TWI588127B - DINT plasticizer and its manufacturing method and use - Google Patents
DINT plasticizer and its manufacturing method and use Download PDFInfo
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本發明涉及一種DINT可塑劑,特別是一種具低移行性之DINT可塑劑製法及其用途。 The invention relates to a DINT plasticizer, in particular to a DINT plasticizer with low mobility and its use.
可塑劑可多方面應用於塑膠中,作為塗佈材料、填充補強材料、加工助劑等。可塑劑與熱塑性塑膠材料係物理性作用,可塑劑可溶於熱塑性塑膠材料中形成均一相,且具有膨潤效果,與未添加可塑劑前之熱塑性塑膠材料相比較,可以有效降低熱塑性塑膠材料的加工溫度,使得熱塑性塑膠材料易受熱流動成型、增加彈性及降低硬度。 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.
可塑劑的應用範圍廣泛,但須符合無味、無色、耐紫外線、耐低溫、耐熱性、耐水解、不易燃燒、低揮發性及不危害人體健康的條件。此外,可塑劑的製造方法必須簡單及符合環保需求,生產過程中最好無副產物及含污染物的廢水產生。 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.
作為可塑劑之原料,可選用由酸與醇合成之酯化物(以下簡稱可塑劑酯化物),其中酸包括二羧酸與多羧酸,醇為6~13個碳之直鏈或具支鏈之醇類,可以為單獨之化合物或混合物。所述可塑劑酯化物的基本製程,由酸或酸酐與醇或混合醇在酸(例如硫酸等)作為觸媒存在下進行酯化反應,合成時反應醇需過量使用,且作為觸媒之酸,需避免在合成過程中造成酯化物產生異味及色相變差,因此,製程中需具備溫和反應條件及多 道純化製程。 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.
在現有技術中,常用於合成所述可塑劑酯化物之觸媒,為含金屬之酯化觸媒,包括含錫、含鈦或含鋯酯化觸媒或含錫、含鈦或含鋯之鹽類、氧化物或可溶性有機化合物之酯化觸媒,這一類金屬觸媒為使用於高於180℃之酯化反應觸媒,例如錫粉、氧化錫、有機鈦酸酯、以及有機鋯酸酯(包括四丁基鋯酸酯、烷基鈦酸酯及鈦金屬螯合物等)。 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.).
製備所述可塑劑酯化物的反應方法,有酯化反應及氫化反應二種。其中,以酯化反應製造所述可塑劑酯化物之專利文獻,有美國專利US 6,310,235B1等,揭示使用酸(例如二羧酸或多羧酸或酸酐)與醇,在鈦系或鋯系或錫系等金屬觸媒存在下,進行酯化反應,酯化反應分兩階段反應,首先以較低溫度(120~160℃)進行單酯化反應,然後再提高溫度至250℃並添加觸媒進行雙酯化反應。反應完成後以鹼金屬或鹼土金屬之氫氧化物水溶液進行中和反應,隨後進行過量反應醇之脫除,乾燥、過濾等操作而製備成所述可塑劑酯化物。此酯化反應製程的缺點,為反應時間較長。 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.
在現有技術中,常用的可塑劑,有鄰苯二甲酸二異辛酯或鄰苯二甲酸二異壬酯等鄰苯二甲酸系可塑劑,以及,對苯二甲酸二異辛基酯(Di(2-ethylhexyl)terephthalate,以下簡稱DOTP可塑劑)。但,根據文獻顯示,鄰苯二甲酸系可塑劑具環境荷爾蒙問題,對生物體及環境產生極大危害。 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.
而對苯二甲酸二異辛基酯可塑劑(DOTP),雖屬於環保型可塑劑,其玻璃轉移溫度(Tg)雖可達-82℃,但用於製造軟質PVC製品時,尤 其是需使用高用量的可塑劑時,有可塑劑移行至製品表面(以下簡稱移行性)之缺點,甚至當添加量達70PHR時,移行率大於2.5%,影響外觀。 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.
有鑑於此,本發明之主要目的在於改善對苯二甲酸酯類之移行性,利用多組成份之異壬醇混合物合成一種對苯二甲酸二異壬基酯(Di-isononyl terephthalate,以下簡稱DINT可塑劑酯化物),作為可塑劑而應用於塑膠製品時,具低移行性,尤其是應用於添加量需高用量(達70PHR以上)之PVC製品,其移行率小於1.4%(移行率愈低愈佳),明顯優於其他可塑劑。 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.
本發明之對苯二甲酸二異壬酯的製造方法,使用對苯二甲酸(PTA)及含多種組成份之異壬醇混合物(INA)為原料,不含鄰苯二甲酸或酸酐,在鈦、錫或無機酸觸媒存在下,進行酯化反應,反應完成後以鹼金屬氫氧化物之水溶液進行中和反應,再脫除過量反應醇,最後進行乾燥、過濾、純化,以取得純度高、色相佳及低移行性之DINT可塑劑酯化物,具體製法包括下列步驟:1)基於反應物總重量(PTA及INA總重量),取23~35wt%對苯二甲酸(PTA)或其衍生物與65~77wt%異壬醇混合物(INA)為原料;其中,所述異壬醇混合物至少包含下列(a)~(g)成份,且全部組成分共計100mol%:(a)異辛醇:0.1~0.25mol%;(b)甲基丙基戊醇:0.03~0.3mol%;(c)2-甲基辛醇:30~35mol%; (d)二甲基庚醇:10~15mol%;(e)5-甲基辛醇:50~55mol%;(f)正壬醇:1~5mol%;(g)異癸醇:1.0~2.5mol%;2)基於反應物總重量(PTA及INA總重量),取0.1~6wt%含金屬觸媒或無機酸觸媒為酯化觸媒;3)在反應壓力5~760mbar及反應溫度200~250℃下,對步驟1)的對苯二甲酸或其衍生物與異壬醇混合物組成,在步驟1)所述酯化觸媒存在下,進行單一步驟酯化反應9~16小時,直至反應混合物的酸價達1mgKOH/g以下;4)完成反應後,反應混合物以含5~20wt%氫氧化物混合物的鹼金屬氫氧化物水溶液中和,直至反應混合物的酸價達0.07mgKOH/g以下時,再進行脫除過量醇、乾燥及過濾,以製得DINT可塑劑酯化物。 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.
本發明所製得的DINT可塑劑酯化物,可以作為可塑劑使用,尤其就可塑劑的成品品質與加工物性而言,皆與對苯二甲酸酯系可塑劑(例如DOTP可塑劑)相當,且用於軟質(可塑劑70PHR以上)塑膠製品具低移行率,移行率小於1.4%,優於DOTP可塑劑,對生物體及環境不會產生危害,故可取代鄰苯二甲酸系可塑劑(例如DOP可塑劑)及DOTP可塑劑。 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.
本發明的對苯二甲酸二異壬基酯(DINT)製法,是使用對苯二甲酸及異壬醇混合物為酯化反應之原料,且選用含金屬觸媒或無機酸觸 媒為酯化觸媒,在所述酯化觸媒存在下,對所述對苯二甲酸及異壬醇混合物進行酯化反應,以製得一種DINT可塑劑酯化物。其中,所述異壬醇混合物組成至少包括下列(a)~(g)成份,且全部組成分共計100mol%:(a)異辛醇:0.1~0.25mol%;(b)甲基丙基戊醇:0.03~0.3mol%;(c)2-甲基辛醇:30~35mol%;(d)二甲基庚醇10~15mol%;(e)5-甲基辛醇:50~55mol%;(f)正壬醇:1~5mol%;及(g)異癸醇:1.5~2.5mol%。 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%.
所述異壬醇混合物中的甲基丙基戊醇使用量,需限定介於0.03~0.3mol%,當使用量小於0.03mol%或大於0.3mol%時,將造成本發明合成之DINT可塑劑當應用於軟質塑膠製品(可塑劑達70PHR以上)的可塑劑移行率高於1.4%。 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%.
此外,所述異壬醇混合物中的異癸醇使用量,同樣需限定介於1.5~2.5mol%,當使用量小於1.5mol%或大於2.5mol%時,也會造成本發明合成之DINT可塑劑當應用於軟質塑膠製品(可塑劑達70PHR以上)的可塑劑移行率高於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%.
所述甲基丙基戊醇得選自1-甲基-1-丙基戊醇、1-甲基-2-丙基戊醇、1-甲基-3-丙基戊醇、1-甲基-5-丙基戊醇、2-甲基-1-丙基戊醇、2-甲基-2-丙基戊醇、2-甲基-3-丙基戊醇、3-甲基-1-丙基戊醇、3-甲基-1-丙基戊醇、3-甲基-2-丙基戊醇、3-甲基-3-丙基戊醇、3-甲基-5-丙基戊醇、4-甲基-1-丙基戊醇、4-甲基-2-丙基戊醇、4-甲基-3-丙基戊醇、4-甲基-5-丙基戊 醇、5-甲基-1-丙基戊醇、5-甲基-2-丙基戊醇、5-甲基-3-丙基戊醇或5-甲基-4-丙基戊醇。 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.
於本發明之對苯二甲酸二異壬基酯(DINT)製法中,用於酯化反應的酯化觸媒,其使用量為合成原料總量之0.1~6.0wt%,且可選用無機酸或金屬觸媒。其中,所述無機酸包括硫酸、硼酸、磷酸、過氯酸或對甲苯磺酸中的一種或以上;而所述金屬觸媒可選用辛酸錫、四異丙基鈦酸酯(TIPT)或四異丁基鈦酸酯(TIBT)中的一種或以上。 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).
於本發明之對苯二甲酸二異壬基酯(DINT)製法中,,用於合成對苯二甲酸與異壬醇混合物原料,均需經化學計量,尤其醇需過量,反應醇投入量需較酸的量多0.1~1mol。 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.
於本發明之對苯二甲酸二異壬基酯(DINT)製法中,得以單一步驟高溫酯化法,在酯化觸媒存在下,使得對苯二甲酸或其衍生物與異壬醇,進行酯化反應及合成DINT可塑劑酯化物。 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.
本發明之DINT可塑劑酯化物製法,包括下列步驟:1)取對苯二甲酸或其衍生物及異壬醇混合物為原料,其莫耳數比為1:2.2~3.8,相當於重量百分比,基於反應物總重量(PTA及INA重量),為取對苯二甲酸或其衍生物23~35wt%及異壬醇混合物取65~77wt%;2)基於DINT可塑劑酯化物總量,取0.1~6wt%含金屬觸媒或無機酸觸媒為酯化觸媒;3)在反應壓力5~760mbar及反應溫度200~250℃下,優選為反應壓力15~700mbar及應應溫度220~240℃下,對步驟1)的對苯二甲酸或其衍生物與異壬醇混合物組成,在步驟1)所述酯化觸媒存在下,進行單一步驟酯化反應9~16小時,直至反應混合物的酸價達1mgKOH/g以下;4)完成反應後,反應混合物以含5~20wt%氫氧化物混合物的鹼金屬氫氧化物水溶液中和,直至反應混合物的酸價達0.07mgKOH/g以下時,再進行脫除過量醇、乾燥及過濾,以製得DINT可塑劑酯化物。 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.
本發明之DINT可塑劑酯化物製法,於反應過程中必須脫除水份,以共沸原理將反應過程之生成水份與反應醇一起脫除,共沸溫度為90~180℃。當反應至反應混合物酸價1mgKOH/g以下時,反應槽內的反應混合物,除了包括欲合成之DINT可塑劑酯化物(即對苯二甲酸二異壬酯)之外,還殘留有部份酯化之二羧酸、過量反應醇以及觸媒。 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.
本發明之DINT可塑劑酯化物製法,於酯化反應完成後進行中和反應,以鹼金屬氫氧化物之水溶液為中和劑,能中和酯化反應中殘留之酸形成鹽類,中和劑濃度為5~25wt%,較佳為9~16wt%,添加量為反應混合物酸價之4~5倍,鹼金屬氫氧化物之水溶液的選擇,以氫氧化鈉水溶液較佳,中和反應後形成之鹽類會凝結沉澱為固態結晶物,容易於製程後段過濾時去除。 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.
當中和反應進行到合成反應混合物的酸價達0.07mgKOH/g以下時,進行蒸餾將醇類含量降至300ppm以下,並使觸媒水解後形成之水解化合物,易於過濾時去除,亦可添加高表面積之吸附劑例如活性碳等,以助於去除水解之觸媒。 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.
移除過量反應醇後進行乾燥及過濾,乾燥製程可藉由通入 惰性氣體例如:氮氣或者不通惰性氣體於反應槽內,之後進行過濾以除去部份反應之羧酸、水解之觸媒產物、吸附劑。過濾之溫度可於室溫下或在加溫狀態下進行,過濾使用之材料為一般使用過濾之材料,例如纖維素、矽藻土、木屑粉等。 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.
本發明之DINT可塑劑酯化物製法,係於室溫下或100℃以下進行過濾純化,將中和後之鹽類、觸媒金屬鹽類與雜質濾除,以取得所製得DINT可塑劑酯化物。尤其,純化後的DINT可塑劑酯化物,純度高於99.8%,且色相達10APHA,使用用途可以作為可塑劑使用。 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.
以本發明製法製得的對苯二甲酸二異壬基酯(DINT),是以多組成份之異壬醇混合物合成而得,不含鄰苯二甲酸原料,作為可塑劑使用時,可塑劑的品質與加工物性,皆與DOP、DINP鄰苯二甲酸系可塑劑相當,且應用於塑膠製品的移行率優於對苯二甲酸二異辛酯(DOTP),尤其塑膠製的可塑劑用量達70PHR時,本發明的DINT可塑劑移行率低於1.4%,可應用於需要使用高配比可塑劑(達70PHR以上)之軟質PVC製品,例如:可應用於管材、電線電纜、運動軟墊、桌墊、遊戲球、手套等軟質PVC製品。 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.
以下舉實施例及比較例,來更明確說明本發明之功效,然而本發明之範疇不受限於此。 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.
以下實施例與比較例經酯化反應所製備成的可塑劑酯化物,按照下列測量方法測量其酸價(mgKOH/g)、純度(%)、色相(APHA)及加工物性。 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.酸價(mgKOH/g):以ASTM D1045測量方法測量。 1. Acid value (mgKOH/g): Measured by ASTM D1045 measurement method.
2.純度(%):以GC(Gas chromatography)測量方法測量。 2. Purity (%): Measured by GC (Gas chromatography) measurement method.
3.色相(APHA):以Color,Pt-Co unit測量方法測量。 3. Hue (APHA): Measured by Color, Pt-Co unit measurement method.
4.加工物性測試:試片的加工配方如下: 4. Processing physical property test: The processing formula of the test piece is as follows:
配方(A)PVC:100PHR,可塑劑:40PHR,鋇鋅安定劑:2PHR。 Formulation (A) PVC: 100 PHR, plasticizer: 40 PHR, bismuth zinc stabilizer: 2 PHR.
配方(B):PVC:100PHR,可塑劑:70PHR,鋇鋅安定劑:2PHR。 Formulation (B): PVC: 100 PHR, plasticizer: 70 PHR, bismuth zinc stabilizer: 2 PHR.
分別將配方(A)或(B)之混合物,混合均勻後於175℃下,使用輥磨機(roller mill)處理5分鐘以形成0.4mm厚之薄片,隨後以配方(A)進行初期著色、耐熱性、透明度、可塑化係數、拉力強度等5項加工物性試驗,另外以配方(A)及(B)進行移行率測試。 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).
將配方(A)所獲之0.4mm厚薄片,使用壓力裝置於185℃下,預熱3分鐘,加熱3分鐘,並隨後冷卻3分鐘,藉此形成4mm厚之薄片,再以分光儀(Spectrophotometer;MS-020 PLUS)進行黃度之檢測。 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.
將配方(A)所獲之0.4mm厚薄片,裁成25cm×1.5cm×0.2cm大小之試片,以自動烘箱(Automatic Testing Oven;Metrtrastat PSD-260)於180℃×2hr下進行耐熱性試驗。 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). .
將配方(A)及(B)所獲之0.4mm厚薄片,冷卻後裁成5cm×5cm,以已知重量之5cm×5cmPVC硬質膠布夾上,上下再以平面玻璃板夾妥,並加壓3kg荷重,置於烘箱內試驗100℃×24hrs,比較其移行性之優劣: 移行滲透率%:Y-X/X×100。X:為已知重量之硬質PVC膠布之重量。 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:為滲透後之硬質PVC膠布之重量 Y: the weight of the hard PVC tape after penetration
將配方(A)所獲之0.4mm厚薄片,使用壓力裝置於185℃下,預熱3分鐘,加熱3分鐘,並隨後冷卻3分鐘,藉此形成4mm厚之薄片,再以光霧度計(Gloss-Haze Meter;VGS-300A)進行透明度之檢測。 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.
將配方(A)所獲之0.4mm厚薄片,如製備檢測透明度之試片方法,熱壓成6mm厚之試片,以硬度測定器上接觸試片15秒讀其數值,然後對照硬度與PHR之關係表,並以下式計算可塑化係數。 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.
可塑化係數=試樣用料量/DOP用料量。 Plasticization coefficient = sample amount / DOP material amount.
將配方(A)所獲之0.4mm厚薄片裁成啞鈴形,以拉力試驗機(Universal test machine;SHIMADZU AG-X)測試拉力強度,拉伸速度:200mm/min。 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.
以DSC(示差熱掃描卡量計;Differentile Scanning Calorimeter;TA-2100),秤重5~10mg可塑劑樣品進行Tg測試。 The Tg test was performed on a DSC (Differentile Scanning Calorimeter; TA-2100) weighing 5-10 mg of the plasticizer sample.
【實施例1】 [Example 1]
按表一配方,以對苯二甲酸(PTA)取119g,與異壬醇混合物(其中含2-甲基-2-丙基戊醇0.2mol%、異癸醇:1.4mol%;南亞塑膠公司製),取311g,觸媒TIPT(四異丙基鈦酸酯)添加量0.71g,將對苯二甲酸、異壬醇混合物及觸媒同時入料至四頸燒瓶中,通氮氣下反應溫度225℃,反應時間9 小時,反應壓力5~760mbar,反應過程中必須脫除水份,反應至酸價1mgKOH/g以下時,以鹼金屬氫氧化合物之水溶液進行中和至合成反應混合物酸價0.07mgKOH/g以下時,進行蒸餾將醇類含量降至300ppm以下,再進行過濾純化後,而製得DINT可塑劑酯化物,且作為可塑劑使用。 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.
所製得DINT可塑劑酯化物的基本物性及加工物性,測試結果如表一,其中,色相10APHA、酸價0.05mgKOH/g、純度:99.8%。DSC之Tg點測試;Tg=-76℃;移行率的測定結果為1.25%(以下簡化為以移行率:1.25%表示),透明度:89.5%、可塑化係數:1.1。 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.
【實施例2】 [Example 2]
如實施例1之製法,按表一配方,將其中之異壬醇混合物(其中含2-甲基-2-丙基戊醇0.2mol%、異癸醇:1.4mol%;南亞塑膠公司製)改成異壬醇混合物(其中含2-甲基-2-丙基戊醇0.03mol%、異癸醇:1.4mol%;南亞公司製)。在相同製程條件下,製得DINT可塑劑酯化物。 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.
所製得DINT可塑劑酯化物的基本物性及加工物性,測試結果如表一,其中,色相10APHA、酸價0.06mgKOH/g、純度:99.8%;DSC之Tg點測試,Tg=-76℃;移行率:1.35%(70PHR時),透明度:89.5%、可塑化係數:1.1。 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.
【實施例3】 [Example 3]
如實施例1之製法,按表一配方,將其中之異壬醇混合物(其中含2-甲基-2-丙基戊醇0.2mol%、異癸醇:1.4mol%;南亞公司製)改成異壬醇混合物(其中含2-甲基-2-丙基戊醇0.3mol%、異癸醇:1.4mol%;南亞塑膠公司製)。在相同製程條件下,製得DINT可塑劑酯化物。 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.
所製得DINT可塑劑酯化物的基本物性及加工物性,測試結果如表一,其中,色相10APHA、酸價0.06mgKOH/g、純度:99.6%;DSC之Tg點測試,Tg=-76℃;移行率:1.3%(70PHR時),透明度:89.4%、可塑化係數:1.1。 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.
【實施例4】 [Embodiment 4]
如實施例1之製法,按表一配方,將其中之異壬醇混合物(其中含2-甲基-2-丙基戊醇0.2mol%、異癸醇:1.4mol%;南亞公司製)改成異壬醇混合物(其中含2-甲基-2-丙基戊醇0.2mol%、異癸醇:1mol%;南亞塑膠公司製)。在相同製程條件下,製得DINT可塑劑酯化物。 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.
所製得DINT可塑劑酯化物的基本物性及加工物性,測試結果如表一,其中,色相10APHA、酸價0.06mgKOH/g、純度:99.7%;DSC之Tg點測試,Tg=-76℃;移行率:1.38%(70PHR時),透明度:89.4%、可塑化係數:1.1。 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.
【實施例5】 [Embodiment 5]
如實施例1之製法,按表一配方,將其中之異壬醇混合物(其中含2-甲基-2-丙基戊醇0.2mol%、異癸醇:1.4mol%;南亞公司製)改成異壬醇混合物(其中含2-甲基-2-丙基戊醇0.2mol%、異癸醇:2.5mol%;南亞公司製)。在相同製程條件下,製得DINT可塑劑酯化物。 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.
所製得DINT可塑劑酯化物的基本物性及加工物性,測試結果如表一,其中,色相10APHA、酸價0.06mgKOH/g、純度:99.7%;DSC之Tg點測試,Tg=-76℃;加工物性測試之移行率:1.4%(70PHR時),透明度:89.5%、可塑化係數:1.1。 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.
【實施例6】 [Embodiment 6]
如實施例1之製法,按表一配方,將其中之異壬醇混合物(其中含2-甲基-2-丙基戊醇0.2mol%、異癸醇:1.4mol%;南亞公司製)改成異壬醇混合物(其中含3-甲基-1-丙基戊醇0.2mol%、異癸醇:1.4mol%;南亞塑膠公司製)。在相同製程條件下,製得DINT可塑劑酯化物。 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.
所製得DINT可塑劑酯化物的基本物性及加工物性,測試結果如表一,其中,色相10APHA、酸價0.06mgKOH/g、純度:99.8%;DSC之Tg點測試,Tg=-76℃;加工物性測試之移行率:1.26%(70PHR時),透明度:89.5%、可塑化係數:1.1。 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.
【比較例1】 [Comparative Example 1]
按表一配方,以對苯二甲酸(PTA)取120g,與異辛醇(2EH)取280g,觸媒TIPT(四異丙基鈦酸酯)添加量0.6g,將對苯二甲酸、異辛醇及觸媒同時入料至四頸燒瓶中,通氮氣下反應溫度225℃,反應時間8小時,反應壓力5~760mbar,反應過程中必須脫除水份,反應至酸價1mgKOH/g以下時,以鹼金屬氫氧化合物之水溶液進行中和至合成反應混合物酸價0.07mgKOH/g以下時,進行蒸餾將醇類含量降至300ppm以下,再進行過濾純化後,而製得對苯二甲酸二異辛酯(DOTP)酯化物,可作為可塑劑使用。 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.
所製得DOTP可塑劑酯化物的基本物性及加工物性,測試結果如表一,其中,色相10APHA、酸價0.06mgKOH/g、純度:99.7%;DSC之Tg點測試,Tg=-82℃;移行率:2.5%(70PHR時),透明度:89.2%、可塑化係數:1.05。 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.
【比較例2】 [Comparative Example 2]
如實施例1之製法,按表一配方,將其中之異壬醇混合物,以含2-甲基-2丙基戊醇0.4mol%之異壬醇混合物取代,在相同製程條件下,製得DINT可塑劑酯化物。。 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. .
所製得DOTP可塑劑酯化物的基本物性及加工物性,測試結果如表一,其中,色相12APHA、酸價0.06mgKOH/g、純度:99.8%;DSC之Tg點測試,Tg=-75℃;移行率:1.5%(70PHR時)。 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).
【比較例3】 [Comparative Example 3]
如實施例1之製法,按表一配方,將其中之醇類以異壬醇混合物(不含2-甲基2-丙基戊醇、異癸醇及其衍生物;Evonik公司製)取代,在相同製程條件下,製得DINT可塑劑酯化物。 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.
所製得DOTP可塑劑酯化物的基本物性及加工物性,測試結果如表一,其中,色相12APHA、酸價0.06mgKOH/g、純度:99.7%;DSC之Tg點測試,Tg=-74℃;移行率:1.8%(70PHR時)。 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).
【比較例4】 [Comparative Example 4]
如實施1之製法,按表一配方,將其中醇類以異壬醇混合物(其中含2-甲基-2-丙基戊醇0.2mol%、異癸醇:2.6mol%)取代,在相同製程條件下,製得DINT可塑劑酯化物。 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.
所製得DOTP可塑劑酯化物的基本物性及加工物性,測試結果如表一,其中,色相12APHA、酸價0.05mgKOH/g、純度:99.8%;DSC之Tg點測試,Tg=-74℃;移行率:1.7%(70PHR時)。 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).
【比較例5】 [Comparative Example 5]
如實施1之製法,按表一配方,將其中醇類以異壬醇混合物(其中含2- 甲基-2-丙基戊醇0.2mol%、異癸醇:0.8mol%)取代,在相同製程條件下,製得DINT可塑劑酯化物。 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%).
所製得DOTP可塑劑酯化物的基本物性及加工物性,測試結果如表一,其中,色相13APHA、酸價0.05mgKOH/g、純度:99.8%;DSC之Tg點測試,Tg=-74℃;移行率:1.6%(70PHR時)。 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).
1.實施例1~6皆以對苯二甲酸(PTA)及不同組成分之異壬醇(INA)混合物合成DINT可塑劑酯化物,其中以實施例1異壬醇混合物含2-甲基-2-丙基戊醇0.2mol%及異癸醇1.4mol%所合成之DINT可塑劑酯化物,其移行率:1.25%為最佳,且可塑劑使用量達70PHR,相較於比較例1~5之可塑劑的移行率皆高於1.4%。 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.實施例1及比較例1以對苯二甲酸(PTA)分別與異壬醇(INA)混合物及2EH合成可塑劑酯化物,其中,實施例1之DINT可塑劑酯化物,其移行率:1.25%,較比較例1之DOTP可塑劑酯化物之移行率:2.5%為佳,此證實選擇使用異壬醇(INA)混合物合成DINT可塑劑酯化物,且作為DINT可塑劑使用時,確實較以2EH合成之DOTP可塑劑更有效改善當可塑劑添加量達70PHR時之移行率,將之應用於製成PVC製品時,PVC製品的表面不易出現可塑劑有移行現象,不但外觀平整且觸感較佳。 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.實施例1與比較例3皆以對苯二甲酸(PTA)及不同組成分之異壬醇(INA)混合物合成DINT可塑劑酯化物,其中,實施例1以異壬醇混合物(含2-甲基-2-丙基戊醇0.2mol%及異癸醇:1.4mol%,南亞塑膠公司製)所合成之DINT可塑劑酯化物,其移行率:1.25%,優於以比較例3之DINT可塑 劑酯化物移行率:1.8%。 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.當可塑劑用量達70PHR時,實施例1~6之移行率,遠優於比較例1~5,當可塑劑用量達40PHR時,實施例1~6之移行率,仍優於比較例1-3。 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.
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