KR100464838B1 - Manufacturing method of unsaturated polyester resin for molding - Google Patents

Abstract

The present invention relates to a method for producing an unsaturated polyester resin for molding excellent in mechanical strength, water resistance, chemical resistance and impact resistance, wherein each of 5 to 5 halogenated dicarboxylic acid, cyclodicarboxylic acid and dicarboxylic acid is used. 1 step of producing a polyester polyol by ester polymerization of 20 parts by weight and 20 to 60 parts by weight of a polyhydric alcoholol; 2 steps of preparing an unsaturated polyester polyol by ester-reacting 20-30 parts by weight of an alkene-based dicarboxylic acid to 100 parts by weight of the polyester polyol; And 3 to blend 0.01 to 3 parts by weight of a polymerization inhibitor, 50 to 100 parts by weight of a liquid vinyl monomer, and 0.03 to 0.2 parts by weight of a curing accelerator to 100 parts by weight of the unsaturated polyester polyol.

Description

Manufacturing method of unsaturated polyester resin for molding

The present invention relates to a method for producing an unsaturated polyester resin for molding, and more particularly, a vinyl binder is added to a polymer obtained by esterifying a polyacid (saturated acid and unsaturated acid) and a polyglycol. It relates to a method for producing an unsaturated polyester resin used for).

The unsaturated polyester resin for molding a composite material is obtained by adding and polymerizing vinyl compounds such as styrene, vinyltoluene, α-methylstyrene and ο-chlorostyrene to a liquid ester condensate (unsaturated polyester) in which polyhydric acid and polyhydric alcohol are polycondensed. As the three-dimensional crosslinked polymer, unsaturated acids, saturated acids, polyalcohols, and the like are used to improve physical properties.

However, the unsaturated polyester resin for molding using a halogenated dicarboxylic acid has improved flame retardancy of the resin itself, but there are limitations in its use because of difficulties in manufacturing and darkening of the color of the resin.

The unsaturated polyester resin for molding using cyclodicarboxylic acid is improved in impact and water resistance of the resin itself, but is not widely used due to poor workability and chemical resistance.

The unsaturated polyester resin for molding to which dicarboxylic acid (phthalic anhydride, isophthalic acid) is applied has excellent workability, but there are problems in flame retardancy, chemical property, and impact strength of a molded article having the required properties of the consumer.

And, in order to solve the shortcomings of the resin prepared by applying each of these saturated acids, an unsaturated polyester resin to which each of three dicarboxylic acids is applied is blended at room temperature, but this has excellent chemical and impact resistance. There is a disadvantage in that partial physical property degradation occurs in the molded article.

Accordingly, the present invention is to solve the above problems, the object of the molding for having excellent flame resistance, chemical resistance and impact strength by appropriately mixing halogenated dicarboxylic acid, cyclo dicarboxylic acid and dicarboxylic acid It is to provide a method for producing an unsaturated polyester resin.

Method for producing an unsaturated polyester resin for molding to achieve the object of the present invention,

1 step of preparing a polyester polyol by ester polymerization of 5 to 20 parts by weight of halogenated dicarboxylic acid, cyclo dicarboxylic acid and dicarboxylic acid and 20 to 60 parts by weight of a polyhydric alcoholol;

Mixing the polyester polyol and the alkene dicarboxylic acid at a ratio of 100: 20 to 30 parts by weight and then performing ester reaction to prepare an unsaturated polyester polyol; And,

It is characterized by consisting of three steps of blending 50 to 100 parts by weight of the liquid vinyl monomer, 0.01 to 0.2 parts by weight of the polymerization inhibitor and 0.03 to 2.0 parts by weight of the curing accelerator to 100 parts by weight of the unsaturated polyester polyol.

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

Preparation of Polyester Polyols (Step 1)

Some or all of 50 to 110 parts by weight of the polyhydric alcohol is placed in a reactor equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a condenser and a filling cooler, and heated and melted while injecting nitrogen gas. Next, some or all of 5-20 parts by weight of halogenated dicarboxylic acid, cyclodicarboxylic acid and dicarboxylic acid and 0.01 to 0.5 parts by weight of catalyst are added together with stirring at a temperature of 80 to 120 ° C. This causes an ester reaction (condensation reaction). Next, the condensed water is separated while maintaining the reaction at 150 ° C. for 1 hour, at 160 ° C. for 30 minutes, and at 180 ° C. for 1 hour, and the reaction temperature is 230 ° C. in a range in which the outflow of alcohol is not more than 5%. The mixture was gradually heated up to 230 ° C., while the acid value was measured while maintaining the reaction at 230 ° C., when the acid value dropped to 3 or less, the mixture was cooled to 100 ° C. or less to prepare a polyester polyol.

In this step, as the halogenated dicarboxylic acid, tetrabromo dicarboxylic acid, dibromo dicarboxylic acid, tetrachloro dicarboxylic acid, dichloro dicarboxylic acid, het acid, and the like are used. The reason for limiting to -20 parts by weight is that when used at 5 parts by weight or less, the viscosity of the molding resin is increased due to the use of an excessive flame retardant when imparting the flame retardancy of the unsaturated polyester resin for molding, causing a problem of poor workability. When used in parts by weight or more, the flame retardancy is excellent, but the impact strength is lowered, so it is necessary to limit the numerical value.

As cyclodicarboxylic acid, 1,4-cyclohexanedicarboxylic acid is used, and when it is used at 5 parts by weight or less, impact strength and water resistance are decreased, and when it is used at 20 parts by weight or more, the strength of molding resin is decreased. It is good to use in the range of -20 weight part.

As dicarboxylic acid, adipic acid, azeaic acid, sebacic acid, phthalic anhydride, isophthalic acid, terephthalic acid, benzoic acid and the like are used. Also, when used in 20 parts by weight or more, halogenated dicarboxylic acid which gives the resin properties, Since the content of cyclodicarboxylic acid is relatively low, the flame retardancy and impact resistance of the product are inferior, so it is used in the range of 5 to 20 parts by weight.

Polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolpropane, di-trimethylolpropane, trimethylolethane, cyclohexane Aliphatic and cycloaliphatic alcohols having at least two reactive hydroxyl groups consisting of dimethanol, pentaneerythritol, and hydroxypivalylhydroxypivalate (HPHP, Eastman) and having 2 to 18 carbon atoms are used alone or in combination of two or more. .

Looking at the reaction and the product of this step is as follows.

In the above formula, R ₁ and R ₂ is glycol,

R ₃ is cyclodicarboxylic acid,

R ₄ is dicarboxylic acid,

R ₅ is a halogenated dicarboxylic acid.

Preparation of Unsaturated Polyester Polyols (Step 2)

While keeping the temperature of the reactor at 80 to 120 ° C, 20 to 60 parts by weight of alkene dicarboxylic acid was added to 100 parts by weight of the polyester polyol prepared above, and then the reactor temperature was gradually raised. Then, condensation water is generated between 160 and 170 ° C. Next, the reaction is maintained at a temperature at which the condensed water is generated for 1 hour to advance the ester reaction between the polyol and the dicarboxylic acid. At this time, the condensed water is separated and collected separately to measure the content of glycol components present in the condensed water.

Then, the reactor was heated to 210 ° C. over about 2 hours, and the acid value of the reactants was measured. The value was 20 or less and the viscosity was diluted to a certain level (polyol / styrene monomer = 5/5 by weight, and then measured by Gardner viscometer as EG / 25 ° C.), the reaction temperature is lowered to produce unsaturated polyester polyols.

The unsaturated polyester polyol thus produced has a hydroxyl group of 20 to 100, a carboxyl group of 20 or less, and a number average molecular weight of 500 to 4,000.

In the above step, fumaric acid and maleic acid are used as the alkene-based dicarboxylic acid, and when it is used in an amount of 20 parts by weight or less, the unsaturation of the unsaturated polyester polyol is lowered. The lower the ductility of the resin, the longer the curing time, and the more than 60 parts by weight of the polyol, the unsaturation of the polyol increases and the crosslinking density after curing increases the hardness of the molded article. As a problem occurs that a crack occurs in the molding during molding, it is used in the range of 20 to 60 parts by weight.

Preparation of unsaturated polyester resin for molding (3 steps)

0.01 to 0.2 parts by weight of a polymerization inhibitor is added to 100 parts by weight of the unsaturated polyester polyol prepared in the above step, 50 to 100 parts by weight of the reactive monomer (styrene monomer) is mixed and diluted, and then blended 0.03 to 0.2 parts by weight of the curing accelerator to form various moldings. An unsaturated polyester resin for molding having suitable curing properties and workability is prepared.

As the polymerization inhibitor, hydroquinone, copper naphthanate, benzoquinone, parateriacaterol, and the like are used, and as a curing accelerator, cobalt naphthanate, copper naphthanate, calcium, naphthanate, potassium hexam, vanadium naphthanate and Same metal salts and organic catalysts such as dimethyl aniline, diethyl aniline, acetyl acetone, dimethyl acetoamide and dibutylamine are used. The curing accelerator was prepared by adding 0.03 to 3.0 parts by weight of cobalt naphthanate (12%), 0 to 1.0 parts by weight of potassium hexam 977 (17%), 0 to 0.5 parts by weight of acetyl acetone and 0 to 1.0 parts by weight of diethyl acetone. It is more preferable to randin.

Hereinafter, the present invention will be described in detail through examples. These examples are intended to illustrate the invention in more detail and are not intended to limit the scope of the invention.

Example 1

0.2 equivalents of isophthalic acid, 0.1 equivalents of adipic acid and 0.55 equivalents of propylene glycol were initially charged into the synthesis equipment and stirred while heating. Then, the condensation water was collected in a separate container while maintaining the reaction at 170 ° C. for 1 hour to calculate the primary condensation water, and the refractive index and the glycol content were calculated. Then, the reaction was heated to 210 ° C. over 11 hours, and the acid value of the reactants was measured every hour by the ISO 2114-1972 test method. When the value dropped below 5, the reaction product was cooled rapidly to 100 ° C. or lower. The remaining acid and glycol (0.15 equivalent of tetrahydrophthalic acid, 0.55 equivalent of maleic acid, 0.12 equivalent of ethylene glycol, 0.43 equivalent of neopentylglycol) were added and stirred. The progress of the reaction was observed, and after the exothermic reaction of maleic acid was completed, the temperature was raised to 160 ° C and maintained for 2 hours. The secondary condensation water generated at this time was also collected in a separate container to measure the refractive index, and the glycol loss of the condensed water was calculated by comparing this value with the intrinsic refractive index of water. The reaction was then heated to 210 ° C. consistently over 5 hours, lowering the reaction temperature when the loss of glycol was at least 10% of the amount of condensed water, held at this temperature for 30 minutes, and again elevated to 210 ° C. The acid value was calculated by titrating with 0.1 normal KOH solution every hour, and styrene monomer was mixed and melted in a solid component of 6: 4 parts by weight, and the viscosity was measured using a Gardner viscometer at room temperature. When the acid value was 30 or less and the Gardner viscosity reached E-G / 25 ° C, the reaction temperature was lowered and a polymerization inhibitor was added, and a styrene monomer was added at 6: 4 parts by weight based on the solid to prepare a resin.

Example 2

First, except that isophthalic acid, adipic acid, hetic acid, tetrahydrophthalic acid were added and reacted, acid and glycol were added in the same amount to prepare a resin in the same manner as in Example 1.

Example 3

First, all raw materials other than styrene monomers were first introduced from the liquid raw materials, and then solid materials were added to prepare resins. In this example, all the raw materials were added in one reaction, and the temperature was increased by ring-opening reaction of maleic acid occurring at 90-100 ° C. after the raw materials were added. The temperature was raised to 210 ° C. over time, and the condensation water generated at this time was collected in the same manner as in Example 1 and reacted while measuring the refractive index.

Example 4

Resin was prepared in the same manner as in Example 1 except that all the acids and glycols except maleic acid were added to react firstly as in Example 1, and the second reaction was performed by adding maleic acid.

Then, the resin prepared in the above examples consisted of 1 part by weight of a curing accelerator [cobalt naphthanate (12%), 0.3 parts by weight of potassium hexane 977 (17%), 0.2 parts by weight of acetyl acetone and 0.5 parts by weight of diethyl acetone. ] Was homogeneously mixed to make a molded product, and its physical properties were tested. The results are as follows.

Table 1. Property comparison table of resin

* As a comparative example, a molding resin used in Korea, that is, a resin produced using cyclodicarboxylic acid, halogenated dicarboxylic acid or dicarboxylic acid as a main material was used.

* Impact resistance is based on IZOD impact test method, other mechanical strength chemical resistance and flame retardancy test method of KSM 3305 thermosetting unsaturated polyester resin.

As can be seen in Table 1, the molded article molded from the unsaturated polyester resin for molding according to the present invention is much superior to the existing ones and physical properties, mechanical strength, moldability, impact resistance and the like much better.

Claims (12)

1 step of preparing a polyester polyol by ester-polymerizing 5 to 20 parts by weight of halogenated dicarboxylic acid, cyclodicarboxylic acid and dicarboxylic acid with 20 to 60 parts by weight of polyhydric alcohol with polyhydric acid; 2 steps of preparing an unsaturated polyester polyol by ester-reacting 20-30 parts by weight of an alkene-based dicarboxylic acid to 100 parts by weight of the polyester polyol; And, 100 parts by weight of the unsaturated polyester polyol in 0.01 to 3 parts by weight of the polymerization inhibitor, 50-100 heavy ring of the liquid vinyl monomer and 0.01 to 0.2 parts by weight of the curing accelerator in three steps The manufacturing method of the unsaturated polyester resin for shaping | molding comprised. The method of claim 1, Halogenated dicarboxylic acid is unsaturated polyester for molding, characterized in that at least one selected from tetrabromo dicarboxylic acid, dibromo dicarboxylic acid, tetrachloro dicarboxylic acid, dichloro dicarboxylic acid, het acid Method for producing a resin. The method of claim 1, Cyclodicarboxylic acid is 1, 4- cyclohexane dicarboxylic acid, The manufacturing method of the unsaturated polyester resin for shaping | molding. The method of claim 1, The dicarboxylic acid is at least one selected from adipic acid, azeaic acid, sebacic acid, phthalic anhydride, isophthalic acid, terephthalic acid, and benzoic acid. The method of claim 1, Polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolpropane, di-trimethylolpropane, trimethylolethane, cyclohexanedi At least two reactive hydroxyl groups consisting of methanol, pentaneerythritol, and hydroxypivalylhydroxypivalate (HPHP, Eastman) and at least one selected from aliphatic and alicyclic alcohols having from 2 to 18 carbon atoms Method for producing unsaturated polyester resin for molding. The method of claim 1, Unsaturated polyester polyol is a hydroxyl group 20-150, a carboxyl group 20 or less, number average molecular weight 500-4000 The manufacturing method of the unsaturated polyester resin for shaping | molding. The method of claim 1, A method for producing an unsaturated polyester resin for molding, characterized in that 1 to 3 parts by weight of the catalyst is further mixed with respect to 100 parts by weight of the mixture of the polyester polyol and the alkene dicarboxylic acid in two steps. The method of claim 7, wherein The catalyst is at least one selected from the group of strong acids consisting of tetraisopropin titanate, paratoluene phosphonic acid, phosphonic acid and sulfonic acid, and metals group consisting of zinc oxide, antimony oxide and dibutylene oxide. The manufacturing method of unsaturated polyester resin for shaping | molding characterized by the above-mentioned. The method of claim 1, A polymerization inhibitor is a method for producing unsaturated polyester resin for molding, characterized in that at least one selected from hydroquinone, toluhydroquinone, copper naphthanate, benzoquinone, and parakeroletone. The method of claim 1, Curing accelerators include cobalt naphthanate, copper naphthanate, calcium naphate, potassium hexane, vanadium naphthenate, metal salts consisting of dimethylaniline, diethylaniline, acetylacetone, dimethylacetoacetamide and dibutylamine and organic catalysts. Method for producing an unsaturated polyester resin for molding, characterized in that at least one selected. The method of claim 1, Curing accelerator is 0.01 to 3.0 parts by weight of cobalt naphthanate (12%), 0 to 1.0 parts by weight of potassium hexane 977 (17%), 0 to 0.5 parts by weight of acetyl acetone and diethyl acetone relative to 100 parts of unsaturated polyester resin A method for producing an unsaturated ester resin for molding, comprising 0 to 1.0 parts by weight. A molded article made of the unsaturated ester resin for molding according to claim 1.