CN101407461A - Preparation method of diethylene glycol dibenzoate - Google Patents
Preparation method of diethylene glycol dibenzoate Download PDFInfo
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- CN101407461A CN101407461A CNA2008102021257A CN200810202125A CN101407461A CN 101407461 A CN101407461 A CN 101407461A CN A2008102021257 A CNA2008102021257 A CN A2008102021257A CN 200810202125 A CN200810202125 A CN 200810202125A CN 101407461 A CN101407461 A CN 101407461A
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- diethylene glycol
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- glycol dibenzoate
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- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 72
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 27
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 27
- 229930195734 saturated hydrocarbon Natural products 0.000 claims abstract description 18
- 239000012043 crude product Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000004042 decolorization Methods 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 238000000967 suction filtration Methods 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 32
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical group C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 10
- 239000011964 heteropoly acid Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 9
- 239000004014 plasticizer Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- -1 then Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229930195733 hydrocarbon Natural products 0.000 description 11
- 150000002430 hydrocarbons Chemical class 0.000 description 11
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000008031 plastic plasticizer Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
一种二甘醇二苯甲酸酯的制备方法，涉及一种作为有机化工产品增塑剂的二甘醇二苯甲酸酯(DEDB)的制备工艺。先按苯甲酸∶二甘醇＝2∶1－1.1份重量比量取；再量取重量为苯甲酸和二甘醇总重量的0.01－0.02倍的质子酸作为催化剂，接着，将苯甲酸和二甘醇投入反应器中，边搅拌边升温到90－200℃，加入催化剂，然后加入饱和烃类作为带水剂，调节温度至90－160℃，保温6－16h，使反应进行完全；在此温度下，减压脱除带水剂，得到二甘醇二苯甲酸酯粗产品，最后加入碱中和，将催化剂去除，再依次进行脱色、抽滤，得到二甘醇二苯甲酸酯。本发明使用饱和烃类带水剂，在质子酸催化下，有效降低了反应温度，抑制了副产物生成，转化率达到98％，产率高，产品成本低，具有很强的工业生产价值。A preparation method of diethylene glycol dibenzoate relates to a preparation process of diethylene glycol dibenzoate (DEDB) as a plasticizer for organic chemical products. First take by benzoic acid: diethylene glycol = 2: 1-1.1 parts by weight ratio; then measure the protonic acid whose weight is 0.01-0.02 times of the total weight of benzoic acid and diethylene glycol as a catalyst, then, benzoic acid and Put diethylene glycol into the reactor, heat up to 90-200°C while stirring, add catalyst, then add saturated hydrocarbons as water-carrying agent, adjust the temperature to 90-160°C, keep warm for 6-16h, to make the reaction complete; At this temperature, remove the water-carrying agent under reduced pressure to obtain the crude product of diethylene glycol dibenzoate, and finally add alkali to neutralize, remove the catalyst, and then perform decolorization and suction filtration in sequence to obtain diethylene glycol dibenzoic acid ester. The invention uses a saturated hydrocarbon water-carrying agent, and under the catalysis of a protonic acid, the reaction temperature is effectively reduced, the generation of by-products is suppressed, the conversion rate reaches 98%, the yield is high, the product cost is low, and it has strong industrial production value.
Description
技术领域 technical field
一种二甘醇二苯甲酸酯的制备方法，涉及一种作为有机化工产品增塑剂的二甘醇二苯甲酸酯(DEDB)的制备工艺。A preparation method of diethylene glycol dibenzoate relates to a preparation process of diethylene glycol dibenzoate (DEDB) as a plasticizer for organic chemical products.
背景技术 Background technique
增塑剂是PVC等塑料加工生产用量最大的助剂，在合成橡胶、涂料、粘合剂、化工合成等许多领域都有它广泛的应用。作为塑料增塑剂的邻苯二甲酸酯(DOP)类由于其原料相对易得、价格较低，占据了增塑剂的80％以上的市场份额。但是DOP被美国癌症研究所(NCI)怀疑有致癌作用后，其他的使用范围受到很大的限制。二甘醇二苯甲酸酯(DEDB)和DOP相比，具有相容性好、耐寒性好、抗静电性、抗污染性能显著、热稳定性突出、挥发性低、耐光变色性好等特点，并且毒性低，是很好的DOP替代品，具有很好的市场前景。Plasticizers are the most widely used additives in the processing and production of PVC and other plastics. They are widely used in many fields such as synthetic rubber, coatings, adhesives, and chemical synthesis. Phthalate esters (DOP), as plastic plasticizers, account for more than 80% of the market share of plasticizers due to their relatively easy availability of raw materials and low prices. However, after DOP was suspected of carcinogenicity by the National Cancer Institute (NCI), other uses were greatly restricted. Compared with DOP, diethylene glycol dibenzoate (DEDB) has the characteristics of good compatibility, good cold resistance, antistatic property, remarkable anti-pollution performance, outstanding thermal stability, low volatility, and good photochromic resistance. , and low toxicity, it is a good DOP substitute and has a good market prospect.
目前，制备DEDB的方法大致有如下5种。A，成兰兴在“河南化工”，1990(7)，第17-18页；李广才等，在“精细石油化工”，1997(1)第22-23页报道了用甲苯作为溶剂带水，硫酸做催化剂制备二甘醇二苯甲酸酯(DEDB)的工艺。由于甲苯毒性大，硫酸腐蚀性强，并且需要较高反应温度，副反应严重，产物颜色深，所以给后处理增加了麻烦。B，吴庆银等.在“辽宁化工”，，1992(2)，第38-40页；Jiang Wei在“Chemical World”，2001(2)，第75页，用甲苯作为溶剂带水，杂多酸作为催化剂制备二甘醇二苯甲酸酯(DEDB)，但是该催化剂来源少，价格高，所以产品成本高。C，王颖，在“沈阳教育学院学报”，2005(7))公开了用甲苯作为溶剂，对甲苯磺酸做催化剂，虽然反应的副反应得到一定控制，但是由于温度高，产品颜色深。D，高永辉等在“.佛山科学技术学院学报”，2000(18)，第43-46页提供了利用二甲苯做带水剂，碱性氧化铝做催化剂，催化合成增塑剂DEDB的研究，该方法反应温度高，操作麻烦，后处理用到过滤，而DEDB比较粘稠，损失大。E，任维衡，在“中南民族学院学报”，1995(14)第10-13页报告了用二甲苯作溶剂，氯化亚锡做催化剂制备二甘醇二苯甲酸酯(DEDB)的工艺，该方法反应温度高，后处理、操作麻烦。At present, there are roughly five methods for preparing DEDB as follows. A, Cheng Lanxing in "Henan Chemical Industry", 1990 (7), pp. 17-18; Li Guangcai et al., in "Fine Petrochemical Industry", 1997 (1) pp. 22-23 reported using toluene as a solvent to carry water, A process for preparing diethylene glycol dibenzoate (DEDB) using sulfuric acid as a catalyst. Because toluene is highly toxic, sulfuric acid is highly corrosive, and requires high reaction temperature, serious side reactions, and dark product color, so it adds trouble to post-processing. B, Wu Qingyin, etc. In "Liaoning Chemical Industry", 1992(2), pp. 38-40; Jiang Wei in "Chemical World", 2001(2), pp. 75, using toluene as a solvent to carry water, heteropolyacid Prepare diethylene glycol dibenzoate (DEDB) as catalyst, but this catalyst source is few, and price is high, so product cost is high. C, Wang Ying, in "Journal of Shenyang Institute of Education", 2005 (7)) discloses using toluene as a solvent and p-toluenesulfonic acid as a catalyst. Although the side reactions of the reaction are controlled to a certain extent, the color of the product is dark due to the high temperature. D, Gao Yonghui et al. in "Journal of Foshan Institute of Science and Technology", 2000 (18), pages 43-46, provided a study on the use of xylene as a water-carrying agent and basic alumina as a catalyst to catalyze the synthesis of plasticizer DEDB. This method has a high reaction temperature, cumbersome operation, and filtration is used for post-treatment, while DEDB is relatively viscous and has a large loss. E, Ren Weiheng, in "Journal of South Central University for Nationalities", 1995 (14) page 10-13, reported using dimethylbenzene as solvent, stannous chloride as catalyst to prepare diethylene glycol dibenzoate (DEDB), The method has a high reaction temperature, troublesome post-processing and operation.
发明内容 Contents of the invention
本发明的目的是寻求一种增塑剂二甘醇二苯甲酸酯(DEDB)的制备工艺。用本发明生产DEDB能克服现有工艺的缺点，大大降低生产DEDB的价格，提高了产品质量，简化后处理流程，使其能很好的适应工业化生产的需要。The purpose of this invention is to seek a kind of preparation technology of plasticizer diethylene glycol dibenzoate (DEDB). The production of DEDB by the present invention can overcome the disadvantages of the existing technology, greatly reduce the price of producing DEDB, improve the product quality, simplify the post-processing flow, and make it well adapt to the needs of industrialized production.
为达上述目的，本发明对生产DEDB工艺做了一系列的改进，我们使用饱和烃类(正己烷、环己烷、石油醚、戊烷等)作为带水剂，使苯甲酸和二甘醇在质子酸催化下，在较低的反应温度下也可顺利进行，并且使产率提高98％。For reaching above-mentioned purpose, the present invention has done a series of improvements to production DEDB technique, we use saturated hydrocarbons (normal hexane, hexanaphthene, sherwood oil, pentane etc.) as water-carrying agent, make benzoic acid and diethylene glycol Under the catalysis of protonic acid, it can also proceed smoothly at a lower reaction temperature, and the yield is increased by 98%.
本发明的化学反应机理：二甘醇和苯甲酸在催化剂的作用下发生酯化反应，酯化反应首先是一分子苯甲酸和一分子二甘醇反应生成苯甲酸单酯，然后单酯继续和一份子的苯甲酸反应，生成DEDB。Chemical reaction mechanism of the present invention: diethylene glycol and benzoic acid take place esterification reaction under the effect of catalyzer, esterification is at first a molecule benzoic acid and a molecule diethylene glycol reaction to generate benzoic acid monoester, then monoester continues and a Molecules of benzoic acid react to generate DEDB.
总反应方程式为：The overall reaction equation is:
具体操作步骤如下：The specific operation steps are as follows:
先按苯甲酸∶二甘醇＝2份∶1-1.1份重量比量取；再按1份苯甲酸和二甘醇总重量量取0.01-0.02份重量的质子酸作为催化剂，接着，将苯甲酸和二甘醇投入反应器中，边搅拌边升温到90-200℃，再加入催化剂，然后加入饱和烃类作为带水剂，带水剂的加入量为苯甲酸重量的0.05-0.2倍，调节温度至90-160℃后保温6-16h，使反应进行完全；然后，在此温度下，减压脱除带水剂，得到二甘醇二苯甲酸酯粗产品，最后加入碱中和，将催化剂去除，再按传统方式依次对二甘醇二苯甲酸酯粗产品进行脱色、抽滤，得到二甘醇二苯甲酸酯。First take by benzoic acid: diethylene glycol = 2 parts: 1-1.1 parts by weight ratio; then take 0.01-0.02 parts by weight of protonic acid as a catalyst according to the total weight of 1 part of benzoic acid and diethylene glycol; then, benzene Put formic acid and diethylene glycol into the reactor, heat up to 90-200°C while stirring, then add catalyst, then add saturated hydrocarbons as water-carrying agent, the amount of water-carrying agent added is 0.05-0.2 times the weight of benzoic acid, Adjust the temperature to 90-160°C and keep it warm for 6-16 hours to complete the reaction; then, at this temperature, remove the water-carrying agent under reduced pressure to obtain the crude product of diethylene glycol dibenzoate, and finally add alkali to neutralize , the catalyst is removed, and then the crude product of diethylene glycol dibenzoate is decolorized and suction-filtered sequentially in a conventional manner to obtain diethylene glycol dibenzoate.
上述的催化剂为杂多酸，或对甲苯磺酸，或盐酸和对甲苯磺酸的混合酸。Above-mentioned catalyst is heteropolyacid, or p-toluenesulfonic acid, or the mixed acid of hydrochloric acid and p-toluenesulfonic acid.
上述的催化剂为1份重量的盐酸和0.4-6份重量的对甲苯磺酸的混合酸。The above-mentioned catalyst is a mixed acid of 1 part by weight of hydrochloric acid and 0.4-6 parts by weight of p-toluenesulfonic acid.
上述作为带水剂的烃类为环己烷、正己烷、石油醚或戊烷。The above-mentioned hydrocarbons as the water-carrying agent are cyclohexane, n-hexane, petroleum ether or pentane.
上述碱为碳酸钙、碳酸钠、碱性树脂或者氢氧化钠。The above-mentioned alkali is calcium carbonate, sodium carbonate, basic resin or sodium hydroxide.
本发明的优点是：The advantages of the present invention are:
1.由于本发明的带水剂是正己烷、环己烷、石油醚、戊烷等饱和烃类，所以苯甲酸和二甘醇在质子酸催化下，在较低的反应温度下可顺利进行反应，并且使产率提高到了98％。1. Since the water-carrying agent of the present invention is saturated hydrocarbons such as n-hexane, hexanaphthene, sherwood oil, pentane, so benzoic acid and diethylene glycol can carry out smoothly under the catalysis of protonic acid at lower reaction temperature reaction, and the yield was increased to 98%.
2.除了对带水剂进行改进外，本发明对催化剂也进行筛选，因此操作简单，反应温度较低，安全、节能，副反应少，对设备损害小，后处理简单，减少了污染。2. In addition to improving the water-carrying agent, the present invention also screens the catalyst, so the operation is simple, the reaction temperature is low, safe, energy-saving, less side reactions, less damage to equipment, simple post-treatment, and reduced pollution.
3.本发明收率高，产品成本低，后处理流程简单，能很好的适应工业化生产要求。3. The invention has high yield, low product cost, simple post-treatment process, and can well meet the requirements of industrial production.
具体实施方式 Detailed ways
本发明的原料苯甲酸、二甘醇以及带水剂和催化剂等均为市售的产品。Raw material benzoic acid of the present invention, diethylene glycol, water-carrying agent and catalyzer etc. are all commercially available products.
实施例1Example 1
在2L的三颈瓶中投入1000g苯甲酸，430g二甘醇，投料比例为2∶1.05，在搅拌的情况下升温(油浴温度180-200℃)，加入杂多酸20g作为催化剂，然后加入饱和烃类环己烷作为带水剂80g，调节温度至145-160℃，保温10-15h，使反应进行完全。在145-160℃温度下，减压脱带水剂，得到粗产品DEDB，经碳酸钙、碳酸钠、碱性树脂或者氢氧化钠除酸，传统脱色得到DEDB。Put 1000g of benzoic acid and 430g of diethylene glycol in a 2L three-necked bottle, and the ratio of feeding is 2:1.05. When stirring, heat up (oil bath temperature 180-200°C), add 20g of heteropolyacid as a catalyst, and then add Saturated hydrocarbon cyclohexane is used as 80g of water-carrying agent, the temperature is adjusted to 145-160°C, and the temperature is kept for 10-15h to complete the reaction. At a temperature of 145-160°C, the dehydration agent is decompressed to obtain the crude product DEDB, which is deacidified by calcium carbonate, sodium carbonate, alkaline resin or sodium hydroxide, and traditionally decolorized to obtain DEDB.
实施例2Example 2
在2L的三颈瓶中投入1000g苯甲酸，480g二甘醇，投料比例为2∶1.1，在搅拌的情况下升温(油浴温度100～120℃)，加入盐酸32g作为催化剂，然后加入饱和烃类带水剂环己烷90g，保温6-8h，调节温度至90-100℃，使反应进行完全。在此温度下，减压脱烃类带水剂，得到粗产品DEDB，经碳酸钙、碳酸钠、碱性树脂或者氢氧化钠除酸，传统脱色得到DEDB。Put 1000g of benzoic acid and 480g of diethylene glycol into a 2L three-necked bottle, the ratio of the feed is 2:1.1, heat up while stirring (oil bath temperature 100-120°C), add 32g of hydrochloric acid as a catalyst, and then add saturated hydrocarbon Water-carrying agent cyclohexane 90g, keep warm for 6-8h, adjust the temperature to 90-100°C to complete the reaction. At this temperature, the hydrocarbon water-carrying agent is removed under reduced pressure to obtain the crude product DEDB, which is deacidified by calcium carbonate, sodium carbonate, alkaline resin or sodium hydroxide, and DEDB is obtained by traditional decolorization.
实施例3Example 3
在2L的三颈瓶中投入1000g苯甲酸，480g二甘醇，投料比例为2∶1.1，在搅拌的情况下升温(油浴温度120-140℃)，加入盐酸20g和对甲苯磺酸8g作为催化剂，然后加入饱和烃类带水剂正己烷50g，调节温度至90-100℃，保温12-16h，使反应进行完全。在此温度下，减压脱烃类带水剂，得到粗产品DEDB，经碳酸钙、碳酸钠、碱性树脂或者氢氧化钠除酸，传统脱色得到DEDB。In the three-necked bottle of 2L, drop into 1000g benzoic acid, 480g diethylene glycol, feed ratio is 2: 1.1, heat up (oil bath temperature 120-140 ℃) under the situation of stirring, add hydrochloric acid 20g and p-toluenesulfonic acid 8g as catalyst, and then add 50 g of n-hexane, a saturated hydrocarbon water-carrying agent, adjust the temperature to 90-100° C., and keep the temperature for 12-16 hours to complete the reaction. At this temperature, the hydrocarbon water-carrying agent is removed under reduced pressure to obtain the crude product DEDB, which is deacidified by calcium carbonate, sodium carbonate, alkaline resin or sodium hydroxide, and DEDB is obtained by traditional decolorization.
实施例4Example 4
在2L的三颈瓶中投入1000g苯甲酸，480g二甘醇，投料比例为2∶1.1，在搅拌的情况下升温(油浴温度110-120℃)，加入盐酸16g和对甲苯磺酸14g作为催化剂，然后加入饱和烃类带水剂正己烷70g，调节温度至95-110℃，保温10-15h，使反应进行完全。在此温度下，减压脱烃类带水剂，得到粗产品DEDB，经碳酸钙、碳酸钠、碱性树脂或者氢氧化钠除酸，传统脱色得到DEDB。In the three-necked bottle of 2L, drop into 1000g benzoic acid, 480g diethylene glycol, feed ratio is 2: 1.1, heat up (oil bath temperature 110-120 ℃) under the situation of stirring, add hydrochloric acid 16g and p-toluenesulfonic acid 14g as catalyst, and then add 70 g of n-hexane, a saturated hydrocarbon water-carrying agent, adjust the temperature to 95-110° C., and keep the temperature for 10-15 hours to complete the reaction. At this temperature, the hydrocarbon water-carrying agent is removed under reduced pressure to obtain the crude product DEDB, which is deacidified by calcium carbonate, sodium carbonate, alkaline resin or sodium hydroxide, and DEDB is obtained by traditional decolorization.
实施例5Example 5
在2L的三颈瓶中投入1000g苯甲酸，480g二甘醇，投料比例为2∶1.1，在搅拌的情况下升温(油浴温度130-150℃)，加入盐酸8g和对甲苯磺酸20g作为催化剂，然后加入饱和烃类带水剂环己烷120g，调节温度至110-120℃，保温6-10h，使反应进行完全。在此温度下，减压脱烃类带水剂，得到粗产品DEDB，经碳酸钙、碳酸钠、碱性树脂或者氢氧化钠除酸，传统脱色得到DEDB。In the three-necked bottle of 2L, drop into 1000g benzoic acid, 480g diethylene glycol, feed ratio is 2: 1.1, heat up (oil bath temperature 130-150 ℃) under the situation of stirring, add hydrochloric acid 8g and p-toluenesulfonic acid 20g as catalyst, then add 120g of cyclohexane, a saturated hydrocarbon water-carrying agent, adjust the temperature to 110-120°C, and keep the temperature for 6-10h to complete the reaction. At this temperature, the hydrocarbon water-carrying agent is removed under reduced pressure to obtain the crude product DEDB, which is deacidified by calcium carbonate, sodium carbonate, alkaline resin or sodium hydroxide, and DEDB is obtained by traditional decolorization.
实施例6Example 6
在2L的三颈瓶中投入1000g苯甲酸，480g二甘醇，投料比例为2∶1.1，在搅拌的情况下升温(油浴温度130-150℃)，加入盐酸4g和对甲苯磺酸24g作为催化剂，然后加入饱和烃类带水剂石油醚200g，调节温度至110-130℃，保温10-15h，使反应进行完全。在此温度下，减压脱烃类带水剂，得到粗产品DEDB，经碳酸钙、碳酸钠、碱性树脂或者氢氧化钠除酸，传统脱色得到DEDB。In the three-necked bottle of 2L, drop into 1000g benzoic acid, 480g diethylene glycol, feed ratio is 2: 1.1, heat up (oil bath temperature 130-150 ℃) under the situation of stirring, add hydrochloric acid 4g and p-toluenesulfonic acid 24g as Catalyst, then add 200g of petroleum ether, a saturated hydrocarbon water-carrying agent, adjust the temperature to 110-130°C, and keep it warm for 10-15h to complete the reaction. At this temperature, the hydrocarbon water-carrying agent is removed under reduced pressure to obtain the crude product DEDB, which is deacidified by calcium carbonate, sodium carbonate, alkaline resin or sodium hydroxide, and DEDB is obtained by traditional decolorization.
实施例7Example 7
在2L的三颈瓶中投入1000g苯甲酸，480g二甘醇，投料比例为2∶1.1，在搅拌的情况下升温(油浴温度120-140℃)，加入对甲苯磺酸32g作为催化剂，然后加入饱和烃类带水剂戊烷150g，调节温度至110-120℃，保温6-10h，使反应进行完全。在此温度下，减压脱烃类带水剂，得到粗产品DEDB，经碳酸钙、碳酸钠、碱性树脂或者氢氧化钠除酸，传统脱色得到DEDB。In the three-necked bottle of 2L, drop into 1000g benzoic acid, 480g diethylene glycol, feed ratio is 2: 1.1, heat up (oil bath temperature 120-140 ℃) under the situation of stirring, add p-toluenesulfonic acid 32g as catalyst, then Add 150 g of saturated hydrocarbon water-carrying agent pentane, adjust the temperature to 110-120° C., and keep it warm for 6-10 hours to complete the reaction. At this temperature, the hydrocarbon water-carrying agent is removed under reduced pressure to obtain the crude product DEDB, which is deacidified by calcium carbonate, sodium carbonate, alkaline resin or sodium hydroxide, and DEDB is obtained by traditional decolorization.
实施例8Example 8
在2L的三颈瓶中投入1000g苯甲酸，470g二甘醇，投料比例为2∶1.08，在搅拌的情况下升温(油浴温度130-150℃)，加入对甲苯磺酸22g作为催化剂，然后加入饱和烃类带水剂环己烷120g，调节温度至120-130℃，保温6-8h，使反应进行完全。在此温度下，减压脱烃类带水剂，得到粗产品DEDB，经碳酸钙、碳酸钠、碱性树脂或者氢氧化钠除酸，传统脱色得到DEDB。In the three-necked bottle of 2L, drop into 1000g benzoic acid, 470g diethylene glycol, feed ratio is 2: 1.08, heat up (oil bath temperature 130-150 ℃) under the situation of stirring, add p-toluenesulfonic acid 22g as catalyst, then Add 120 g of cyclohexane, a saturated hydrocarbon water-carrying agent, adjust the temperature to 120-130° C., and keep it warm for 6-8 hours to complete the reaction. At this temperature, the hydrocarbon water-carrying agent is removed under reduced pressure to obtain the crude product DEDB, which is deacidified by calcium carbonate, sodium carbonate, alkaline resin or sodium hydroxide, and DEDB is obtained by traditional decolorization.
实施例9Example 9
在2L的三颈瓶中投入1000g苯甲酸，460g二甘醇，投料比例为2∶1.05，在搅拌的情况下升温(油浴温度130-150℃)，加入对甲苯磺酸30g作为催化剂，然后加入饱和烃类带水剂环己烷130g，调节温度至120-130℃，保温6-8h，使反应进行完全。在此温度下，减压脱烃类带水剂，得到粗产品DEDB，经碳酸钙、碳酸钠、碱性树脂或者氢氧化钠除酸，传统脱色得到DEDB。In the three-necked bottle of 2L, drop into 1000g benzoic acid, 460g diethylene glycol, feed ratio is 2: 1.05, heat up (oil bath temperature 130-150 ℃) under the situation of stirring, add p-toluenesulfonic acid 30g as catalyst, then Add 130 g of cyclohexane, a saturated hydrocarbon water-carrying agent, adjust the temperature to 120-130° C., and keep it warm for 6-8 hours to complete the reaction. At this temperature, the hydrocarbon water-carrying agent is removed under reduced pressure to obtain the crude product DEDB, which is deacidified by calcium carbonate, sodium carbonate, alkaline resin or sodium hydroxide, and DEDB is obtained by traditional decolorization.
实施例10Example 10
在2L的三颈瓶中投入1000g苯甲酸，445g二甘醇，投料比例为2∶1.02，在搅拌的情况下升温(油浴温度120-140℃)，加入对甲苯磺酸28g作为催化剂，然后加入饱和烃类带水剂正己烷140g，调节温度至95-100℃，保温8-12h，使反应进行完全。在此温度下，减压脱烃类带水剂，得到粗产品DEDB，经碳酸钙、碳酸钠、碱性树脂或者氢氧化钠除酸，传统脱色得到DEDB。In the three-necked flask of 2L, drop into 1000g benzoic acid, 445g diethylene glycol, feed ratio is 2: 1.02, heat up (oil bath temperature 120-140 ℃) under the situation of stirring, add p-toluenesulfonic acid 28g as catalyst, then Add 140 g of n-hexane, a saturated hydrocarbon water-carrying agent, adjust the temperature to 95-100° C., and keep it warm for 8-12 hours to complete the reaction. At this temperature, the hydrocarbon water-carrying agent is removed under reduced pressure to obtain the crude product DEDB, which is deacidified by calcium carbonate, sodium carbonate, alkaline resin or sodium hydroxide, and DEDB is obtained by traditional decolorization.
实施例11Example 11
在2L的三颈瓶中投入1000g苯甲酸，430g二甘醇，投料比例为2∶1，在搅拌的情况下升温(油浴温度140-160℃)，加入对甲苯磺酸16g作为催化剂，然后加入饱和烃类带水剂环己烷100g，调节温度至110-120℃，保温11-13h，使反应进行完全。在此温度下，减压脱烃类带水剂，得到粗产品DEDB，经碳酸钙、碳酸钠、碱性树脂或者氢氧化钠除酸，传统脱色得到DEDB。In the three-necked bottle of 2L, drop into 1000g benzoic acid, 430g diethylene glycol, feed ratio is 2: 1, heat up (oil bath temperature 140-160 ℃) under the situation of stirring, add p-toluenesulfonic acid 16g as catalyst, then Add 100 g of cyclohexane, a saturated hydrocarbon water-carrying agent, adjust the temperature to 110-120° C., and keep it warm for 11-13 hours to complete the reaction. At this temperature, the hydrocarbon water-carrying agent is removed under reduced pressure to obtain the crude product DEDB, which is deacidified by calcium carbonate, sodium carbonate, alkaline resin or sodium hydroxide, and DEDB is obtained by traditional decolorization.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351703A (en) * | 2011-08-24 | 2012-02-15 | 南通大学 | Preparation method of diethylene glycol dibenzoate |
| CN102399147A (en) * | 2011-09-22 | 2012-04-04 | 江苏康恒化工有限公司 | Preparation method of 1, 4-cyclohexanedimethanol dibenzoate |
| CN103086891A (en) * | 2013-02-22 | 2013-05-08 | 厦门大学 | Preparation method of plasticizer diethylene glycol dibenzoate |
| CN103524727A (en) * | 2013-09-29 | 2014-01-22 | 河南新大新材料股份有限公司 | Preparation method of dibenzoate polyethylene glycol plasticizer |
| CN103848742A (en) * | 2013-12-19 | 2014-06-11 | 广州正道环保新材料有限公司 | Method for efficiently producing diethylene glycol dibenzoate |
| CN104086344A (en) * | 2014-07-01 | 2014-10-08 | 杭州师范大学 | Synthesis method of phenol by aromatic esterification by using heteropoly acid as catalyst |
| CN106674006A (en) * | 2016-12-20 | 2017-05-17 | 广州印田新材料有限公司 | Benzoate preparation process |
| US11427699B2 (en) * | 2016-05-18 | 2022-08-30 | Lg Chem, Ltd. | Plasticizer composition, resin composition and methods of preparing the same |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351703A (en) * | 2011-08-24 | 2012-02-15 | 南通大学 | Preparation method of diethylene glycol dibenzoate |
| CN102351703B (en) * | 2011-08-24 | 2013-09-18 | 南通大学 | Preparation method of diethylene glycol dibenzoate |
| CN102399147A (en) * | 2011-09-22 | 2012-04-04 | 江苏康恒化工有限公司 | Preparation method of 1, 4-cyclohexanedimethanol dibenzoate |
| CN103086891A (en) * | 2013-02-22 | 2013-05-08 | 厦门大学 | Preparation method of plasticizer diethylene glycol dibenzoate |
| CN103086891B (en) * | 2013-02-22 | 2015-12-23 | 厦门大学 | The preparation method of elasticizer diethylene glycol dibenzoate |
| CN103524727A (en) * | 2013-09-29 | 2014-01-22 | 河南新大新材料股份有限公司 | Preparation method of dibenzoate polyethylene glycol plasticizer |
| CN103848742A (en) * | 2013-12-19 | 2014-06-11 | 广州正道环保新材料有限公司 | Method for efficiently producing diethylene glycol dibenzoate |
| CN103848742B (en) * | 2013-12-19 | 2016-04-27 | 广州正道环保新材料有限公司 | The method of High-efficient Production diethylene glycol dibenzoate |
| CN104086344A (en) * | 2014-07-01 | 2014-10-08 | 杭州师范大学 | Synthesis method of phenol by aromatic esterification by using heteropoly acid as catalyst |
| CN104086344B (en) * | 2014-07-01 | 2016-02-03 | 杭州师范大学 | A kind of synthetic method of aromatic ester of heteropoly acid catalysis phenol |
| US11427699B2 (en) * | 2016-05-18 | 2022-08-30 | Lg Chem, Ltd. | Plasticizer composition, resin composition and methods of preparing the same |
| CN106674006A (en) * | 2016-12-20 | 2017-05-17 | 广州印田新材料有限公司 | Benzoate preparation process |
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