.2 M.2 M.3 Amount (g) 60 45 60 45 60 Monomer type Styrene Styrene Styrene Styrene Styrene Monomer addition amount (g) 285 285 285 285 285 TBS addition amount (g) 15 15 15 15 15 Initiator ^* amount added (g) 9 9 9 9 9 Solid content (%) 20.0 19.7 20.5 19.6 20.0 Viscosity (cps / 25 ℃) 27000 24000 35000 32000 35000

Table 2 Continued

POP.6 POP.7 POP.8 POP.9 POP.10 Polyol Type Es.1 Es.1 Es.1 Es.2 Es.2 Additive amount (g) 450 450 450 450 450 Addition amount (g) 675 690 675 690 705 Dispersion Stabilizer Type M.3 M.4 M.4 M.1 M.1 Amount (g) 75 60 75 60 45 Monomer type Styrene Styrene Styrene Styrene Styrene Monomer addition (g) 285 285 285 285 285 TBS addition amount (g) 15 15 15 15 15 Initiator ^* amount added (g) 9 9 9 9 9 Solid content (%) 19.9 19.7 20.3 19.5 20.0 Viscosity (cps / 25 ℃) 39000 38000 42000 29000 27000

Table 2 Continued

POP.11 POP.12 POP.13 POP.14 POP.15 Polyol Type Es.2 Es.2 Es.2 Es.2 Es.2 Additive amount (g) 450 450 450 450 450 Addition amount (g) 695 675 690 675 690 Dispersion Stabilizer Type M.2 M.2 M.3 M.3 M.4 Amount (g) 60 45 60 75 60 Monomer type Styrene Styrene Styrene Styrene Styrene Monomer addition amount (g) 285 285 285 285 285 TBS addition amount (g) 15 15 15 15 15 Initiator ^* amount added (g) 9 9 9 9 9 Solid content (%) 19.2 19.9 20.4 19.8 20.0 Viscosity (cps / 25 ℃) 36000 32000 44000 48000 48000

Vazo-67: 2,2'-azobis (2-methylbutanenitrile) polymerization catalyst

[Manufacturer: E. J. du Pont de Nemours and Co.]

Examples 20-23: Preparation of polymer polyols-change of TBS addition amount (POP. 16-19)

In the same manner as in Example 5, a polymer polyol was prepared by adding a reactant in an amount of monomer and TBS added as illustrated in the following [Table 3].

Table 3 Production Examples of Polymer Polyols (POP. 16-18)

POP.16 POP.17 POP.18 Polyol Type Es.1 Es.1 Es.1 Additive amount (g) 450 450 450 Addition amount (g) 690 690 690 Dispersion Stabilizer Type M.1 M.1 M.1 Amount (g) 60 60 60 Monomer type Styrene Styrene Styrene Monomer addition amount (g) 300 292.5 277.5 TBS addition amount (g) 0 7.5 22.5 Initiator ^* amount added (g) 9 9 9 Solid content (%) 19.2 19.9 20.4 Viscosity (cps / 25 ℃) 24000 33000 39000

Vazo-67: 2,2'-azobis (2-methylbutanenitrile) polymerization catalyst

[Manufacturer: E. J. du Pont de Nemours and Co.]

Comparative Example 1 Use of Ultra-Adaptive Adipic Polyester Polyol

Polyol (450 g) is charged into a three-liter reactor with a volume of 3 liters with a stirrer, condenser, thermometer, and addition tube. As the polyol, an adipic acid-based polyester polyol having a mean hydroxyl value of 75 (diethylene glycol 50 mol% / ethylene glycol 50 mol%) was used. In addition, styrene (300 g), the remaining adipic acid-based polyester polyol (Es. 1) (690 g), a dispersion stabilizer (M. 1, 60 g), Vazo-67 (9 g) is mixed to prepare an injection composition. . The supernatant polyol was heated to 120 ° C. and then the feed was fed into the reactor for 4 hours continuously while maintaining 115-125 ° C. After the addition is complete, hold for 0.5 to 1 hour, then remove the unreacted monomer for 7 hours at <5 mmHg and 120 ° C. Solid content: 20%, Viscosity: 16,000 cps / 25 ℃

Test Example: Preparation of Polyurethane Foam

Polyurethane foam was prepared using the polymer polyol prepared in Example 5-23, Comparative Example 1, the compounding ratio and physical properties are shown in [Table 5].

First, the polyol mixture in the composition according to Table 5 is sufficiently mixed at a stirring speed of 4500 rpm for 1 minute. Weigh the well-mixed polyol mixture and prepolymer at the mixing ratio of Table 5 and mix it for 6 seconds at a stirring speed of 4500rpm.The width (200mm) x length (200mm) x thickness (2mm) and width (150mm) previously adjusted to 80 ° C ) The top was closed and foamed after injection into a mold made of iron having a length x length (150 mm) x thickness (10 mm). After heat curing for 1 hour, the foamed foam was released. The obtained foam was measured for flame retardancy and physical properties after staying for 24 hours.

The flame retardancy is in accordance with FMVSS 302 and is expressed in combustion rate mm / min.

Tensile strength and elongation in physical properties were measured by a universal tensile tester, and hardness was measured by Shore A hardness tester. The measurement results are shown in the following [Table 6].

[Table 5] Compounding ratio during polyurethane production

Polyol mixture

Polymer polyol Aromatic polyester polyol (Es. 1, Example 1) Ethylene glycol distilled water foam stabilizer ^{2 )} Accelerator ^{3 )} 55.6g 55.6g 6.2g ^{1 )} 0.6g 0.6g 1.125g

1) In case of comparative example 12.5g

2) Foaming Agent (DC-193)

3) Amine Catalyst (33LV)

Flame Retardant and Physical Property Specimens (200mmx200mmx2mm mold)

Polyol Mixture Prepolymer ^{3 )} 20g 22g

3) Prepolymer (NCO Content 20%) (Samsung Polymer, UTI-4830)

For hardness specimens (150mmx150mmx10mm mold)

Polyol Mixture Prepolymer ^{3 )} 40g 44g

3) Prepolymer (NCO Content 20%) (Samsung Polymer, UTI-4830)

[Table 6] Mechanical Properties of Polyurethane Foam

Density (g / cm 3) Shore A Tensile Strength (kg / ㎠) Elongation (%) Burning speed (mm / min) POP.1 0.35 62 0.43 110 0 POP.2 0.34 60 0.42 105 0 POP.3 0.36 58 0.40 120 0 POP.4 0.35 59 0.40 100 0 POP.5 0.33 60 0.42 115 0 POP.6 0.37 59 0.43 105 0 POP.7 0.35 58 0.41 108 0 POP.8 0.36 60 0.41 110 0 POP.9 0.34 62 0.46 172 0 POP.10 0.36 64 0.45 175 0 POP.11 0.35 65 0.49 165 0 POP.12 0.37 64 0.47 185 0 POP.13 0.34 61 0.46 175 0 POP.14 0.35 62 0.47 170 0 POP.15 0.37 58 0.42 168 0 POP.16 0.33 63 0.50 106 0 POP.17 0.35 64 0.48 108 0 POP.18 0.39 54 0.38 110 0 Comparative Example 1 0.35 65 0.53 240 75

In Table 6, when the aromatic polyester polyol and TBS are used (POP. 1 to 18), the flame retardancy is remarkably different compared to Comparative Example 1 using the adipic acid-based polyester polyol. In other words, when the adipic acid-based polyester polyol is used, the specimen burns out, but when the aromatic polyester polyol and TBS are used, the flame retardancy is excellent. In addition, it can be seen that the lower the average hydroxyl value of the used aromatic polyester polyol (POP 9-15), the better the mechanical properties. Physical properties are affected by the average hydroxyl value and unsaturated polyacid content of the dispersion stabilizer used (POP.1 ~ 8, 9 ~ 15) .The lower the average hydroxyl group, the higher the unsaturated polyacid content, the higher the mechanical properties. Able to know. However, as the amount of TBS used increased (POP. 16-18), the mechanical properties fell slightly.

As described above, the present patent uses an aromatic polyester polyol as a base polyol, and in order to introduce flame retardancy, a tribromostyrene compound is introduced in the production of a polymer polyol, so that the flame retardancy is required in the construction field, automobile, electric / electronic, etc. New polyester-based polymer polyols suitable for use in aircraft applications have been prepared. The obtained polymer polyol was able to improve the point that the polymer polyol using the existing adipic acid-based polyester polyol was easily burned and had excellent dispersion stability.

Claims (10)

A mixture of 1-10% by weight of styrene halide and 90-99% by weight of ethylenically unsaturated monomer is added to the aromatic polyester polyol for polymerization. Herein, the aromatic polyester polyol has a functional group of 2-3 and an OH value of 50 to 700, wherein the method of producing a flame retardant polymer polyol. delete  The method of claim 1, wherein the ethylenically unsaturated monomer is styrene, acrylonitrile, acrylate, methacrylonitrile, acryloin, methyl methacrylate, vinyl acetate art, vinyl chloride, vinylidene chloride, acrylic And amide, methacrylamide, and mixtures thereof. The method of claim 1, wherein the halogenated styrene is monobromo styrene, dibro styrene, tribromo styrene, tetrabromo styrene, pentabromo styrene, monochloro styrene, dichloro styrene, trichloro styrene, tetrachloro styrene, Characterized in that it is selected from the group consisting of pentachlorostyrene. 5. The method of claim 4, wherein said halogenated styrene is tribromostyrene. 2. The process according to claim 1, wherein 5 to 60 parts by weight of the mixture is polymerized with respect to 100 parts by weight of the aromatic polyester polyol. The method according to claim 1, wherein an unsaturated polyester polyol containing unsaturated polyacid is used as a dispersion stabilizer. A copolymer of 1 to 10% by weight of tribromostyrene and 90 to 99% by weight of ethylenically unsaturated monomer is included in 100 parts by weight of an aromatic polyester polyol having 2 to 3 functional groups and 50 to 700 OH. Flame retardant polymer polyol dispersion, characterized in that dispersed by weight. 9. Flame retardant polymer polyol dispersion according to claim 8, characterized in that it is dispersed with an unsaturated polyester polyol dispersant containing unsaturated polyacids. A flame-retardant polyurethane foam prepared by reacting the flame-retardant polymer polyol dispersion of claim 8 with a prepolymer under a foam stabilizer, a crosslinking agent, a catalyst and a blowing agent.