CN106854276A - By C36Method for preparing amphoteric high-molecular surfactant from dimer fatty acid - Google Patents
By C36Method for preparing amphoteric high-molecular surfactant from dimer fatty acid Download PDFInfo
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- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 59
- 239000000194 fatty acid Substances 0.000 title claims abstract description 59
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 59
- 150000004665 fatty acids Chemical class 0.000 title claims abstract description 59
- 239000000539 dimer Substances 0.000 title claims abstract description 37
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 79
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 65
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 64
- 229920000728 polyester Polymers 0.000 claims abstract description 58
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 29
- 239000003054 catalyst Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 20
- 230000032050 esterification Effects 0.000 claims description 12
- 238000005886 esterification reaction Methods 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 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 group C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 9
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 9
- 239000001119 stannous chloride Substances 0.000 claims description 9
- 235000011150 stannous chloride Nutrition 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 3
- 150000007513 acids Chemical class 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 12
- 229920000642 polymer Polymers 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 1
- AMOKUAKXKXBFIW-WJDWOHSUSA-N 9-[(z)-non-3-enyl]-10-octylnonadecanedioic acid Chemical compound OC(=O)CCCCCCCCC(CCCCCCCC)C(CCCCCCCC(O)=O)CC\C=C/CCCCC AMOKUAKXKXBFIW-WJDWOHSUSA-N 0.000 description 19
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 5
- 231100000053 low toxicity Toxicity 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
Abstract
Description
技术领域 technical field
本发明提供了一种以C36二聚脂肪酸为原料制备两性高分子表面活性剂的方法，涉及油脂化学、高分子表面活性剂等技术领域。 The invention provides a method for preparing an amphoteric polymer surfactant by using C36 dimerized fatty acid as a raw material, and relates to the technical fields of oleochemistry, polymer surfactant and the like.
背景技术 Background technique
二聚脂肪酸为天然油脂化工产品，其毒性低、来源广泛且原料可再生，是优良的合成新型高分子材料的原料。二聚脂肪酸还具有良好的耐水性和密封性，对金属等材料具有强烈的粘附性，毒性低，不易燃，-20℃不结晶、不失透明流动性，250℃不蒸发、不凝胶化等优良特性。由二聚脂肪酸与聚乙二醇反应生成的聚酯，分子中既含有呈一定刚性和空间位阻的亲油性基团，还含有亲水性的聚醚链，所以是一种酯醚非离子型高分子表面活性剂，它具有脂肪醇类和聚醚类表面活性剂复配使用的性能，由于其分子量大，具有低分子表面活性剂所没有的一些特性，如良好的稳泡力、润湿性、乳化和增稠力，毒性小，有良好的保护胶体和增溶能力，在众多工业领域得到广泛应用。 Dimerized fatty acid is a natural oil chemical product with low toxicity, wide sources and renewable raw materials. It is an excellent raw material for synthesizing new polymer materials. Dimerized fatty acid also has good water resistance and airtightness, strong adhesion to metal and other materials, low toxicity, non-flammable, no crystallization at -20°C, no loss of transparent fluidity, no evaporation and no gel at 250°C Chemical and other excellent characteristics. The polyester produced by the reaction of dimer fatty acid and polyethylene glycol contains not only lipophilic groups with certain rigidity and steric hindrance in the molecule, but also hydrophilic polyether chains, so it is a kind of ester ether nonionic High molecular surfactant, it has the performance of compounding fatty alcohol and polyether surfactant, because of its large molecular weight, it has some characteristics that low molecular surfactant does not have, such as good foam stability, wetting Wetting, emulsifying and thickening power, low toxicity, good protective colloid and solubilizing ability, widely used in many industrial fields.
C36二聚脂肪酸聚乙二醇聚酯硫酸酯盐是以C36二聚脂肪酸和聚乙二醇为原料，通过控制缩聚时二者的摩尔比等因素，制备了相对分子质量较大且呈窄分布的聚酯，然后再用氨基磺酸选择性硫酸化聚酯的端羟基以提高其亲水性能。合成聚酯硫酸酯盐中缩聚的工艺和合成条件的差别，均影响聚酯硫酸酯盐的性质和应用性能。 C 36 dimerized fatty acid polyethylene glycol polyester sulfate is based on C 36 dimerized fatty acid and polyethylene glycol as raw materials, by controlling factors such as the molar ratio of the two during polycondensation, a relatively large molecular weight and Narrow distribution of polyester, and then use sulfamic acid to selectively sulfate the terminal hydroxyl groups of the polyester to improve its hydrophilic properties. The differences in the polycondensation process and synthesis conditions in the synthesis of polyester sulfate affect the properties and application performance of polyester sulfate.
聚酯硫酸酯盐是一种新型的两性高分子表面活性剂，它既具有非离子表面活性剂的性质，也具有阴离子表面活性剂的一些特性，表现出优良的应用性能。它毒性低、生物降解性和环境亲和力好。目前，以二聚酸为主要原料合成表面活性剂，特别是合成高分子表面活性剂的研究工作，国内尚未见文献报道，在我国尚属首次，具有重大的社会意义及广阔的应用前景。 Polyester sulfate salt is a new type of amphoteric polymer surfactant, which has both the properties of nonionic surfactant and some characteristics of anionic surfactant, showing excellent application performance. It has low toxicity, good biodegradability and environmental affinity. At present, the research work on the synthesis of surfactants with dimer acid as the main raw material, especially the synthesis of polymer surfactants, has not been reported in the literature in my country, and it is the first time in China. It has great social significance and broad application prospects.
说明内容Explanation content
本发明的目的是提供一种以C36二聚脂肪酸为原料制备两性高分子表面活性剂的方法，以C36二聚脂肪酸、聚乙二醇、氨基磺酸为原料，在催化剂作用下，通过研究不同催化剂浓度、反应时间、反应温度、反应物配比对聚合反应的酯化率影响来分析合成聚酯的反应规律，为合成聚酯的制备条件作参考。通过氨基磺酸的选择性，提高C36二聚脂肪酸聚乙二醇的亲水性能，合成一种低毒、生物降解性和环境亲和力好的一种新型两性高分子表面活性剂。 The purpose of this invention is to provide a kind of method with C 36 dimerized fatty acid as raw material preparation amphoteric macromolecule surfactant, with C 36 dimerized fatty acid, Polyethylene Glycol, sulfamic acid as raw material, under catalyst action, by Study the effect of different catalyst concentration, reaction time, reaction temperature, and reactant ratio on the esterification rate of polymerization reaction to analyze the reaction law of synthetic polyester, and provide reference for the preparation conditions of synthetic polyester. Through the selectivity of sulfamic acid, the hydrophilic property of C 36 dimerized fatty acid polyethylene glycol is improved, and a new type of amphoteric polymer surfactant with low toxicity, good biodegradability and environmental affinity is synthesized.
本发明的目的通过以下技术方案来实现。 The object of the present invention is achieved through the following technical solutions.
一种以C36二聚脂肪酸为原料制备两性高分子表面活性剂的方法，其特征在于包括下列步骤： A method for preparing amphoteric macromolecule surfactant with C36 dimerized fatty acid as raw material, is characterized in that comprising the following steps:
1）利用直接缩聚法制备C36二聚脂肪酸和聚乙二醇的聚酯； 1) Prepare C 36 dimerized fatty acid and polyethylene glycol polyester by direct polycondensation method;
2）步骤1）产物与氨基磺酸反应制备两性高分子表面活性剂——C36二聚脂肪酸聚乙二醇聚酯硫酸酯盐。 2) The product of step 1) is reacted with sulfamic acid to prepare an amphoteric polymer surfactant——C 36 dimerized fatty acid polyethylene glycol polyester sulfate salt.
所述步骤1）之利用直接缩聚法制备C36二聚脂肪酸和聚乙二醇的聚酯是指在配有冷凝装置、真空装置、温度计、搅拌装置、油浴加热装置和烧瓶的反应容器中加入一定摩尔比的C36二聚脂肪酸和聚乙二醇，再加入催化剂，抽真空，在一定反应温度下搅拌反应一定时间，得到C36二聚酸聚乙二醇聚酯； The step 1) of preparing the polyester of C36 dimer fatty acid and polyethylene glycol by direct polycondensation method refers to the reaction vessel equipped with a condensation device, a vacuum device, a thermometer, a stirring device, an oil bath heating device and a flask Add C 36 dimer fatty acid and polyethylene glycol in a certain molar ratio, then add a catalyst, vacuumize, stir and react for a certain period of time at a certain reaction temperature to obtain C 36 dimer acid polyethylene glycol polyester;
所述步骤2）之步骤1）产物与氨基磺酸反应制备两性高分子表面活性剂——C36二聚脂肪酸聚乙二醇聚酯硫酸酯盐是指在配有冷凝装置、真空装置、温度计、搅拌装置、油浴加热装置和烧瓶的反应容器中加入C36二聚酸聚乙二醇聚酯，再定量加入经过研磨的氨基磺酸，催化剂，放入已恒温的油浴中，在一定反应时间和聚合温度条件下进行反应，待反应生成C36二聚脂肪酸聚乙二醇聚酯硫酸酯盐后停止反应，算出产物的酯化率，并对产物进行表面活性分析。 The product of step 1) of step 2) is reacted with sulfamic acid to prepare amphoteric polymer surfactant - C 36 dimerized fatty acid polyethylene glycol polyester sulfate salt refers to the product equipped with condensing device, vacuum device, thermometer , stirring device, oil bath heating device and the reaction vessel of the flask, add C 36 dimer acid polyethylene glycol polyester, then quantitatively add through grinding sulfamic acid, catalyst, put into the oil bath of constant temperature, at a certain The reaction is carried out under the conditions of reaction time and polymerization temperature, and the reaction is stopped after the reaction generates C 36 dimeric fatty acid polyethylene glycol polyester sulfate salt, the esterification rate of the product is calculated, and the surface activity analysis is carried out to the product.
所述步骤1）中二聚脂肪酸和聚乙二醇的摩尔比值为1∶0.05~5.5。 The molar ratio of dimer fatty acid and polyethylene glycol in the step 1) is 1:0.05-5.5.
所述步骤1）中催化剂为氯化亚锡，用量为反应物总质量的0.05%~4.5%。 The catalyst in the step 1) is stannous chloride, and the dosage is 0.05%-4.5% of the total mass of reactants.
所述步骤1）中反应温度为150~230℃。 The reaction temperature in the step 1) is 150-230°C.
所述步骤1）中反应时间为4.5~8h。 The reaction time in the step 1) is 4.5~8h.
所述步骤2）中催化剂为尿素。 The catalyst in step 2) is urea.
所述步骤2）中C36二聚酸聚乙二醇聚酯、氨基磺酸和催化剂的摩尔比值为1∶0.05~5.5∶0.05~4.5。 The molar ratio of C36 dimer acid polyethylene glycol polyester, sulfamic acid and catalyst in the step 2) is 1:0.05~5.5:0.05~4.5.
所述步骤2）中反应温度为80~180℃。 The reaction temperature in the step 2) is 80-180°C.
所述步骤2）中反应时间为0.5~6.5h。 The reaction time in the step 2) is 0.5~6.5h.
本发明现有技术相比具有以下优点： Compared with the prior art of the present invention, it has the following advantages:
本发明采用C36二聚脂肪酸、聚乙二醇为原料，在催化剂作用下，通过缩聚反应制备聚酯，再用氨基磺酸酸化制备聚酯硫酸酯盐，即两性高分子表面活性剂。主要是通过先制备C36二聚脂肪酸与聚乙二醇的聚酯，再用氨基磺酸酸化制备聚酯硫酸酯盐，即制备两性高分子表面活性剂。特别是采用配有冷凝装置、真空装置、温度计、搅拌装置、油浴加热装置和烧瓶的反应容器中加入摩尔比值为1∶1.2的C36二聚脂肪酸和聚乙二醇，再加入催化剂氯化亚锡，加入量为反应物总质量的0.3%，在反应温度为150~230℃条件下搅拌反应4.5~8h，得到C36二聚酸聚乙二醇聚酯；然后在配有冷凝装置、真空装置、温度计、搅拌装置、油浴加热装置和烧瓶的反应容器中加入摩尔比值为1∶0.05~5.5∶0.05~4.5的C36二聚酸聚乙二醇聚酯、氨基磺酸和尿素，放入已恒温的油浴中，在80~180℃的条件下搅拌反应0.5~6.5h，待反应生成C36二聚脂肪酸聚乙二醇聚酯硫酸酯盐后停止反应，算出产物的酯化率，并对产物进行表面活性分析。 The invention adopts C36 dimer fatty acid and polyethylene glycol as raw materials, under the action of a catalyst, the polyester is prepared through polycondensation reaction, and then acidified with sulfamic acid to prepare polyester sulfate salt, that is, the amphoteric macromolecular surfactant. Mainly by first preparing the polyester of C 36 dimer fatty acid and polyethylene glycol, and then acidifying the polyester with sulfamic acid to prepare the polyester sulfate salt, that is, preparing the amphoteric polymer surfactant. In particular, add C36 dimer fatty acid and polyethylene glycol with a molar ratio of 1:1.2 into a reaction vessel equipped with a condensing device, a vacuum device, a thermometer, a stirring device, an oil bath heating device and a flask, and then add a catalyst for chlorination. The addition amount of stannous is 0.3% of the total mass of the reactants, and the reaction temperature is 150~230°C under the condition of stirring and reacting for 4.5~8h to obtain C 36 dimer acid polyethylene glycol polyester; In the reaction vessel of vacuum device, thermometer, stirring device, oil bath heating device and flask, add molar ratio as 1: 0.05～5.5: 0.05～4.5 C 36 dimer acid polyethylene glycol polyester, sulfamic acid and urea, Put it in a constant temperature oil bath, stir and react at 80~180℃ for 0.5~6.5h, stop the reaction after the reaction produces C 36 dimer fatty acid polyethylene glycol polyester sulfate salt, and calculate the esterification of the product rate, and the product was subjected to surface activity analysis.
由此可见，本发明采用的主要原料为C36二聚脂肪酸、聚乙二醇和氨基磺酸，先将C36二聚脂肪酸与聚乙二醇进行聚合，得到C36二聚脂肪酸聚乙二醇聚酯，然后用氨基磺酸酸化C36二聚脂肪酸聚乙二醇聚酯，得到了低毒、具有良好生物降解性、稳泡力、润湿性、环境亲和力、乳化和增稠力的两性高分子表面活性剂。反应过程中始终以直接抽真空代替氮气保护，既能排除反应生成的水分，又能避免反应物的氧化，简化合成工艺，降低反应成本，环保节能。以尿素为催化剂，使反应向生成聚酯硫酸盐的方向进行，有利于酯化率的提高，并极大的改善了产品的外观色泽。用氨基磺酸作为硫酸化试剂，能很好的酸化端羟基，对苯环或双键没有影响，产物纯度高、操作方便，而且能够根据不同要求很方便地控制硫酸酯化深度；若需要其他盐类，可以很方便地转化。 This shows that the main raw material that the present invention adopts is C 36 dimer fatty acid, polyethylene glycol and sulfamic acid, first C 36 dimer fatty acid and polyethylene glycol are polymerized to obtain C 36 dimer fatty acid polyethylene glycol Polyester, followed by acidification of C 36 dimerized fatty acid polyethylene glycol polyester with sulfamic acid to obtain amphoteric Polymer surfactant. During the reaction process, direct vacuuming is always used instead of nitrogen protection, which can not only eliminate the moisture generated by the reaction, but also avoid the oxidation of the reactants, simplify the synthesis process, reduce the reaction cost, and be environmentally friendly and energy-saving. Urea is used as a catalyst to make the reaction proceed in the direction of producing polyester sulfate, which is beneficial to the improvement of the esterification rate and greatly improves the appearance and luster of the product. Using sulfamic acid as a sulfating reagent can acidify terminal hydroxyl groups well without affecting benzene rings or double bonds. The product has high purity and is easy to operate, and can easily control the sulfation depth according to different requirements; Salts can be converted easily.
具体实施方式 detailed description
以下通过具体实施例说明本发明，但本发明并不仅仅限定于这些实施例。 The present invention is illustrated below through specific examples, but the present invention is not limited to these examples.
实施例Example 11
在配有冷凝装置、真空装置、温度计、搅拌装置、油浴加热装置和烧瓶的反应容器中加入摩尔比值为1∶1.2的C36二聚脂肪酸和聚乙二醇，再加入催化剂氯化亚锡，加入量为反应物总质量的0.3%，抽真空，在反应温度为200℃条件下搅拌反应6h，得到C36二聚酸聚乙二醇聚酯；然后在配有冷凝装置、真空装置、温度计、搅拌装置、油浴加热装置和烧瓶的反应容器中加入摩尔比值为1∶1∶1.1的C36二聚酸聚乙二醇聚酯、氨基磺酸和尿素，放入已恒温的油浴中，在150℃的条件下搅拌反应3h。待反应生成C36二聚脂肪酸聚乙二醇聚酯硫酸酯盐后停止反应，经计算产物的酯化率为50.29%。 In the reaction vessel equipped with condensing device, vacuum device, thermometer, stirring device, oil bath heating device and flask, add C36 dimer fatty acid and polyethylene glycol with a molar ratio of 1: 1.2, and then add the catalyst stannous chloride , the addition amount is 0.3% of the total mass of the reactants, vacuumize, and stir the reaction for 6h at a reaction temperature of 200°C to obtain C 36 dimer acid polyethylene glycol polyester; then equipped with a condensing device, a vacuum device, Add C36 dimer acid polyethylene glycol polyester, sulfamic acid and urea with a molar ratio of 1:1:1.1 into the reaction vessel of the thermometer, stirring device, oil bath heating device and flask, and put it into the constant temperature oil bath , the reaction was stirred at 150°C for 3h. After the reaction generates C 36 dimeric fatty acid polyethylene glycol polyester sulfate, the reaction is stopped, and the calculated esterification rate of the product is 50.29%.
实施例Example 22
在配有冷凝装置、真空装置、温度计、搅拌装置、油浴加热装置和烧瓶的反应容器中加入摩尔比值为1∶1.2的C36二聚脂肪酸和聚乙二醇，再加入催化剂氯化亚锡，加入量为反应物总质量的0.3%，抽真空，在反应温度为200℃条件下搅拌反应6h，得到C36二聚酸聚乙二醇聚酯；然后在配有冷凝装置、真空装置、温度计、搅拌装置、油浴加热装置和烧瓶的反应容器中加入摩尔比值为1∶1∶0.9的C36二聚酸聚乙二醇聚酯、氨基磺酸和尿素，放入已恒温的油浴中，在130℃的条件下搅拌反应3h。待反应生成C36二聚脂肪酸聚乙二醇聚酯硫酸酯盐后停止反应，经计算产物的酯化率为55.02%。 In the reaction vessel equipped with condensing device, vacuum device, thermometer, stirring device, oil bath heating device and flask, add C36 dimer fatty acid and polyethylene glycol with a molar ratio of 1: 1.2, and then add the catalyst stannous chloride , the addition amount is 0.3% of the total mass of the reactants, vacuumize, and stir the reaction for 6h at a reaction temperature of 200°C to obtain C 36 dimer acid polyethylene glycol polyester; then equipped with a condensing device, a vacuum device, Add C36 dimer acid polyethylene glycol polyester, sulfamic acid and urea with a molar ratio of 1:1:0.9 into the reaction vessel of thermometer, stirring device, oil bath heating device and flask, and put it into the oil bath with constant temperature. , the reaction was stirred at 130° C. for 3 h. After the reaction generates C 36 dimeric fatty acid polyethylene glycol polyester sulfate, the reaction is stopped, and the calculated esterification rate of the product is 55.02%.
实施例Example 33
在配有冷凝装置、真空装置、温度计、搅拌装置、油浴加热装置和烧瓶的反应容器中加入摩尔比值为1∶1.2的C36二聚脂肪酸和聚乙二醇，再加入催化剂氯化亚锡，加入量为反应物总质量的0.3%，抽真空，在反应温度为200℃条件下搅拌反应6h，得到C36二聚酸聚乙二醇聚酯；然后在配有冷凝装置、真空装置、温度计、搅拌装置、油浴加热装置和烧瓶的反应容器中加入摩尔比值为1∶1.15∶1.1的C36二聚酸聚乙二醇聚酯、氨基磺酸和尿素，放入已恒温的油浴中，在130℃的条件下搅拌反应1h。待反应生成C36二聚脂肪酸聚乙二醇聚酯硫酸酯盐后停止反应，经计算产物的酯化率为61.84%。 In the reaction vessel equipped with condensing device, vacuum device, thermometer, stirring device, oil bath heating device and flask, add C36 dimer fatty acid and polyethylene glycol with a molar ratio of 1: 1.2, and then add the catalyst stannous chloride , the addition amount is 0.3% of the total mass of the reactants, vacuumize, and stir the reaction for 6h at a reaction temperature of 200°C to obtain C 36 dimer acid polyethylene glycol polyester; then equipped with a condensing device, a vacuum device, Add C36 dimer acid polyethylene glycol polyester, sulfamic acid and urea with a molar ratio of 1: 1.15: 1.1 into the reaction vessel of thermometer, stirring device, oil bath heating device and flask, and put it into the oil bath with constant temperature. , the reaction was stirred at 130 °C for 1 h. After the reaction generates C 36 dimeric fatty acid polyethylene glycol polyester sulfate, the reaction is stopped, and the calculated esterification rate of the product is 61.84%.
实施例Example 44
在配有冷凝装置、真空装置、温度计、搅拌装置、油浴加热装置和烧瓶的反应容器中加入摩尔比值为1∶1.2的C36二聚脂肪酸和聚乙二醇，再加入催化剂氯化亚锡，加入量为反应物总质量的0.3%，抽真空，在反应温度为200℃条件下搅拌反应6h，得到C36二聚酸聚乙二醇聚酯；然后在配有冷凝装置、真空装置、温度计、搅拌装置、油浴加热装置和烧瓶的反应容器中加入摩尔比值为1∶1∶1.1的C36二聚酸聚乙二醇聚酯、氨基磺酸和尿素，放入已恒温的油浴中，在120℃的条件下搅拌反应3h。待反应生成C36二聚脂肪酸聚乙二醇聚酯硫酸酯盐后停止反应，经计算产物的酯化率为69.90%。 In the reaction vessel equipped with condensing device, vacuum device, thermometer, stirring device, oil bath heating device and flask, add C36 dimer fatty acid and polyethylene glycol with a molar ratio of 1: 1.2, and then add the catalyst stannous chloride , the addition amount is 0.3% of the total mass of the reactants, vacuumize, and stir the reaction for 6h at a reaction temperature of 200°C to obtain C 36 dimer acid polyethylene glycol polyester; then equipped with a condensing device, a vacuum device, Add C36 dimer acid polyethylene glycol polyester, sulfamic acid and urea with a molar ratio of 1:1:1.1 into the reaction vessel of the thermometer, stirring device, oil bath heating device and flask, and put it into the constant temperature oil bath , the reaction was stirred at 120° C. for 3 h. After the reaction generates C 36 dimeric fatty acid polyethylene glycol polyester sulfate, the reaction is stopped, and the calculated esterification rate of the product is 69.90%.
实施例Example 55
在配有冷凝装置、真空装置、温度计、搅拌装置、油浴加热装置和烧瓶的反应容器中加入摩尔比值为1∶1.2的C36二聚脂肪酸和聚乙二醇，再加入催化剂氯化亚锡，加入量为反应物总质量的0.3%，抽真空，在反应温度为200℃条件下搅拌反应6h，得到C36二聚酸聚乙二醇聚酯；然后在配有冷凝装置、真空装置、温度计、搅拌装置、油浴加热装置和烧瓶的反应容器中加入摩尔比值为1∶1∶1.1的C36二聚酸聚乙二醇聚酯、氨基磺酸和尿素，放入已恒温的油浴中，在130℃的条件下搅拌反应3h。待反应生成C36二聚脂肪酸聚乙二醇聚酯硫酸酯盐后停止反应，经计算产物的酯化率为74.03%。 In the reaction vessel equipped with condensing device, vacuum device, thermometer, stirring device, oil bath heating device and flask, add C36 dimer fatty acid and polyethylene glycol with a molar ratio of 1: 1.2, and then add the catalyst stannous chloride , the addition amount is 0.3% of the total mass of the reactants, vacuumize, and stir the reaction for 6h at a reaction temperature of 200°C to obtain C 36 dimer acid polyethylene glycol polyester; then equipped with a condensing device, a vacuum device, Add C36 dimer acid polyethylene glycol polyester, sulfamic acid and urea with a molar ratio of 1:1:1.1 into the reaction vessel of the thermometer, stirring device, oil bath heating device and flask, and put it into the constant temperature oil bath , the reaction was stirred at 130° C. for 3 h. After the reaction generates C 36 dimeric fatty acid polyethylene glycol polyester sulfate, the reaction is stopped, and the calculated esterification rate of the product is 74.03%.
实施例Example 66
在配有冷凝装置、真空装置、温度计、搅拌装置、油浴加热装置和烧瓶的反应容器中加入摩尔比值为1∶1.2的C36二聚脂肪酸和聚乙二醇，再加入催化剂氯化亚锡，加入量为反应物总质量的0.3%，抽真空，在反应温度为200℃条件下搅拌反应6h，得到C36二聚酸聚乙二醇聚酯；然后在配有冷凝装置、真空装置、温度计、搅拌装置、油浴加热装置和烧瓶的反应容器中加入摩尔比值为1∶1.15∶1.1的C36二聚酸聚乙二醇聚酯、氨基磺酸和尿素，放入已恒温的油浴中，在130℃的条件下搅拌反应2h。待反应生成C36二聚脂肪酸聚乙二醇聚酯硫酸酯盐后停止反应，经计算产物的酯化率为78.56%。 In the reaction vessel equipped with condensing device, vacuum device, thermometer, stirring device, oil bath heating device and flask, add C36 dimer fatty acid and polyethylene glycol with a molar ratio of 1: 1.2, and then add the catalyst stannous chloride , the addition amount is 0.3% of the total mass of the reactants, vacuumize, and stir the reaction for 6h at a reaction temperature of 200°C to obtain C 36 dimer acid polyethylene glycol polyester; then equipped with a condensing device, a vacuum device, Add C36 dimer acid polyethylene glycol polyester, sulfamic acid and urea with a molar ratio of 1: 1.15: 1.1 into the reaction vessel of thermometer, stirring device, oil bath heating device and flask, and put it into the oil bath with constant temperature. , the reaction was stirred at 130° C. for 2 h. After the reaction generates C 36 dimeric fatty acid polyethylene glycol polyester sulfate, the reaction is stopped, and the calculated esterification rate of the product is 78.56%.
实施例Example 77
在配有冷凝装置、真空装置、温度计、搅拌装置、油浴加热装置和烧瓶的反应容器中加入摩尔比值为1∶1.2的C36二聚脂肪酸和聚乙二醇，再加入催化剂氯化亚锡，加入量为反应物总质量的0.3%，抽真空，在反应温度为200℃条件下搅拌反应6h，得到C36二聚酸聚乙二醇聚酯；然后在配有冷凝装置、真空装置、温度计、搅拌装置、油浴加热装置和烧瓶的反应容器中加入摩尔比值为1.0∶1.2∶1.2的C36二聚酸聚乙二醇聚酯、氨基磺酸和尿素，放入已恒温的油浴中，在130℃的条件下搅拌反应2.8h，待反应生成C36二聚脂肪酸聚乙二醇聚酯硫酸酯盐后停止反应，经计算产物的酯化率为81.17%。产物在25℃，临界胶束浓度时的表面张力为3.021mN/m，与K12相当；CMC为1.07mmol/L，远低于K12；乳化性能和乳化稳定性与OP-10相当；与K12相比，产物表现出了很好的抑泡性能。 In the reaction vessel equipped with condensing device, vacuum device, thermometer, stirring device, oil bath heating device and flask, add C36 dimer fatty acid and polyethylene glycol with a molar ratio of 1: 1.2, and then add the catalyst stannous chloride , the addition amount is 0.3% of the total mass of the reactants, vacuumize, and stir the reaction for 6h at a reaction temperature of 200°C to obtain C 36 dimer acid polyethylene glycol polyester; then equipped with a condensing device, a vacuum device, Add C36 dimer acid polyethylene glycol polyester, sulfamic acid and urea with a molar ratio of 1.0: 1.2: 1.2 into the reaction vessel of the thermometer, stirring device, oil bath heating device and flask, and put it into an oil bath with constant temperature. In the process, the reaction was stirred at 130°C for 2.8 hours, and the reaction was stopped after the reaction produced C 36 dimeric fatty acid polyethylene glycol polyester sulfate salt. The esterification rate of the product was calculated to be 81.17%. The surface tension of the product at 25°C and the critical micelle concentration is 3.021mN/m, comparable to K 12 ; the CMC is 1.07mmol/L, much lower than K 12 ; the emulsifying performance and emulsification stability are comparable to OP-10; Compared with K 12 , the product showed a good antifoam performance.
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