Λ 6 Β6 ^06212 五、發明説明（1 ) (請先閲讀背面之注意事項再填寫本頁) 本發明係關於以丙二醇單甲基醚與丙酸爲原料所合 成而得丙二醇單甲基醚丙酸酯，其構造方式可以下列表示 ch3 〇Λ 6 Β6 ^ 06212 V. Description of the invention (1) (Please read the precautions on the back before filling in this page) This invention relates to propylene glycol monomethyl ether propylene synthesized from propylene glycol monomethyl ether and propionic acid as raw materials The acid ester, its structure can be expressed as ch3 below.
—I II CH3-0-CH-CH2-0-C-CH2CH3 有機酯類化合物係一種良好的溶劑，爲合成樹脂業界， 如塗料、墨水、接著劑及湳潔劑等所大量使用。目前，醚 類化合物主要分成E系列及P系列二大類。E系列醚類化 合物係指由醇類與環氧乙烷合成而得，p系列醚類化合物 係指由醇類與環氧丙烷合成而得。其相關酯類化合物以乙 酸酯爲主，未有丙酸酯類之產物被開發出來。近年來發現 E系列醚類或其乙酸酯類化合物吸人入體後易分解爲烷氧 乙酸醚，而誘發對紅血球類異常及生殖器官之毒害。但P 罘列則無此毒害。目前，p系列之丙二醇單甲基醚乙酸酯 對於不飽和聚酯或聚氨酯類樹脂之溶解性及其塗膜之乾燥 性不佳，因此，開發溶解性及乾燥性均佳且低毒性的溶劑 已刻不容緩。本發明係針對此一需求，積極硏究開發，終 於製造出丙二醇單甲基醚丙酸酯具有上述良好效果。 經濟部屮央標準局貝工消#合作社印製 本發明之一目的，在於提供新穎丙二醇單甲基醚丙酸 酯化合物。 κ丙 本發明次一目的，在於提供丙二醇單甲@§"酯之製法， 係利用甲醇與環氧丙烷於高溫高壓下所合成之丙二醇單甲 基醚（以下簡稱PGM)，與丙酸於酸性觸媒存在下反應生 成丙二醇單甲基醚丙酯（以下簡稱PMP)。 本發明又一目的，在於使用丙二醇單甲基醚丙酸酯爲 本紙張尺度逍用中國Η家標準(CNS)甲4規格（210x297公釐）一 3—— Λ 6 Β6 206212 五、發明説明（2) 溶劑，尤指用於塗料、墨水、接着劑和淸潔劑等方面° 本發明之製造法可採用分批法及連續法二種。一般經 過反應後未能去除生成的水份，則反應系容易達成平衡狀 態，使產能無法增加，工業生產上極爲不利。因此，本發 明之製程中，不論分批法或連續法，在反應系中均得添加 芳香族系化合物爲水之共沸物，所添加共沸成分必需與水 不互溶，且與水具有共沸特性，芳香族系化合物具備良好 的效果。分批法係將反應物及共沸溶劑匱人反躐器中，在 共沸溫度下進行反應.同時進行脫水，而令共沸溶劑闾流， 當反應完成後，經分餾將產品及共沸溶劑分離可得高純度 產品。連續法係一方面以一定速率進料一方面在反應過程 中陸續由分餾塔頂取出水分，共沸溶劑則囘流，並將反應 器內含生成物PMP濃度達某一程度之反應系溶液移人精餾 塔，將少部分未反應之醚類及酸類與pMP分餾，卽可得高 純度產品。 本發明製法是令PGM與丙酸在酸性觸媒和共沸劑存在 下，於80 =C以上高溫進行酯化反應，製成PMP，再經精餾 分離以脫酸脫水，而得高純度之PMP。 PGM與丙酸的添加量，以丙酸之莫耳數爲準，一般可 在莫耳比0.6〜3.0之範圍進行，其中PGM對丙酸過量， 莫耳比1 .1〜1 · 5爲佳。莫耳比小於0.6或大於3。0，反應 後反應系中一方之未反應殘餘量過多，在精餾過程不但將 多消耗能源及增加精餾時間降低產能外，丙酸過量太多， 卽莫耳比小於〇。6，反應速度有明顯下降的現象，其原因 本紙張尺度边用中國國家標準（CNS)甲4規格(210x297公货） (請先閲讀背面之注意^項再填寫本頁) 裝· 線· 經濟部屮央標準局Μ工消费合作社印製 Λ 6 Β6 五、發明説明（3 ) 尙不明，惟推測酸性觸媒受到緩衝作用。 (請先閱讀背面之注意事項再填寫本頁) ’本發明所用觸媒有無機酸，例如硫酸、鹽酸及磷酸等， 有機酸例如乙酸、草酸、檸檬酸、對一甲苯磺酸、甲烷磺 酸等，其中以強酸性的硫酸、對一甲笨磺酸或甲烷磺酸爲 佳。本發明所得丙二醇單甲基醚丙酸酯之沸點爲， 其他反應物及生成物之沸點分別爲丙二醇單甲基醚爲120 °C，丙酸爲140. 8Ό，水爲lOOC ，比較一般丙二醇單甲 基醚乙酸酯爲146C ，乙酸爲118X：，丙二醇單甲基醚爲 120 C之情形，在精餾上較容易，爲本發明在製程上的功 效之一。另一方面，PMP對代謝器官之毒害較低，依美國 環保署所公佈 NOEL ( No Observable Effect Level )値·’ E系列醍類對兔子爲30 ppm ，而P系列爲3000 PPm «本 發明PMP屬於P系列，對生殖器官之毒害影響極微，爲另 —功效。爲鏍。再者PMP對各種樹脂之溶解力較強， 例如丙二醇單甲基醚乙酸酯對酸醇樹脂之最終溶劑百分比 爲70 %，但本發明丙二醇單甲基醚内酸酯則可達90 %以上， 爲一極佳溶劑.。 經濟部屮央標準局具工消贽合作社印1 本發明在製程上，反應後須經二次精餾，在一次精餾 中，可先脫水及脫酸過程，爲增加脫水脫酸之效率，節省 能源，添加對總原料之6 — 30 %的共沸劑，例如苯、甲笨、 二甲笨及環己烷等芳香族系有機溶劑，以降低精餾共沸溫 度。二次精餾時，只剩下醚類及酯類二成分，可利用其沸 點差，容易地將該二成分完全分餾，而得純度極高之產品。 本發明以下實施例說明，但未限於所擧的實施例中。 本紙張尺度逍用中國國家標準(CNS)甲4規格(210><297公龙） —5 ~- Λ 6 13 6 206212 五、發明説明（4) 實施例一 (請先閱讀背面之注意事項再塡寫本頁) 3 L之反應器添加1172 ml之PGM及746ml之丙酸· 混合再加人二甲笨2 0〇m 1及對--甲苯磺酸10 g後，開始. 加熱升溫達環流溫度（142 =c )反應5小時。在此期間同 時進行脫水，以利反應之進行°取反應液以氣相層析分析 其組成含量，結果爲PMP 69»91 .¾ ’ PGM 15·34 %， 丙酸6·33%，二甲苯7.78 %，水0.59%，將此組成反 應液經二次精餾可得純度99.9 %以上之ΡΜΡ化合物。 此ΡΜΡ化合物之NMR iH圇譜如圖一，質量分析圖譜 如圖二所示，由圖推測其構造如下 ch3 0—I II CH3-0-CH-CH2-0-C-CH2CH3 organic ester compound is a good solvent, which is widely used in the synthetic resin industry, such as coatings, inks, adhesives and cleaning agents. At present, ether compounds are mainly divided into E series and P series. E series ether compounds refer to the synthesis of alcohol and ethylene oxide, and p series ether compounds refer to the synthesis of alcohol and propylene oxide. The related ester compounds are mainly acetate, and no propionate products have been developed. In recent years, it has been found that E series ethers or its acetate compounds are easily decomposed into alkoxyacetate after inhalation into the body, which induces the toxicity to red blood cell abnormalities and reproductive organs. But P Fanglie has no such poison. At present, the p series propylene glycol monomethyl ether acetate is not good for the solubility of unsaturated polyester or polyurethane resins and the dryness of the coating film. Therefore, a solvent with good solubility and dryness and low toxicity is developed. It is urgent. The present invention is actively researched and developed in response to this demand, and finally produces propylene glycol monomethyl ether propionate with the above-mentioned good effects. Printed by the Cooperative Society of the Ministry of Economic Affairs, Beiyang Standard Bureau, Bei Gong Xiao # Cooperative Society One object of the present invention is to provide a novel propylene glycol monomethyl ether propionate compound. κ Propylene The second object of the present invention is to provide a method for producing propylene glycol monomethyl ester @ § " ester, which is a propylene glycol monomethyl ether (hereinafter referred to as PGM) synthesized by using methanol and propylene oxide under high temperature and high pressure, and propionic acid in Propylene glycol monomethyl ether propyl ester (hereinafter referred to as PMP) is reacted in the presence of an acid catalyst. Another object of the present invention is to use propylene glycol monomethyl ether propionate as the paper standard and use Chinese H Home Standard (CNS) A 4 specifications (210x297 mm)-3-Λ 6 Β6 206212 five. Description of the invention ( 2) Solvents, especially those used in coatings, inks, adhesives, and cleaning agents. ° The manufacturing method of the present invention can use either a batch method or a continuous method. Generally, after the reaction fails to remove the generated water, the reaction system can easily reach a state of equilibrium, so that the production capacity cannot be increased, which is extremely disadvantageous in industrial production. Therefore, in the process of the present invention, regardless of the batch method or the continuous method, an aromatic compound is added to the reaction system as an azeotrope of water, and the added azeotropic component must be immiscible with water and have Boiling characteristics, aromatic compounds have good effects. The batch method is to react the reactants and azeotropic solvent in the reactor, and perform the reaction at the azeotropic temperature. At the same time, the dehydration is performed to cause the azeotropic solvent to flow. When the reaction is completed, the product and the azeotrope are separated by fractional distillation Solvent separation can obtain high purity products. On the one hand, the continuous method system feeds at a certain rate. On the one hand, during the reaction, water is continuously taken from the top of the fractionation tower, and the azeotropic solvent is refluxed, and the reaction system solution containing the concentration of the product PMP in the reactor to a certain degree is moved. The human distillation tower fractionates a small part of unreacted ethers and acids with pMP to obtain high-purity products. The preparation method of the invention is to make PGM and propionic acid in the presence of an acid catalyst and an azeotrope to carry out an esterification reaction at a high temperature above 80 = C to form PMP, which is then separated by rectification and deacidification to obtain high purity. PMP. The added amount of PGM and propionic acid is based on the molar number of propionic acid, and can generally be carried out in the range of molar ratio 0.6 ~ 3.0, where the excess of PGM to propionic acid, molar ratio 1.1 ~ 1.5 is better . The molar ratio is less than 0.6 or greater than 3.0. After the reaction, there is too much unreacted residual amount in one of the reaction systems. In the rectification process, not only will it consume more energy and increase the rectification time, but also reduce the production capacity, there will be too much excess propionic acid. Ear ratio is less than 〇. 6. The reaction speed is obviously reduced, the reason is that the paper standard uses the Chinese National Standard (CNS) A 4 specifications (210x297 public goods) (please read the note ^ on the back first and then fill in this page) Pack · Line · Economy Printed by the Ministry of Standards and Technology Bureau, M Industry Consumer Cooperative Society Λ 6 Β6 V. Description of the invention (3) It is unknown, but it is speculated that the acid catalyst is buffered. (Please read the precautions on the back before filling this page) 'The catalysts used in this invention are inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, etc. Organic acids such as acetic acid, oxalic acid, citric acid, p-toluenesulfonic acid and methanesulfonic acid Etc., among which strong acidic sulfuric acid, p-methylsulfonic acid or methanesulfonic acid is preferred. The boiling point of the propylene glycol monomethyl ether propionate obtained in the present invention is that the boiling points of the other reactants and products are respectively 120 ° C for propylene glycol monomethyl ether, 140. 8Ό for propionic acid, and 100 ° C for water. Methyl ether acetate is 146C, acetic acid is 118X :, propylene glycol monomethyl ether is 120 C, it is easier in rectification, which is one of the functions of the invention in the process. On the other hand, PMP is less toxic to metabolic organs. According to the NOEL (No Observable Effect Level) published by the US Environmental Protection Agency, the 'E series of dinosaurs is 30 ppm for rabbits, while the P series is 3000 PPm. The P series has very little effect on the toxicity of reproductive organs, and it has another effect. For Liao. In addition, PMP has strong dissolving power to various resins, for example, the final solvent percentage of propylene glycol monomethyl ether acetate to acid alcohol resin is 70%, but the propylene glycol monomethyl ether lactate of the present invention can reach more than 90% , Is an excellent solvent. The Ministry of Economic Affairs, Central Bureau of Standards, Gongong Xiaozhi Cooperative Printed 1 The present invention requires a secondary rectification after the reaction in the process. In the primary rectification, dehydration and deacidification processes can be performed first, in order to increase the efficiency of dehydration and deacidification. To save energy, add 6-30% of the total raw materials to the azeotropic agent, such as benzene, methyl stupid, dimethyl stupid and cyclohexane aromatic organic solvents to reduce the azeotropic temperature of distillation. During the second rectification, only the ether and ester components remain, and the difference in boiling point can be used to easily fractionate the two components to obtain a product with extremely high purity. The following embodiments of the present invention are described, but are not limited to the listed embodiments. This paper uses the Chinese National Standard (CNS) A4 specifications (210 > < 297 male dragon) — 5 ~-Λ 6 13 6 206212 V. Description of the invention (4) Example 1 (please read the notes on the back first (This page will be written on this page.) The 3 L reactor is filled with 1172 ml of PGM and 746 ml of propionic acid. After mixing, add 2 gm 2 of 200 m 1 and 10 g of p-toluenesulfonic acid. The circulation temperature (142 = c) was reacted for 5 hours. During this period, dehydration was carried out at the same time to facilitate the reaction. ° The reaction liquid was analyzed by gas chromatography for its composition, and the result was PMP 69 »91 .¾ 'PGM 15 · 34%, propionic acid 6.33%, xylene 7.78%, water 0.59%, the secondary reaction of this composition reaction liquid can obtain PMP compound with purity above 99.9%. The NMR iH spectrum of this PMP compound is shown in Figure 1, and the mass analysis spectrum is shown in Figure 2. The structure is speculated as follows: ch3 0
I II CH3-0-CH-CH2-0-C-CH2CH3 實施例二 3 L之反應器中加人1172 ml之PGM及746 ml之 丙酸。混合後再加人對一甲笨磺酸g,開始加熱升溫達 水與丙酸之共沸溫度99. 1 t：，進行環流，並反應5小 時。因未加共沸溶劑，無法將水分層分離，因此，反應 易達平衡狀態。取反應液以氣相層析分析其組成含量， 經濟部屮央標準局員工消费合作社印製 其結果爲 PMP 44.6%，PGM 27.6%，丙酸 22.4%， 水含量5。4 %。 比較例 3 L之反應器中加入1172ml之PGM及572 ml 之乙酸。混合後，再添加對一甲笨磺酸10 g後，開始加 熱升溫達環流溫度97. 5 X：，反應5小時。取反應液以 本紙張尺度边用中國國家樣準(CNS)甲4規格(210x297公龙）_ ΰ Λ 6 Η 6 206212 五、發明説明（5) 氣相層析分析其組成含i l:，結果爲丙二醇單甲基醚乙酸酯 4 4 . 〇 %，乙酸 2 0 ,1 %，PG M 2 9 · 7 % ’ 水 5.8 % ’ 將此反應液經二次精餾可得純度99 %之丙二醇單甲基醚乙 酸酯，问其收率甚低，不合工業效率。 (誚先閗讀背面之注意事取洱艰巧木玎) 裝. 線· 經濟部屮央捣準杓Μ工>i')er合作社印製 本紙58：尺度边用中國因家標準（CNS) TM規怙（210x297公址） 7I II CH3-0-CH-CH2-0-C-CH2CH3 Example 2 A 3 L reactor was charged with 1172 ml of PGM and 746 ml of propionic acid. After mixing, add one g of methanesulfonic acid, and start heating up to the azeotropic temperature of water and propionic acid of 99.1 t: perform circulation and react for 5 hours. Since the azeotropic solvent is not added, the water layer cannot be separated, so the reaction is easily in equilibrium. The composition of the reaction liquid was analyzed by gas chromatography, and it was printed by the Employee Consumer Cooperative of the Bureau of Standards of the Ministry of Economic Affairs. The results were PMP 44.6%, PGM 27.6%, propionic acid 22.4%, and water content 5.4%. Comparative Example 3 L reactor was charged with 1172 ml of PGM and 572 ml of acetic acid. After mixing, 10 g of para-methanesulfonic acid was added, and heating was started to reach a circulation temperature of 97.5 X :, and the reaction was conducted for 5 hours. Take the reaction solution at the size of this paper and use the Chinese National Standard (CNS) A4 specifications (210x297 male dragon) _ ΰ Λ 6 Η 6 206212 V. Description of the invention (5) Gas chromatography analysis of the composition containing il :, results Propylene glycol monomethyl ether acetate 44. 0%, acetic acid 20, 1%, PGM 29.7% 'water 5.8%' This reaction solution was subjected to secondary distillation to obtain propylene glycol with a purity of 99% The yield of monomethyl ether acetate is very low, which is not in line with industrial efficiency. (I will read the precautions on the back from the hard and fragile wood) Installed. Thread · The Ministry of Economic Affairs of the Ministry of Economic Affairs of the People's Republic of China Co., Ltd. printed the original paper 58: the standard side of the Chinese home standard (CNS ) TM Regulations (210x297 public address) 7