TWI588127B - DINT plasticizer and its manufacturing method and use - Google Patents

Description

DINT plasticizer, manufacturing method and use thereof

The invention relates to a DINT plasticizer, in particular to a DINT plasticizer with low mobility and its use.

Plasticizers can be applied to plastics in many ways, as coating materials, filling and reinforcing materials, processing aids, etc. The plasticizer and the thermoplastic plastic material are physically active, and the plasticizer is soluble in the thermoplastic plastic material to form a uniform phase, and has a swelling effect, and can effectively reduce the processing of the thermoplastic plastic material compared with the thermoplastic plastic material before the plasticizer is not added. The temperature makes the thermoplastic plastic material susceptible to heat flow, increased elasticity and reduced hardness.

Plasticizers are used in a wide range of applications, but must be odorless, colorless, UV resistant, low temperature resistant, heat resistant, hydrolysis resistant, non-flammable, low volatility and non-hazardous. In addition, the plasticizer manufacturing method must be simple and environmentally friendly, and it is preferable to produce no by-products and wastewater containing pollutants in the production process.

As a raw material of the plasticizer, an esterified product of an acid and an alcohol (hereinafter referred to as a plasticizer ester compound) may be selected, wherein the acid includes a dicarboxylic acid and a polycarboxylic acid, and the alcohol is a linear or branched chain of 6 to 13 carbons. The alcohols may be individual compounds or mixtures. The basic process of the plasticizer ester ester is carried out by esterification reaction of an acid or an acid anhydride with an alcohol or a mixed alcohol in the presence of an acid (for example, sulfuric acid or the like) as a catalyst, and the reaction alcohol is used in excess during the synthesis, and the acid is used as a catalyst. It is necessary to avoid the occurrence of odor and deterioration of the color of the ester during the synthesis process. Therefore, it is necessary to have mild reaction conditions and many processes in the process. Road purification process.

In the prior art, a catalyst commonly used for synthesizing the plasticizer esterate is a metal-containing esterification catalyst including tin-containing, titanium-containing or zirconate-containing catalyst or tin-containing, titanium-containing or zirconium-containing catalyst. An esterification catalyst for salts, oxides or soluble organic compounds. This type of metal catalyst is used in esterification catalysts above 180 ° C, such as tin powder, tin oxide, organic titanates, and organic zirconic acid. Ester (including tetrabutyl zirconate, alkyl titanate and titanium metal chelate, etc.).

The reaction method for preparing the plasticizer ester compound has two kinds of esterification reaction and hydrogenation reaction. Among them, the patent document for producing the plasticizer ester ester by esterification reaction, US Pat. No. 6,310,235 B1, etc., discloses the use of an acid (for example, a dicarboxylic acid or a polycarboxylic acid or an acid anhydride) and an alcohol, in a titanium or zirconium or In the presence of a metal catalyst such as tin, the esterification reaction is carried out. The esterification reaction is carried out in two stages. First, the monoesterification reaction is carried out at a lower temperature (120 to 160 ° C), and then the temperature is raised to 250 ° C and a catalyst is added. The diesterification reaction is carried out. After the completion of the reaction, the neutralization reaction is carried out with an aqueous solution of an alkali metal or an alkaline earth metal hydroxide, followed by removal of excess reaction alcohol, drying, filtration, and the like to prepare the plasticizer ester compound. The disadvantage of this esterification process is that the reaction time is long.

In the prior art, commonly used plasticizers are phthalic acid plasticizers such as diisooctyl phthalate or diisononyl phthalate, and diisooctyl terephthalate (Di) (2-ethylhexyl) terephthalate, hereinafter referred to as DOTP plasticizer). However, according to the literature, phthalic acid-based plasticizers have environmental hormone problems, which are extremely harmful to organisms and the environment.

The diisooctyl terephthalate plasticizer (DOTP), although an environmentally friendly plasticizer, has a glass transition temperature (Tg) of -82 ° C, but is used for the manufacture of soft PVC products. When it is necessary to use a high amount of plasticizer, there is a disadvantage that the plasticizer migrates to the surface of the product (hereinafter referred to as migration property), and even when the addition amount reaches 70 PHR, the migration rate is more than 2.5%, which affects the appearance.

In view of the above, the main object of the present invention is to improve the migration of terephthalic esters, and to synthesize a di-isononyl terephthalate (hereinafter referred to as DINT) by using a mixture of different components of isodecyl alcohol. Plasticizer ester), when used as a plasticizer in plastic products, has low mobility, especially for PVC products with high dosage (up to 70PHR), the migration rate is less than 1.4% (the lower the migration rate) The better), significantly better than other plasticizers.

The method for producing diisononyl terephthalate of the present invention comprises using terephthalic acid (PTA) and an isodecyl alcohol mixture (INA) containing a plurality of components as raw materials, without phthalic acid or anhydride, in titanium In the presence of tin or an inorganic acid catalyst, the esterification reaction is carried out. After the reaction is completed, the neutralization reaction is carried out with an aqueous solution of an alkali metal hydroxide, and then the excess reaction alcohol is removed, and finally dried, filtered, and purified to obtain a high purity. DINT plasticizer esters with good hue and low mobility, the specific method includes the following steps: 1) taking 23~35 wt% of terephthalic acid (PTA) or its derivative based on the total weight of the reactants (total weight of PTA and INA) And a mixture of 65-77 wt% isodecyl alcohol (INA) as a raw material; wherein the isodecyl alcohol mixture comprises at least the following components (a) to (g), and all the components are 100 mol% in total: (a) isooctanol : 0.1 to 0.25 mol%; (b) methyl propyl pentanol: 0.03 to 0.3 mol%; (c) 2-methyl octanol: 30 to 35 mol%; (d) dimethyl heptanol: 10 to 15 mol%; (e) 5-methyloctanol: 50 to 55 mol%; (f) n-nonanol: 1 to 5 mol%; (g) isodecyl alcohol: 1.0~ 2.5 mol%; 2) based on the total weight of the reactants (total weight of PTA and INA), 0.1 to 6 wt% of a metal-containing catalyst or a mineral acid catalyst is used as an esterification catalyst; 3) at a reaction pressure of 5 to 760 mbar and a reaction temperature 200~250 ° C, the composition of the terephthalic acid or its derivative of step 1) and isodecyl alcohol mixture, in the presence of the esterification catalyst in step 1), a single step of esterification reaction for 9 to 16 hours, Until the acid value of the reaction mixture reaches 1 mgKOH/g or less; 4) After the completion of the reaction, the reaction mixture is neutralized with an aqueous alkali metal hydroxide solution containing 5 to 20% by weight of the hydroxide mixture until the acid value of the reaction mixture reaches 0.07 mgKOH/ When g is below, the excess alcohol is removed, dried and filtered to obtain a DINT plasticizer ester.

The DINT plasticizer ester compound obtained by the invention can be used as a plasticizer, especially in terms of the finished product quality and processing property of the plasticizer, and is equivalent to a terephthalate plasticizer (for example, a DOTP plasticizer). And used for soft (plasticizer 70PHR or more) plastic products with low migration rate, migration rate is less than 1.4%, better than DOTP plasticizer, no harm to the organism and the environment, it can replace the phthalic acid plasticizer ( For example, DOP plasticizers) and DOTP plasticizers.

The method for preparing diisononyl terephthalate (DINT) of the present invention is to use a mixture of terephthalic acid and isodecyl alcohol as a raw material for esterification reaction, and a metal catalyst or inorganic acid contact is selected. The medium is an esterification catalyst, and the terephthalic acid and the isodecyl alcohol mixture are subjected to an esterification reaction in the presence of the esterification catalyst to obtain a DINT plasticizer ester compound. Wherein the isodecyl alcohol mixture composition comprises at least the following components (a) to (g), and all the components are 100 mol% in total: (a) isooctanol: 0.1 to 0.25 mol%; (b) methylpropyl pentane Alcohol: 0.03~0.3mol%; (c) 2-methyloctanol: 30~35mol%; (d) dimethylheptanol 10~15mol%; (e) 5-methyloctanol: 50~55mol% (f) n-nonanol: 1 to 5 mol%; and (g) isodecyl alcohol: 1.5 to 2.5 mol%.

The amount of methyl propyl pentanol used in the isodecyl alcohol mixture is limited to be 0.03 to 0.3 mol%, and when used in an amount less than 0.03 mol% or more than 0.3 mol%, the DINT plasticizer synthesized in the present invention is caused. When applied to soft plastic products (plasticizers up to 70PHR), the plasticizer migration rate is higher than 1.4%.

In addition, the amount of isodecyl alcohol used in the isodecyl alcohol mixture is also limited to 1.5 to 2.5 mol%, and when used in an amount less than 1.5 mol% or more than 2.5 mol%, the DINT plasticity of the synthesis of the present invention may also be caused. When applied to soft plastic products (plasticizers up to 70PHR), the plasticizer migration rate is higher than 1.4%.

The methyl propyl pentanol is selected from the group consisting of 1-methyl-1-propylpentanol, 1-methyl-2-propylpentanol, 1-methyl-3-propylpentanol, 1-methyl 5-methylpentanol, 2-methyl-1-propylpentanol, 2-methyl-2-propylpentanol, 2-methyl-3-propylpentanol, 3-methyl- 1-propylpentanol, 3-methyl-1-propylpentanol, 3-methyl-2-propylpentanol, 3-methyl-3-propylpentanol, 3-methyl-5- Propyl pentanol, 4-methyl-1-propylpentanol, 4-methyl-2-propylpentanol, 4-methyl-3-propylpentanol, 4-methyl-5-propyl E Alcohol, 5-methyl-1-propylpentanol, 5-methyl-2-propylpentanol, 5-methyl-3-propylpentanol or 5-methyl-4-propylpentanol.

In the method for producing diisononyl terephthalate (DINT) of the present invention, the esterification catalyst used for the esterification reaction is used in an amount of 0.1 to 6.0% by weight based on the total amount of the synthetic raw materials, and a mineral acid may be selected. Or metal catalyst. Wherein, the inorganic acid comprises one or more of sulfuric acid, boric acid, phosphoric acid, perchloric acid or p-toluenesulfonic acid; and the metal catalyst may be selected from tin octylate, tetraisopropyl titanate (TIPT) or One or more of isobutyl titanate (TIBT).

In the method for preparing diisononyl terephthalate (DINT) according to the present invention, the raw materials for synthesizing the mixture of terephthalic acid and isodecyl alcohol are required to be stoichiometrically, in particular, an excess of alcohol is required, and the amount of the reaction alcohol is required. More than 0.1~1mol of acid.

In the process for preparing diisononyl terephthalate (DINT) of the present invention, a single step high temperature esterification method is used to carry out terephthalic acid or its derivative with isodecyl alcohol in the presence of an esterification catalyst. Esterification reaction and synthesis of DINT plasticizer esterate.

The DINT plasticizer ester preparation method of the invention comprises the following steps: 1) taking a terephthalic acid or a derivative thereof and a mixture of isodecyl alcohol as a raw material, and the molar ratio thereof is 1:2.2 to 3.8, which is equivalent to a weight percentage. Based on the total weight of the reactants (PTA and INA weight), 23 to 35 wt% of terephthalic acid or its derivative and 65 to 77 wt% of isodecyl alcohol mixture; 2) 0.1 based on the total amount of DINT plasticizer esterification. ~6wt% of metal-containing catalyst or inorganic acid catalyst is esterification catalyst; 3) at reaction pressure 5~760mbar and reaction temperature 200~250°C, preferably reaction pressure 15~700mbar and response temperature 220~240°C Next, the composition of the terephthalic acid or its derivative of the step 1) and the isodecyl alcohol mixture is subjected to a single step esterification reaction in the presence of the esterification catalyst of the step 1) for 9 to 16 hours until the reaction mixture The acid value is up to 1 mgKOH/g or less; 4) after completion of the reaction, the reaction mixture is neutralized with an aqueous alkali metal hydroxide solution containing 5 to 20% by weight of the hydroxide mixture until the acid value of the reaction mixture reaches 0.07 mgKOH/g or less. The excess alcohol is removed, dried and filtered to produce a DINT plasticizer ester.

The DINT plasticizer ester preparation method of the invention must remove water during the reaction, and the water formed in the reaction process is removed together with the reaction alcohol by the azeotropic principle, and the azeotropic temperature is 90-180 °C. When the reaction to the acid value of the reaction mixture is less than 1 mgKOH/g, the reaction mixture in the reaction tank contains, in addition to the DINT plasticizer ester to be synthesized (ie, diisononyl terephthalate), a partial ester remains. Dicarboxylic acid, excess reactive alcohol, and catalyst.

The DINT plasticizer ester preparation method of the invention performs neutralization reaction after completion of the esterification reaction, and uses an aqueous solution of an alkali metal hydroxide as a neutralizing agent to neutralize residual acid in the esterification reaction to form a salt, and neutralize The concentration of the agent is 5 to 25 wt%, preferably 9 to 16 wt%, and the amount of addition is 4 to 5 times the acid value of the reaction mixture. The selection of the aqueous solution of the alkali metal hydroxide is preferably a sodium hydroxide aqueous solution, and the neutralization reaction is carried out. The salt formed later will coagulate and precipitate as a solid crystal, which is easy to remove during filtration in the latter stage of the process.

When the neutralization reaction proceeds until the acid value of the synthesis reaction mixture reaches 0.07 mgKOH/g or less, distillation is carried out to reduce the alcohol content to 300 ppm or less, and the hydrolyzed compound formed by hydrolysis of the catalyst is easily removed by filtration, and may be added high. A surface area adsorbent such as activated carbon or the like to help remove the catalyst for hydrolysis.

After removing excess alcohol, drying and filtering, the drying process can be carried out by An inert gas such as nitrogen or an inert gas is not contained in the reaction vessel, followed by filtration to remove a portion of the reacted carboxylic acid, the hydrolyzed catalyst product, and the adsorbent. The temperature of the filtration can be carried out at room temperature or under heating, and the material used for filtration is generally a filter material such as cellulose, diatomaceous earth, wood dust, or the like.

The DINT plasticizer ester method of the invention is prepared by filtration and purification at room temperature or below, and the neutralized salt, catalytic metal salt and impurities are filtered to obtain the DINT plasticizer ester obtained. Compound. In particular, the purified DINT plasticizer ester compound has a purity higher than 99.8% and a hue of 10 APHA, and can be used as a plasticizer for use.

The diisodecyl terephthalate (DINT) obtained by the method of the present invention is synthesized by using a mixture of different components of isodecyl alcohol, does not contain a raw material of phthalic acid, and is used as a plasticizer, a plasticizer. The quality and processing properties are the same as DOP and DINP phthalic acid plasticizers, and the migration rate of plastic products is better than that of diisooctyl terephthalate (DOTP), especially for plastics. At 70 PHR, the DINT plasticizer migration rate of the present invention is less than 1.4%, and can be applied to soft PVC products requiring high proportion plasticizers (above 70 PHR or more), for example, can be applied to pipes, wires and cables, sports cushions, tables. Soft PVC products such as mats, game balls and gloves.

The effects of the present invention will be more clearly explained by the following examples and comparative examples, but the scope of the present invention is not limited thereto.

The plasticizer esters prepared by the esterification reaction of the following examples and comparative examples were measured for acid value (mgKOH/g), purity (%), hue (APHA) and processed properties according to the following measurement methods.

1. Acid value (mgKOH/g): Measured by ASTM D1045 measurement method.

2. Purity (%): Measured by GC (Gas chromatography) measurement method.

3. Hue (APHA): Measured by Color, Pt-Co unit measurement method.

4. Processing physical property test: The processing formula of the test piece is as follows:

Formulation (A) PVC: 100 PHR, plasticizer: 40 PHR, bismuth zinc stabilizer: 2 PHR.

Formulation (B): PVC: 100 PHR, plasticizer: 70 PHR, bismuth zinc stabilizer: 2 PHR.

The mixture of the formula (A) or (B) was separately mixed and then treated at 175 ° C for 5 minutes using a roller mill to form a 0.4 mm thick sheet, followed by initial coloring with the formula (A). Five workability tests, such as heat resistance, transparency, plasticity coefficient, and tensile strength, were also tested for migration rates using formulations (A) and (B).

a. Initial coloring method:

The 0.4 mm thick sheet obtained in the formula (A) was preheated at 185 ° C for 3 minutes using a pressure device, heated for 3 minutes, and then cooled for 3 minutes, thereby forming a sheet of 4 mm thick, and then a spectrometer (Spectrophotometer) ; MS-020 PLUS) for yellowness detection.

b. Heat resistance measurement method:

The 0.4 mm thick sheet obtained by the formula (A) was cut into pieces of 25 cm × 1.5 cm × 0.2 cm, and subjected to a heat resistance test at 180 ° C × 2 hr in an automatic oven (Automatic Testing Oven; Metrtrastat PSD-260). .

c. Method for measuring the mobility rate:

The 0.4 mm thick sheets obtained by the formulas (A) and (B) were cooled, cut into 5 cm × 5 cm, and clamped on a 5 cm × 5 cm PVC hard tape of known weight, and then placed up and down with a flat glass plate and pressurized. 3kg load, placed in an oven test 100 ° C × 24hrs, compare the pros and cons of its migration: Migration permeability %: Y-X/X×100. X: is the weight of a hard PVC tape of known weight.

Y: the weight of the hard PVC tape after penetration

d. Method of measuring transparency:

The 0.4 mm thick sheet obtained in the formula (A) was preheated at 185 ° C for 3 minutes using a pressure device, heated for 3 minutes, and then cooled for 3 minutes, thereby forming a sheet of 4 mm thick, and then by haze meter. (Gloss-Haze Meter; VGS-300A) for the detection of transparency.

e. Determination of plasticization coefficient:

The 0.4 mm thick sheet obtained by the formula (A), if prepared by the test piece method for detecting transparency, is hot pressed into a 6 mm thick test piece, and the test piece is contacted for 15 seconds on the hardness tester, and the value is compared, and then the hardness and PHR are compared. The relationship table, and the plasticization coefficient is calculated by the following formula.

Plasticization coefficient = sample amount / DOP material amount.

f. Method of testing tensile strength

The 0.4 mm thick sheet obtained in the formula (A) was cut into a dumbbell shape, and the tensile strength was measured by a tensile tester (Universal test machine; SHIMADZU AG-X), and the stretching speed was 200 mm/min.

g.Tg point test method

The Tg test was performed on a DSC (Differentile Scanning Calorimeter; TA-2100) weighing 5-10 mg of the plasticizer sample.

[Example 1]

According to the formula of Table 1, 119g of terephthalic acid (PTA), mixed with isodecyl alcohol (containing 2-methyl-2-propylpentanol 0.2mol%, isodecyl alcohol: 1.4mol%; South Asia Plastics Co., Ltd. ), taking 311g, catalyst TIPT (tetraisopropyl titanate) added 0.71g, terephthalic acid, isodecyl alcohol mixture and catalyst simultaneously into the four-necked flask, the reaction temperature under nitrogen 225 ° C, reaction time 9 When the reaction pressure is 5 to 760 mbar, the water must be removed during the reaction, and when the reaction is carried out until the acid value is 1 mgKOH/g or less, the aqueous solution of the alkali metal hydroxide is neutralized until the acid value of the synthesis reaction mixture is 0.07 mgKOH/g or less. Distillation is carried out to reduce the alcohol content to less than 300 ppm, and then subjected to filtration and purification to obtain a DINT plasticizer ester compound, which is used as a plasticizer.

The basic physical properties and processed physical properties of the DINT plasticizer ester compound were obtained. The test results are shown in Table 1, wherein the color phase 10APHA, the acid value was 0.05 mgKOH/g, and the purity was 99.8%. DSC Tg point test; Tg = -76 ° C; transition rate measurement result is 1.25% (hereinafter simplified to transfer rate: 1.25%), transparency: 89.5%, plasticization coefficient: 1.1.

[Example 2]

According to the preparation method of the first embodiment, a mixture of isodecyl alcohol (including 2-methyl-2-propylpentanol 0.2 mol%, isodecyl alcohol: 1.4 mol%; manufactured by Nanya Plastics Co., Ltd.) was prepared according to the formulation of Table 1. It was changed to a mixture of isodecyl alcohol (containing 0.03 mol% of 2-methyl-2-propylpentanol and isopropanol: 1.4 mol%; manufactured by Nanya). DINT plasticizer esterates were prepared under the same process conditions.

The basic physical properties and processing properties of the prepared DINT plasticizer ester compound, the test results are shown in Table 1, wherein the color phase 10APHA, acid value 0.06mgKOH / g, purity: 99.8%; DSC Tg point test, Tg = -76 ° C; Migration rate: 1.35% (at 70PHR), transparency: 89.5%, plasticization coefficient: 1.1.

[Example 3]

According to the preparation method of Example 1, according to the formula of Table 1, the isodecyl alcohol mixture (containing 2-methyl-2-propylpentanol 0.2 mol%, isodecyl alcohol: 1.4 mol%; manufactured by Nanya Company) was changed. An isodecyl alcohol mixture (containing 2-methyl-2-propylpentanol 0.3 mol%, isodecyl alcohol: 1.4 mol%; manufactured by Nanya Plastics Co., Ltd.). DINT plasticizer esterates were prepared under the same process conditions.

The basic physical properties and processing properties of the DINT plasticizer ester compound prepared, the test results are shown in Table 1, wherein the color phase 10APHA, acid value 0.06mgKOH / g, purity: 99.6%; DSC Tg point test, Tg = -76 ° C; Migration rate: 1.3% (at 70PHR), transparency: 89.4%, plasticization coefficient: 1.1.

[Embodiment 4]

According to the preparation method of Example 1, according to the formula of Table 1, the isodecyl alcohol mixture (containing 2-methyl-2-propylpentanol 0.2 mol%, isodecyl alcohol: 1.4 mol%; manufactured by Nanya Company) was changed. An isodecyl alcohol mixture (containing 0.2 mol% of 2-methyl-2-propylpentanol, isodecyl alcohol: 1 mol%; manufactured by Nanya Plastics Co., Ltd.). DINT plasticizer esterates were prepared under the same process conditions.

The basic physical properties and processing properties of the DINT plasticizer ester compound prepared, the test results are shown in Table 1, wherein the color phase 10APHA, acid value 0.06mgKOH / g, purity: 99.7%; DSC Tg point test, Tg = -76 ° C; Migration rate: 1.38% (at 70 PHR), transparency: 89.4%, plasticization coefficient: 1.1.

[Embodiment 5]

According to the preparation method of Example 1, according to the formula of Table 1, the isodecyl alcohol mixture (containing 2-methyl-2-propylpentanol 0.2 mol%, isodecyl alcohol: 1.4 mol%; manufactured by Nanya Company) was changed. An isodecyl alcohol mixture (containing 0.2 mol% of 2-methyl-2-propylpentanol, isodecyl alcohol: 2.5 mol%; manufactured by Nanya). DINT plasticizer esterates were prepared under the same process conditions.

The basic physical properties and processing properties of the DINT plasticizer ester compound prepared, the test results are shown in Table 1, wherein the color phase 10APHA, acid value 0.06mgKOH / g, purity: 99.7%; DSC Tg point test, Tg = -76 ° C; The migration rate of processed physical property test: 1.4% (at 70PHR), transparency: 89.5%, plasticization coefficient: 1.1.

[Embodiment 6]

According to the preparation method of Example 1, according to the formula of Table 1, the isodecyl alcohol mixture (containing 2-methyl-2-propylpentanol 0.2 mol%, isodecyl alcohol: 1.4 mol%; manufactured by Nanya Company) was changed. An isodecyl alcohol mixture (containing 3-methyl-1-propylpentanol 0.2 mol%, isodecyl alcohol: 1.4 mol%; manufactured by Nanya Plastics Co., Ltd.). DINT plasticizer esterates were prepared under the same process conditions.

The basic physical properties and processing properties of the prepared DINT plasticizer ester compound, the test results are shown in Table 1, wherein the color phase 10APHA, acid value 0.06mgKOH / g, purity: 99.8%; DSC Tg point test, Tg = -76 ° C; The migration rate of processed physical property test: 1.26% (at 70PHR), transparency: 89.5%, plasticization coefficient: 1.1.

[Comparative Example 1]

According to the formula of Table 1, 120g of terephthalic acid (PTA), 280g of isooctyl alcohol (2EH), and 0.6g of catalyst TIPT (tetraisopropyl titanate), terephthalic acid, different The octanol and the catalyst are simultaneously fed into a four-necked flask. The reaction temperature is 225 ° C under nitrogen, the reaction time is 8 hours, and the reaction pressure is 5 to 760 mbar. The water must be removed during the reaction, and the reaction is carried out until the acid value is 1 mgKOH/g or less. In the case of neutralization with an aqueous solution of an alkali metal hydroxide to a pH of 0.07 mgKOH/g or less of the synthesis reaction mixture, distillation is carried out to reduce the alcohol content to 300 ppm or less, followed by filtration and purification to obtain terephthalic acid. Diisooctyl ester (DOTP) esterate can be used as a plasticizer.

The basic physical properties and processing properties of the prepared DOTP plasticizer ester compound, the test results are shown in Table 1, wherein the color phase 10APHA, acid value 0.06mgKOH / g, purity: 99.7%; DSC Tg point test, Tg = -82 ° C; Migration rate: 2.5% (at 70 PHR), transparency: 89.2%, plasticization coefficient: 1.05.

[Comparative Example 2]

As in the preparation method of Example 1, according to the formulation of Table 1, the isodecyl alcohol mixture was replaced by a mixture of isopropanol containing 0.4 mol% of 2-methyl-2-propylpentanol, and the same process conditions were obtained. DINT plasticizer esterified. .

The basic physical properties and processing properties of the prepared DOTP plasticizer ester compound, the test results are shown in Table 1, wherein the hue 12APHA, acid value 0.06mgKOH / g, purity: 99.8%; DSC Tg point test, Tg = -75 ° C; Migration rate: 1.5% (at 70PHR).

[Comparative Example 3]

As in the preparation method of Example 1, the alcohols in the formula 1 were replaced with a mixture of isodecyl alcohol (excluding 2-methyl 2-propylpentanol, isodecyl alcohol and derivatives thereof; manufactured by Evonik Co., Ltd.). DINT plasticizer esterates were prepared under the same process conditions.

The basic physical properties and processing properties of the prepared DOTP plasticizer ester compound, the test results are shown in Table 1, wherein the hue 12APHA, acid value 0.06mgKOH / g, purity: 99.7%; DSC Tg point test, Tg = -74 ° C; Migration rate: 1.8% (at 70PHR).

[Comparative Example 4]

According to the preparation method of the first embodiment, the alcohol is replaced by a mixture of isodecyl alcohol (containing 2-methyl-2-propylpentanol 0.2 mol%, isodecyl alcohol: 2.6 mol%) according to the formulation of Table 1. DINT plasticizer esterates were prepared under process conditions.

The basic physical properties and processing properties of the prepared DOTP plasticizer ester compound, the test results are shown in Table 1, wherein the hue 12APHA, acid value 0.05mgKOH / g, purity: 99.8%; DSC Tg point test, Tg = -74 ° C; Migration rate: 1.7% (at 70 PHR).

[Comparative Example 5]

According to the method of the first embodiment, according to the formula of Table 1, the alcohol is a mixture of isodecyl alcohol (including 2- A DINT plasticizer esterified product was obtained under the same process conditions by substituting methyl 2-propylpentanol (0.2 mol%, isodecyl alcohol: 0.8 mol%).

The basic physical properties and processing properties of the prepared DOTP plasticizer ester compound, the test results are shown in Table 1, wherein the hue 13APHA, acid value 0.05mgKOH / g, purity: 99.8%; DSC Tg point test, Tg = -74 ° C; Migration rate: 1.6% (at 70PHR).

【Results and discussion】

1. Each of Examples 1 to 6 synthesizes a DINT plasticizer esterified product from terephthalic acid (PTA) and a mixture of isodecyl alcohols (INA) of different compositions, wherein the isodecyl alcohol mixture of Example 1 contains 2-methyl- DINT plasticizer esterified by 2-methylpentanol 0.2 mol% and isodecyl alcohol 1.4 mol%, the migration rate: 1.25% is the best, and the plasticizer usage is 70 PHR, compared with Comparative Example 1~ The migration rate of 5 plasticizers is higher than 1.4%.

2. Example 1 and Comparative Example 1 synthesize a plasticizer esterified product of terephthalic acid (PTA) with isodecyl alcohol (INA) and 2EH, respectively, wherein DINT plasticizer esterified product of Example 1 has a migration rate: 1.25%, the migration rate of the DOTP plasticizer esterified product of Comparative Example 1 is preferably 2.5%, which confirms that the DINT plasticizer ester compound is synthesized by using a mixture of isodecyl alcohol (INA), and when used as a DINT plasticizer, it is indeed The DOTP plasticizer synthesized by 2EH is more effective in improving the migration rate when the plasticizer is added up to 70PHR. When it is applied to PVC products, the surface of the PVC product is not prone to the migration of the plasticizer, not only the appearance is flat and the touch is felt. Preferably.

3. Both Example 1 and Comparative Example 3 synthesize DINT plasticizer esterified product with terephthalic acid (PTA) and a mixture of different constituents of isodecyl alcohol (INA), wherein Example 1 is a mixture of isodecyl alcohol (including 2 - Methyl-2-propylpentanol 0.2 mol% and isodecyl alcohol: 1.4 mol%, manufactured by Nanya Plastics Co., Ltd.) DINT plasticizer ester compound, the migration rate: 1.25%, better than that of Comparative Example 3 DINT plastic Agent ester transfer rate: 1.8%.

4. When the amount of plasticizer reaches 70 PHR, the migration rates of Examples 1 to 6 are much better than those of Comparative Examples 1 to 5. When the amount of plasticizer reaches 40 PHR, the migration rates of Examples 1 to 6 are still better than the comparative examples. 1-3.

Claims (10)

A method for producing a DINT plasticizer, which comprises using terephthalic acid or a derivative thereof and a mixture of isodecyl alcohol as a raw material for the esterification reaction, and has a molar ratio of 1:2.2 to 3.8, and is selected from a metal-containing catalyst or inorganic The acid catalyst is synthesized in the presence of an esterification catalyst to obtain a DINT esterified product, which is characterized in that the isodecyl alcohol mixture is composed of the following (a) to (g) components together and is 100 mol%, and The DINT ester obtained has a glass transition temperature (Tg) of less than -75 ° C and is used as a DINT plasticizer: (a) isooctanol: 0.1 to 0.25 mol%; (b) methyl propyl pentanol: 0.03 to 0.3 Mol%; (c) 2-methyloctanol: 30 to 35 mol%; (d) dimethyl heptanol: 10 to 15 mol%; (e) 5-methyloctanol: 50 to 55 mol%; (f) N-decyl alcohol: 1 to 5 mol%; (g) isodecyl alcohol: 1.0 to 2.5 mol%. A method for producing a DINT plasticizer, which comprises the following steps of preparing a DINT esterified product for use as a plasticizer: 1) taking terephthalic acid or a derivative thereof based on the total weight of the reactants (PTA and INA weight) 23~35wt% and isodecyl alcohol mixture 65~77wt%; wherein the isodecyl alcohol mixture comprises at least the following components (a) to (g), and the total composition is 100 mol%: (a) isooctanol: 0.1 ~0.25 mol%, (b) methyl propyl pentyl alcohol: 0.03 to 0.3 mol%, (c) 2-methyl octanol: 30 to 35 mol%, (d) dimethyl heptanol: 10 to 15 mol%, (e) 5-methyl octanol: 50 to 55 mol%, (f) n-nonanol: 1 to 5 mol%, (g) isodecyl alcohol: 1.0 to 2.5 mol%; 2) based on the total amount of DINT, 0.1 ~6.0wt% of a metal-containing catalyst or a mineral acid catalyst is an esterification catalyst; 3) a terephthalic acid or a derivative thereof in the step 1) at a reaction pressure of 5 to 760 mbar and a reaction temperature of 200 to 250 ° C a mixture of isodecyl alcohol, in the presence of the metal-containing catalyst or inorganic acid catalyst of step 2), a single step esterification reaction for 9-16 hours until the acid value of the reaction mixture reaches 1 mgKOH/g or less; 4) After completion of the reaction, the reaction mixture is neutralized with an aqueous alkali metal hydroxide solution containing 5 to 20% by weight of a hydroxide mixture until the acid value of the reaction mixture reaches 0.07 mgKOH/g or less, and the excess alcohol is removed, dried and filtered. To produce the DINT esterate. The production method according to the first or second aspect of the invention, wherein the inorganic acid catalyst is one or more selected from the group consisting of sulfuric acid, boric acid, phosphoric acid, perchloric acid or p-toluenesulfonic acid. The manufacturing method according to claim 1 or 2, wherein the metal-containing catalyst is selected from the group consisting of tin octylate, tetraisopropyl titanate (TIPT) or tetraisobutyl titanate (TIBT). One or more of them. The production method according to Item 1 or 2, wherein the (b) methyl propyl pentanol component in the isodecyl alcohol mixture is selected from the group consisting of 1-methyl-1-propylpenta Alcohol, 1-methyl-2-propylpentanol, 1-methyl-3-propylpentanol, 1-methyl-5-propylpentanol, 2-methyl-1-propylpentanol, 2-methyl-2-propylpentanol, 2-methyl-3-propylpentanol, 3-methyl-1-propylpentanol, 3-methyl-1-propylpentanol, 3- Methyl-2-propylpentanol, 3-methyl-3-propylpentanol, 3-methyl-5-propylpentanol, 4-methyl-1-propylpentanol, 4-methyl -2-propylpentanol, 4-methyl-3-propylpentanol, 4-methyl-5-propylpentanol, 5-methyl-1-propyl Pentanol, 5-methyl-2-propylpentanol, 5-methyl-3-propylpentanol or 5-methyl-4-propylpentanol. The production method according to the first or second aspect of the invention, wherein, in the component of the isodecyl alcohol mixture, (b) the methyl propyl pentanol component is 0.2 mol% of 2-methyl-2. - propylpentanol was substituted, (g) the isodecyl alcohol component was substituted with 1.4 mol% of isodecyl alcohol, and the sum of the other components was 98.4 mol%. The production method according to item 2 of the patent application, wherein the step 4) after completion of the esterification reaction, removes the catalyst with water vapor and activated carbon. The production method according to item 2 of the patent application, wherein the step 4) the aqueous alkali metal hydroxide solution is used in excess, which is equivalent to 4 to 5 times the acid value of the reaction mixture. A DINT plasticizer prepared by the DINT ester compound synthesized by the manufacturing method of claim 1 or 2. A soft PVC product characterized in that the composition comprises at least PVC 100 PHR and DINT plasticizer 70 PHR of claim 9 and the migration rate of the DINT plasticizer is less than 1.4%.