Plasticizer and method for producing the same

Abstract

The application discloses a high-surface-tension plasticizer and a manufacturing method thereof. The manufacturing method of the high-surface-tension plasticizer comprises the following steps: mixing a dibasic acid, a dibasic alcohol and a catalyst to form a reaction mixture, and reacting the reaction mixture in a temperature range of 130 DEG C to 220 DEG C to form a semi-finished product. A capping alcohol is added to the semi-finished product, and the mixture is reacted in a temperature range of 205 DEG C to 220 DEG C to form a crude plasticizer. The crude plasticizer is purified in a pressure range of 760 torr to 5 torr to obtain a plasticizer. The molar ratio of the dibasic acid, the dibasic alcohol and the capping alcohol is 1:0.6-0.9:0.3-0.6. The dibasic acid comprises adipic acid, the dibasic alcohol comprises a polyglycol and a saturated fatty alcohol, and the capping alcohol comprises isooctanol, isodecanol or 2-propylheptanol.

Description

Technical Field

[0001] This invention relates to a plasticizer and a method for manufacturing the same, and more particularly to a plasticizer with high surface tension and a method for manufacturing the same. Background Technology

[0002] Plasticizers are widely used in the production of plastic materials, coatings, dyes, adhesives, and plaster. The addition of plasticizers liquefies materials or softens their texture, making them easier to shape. Currently, the most widely used plasticizers are phthalates (PAEs), but with prolonged use, the safety of phthalates has been increasingly questioned.

[0003] In 2008, the European Chemicals Agency (ECHA) added phthalates to its list of substances of very high concern (SVHCs) and limited their content in products to no more than 0.1 wt%. The regulated phthalates include di-n-butyl phthalate (DBP), di(2-ethylhexyl) phthalate (DEHP), and benzyl butyl phthalate (BBP). Consequently, the industry began developing various environmentally friendly plasticizers to replace traditional phthalate plasticizers.

[0004] Also driven by environmental requirements, downstream manufacturers are increasingly favoring water-based manufacturing processes. In water-based manufacturing, all additives, including plasticizers, need to possess a certain degree of hydrophilicity to ensure uniform mixing with materials. If the hydrophilicity of the plasticizer is insufficient, it can easily lead to plasticizer precipitation, negatively impacting product quality, such as poor adhesion and insufficient printability.

[0005] However, the surface tension of environmentally friendly plasticizers currently on the market generally falls between 33 and 35 dynes (25°C). Environmentally friendly plasticizers with this surface tension range cannot be effectively applied to water-based manufacturing processes. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to provide a plasticizer and its manufacturing method in view of the shortcomings of the prior art.

[0007] To address the aforementioned technical problems, one technical solution adopted by this invention is to provide a method for manufacturing a plasticizer. The method for manufacturing the plasticizer includes the following steps: mixing a diacid, a diol, and a catalyst to form a reaction mixture; reacting the reaction mixture at a temperature range of 130°C to 220°C to form a semi-finished product; adding a capped alcohol to the semi-finished product and reacting it at a temperature range of 205°C to 220°C to form a crude plasticizer; and purifying the crude plasticizer at a pressure range of 760 torts to 5 torts to obtain a plasticizer. The molar ratio of diacid:diol:capped alcohol is 1:0.6 to 0.9:0.3 to 0.6. The diacid includes adipic acid, the diol includes a polyglycol and a saturated fatty alcohol, and the capped alcohol includes isooctanol, isodecanol, or 2-propylheptanol.

[0008] Furthermore, polyglycol is selected from the group consisting of: ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, dipropylene glycol and tripropylene glycol.

[0009] Furthermore, saturated fatty alcohols are selected from the group consisting of: ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 2-methyl-2,4-pentanediol and 2-methyl-1,3-propanediol.

[0010] Furthermore, the number of moles of polyethylene glycol added is less than or equal to the number of moles of saturated fatty alcohol added, and the molar ratio of polyethylene glycol in the diol is greater than or equal to 0.25.

[0011] Furthermore, the molar ratio of polyglycol to saturated fatty alcohol is 1:1 to 1:3.

[0012] Furthermore, the reaction mixture was reacted at multiple holding stages in a heating program, with the temperature range being 130°C to 220°C. The crude plasticizer was purified at multiple low-pressure stages in a vacuum program to obtain the plasticizer, with the pressure range being 760 torts to 5 torts.

[0013] Furthermore, the multiple holding temperature stages are a first holding temperature stage, a second holding temperature stage, a third holding temperature stage, a fourth holding temperature stage, and a fifth holding temperature stage. A predetermined temperature value for the first holding temperature stage is in the range of 130°C to 150°C, a predetermined temperature value for the second holding temperature stage is in the range of 150°C to 170°C, a predetermined temperature value for the third holding temperature stage is in the range of 170°C to 190°C, a predetermined temperature value for the fourth holding temperature stage is in the range of 190°C to 205°C, and a predetermined temperature value for the fifth holding temperature stage is in the range of 205°C to 220°C.

[0014] Furthermore, the heating process is terminated when the acid value of the semi-finished product is 70 to 90 mg KOH / g.

[0015] Furthermore, when the acid value of the crude plasticizer is 10 to 30 mg KOH / g, the decompression procedure is initiated.

[0016] Furthermore, the multiple low-pressure stages are a first low-pressure stage, a second low-pressure stage, a third low-pressure stage, a fourth low-pressure stage, and a fifth low-pressure stage. The predetermined pressure value of the first low-pressure stage is in the range of 750 to 400 to 100 to 150 to 150 to 150 to 10 ...

[0017] To address the aforementioned technical problems, another technical solution adopted by this invention is to provide a plasticizer. The plasticizer is synthesized from a diacid, a diol, a capped alcohol, and a catalyst. The molar ratio of the diacid:diol:capped alcohol is 1:0.6 to 0.9:0.3 to 0.6. The diacid includes adipic acid, the diol includes a polyglycol and a saturated fatty alcohol, and the capped alcohol includes isooctanol, isodecanol, or 2-propylheptanol. The surface tension of the plasticizer is 36 to 38 dynes.

[0018] Furthermore, the hue alpha value of the plasticizer is less than 100.

[0019] Furthermore, the viscosity of the plasticizer ranges from 1500 cps to 3000 cps.

[0020] Furthermore, the weight-average molecular weight of the plasticizer is 2500 g / mol to 3500 g / mol.

[0021] Furthermore, polyglycol is selected from the group consisting of: ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, dipropylene glycol and tripropylene glycol.

[0022] Furthermore, saturated fatty alcohols are selected from the group consisting of: ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 2-methyl-2,4-pentanediol, 2-methyl-1,3-propanediol, 1,6-hexanediol, and 1,10-decanediol.

[0023] Furthermore, the molar ratio of polyglycol to saturated fatty alcohol is 1:1 to 1:3.

[0024] One of the beneficial effects of the present invention is that the plasticizer and its manufacturing method provided by the present invention can improve the surface tension of the plasticizer by using the technical solutions of "diol including a polyglycol and a saturated fatty alcohol" and "diacid including adipic acid".

[0025] To further understand the features and technical content of the present invention, please refer to the following detailed description and drawings of the present invention. However, the drawings provided are for reference and illustration only and are not intended to limit the present invention. Attached Figure Description

[0026] Figure 1 This is a schematic flowchart of the manufacturing method of the plasticizer of the present invention. Detailed Implementation

[0027] The following specific examples illustrate the embodiments of the "plasticizer and its manufacturing method" disclosed in this invention. Those skilled in the art can understand the advantages and effects of this invention from the content disclosed in this specification. This invention can be implemented or applied through other different specific embodiments, and the details in this specification can also be modified and changed based on different viewpoints and applications without departing from the concept of this invention. Furthermore, the accompanying drawings of this invention are for simple illustrative purposes only and are not depictions of actual dimensions, as stated in advance. The following embodiments will further describe the relevant technical content of this invention in detail, but the disclosed content is not intended to limit the scope of protection of this invention. In addition, the term "or" used herein may, depending on the actual situation, include any combination of any one or more of the associated listed items.

[0028] This invention provides a plasticizer and its manufacturing method. The plasticizer of this invention does not belong to the phthalate class, therefore there are no safety concerns. The plasticizer of this invention is an environmentally friendly plasticizer and has high surface tension, making it suitable for use in water-based manufacturing processes. Specifically, the surface tension of the plasticizer of this invention, measured at 25°C, is greater than 36 dynes (even greater than 37 dynes), which is higher than the surface tension of currently available environmentally friendly plasticizers (33 to 35 dynes) and polymeric plasticizers (35 to 37 dynes).

[0029] The plasticizer of this invention is synthesized from specific diacids, diols, and capped alcohols. By selecting the components, the overall hydrophilicity of the plasticizer can be improved. In this invention, the hydrophilicity of the plasticizer can be quantified by its surface tension.

[0030] Please see Figure 1 As shown, the method for manufacturing the plasticizer of the present invention includes the following steps. In step S1, a dicarboxylic acid, a diol, and a catalyst are added to a reactor to form a reaction mixture, and the temperature of the reaction tank is set to 150°C and the pressure is atmospheric pressure.

[0031] The aforementioned dicarboxylic acids include adipic acid.

[0032] The aforementioned diol includes a polyglycol and a saturated fatty alcohol, wherein the polyglycol has 2 to 9 carbon atoms (preferably 2 to 6), and the saturated fatty alcohol has 2 to 10 carbon atoms (preferably 2 to 6). In an exemplary embodiment, the diol is a mixture of a polyglycol and a saturated fatty alcohol. Compared to using a saturated fatty alcohol alone, mixing the polyglycol and saturated fatty alcohol can improve the structure of the plasticizer and further enhance its surface tension. In particular, when the saturated fatty alcohol is 2-methyl-1,3-propanediol, the addition of the polyglycol can particularly improve the structure of the plasticizer.

[0033] In one exemplary embodiment, the molar number of polyethylene glycol added is less than or equal to the molar number of saturated fatty alcohol added, and the minimum molar ratio of polyethylene glycol in the diol is 0.25. This invention controls the structure of the plasticizer by controlling the content of polyethylene glycol and fatty alcohol in the plasticizer, thereby achieving the effect of increasing the surface tension of the plasticizer. The mixed molar ratio of polyethylene glycol and saturated fatty alcohol is 1:1 to 1:3, preferably 1:1.5 to 1:2.5. For example, the mixed molar ratio of polyethylene glycol and saturated fatty alcohol can be 1:1.7, 1:1.9, 1:2.1, or 1:2.3.

[0034] Specifically, polyglycols can be selected from the group consisting of the following: ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and tripropylene glycol. Saturated fatty alcohols may be selected from the group consisting of: ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 2-methyl-2,4-pentanediol, 2-methyl-1,3-propanediol, 1,6-hexanediol, and 1,10-decanediol.

[0035] The catalyst described above can be a titanium catalyst, a tin catalyst, a sodium catalyst, a zinc catalyst, or a magnesium catalyst. Specifically, the catalyst is selected from the group consisting of: titanates, stannous oxide, stannous oxalate, sodium aluminate, titanium oxide, zinc oxide, and magnesium oxide. Preferably, the catalyst is a titanate.

[0036] In step S2, the reaction mixture is subjected to multiple holding temperatures within a heating program to form a semi-finished product. During the heating program, the high temperature (above 100°C) evaporates the water produced by the esterification reaction, thus removing moisture.

[0037] The temperature range of the heating program can be any range between 130°C and 220°C. In this embodiment, the temperature range of the heating program is 140°C to 210°C. Multiple predetermined temperature values ​​are selected from the temperature range and used as fixed temperatures in multiple holding stages. In some embodiments, the multiple predetermined temperature values ​​may include upper and lower limits of the temperature range, but this is not a limitation. That is, the multiple predetermined temperature values ​​may also not include upper and lower limits of the temperature range. The number of predetermined temperature values ​​can be greater than or equal to 3, and preferably, the number of predetermined temperature values ​​can be greater than or equal to 4.

[0038] For example, when the temperature range is 130°C to 220°C, the multiple predetermined temperature values ​​can be any value in the range of 130°C to 220°C, such as but not limited to: 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C or 210°C, and can selectively cover 130°C to 220°C (upper and lower limits).

[0039] To control the reaction rate of the reaction mixture, the present invention regulates the temperature of each holding stage. In an exemplary embodiment, the multiple holding stages in the heating process are performed sequentially from low to high temperature, namely a first holding stage, a second holding stage, a third holding stage, a fourth holding stage, and a fifth holding stage. The predetermined temperature value of the first holding stage is in the range of 130°C to 150°C, the predetermined temperature value of the second holding stage is in the range of 150°C to 170°C, the predetermined temperature value of the third holding stage is in the range of 170°C to 190°C, the predetermined temperature value of the fourth holding stage is in the range of 190°C to 205°C, and the predetermined temperature value of the fifth holding stage is in the range of 205°C to 220°C. The duration of each of the first, second, third, fourth, and fifth holding stages is 0.5 hours to 4 hours.

[0040] In the heating process, the duration of the holding phase can be adjusted based on the number of predetermined temperature values ​​or the difference between the predetermined temperature values. Specifically, when there are many predetermined temperature values, the duration of each holding phase can be shortened; conversely, when there are few predetermined temperature values, the duration of each holding phase can be lengthened. When the difference between the predetermined temperature values ​​is large, the duration of each holding phase can be lengthened; conversely, when the difference between the predetermined temperature values ​​is small, the duration of each holding phase can be shortened.

[0041] Throughout the entire heating process, the overall average heating rate of the reaction mixture was 5°C / hour to 8°C / hour.

[0042] During the heating process, the reactants can fully react and polymerize, avoiding the formation of incompletely polymerized low-molecular-weight polymers. The formation of low-molecular-weight polymers can negatively impact the viscosity uniformity of the final product, causing inconsistencies in plasticizer quality. Furthermore, when using plasticizers later, low-molecular-weight polymers may seep out during processing, resulting in poor processability.

[0043] If the reaction mixture is heated in a continuously increasing manner (the reactor temperature changes over time), the capped alcohol is likely to react with the diacid at the beginning, causing the terminal acid group of the diacid to be replaced, preventing further polymerization and resulting in a low molecular weight polymer. Therefore, this invention uses a heating program that includes multiple holding stages to reduce the formation of low molecular weight polymers.

[0044] In step S3, when the acid value of the semi-finished product is between 70 mg KOH / g and 90 mg KOH / g, the heating process (step S2) can be stopped. A capped alcohol is added to the semi-finished product, and the reaction is maintained at a temperature of 205°C to 220°C to obtain a crude plasticizer. By adjusting the timing of the capped alcohol addition, the molecular weight of the synthesized plasticizer can be controlled, thereby achieving the effect of controlling the viscosity of the plasticizer.

[0045] The aforementioned capped alcohols include isooctanol, isodecanol, or 2-propylheptanol.

[0046] In one exemplary embodiment, the molar ratio of diacid:diol:terminated alcohol is 1:0.6 to 0.9:0.3 to 0.6. More preferably, the molar ratio of diacid:diol:terminated alcohol is 1:0.75 to 0.9:0.3 to 0.45. Even more preferably, the molar ratio of diacid:diol:terminated alcohol is 1:0.85 to 0.89:0.32 to 0.40.

[0047] It is worth noting that by selecting the above-mentioned types of dicarboxylic acids, diols, and capped alcohols, plasticizers with high surface tension can be synthesized. In particular, the use of polyglycol and saturated fatty alcohols as diols can significantly improve the surface tension of the plasticizers.

[0048] In step S4, when the acid value of the crude plasticizer is between 10 mg KOH / g and 30 mg KOH / g, the remaining capped alcohol is added to the crude plasticizer, and a depressurization process can be started.

[0049] During the depressurization process, low-boiling-point substances (i.e., low molecular weight polymers) generated during the polymerization reaction can be removed to maintain the viscosity uniformity of the plasticizer. As a result, the plasticizer of this invention has the advantages of good processability, low odor, and good color.

[0050] The pressure range of the decompression procedure can be any range between 760 tors and 5 tors. In one exemplary embodiment, the pressure range of the decompression procedure can be between 750 tors and 10 tors. Multiple predetermined pressure values ​​are selected from the pressure range as pressures for multiple low-pressure stages. In some embodiments, the multiple predetermined pressure values ​​may include upper and lower limits of the pressure range, but this is not a limitation. That is, the multiple predetermined pressure values ​​may also not include upper and lower limits of the pressure range. The number of predetermined pressure values ​​can be greater than or equal to 3, preferably greater than or equal to 4.

[0051] For example, when the pressure range is 760 torts to 5 torts, the multiple predetermined pressure values ​​can be any value from 760 torts to 5 torts, such as, but not limited to: 750 torts, 700 torts, 600 torts, 500 torts, 400 torts, 300 torts, 200 torts, 100 torts, 50 torts or 10 torts, and may selectively include 760 torts and 5 torts (upper and lower limits).

[0052] To control the purification effect of the semi-finished product, this embodiment regulates the pressure of each low-pressure stage. In one exemplary embodiment, the multiple low-pressure stages in the decompression procedure are performed sequentially from high to low pressure, namely a first low-pressure stage, a second low-pressure stage, a third low-pressure stage, a fourth low-pressure stage, and a fifth low-pressure stage. The predetermined pressure value of the first low-pressure stage is in the range of 760 to 450 to 10 ...5 to 100 to 100 to 150 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 150 to 100 to 100 to 150 to 100 to 100 to 150 to 100 to 100 to 150 to 100 to 100 to 150 to 100 to 100 to 150 to 100 to 100 to 150 to 100 to 100 to 150 to 100 to 100 to 150 to 100 to

[0053] In the decompression procedure, the duration of the low-pressure phase can be adjusted based on the number of predetermined pressure values ​​or the difference between predetermined pressure values. Specifically, when the number of predetermined pressure values ​​is large, the duration of each low-pressure phase can be shortened; conversely, when the number of predetermined pressure values ​​is small, the duration of each low-pressure phase can be lengthened. When the difference between predetermined pressure values ​​is large, the duration of each low-pressure phase can be lengthened; conversely, when the difference between predetermined pressure values ​​is small, the duration of each low-pressure phase can be shortened.

[0054] Throughout the entire decompression process, the overall average decompression rate of the semi-finished product ranges from 75 to 125 to 1 hour.

[0055] In step S5, a sample is taken from the reactor and its acid value is measured. When the acid value of the plasticizer is less than 1 mg KOH / g, a full vacuum is applied, for example, but not limited to, reducing the pressure inside the reactor to below 10 Torr. Next, the viscosity of the plasticizer is measured. When the viscosity of the plasticizer is between 2500 cps and 3500 cps (25°C), the reaction is stopped, the vacuum is stopped, and the temperature is lowered to 40°C for discharge. After cooling, the plasticizer of the present invention is obtained. In a preferred embodiment, the reaction is stopped when the viscosity of the plasticizer is between 2800 cps and 3200 cps (25°C).

[0056] Based on the above, the method for preparing the plasticizer of the present invention can control the molecular weight and viscosity of the plasticizer, giving it good processing characteristics for future application in water-based plastic materials, water-based resin coatings, or other water-based manufacturing processes. Furthermore, the method for preparing the plasticizer of the present invention can reduce the generation of low molecular weight polymers, preventing the subsequent leakage of low molecular weight polymers and negatively impacting the quality of the final product.

[0057] [Experimental Test]

[0058] To demonstrate the effectiveness of this invention in enhancing the surface tension of plasticizers using specific diols, this invention provides plasticizers according to steps S1 to S5 above, as described in Examples 1 to 5, which exhibit high surface tension. The main difference between Examples 1 to 3 lies in the use of different types of diols. Specifically, Example 1 uses diethylene glycol (polyethylene glycol) and 2-methyl-1,3-propanediol as diols, Example 2 uses dipropylene glycol (polyethylene glycol) and 2-methyl-1,3-propanediol as diols, and Example 3 uses triethylene glycol (polyethylene glycol) and 2-methyl-1,3-propanediol as diols. The main difference between Examples 1, 4, and 5 lies in the use of different types of end-capping alcohols. Specifically, Example 1 uses isooctanol as an end-capping alcohol, Example 4 uses isodecanol as an end-capping alcohol, and Example 5 uses 2-propylheptanol as an end-capping alcohol. The specific operating steps are described below.

[0059] [Example 1]

[0060] 280 g of adipic acid (1.92 mol), 100 g of 2-methyl-1,3-propanediol (1.11 mol), 60 g of diethylene glycol (0.57 mol), and 0.5 g of titanium catalyst were added to a reactor and stirred at 140 °C and 760 Torr to form a reaction mixture. The reaction mixture was subjected to the heating program in step S2 according to the multiple holding temperature stages in Table 1 to produce a semi-finished product. During the heating program, the water and alcohol produced in the reaction were discharged.

[0061] Table 1

[0062] First stage of temperature maintenance 140℃ 2 hours Second phase of temperature maintenance 160℃ 2 hours Third temperature holding phase 180℃ 2 hours Fourth temperature holding stage 200℃ 2 hours Fifth temperature holding stage 210℃ 3 hours

[0063] The heating process was stopped when the acid value of the semi-finished product was less than 90 mg KOH / g. Next, 90 g of isooctanol (0.69 mol) was added to the semi-finished product, and the temperature was maintained at 210°C to generate a crude plasticizer. In Example 1, the molar ratio of diacid:diol:terminated alcohol was 1:0.87:0.36.

[0064] When the acid value of the crude plasticizer is less than 30 mg KOH / g, the reactor is evacuated. According to the multiple low-pressure stages in Table 2, the crude plasticizer is subjected to the decompression procedure in step S4 to obtain the plasticizer.

[0065] Table 2

[0066] First low-pressure phase 500 Torr 1 hour Second low-pressure phase 350 Torr 1 hour Third low-pressure phase 250 Torr 1 hour Fourth low-pressure stage 100Torr 1 hour Fifth low-pressure stage 10Torr 1 hour

[0067] When the acid value of the plasticizer is less than 1 mg KOH / g, the decompression procedure is ended (step S4). Next, the reactor is fully evacuated to a pressure less than 10 torr. When the viscosity of the plasticizer reaches 3000 cps, the reaction is stopped, and the evacuation is halted. After cooling to 40°C, the plasticizer of Example 1 is obtained (step S5).

[0068] [Example 2]

[0069] 280 g of adipic acid (1.92 mol), 100 g of 2-methyl-1,3-propanediol (1.11 mol), 80 g of dipropylene glycol (0.60 mol), and 0.5 g of titanium catalyst were added to a reactor and stirred at 140 °C and 760 Torr to form a reaction mixture.

[0070] Example 2 is similar to Example 1. When the reactor temperature rises to 150°C due to the exothermic reaction, the reaction mixture is subjected to the heating procedure in step S2 according to the multiple holding temperature stages in Table 1 of Example 1 to generate a semi-finished product. During the heating procedure, the water and alcohol produced in the reaction are discharged.

[0071] The heating process was stopped when the acid value of the semi-finished product was less than 90 mg KOH / g. Next, 90 g of isooctanol (0.69 mol) was added to the semi-finished product, and the temperature was maintained at 210°C to generate a crude plasticizer. In Example 2, the molar ratio of diacid:diol:terminated alcohol was 1:0.89:0.36.

[0072] When the acid value of the crude plasticizer is less than 30 mg KOH / g, the reactor is evacuated. According to the multiple low-pressure stages in Table 2, the crude plasticizer is subjected to the decompression procedure in step S4 to obtain the plasticizer.

[0073] When the acid value of the plasticizer is less than 1 mg KOH / g, the decompression procedure is ended (step S4). Next, the reactor is fully evacuated to a pressure less than 10 torr. When the viscosity of the plasticizer reaches 3000 cps, the reaction is stopped, and the evacuation is halted. After cooling to 40°C, the plasticizer of Example 2 is obtained (step S5).

[0074] [Example 3]

[0075] 280 g of adipic acid (1.94 mol), 100 g of 2-methyl-1,3-propanediol (1.11 mol), 85 g of triethylene glycol (0.57 mol), and 0.5 g of titanium catalyst were added to a reactor and stirred at 140 °C and 760 Torr to form a reaction mixture. Example 3 was similar to Example 1, but when the reactor temperature rose to 150 °C due to the exothermic reaction, the reaction mixture was subjected to the heating procedure in step S2 according to the multiple holding temperature stages in Table 1 of Example 1 to produce a semi-finished product. During the heating procedure, the water and alcohol produced in the reaction were discharged.

[0076] The heating process was stopped when the acid value of the semi-finished product was less than 90 mg KOH / g. Next, 90 g of isooctanol (0.69 mol) was added to the semi-finished product, and the temperature was maintained at 210°C to generate a crude plasticizer. In Example 3, the molar ratio of diacid:diol:terminated alcohol was 1:0.87:0.36.

[0077] When the acid value of the crude plasticizer is less than 30 mg KOH / g, the reactor is evacuated. According to the multiple low-pressure stages in Table 2, the crude plasticizer is subjected to the decompression procedure in step S4.

[0078] When the acid value of the plasticizer is less than 1 mg KOH / g, the decompression procedure is ended (step S4). Next, the reactor is fully evacuated to a pressure less than 10 Torr. When the viscosity of the plasticizer reaches 3000 cps, the reaction is stopped, and the evacuation is halted. After cooling to 40°C, the plasticizer of Example 3 is obtained (step S5).

[0079] [Example 4]

[0080] 280 g of adipic acid (1.92 mol), 100 g of 2-methyl-1,3-propanediol (1.11 mol), 60 g of diethylene glycol (0.57 mol), and 0.5 g of titanium catalyst were added to a reactor and stirred at 140 °C and 760 Torr to form a reaction mixture.

[0081] Example 4 is similar to Example 1. When the reactor temperature rises to 150°C due to the exothermic reaction, the reaction mixture is subjected to the heating procedure in step S2 according to the multiple holding temperature stages in Table 1 of Example 1 to generate a semi-finished product. During the heating procedure, the water and alcohol produced in the reaction are discharged.

[0082] The heating process was stopped when the acid value of the semi-finished product was less than 90 mg KOH / g. Next, 110 g of isodecanol (0.69 mol) was added to the semi-finished product, and the temperature was maintained at 210°C to generate a crude plasticizer. In Example 1, the molar ratio of diacid:diol:terminated alcohol was 1:0.87:0.36.

[0083] When the acid value of the crude plasticizer is less than 30 mg KOH / g, the reactor is evacuated. According to the multiple low-pressure stages in Table 2, the crude plasticizer is subjected to the decompression procedure in step S4 to obtain the plasticizer.

[0084] When the acid value of the plasticizer is less than 1 mg KOH / g, the decompression procedure is ended (step S4). Next, the reactor is fully evacuated to a pressure less than 10 torr. When the viscosity of the plasticizer reaches 3000 cps, the reaction is stopped, and the evacuation is halted. After cooling to 40°C, the plasticizer of Example 1 is obtained (step S5).

[0085] [Example 5]

[0086] 280 g of adipic acid (1.92 mol), 100 g of 2-methyl-1,3-propanediol (1.11 mol), 60 g of diethylene glycol (0.57 mol), and 0.5 g of titanium catalyst were added to a reactor and stirred at 140 °C and 760 Torr to form a reaction mixture.

[0087] Example 5 is similar to Example 1. When the reactor temperature rises to 150°C due to the exothermic reaction, the reaction mixture is subjected to the heating procedure in step S2 according to the multiple holding temperature stages in Table 1 of Example 1 to generate a semi-finished product. During the heating procedure, the water and alcohol produced in the reaction are discharged.

[0088] The heating process was stopped when the acid value of the semi-finished product was less than 90 mg KOH / g. Next, 110 g of 2-propylheptanol (0.69 mol) was added to the semi-finished product, and the temperature was maintained at 210°C to generate a crude plasticizer. In Example 1, the molar ratio of diacid:diol:terminated alcohol was 1:0.87:0.36.

[0089] When the acid value of the crude plasticizer is less than 30 mg KOH / g, the reactor is evacuated. According to the multiple low-pressure stages in Table 2, the crude plasticizer is subjected to the decompression procedure in step S4 to obtain the plasticizer.

[0090] When the acid value of the plasticizer is less than 1 mg KOH / g, the decompression procedure is ended (step S4). Next, the reactor is fully evacuated to a pressure less than 10 torr. When the viscosity of the plasticizer reaches 3000 cps, the reaction is stopped, and the evacuation is halted. After cooling to 40°C, the plasticizer of Example 1 is obtained (step S5).

[0091] [Comparative Example 1]

[0092] The main difference between Comparative Example 1 and Example 1 is that Comparative Example 1 uses 2-methyl-1,3-propanediol and neopentyl glycol as diols, that is, no polyglycol is added to Comparative Example 1.

[0093] 280 g of adipic acid (1.92 mol), 100 g of 2-methyl-1,3-propanediol (1.11 mol), 60 g of neopentyl glycol (0.57 mol) and 0.5 g of titanium catalyst were added to a reactor and stirred at 140 °C and 760 Torr to form a reaction mixture.

[0094] Comparative Example 1 is similar to Example 1. When the reactor temperature rises to 150°C due to the exothermic reaction, the reaction mixture is subjected to the heating procedure in step S2 according to the multiple holding temperature stages in Table 1 of Example 1 to generate a semi-finished product. During the heating procedure, the water and alcohol produced in the reaction are discharged.

[0095] The heating process was stopped when the acid value of the semi-finished product was less than 90 mg KOH / g. Next, 90 g of isooctanol (0.69 mol) was added to the semi-finished product, and the temperature was maintained at 210°C to generate the semi-finished product. In Comparative Example 1, the molar ratio of dicarboxylic acid:diol:terminated alcohol was 1:0.88:0.36.

[0096] When the acid value of the crude plasticizer is less than 30 mg KOH / g, the reactor is evacuated. According to the multiple low-pressure stages in Table 2, the crude plasticizer is subjected to the decompression procedure in step S4 to obtain the plasticizer.

[0097] When the acid value of the plasticizer is less than 1 mg KOH / g, the decompression procedure is ended (step S4). Next, the reactor is evacuated to a full vacuum until the pressure is less than 10 Torr. When the viscosity of the plasticizer reaches 3000 cps, the reaction is stopped, and the vacuum process is halted. After cooling to 40°C, the plasticizer of Comparative Example 1 is obtained (step S5).

[0098] For easy comparison of the properties of the plasticizers in Examples 1 to 5 and Comparative Example 1, please refer to Table 3 below. The viscosity of the plasticizer was measured at 25°C using a viscometer. Surface tension was measured using a dyne testpen on PVC fabric with a hardness of 43 PHR (parts per hundred resin).

[0099] Table 3

[0100]

[0101]

[0102] As shown in Table 3, the present invention uses polyglycol and saturated fatty alcohol as raw materials for synthesizing plasticizers, which can increase the surface tension of the plasticizer (36 dyne to 38 dyne). Therefore, the plasticizer of the present invention can replace conventional phthalate plasticizers as an environmentally friendly plasticizer. Furthermore, the plasticizer of the present invention can also be used in water-based manufacturing processes.

[0103] Comparing Examples 1 to 5 with Comparative Example 1, the addition of polyethylene glycol effectively increases the surface tension of the plasticizer. Furthermore, when polyethylene glycol and saturated fatty alcohols are present simultaneously, the structure of the plasticizer is improved, resulting in a higher surface tension compared to when no polyethylene glycol is added. This effect is most pronounced when the plasticizer is further combined with adipic acid as a dicarboxylic acid and isooctyl alcohol as the terminal alcohol.

[0104] Furthermore, the plasticizer of the present invention has a hue alpha value of less than 100, therefore, adding the plasticizer of the present invention to plastic materials will not negatively affect the quality and appearance of the plastic materials. Preferably, the hue alpha value of the plasticizer is between 40 and 95. For example, the hue alpha value of the plasticizer is 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90.

[0105] The plasticizer of the present invention has a viscosity of 1500 cps to 3000 cps at 25°C to provide good processing characteristics. Preferably, the plasticizer has a viscosity of 1700 cps to 2500 cps at 25°C. For example, the plasticizer has a viscosity of 1800 cps, 1900 cps, 2000 cps, 2100 cps, 2200 cps, 2300 cps, or 2400 cps at 25°C.

[0106] The weight-average molecular weight of the plasticizer is from 2500 g / mol to 3500 g / mol. Preferably, the weight-average molecular weight of the plasticizer is from 2600 g / mol to 3300 g / mol. For example, the weight-average molecular weight of the plasticizer is 2700 g / mol, 2800 g / mol, 2900 g / mol, 3000 g / mol, 3100 g / mol, or 3200 g / mol.

[0107] The plasticizer has an acid value of 0.1 mg KOH / g to 1 mg KOH / g. Preferably, the plasticizer has an acid value of 0.2 mg KOH / g to 0.5 mg KOH / g. For example, the plasticizer has an acid value of 0.25 mg KOH / g, 0.30 mg KOH / g, 0.35 mg KOH / g, 0.40 mg KOH / g, or 0.45 mg KOH / g.

[0108] The OH valence of the plasticizer is from 0.5 mg KOH / g to 2.5 mg KOH / g. Preferably, the OH valence of the plasticizer is from 0.8 mg KOH / g to 2.0 mg KOH / g. For example, the OH valence of the plasticizer is 1.0 mg KOH / g, 1.2 mg KOH / g, 1.4 mg KOH / g, 1.6 mg KOH / g, or 1.8 mg KOH / g.

[0109] [Beneficial Effects of the Examples]

[0110] One of the beneficial effects of the present invention is that the plasticizer and its manufacturing method provided by the present invention can improve the surface tension of the plasticizer by using the technical solutions of "diol including a polyglycol and a saturated fatty alcohol" and "the dicarboxylic acid including adipic acid".

[0111] Furthermore, the plasticizer and its manufacturing method provided by the present invention improve the surface tension of the plasticizer by using a technical solution of "diol including a polyglycol and a saturated fatty alcohol".

[0112] Furthermore, the plasticizer and its manufacturing method provided by the present invention improve the appearance quality of the plasticizer by employing the technical solutions of "the reaction mixture is reacted at multiple holding temperature stages in a heating process" and "the crude plasticizer is purified at multiple low pressure stages in a decompression process".

[0113] The content disclosed above is only a preferred and feasible embodiment of the present invention, and is not intended to limit the scope of protection of the claims of the present invention. Therefore, all equivalent technical changes made based on the content of the present invention specification and drawings are included within the scope of protection of the claims of the present invention.

Claims

1. A method for manufacturing a plasticizer, characterized in that, The manufacturing method includes: A diacid, a diol, and a catalyst are mixed to form a reaction mixture, wherein the diacid includes adipic acid, and the diol includes a polyglycol and a saturated fatty alcohol, wherein the molar ratio of the polyglycol to the saturated fatty alcohol is 1:1.5 to 1:2.

5. The reaction mixture is reacted in a temperature range of 130°C to 220°C during multiple holding phases of a heating program to form a semi-finished product; When the acid value of the semi-finished product is 70 to 90 mg KOH / g, the heating process is terminated, and a capping alcohol is added to the semi-finished product. The reaction is carried out at a temperature range of 205°C to 220°C to form a crude plasticizer. The capping alcohol includes isooctanol, isodecanol, or 2-propylheptanol, and the molar ratio of diacid:diol:capping alcohol is 1:0.6 to 0.9:0.3 to 0.

6. When the acid value of the crude plasticizer is 10 to 30 mg KOH / g, a decompression procedure is initiated, and the crude plasticizer is purified in a pressure range of 760 to 5 to obtain a plasticizer. The polyglycol is selected from the group consisting of triethylene glycol, dipropylene glycol and tripropylene glycol.

2. The manufacturing method according to claim 1, characterized in that, The saturated fatty alcohol is selected from the group consisting of: ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 2-methyl-2,4-pentanediol, 2-methyl-1,3-propanediol, 1,6-hexanediol and 1,10-decanediol.

3. The manufacturing method according to claim 1, characterized in that, The crude plasticizer is purified at multiple low-pressure stages of a decompression procedure to obtain the plasticizer, wherein the pressure range of the decompression procedure is from 760 tort to 5 tort.

4. The manufacturing method according to claim 1, characterized in that, The multiple temperature holding stages are a first temperature holding stage, a second temperature holding stage, a third temperature holding stage, a fourth temperature holding stage, and a fifth temperature holding stage. A predetermined temperature value for the first temperature holding stage is located in the range of 130°C to 150°C, a predetermined temperature value for the second temperature holding stage is located in the range of 150°C to 170°C, a predetermined temperature value for the third temperature holding stage is located in the range of 170°C to 190°C, a predetermined temperature value for the fourth temperature holding stage is located in the range of 190°C to 205°C, and a predetermined temperature value for the fifth temperature holding stage is located in the range of 205°C to 220°C.

5. The manufacturing method according to claim 3, characterized in that, The multiple low-pressure stages are a first low-pressure stage, a second low-pressure stage, a third low-pressure stage, a fourth low-pressure stage, and a fifth low-pressure stage. A predetermined pressure value for the first low-pressure stage is in the range of 750 to 400 to 100 to 150 to 150 to 150 to 10 ...

6. A plasticizer, characterized in that, The plasticizer is synthesized from a diacid, a diol, and a capping alcohol, wherein the molar ratio of diacid:diol:capping alcohol is 1:0.6 to 0.9:0.3 to 0.6, the diacid includes adipic acid, the diol includes a polyglycol and a saturated fatty alcohol, the molar ratio of the polyglycol and the saturated fatty alcohol is 1:1.5 to 1:2.5, the capping alcohol includes isooctanol, isodecanol, or 2-propylheptanol, and the surface tension of the plasticizer is 36 to 38 dynes. The polyglycol is selected from the group consisting of triethylene glycol, dipropylene glycol and tripropylene glycol.

7. The plasticizer according to claim 6, characterized in that, The hue alpha value of the plasticizer is less than 100.

8. The plasticizer according to claim 6, characterized in that, The viscosity of the plasticizer is between 1500 cps and 3000 cps.

9. The plasticizer according to claim 6, characterized in that, The plasticizer has a weight-average molecular weight of 2500 g / mol to 3500 g / mol.

10. The plasticizer according to claim 6, characterized in that, The saturated fatty alcohol is selected from the group consisting of: ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 2-methyl-2,4-pentanediol, 2-methyl-1,3-propanediol, 1,6-hexanediol and 1,10-decanediol.

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