CN103980150B - A kind of synthetic method of fatty alcohol ether alkanoylamino acid sodium - Google Patents
A kind of synthetic method of fatty alcohol ether alkanoylamino acid sodium Download PDFInfo
- Publication number
- CN103980150B CN103980150B CN201410144752.5A CN201410144752A CN103980150B CN 103980150 B CN103980150 B CN 103980150B CN 201410144752 A CN201410144752 A CN 201410144752A CN 103980150 B CN103980150 B CN 103980150B
- Authority
- CN
- China
- Prior art keywords
- alcohol ether
- fatty alcohol
- sodium
- acid sodium
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 155
- 239000011734 sodium Substances 0.000 title claims abstract description 49
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 49
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 37
- 239000002253 acid Substances 0.000 title claims abstract description 17
- 238000010189 synthetic method Methods 0.000 title claims description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 68
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 30
- -1 sodium haloalkyl carboxylate Chemical class 0.000 claims abstract description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001413 amino acids Chemical class 0.000 claims abstract description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000006482 condensation reaction Methods 0.000 claims abstract description 3
- 235000001014 amino acid Nutrition 0.000 claims description 23
- 229940024606 amino acid Drugs 0.000 claims description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 claims description 5
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000004471 Glycine Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 3
- 235000004279 alanine Nutrition 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- AGPKZVBTJJNPAG-WHFBIAKZSA-N L-isoleucine Chemical compound CC[C@H](C)[C@H](N)C(O)=O AGPKZVBTJJNPAG-WHFBIAKZSA-N 0.000 claims description 2
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 claims description 2
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 229960000310 isoleucine Drugs 0.000 claims description 2
- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004474 valine Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 9
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims 4
- 125000002837 carbocyclic group Chemical group 0.000 claims 4
- UWLMQFDPGCYPBE-UHFFFAOYSA-N 3-chloropropanoic acid;sodium Chemical group [Na].OC(=O)CCCl UWLMQFDPGCYPBE-UHFFFAOYSA-N 0.000 claims 1
- 101100148780 Caenorhabditis elegans sec-16A.1 gene Proteins 0.000 claims 1
- XHWDALZMZIHQSV-UHFFFAOYSA-N [Na].OC(=O)CCCBr Chemical compound [Na].OC(=O)CCCBr XHWDALZMZIHQSV-UHFFFAOYSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 claims 1
- 238000005917 acylation reaction Methods 0.000 claims 1
- 125000005257 alkyl acyl group Chemical group 0.000 claims 1
- 238000010790 dilution Methods 0.000 claims 1
- 239000012895 dilution Substances 0.000 claims 1
- SMPAPEKFGLKOIC-UHFFFAOYSA-N oxolane;hydrochloride Chemical compound Cl.C1CCOC1 SMPAPEKFGLKOIC-UHFFFAOYSA-N 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 7
- 239000008233 hard water Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 description 12
- 210000003739 neck Anatomy 0.000 description 9
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 9
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 8
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- 230000020477 pH reduction Effects 0.000 description 4
- 235000019260 propionic acid Nutrition 0.000 description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 3
- LIOTZBNOJXQXIL-UHFFFAOYSA-M sodium;3-chloropropanoate Chemical compound [Na+].[O-]C(=O)CCCl LIOTZBNOJXQXIL-UHFFFAOYSA-M 0.000 description 3
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 2
- AINKPXPXFDRVSA-UHFFFAOYSA-M sodium;4-bromobutanoate Chemical compound [Na+].[O-]C(=O)CCCBr AINKPXPXFDRVSA-UHFFFAOYSA-M 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-M Aminoacetate Chemical compound NCC([O-])=O DHMQDGOQFOQNFH-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- WWIXUCPRSXOWRZ-UHFFFAOYSA-N C(CCC)(=O)Cl.O1CCCC1 Chemical compound C(CCC)(=O)Cl.O1CCCC1 WWIXUCPRSXOWRZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Chemical group 0.000 description 1
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 1
- 239000004247 glycine and its sodium salt Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 1
- 235000013923 monosodium glutamate Nutrition 0.000 description 1
- 239000004223 monosodium glutamate Substances 0.000 description 1
- 125000000075 primary alcohol group Chemical group 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- MFBOGIVSZKQAPD-UHFFFAOYSA-M sodium butyrate Chemical compound [Na+].CCCC([O-])=O MFBOGIVSZKQAPD-UHFFFAOYSA-M 0.000 description 1
- 229940029258 sodium glycinate Drugs 0.000 description 1
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 1
- 235000010334 sodium propionate Nutrition 0.000 description 1
- 239000004324 sodium propionate Substances 0.000 description 1
- 229960003212 sodium propionate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- WUWHFEHKUQVYLF-UHFFFAOYSA-M sodium;2-aminoacetate Chemical compound [Na+].NCC([O-])=O WUWHFEHKUQVYLF-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种脂肪醇醚烷酰基氨基酸钠的合成方法，脂肪醇醚和氢氧化钠进行碱处理反应后，与脂肪醇醚和卤代烷基羧酸钠的混合物进行反应，用酸液酸化生成的脂肪醇醚烷基羧酸钠，再经提取、水洗和干燥，得脂肪醇醚烷基羧酸，干燥的脂肪醇醚烷基羧酸与氯化亚砜进行酰化反应，其生成物脂肪醇醚烷基酰氯用干燥的四氢呋喃溶解，最后与氨基酸钠进行缩合反应，制得脂肪醇醚烷酰基氨基酸钠，产物具有良好的抑菌和杀菌及相容性能，并具有耐硬水性能。The invention discloses a method for synthesizing fatty alcohol ether alkanoyl amino acid sodium. After the fatty alcohol ether and sodium hydroxide are subjected to an alkali treatment reaction, they are reacted with a mixture of fatty alcohol ether and sodium haloalkyl carboxylate, and acidified with an acid solution to produce The sodium fatty alcohol ether alkyl carboxylate is extracted, washed and dried to obtain fatty alcohol ether alkyl carboxylic acid, and the dried fatty alcohol ether alkyl carboxylic acid is acylated with thionyl chloride, and the product fat Alcohol ether alkyl chloride is dissolved in dry tetrahydrofuran, and finally undergoes condensation reaction with amino acid sodium to obtain fatty alcohol ether alkanoyl amino acid sodium. The product has good antibacterial, bactericidal and compatible properties, and has hard water resistance.
Description
技术领域 technical field
本发明涉及氨基酸表面活性剂合成技术领域，尤指一种脂肪醇醚烷酰基氨基酸钠的合成方法。The invention relates to the technical field of amino acid surfactant synthesis, in particular to a method for synthesizing fatty alcohol ether alkanoyl amino acid sodium.
背景技术 Background technique
表面活性剂是一种能使目标溶液表面张力显著下降的物质，可降低两种液体或液体-固体间的表面张力，作为工业味精的表面活性剂，因在生产和生活中的独特功效，广泛应用于国民经济发展的各个领域，被认为是一种典型的品种多、用途广、需求量大的精细化工产品，但是，大量的表面活性剂进入水中和土壤中，会破坏环境，污染土壤，所以，我们在关注表面活性剂性能的同时，也应更加关注表面活性剂的生物降解和生物适应能力，因此，对研发高生物降解性和生物相溶性的高性能表面活性剂的需求越来越大。 Surfactant is a substance that can significantly reduce the surface tension of the target solution, and can reduce the surface tension between two liquids or liquid-solid. As a surfactant for industrial monosodium glutamate, it is widely used in production and life because of its unique effects Used in various fields of national economic development, it is considered to be a typical fine chemical product with many varieties, wide uses and high demand. However, if a large amount of surfactants enter the water and soil, it will damage the environment and pollute the soil. Therefore, while we pay attention to the performance of surfactants, we should also pay more attention to the biodegradation and bioadaptability of surfactants. Therefore, there is an increasing demand for the development of high-performance surfactants with high biodegradability and biocompatibility. Big.
氨基酸表面活性剂不仅对环境和生物体的安全性高，对头发和皮肤作用温和，刺激性小、低毒，而且还有其他各种表面活性剂良好的相容性，以及良好的抑菌和杀菌性能，正是因为它所具有的这些优良的表面性能，使其不仅满足了对环境友好的要求，而且也满足了人们对产品温和性和安全性不断提高的要求，用氨基酸制备表面活性剂，必须利用氨基酸的氨基或羧基的反应特性，引入疏水基团，在一定程度上，疏水基团的特性影响着氨基酸表面活性剂的性能。 Amino acid surfactants are not only highly safe to the environment and organisms, mild to hair and skin, less irritating, and less toxic, but also have good compatibility with various other surfactants, as well as good antibacterial and antibacterial properties. Bactericidal properties, precisely because of these excellent surface properties, make it not only meet the requirements of environmental friendliness, but also meet people's continuous improvement of product mildness and safety requirements, using amino acids to prepare surfactants , the amino or carboxyl reaction characteristics of amino acids must be used to introduce hydrophobic groups. To a certain extent, the characteristics of hydrophobic groups affect the performance of amino acid surfactants.
发明内容 Contents of the invention
本发明的目的在于提供一种脂肪醇醚烷酰基氨基酸钠的合成方法。 The object of the present invention is to provide a kind of synthetic method of fatty alcohol ether alkanoyl amino acid sodium.
本发明的技术解决方案是：脂肪醇醚和氢氧化钠进行碱处理反应后，与脂肪醇醚和卤代烷基羧酸钠的混合物进行反应，用酸液酸化生成的脂肪醇醚烷基羧酸钠，再经提取、水洗和干燥，得脂肪醇醚烷基羧酸，干燥的脂肪醇醚烷基羧酸与氯化亚砜进行酰化反应，其生成物脂肪醇醚烷基酰氯用干燥的四氢呋喃溶解，最后与氨基酸钠进行缩合反应，制得脂肪醇醚烷酰基氨基酸钠，具体包含以下步骤： The technical solution of the present invention is: after fatty alcohol ether and sodium hydroxide carry out alkaline treatment reaction, react with the mixture of fatty alcohol ether and sodium halogenated alkyl carboxylate, acidify the fatty alcohol ether sodium alkyl carboxylate that generates with acid solution , and then extracted, washed with water and dried to obtain fatty alcohol ether alkyl carboxylic acid, the dried fatty alcohol ether alkyl carboxylic acid is acylated with thionyl chloride, and the fatty alcohol ether alkyl chloride of the product can be used in dry tetrahydrofuran Dissolving, and finally carrying out condensation reaction with amino acid sodium to obtain fatty alcohol ether alkanoyl amino acid sodium, which specifically includes the following steps:
1)．脂肪醇醚（Ⅰ）和氢氧化钠在105℃～115℃，搅拌和通氮气保护，进行减压真空条件下的碱处理反应2～4小时后，降温至50℃～60℃，生成脂肪醇醚钠（Ⅱ）；其主要化学反应为： 1). Fatty alcohol ether (I) and sodium hydroxide are stirred at 105°C to 115°C and protected by nitrogen, carry out alkali treatment reaction under reduced pressure and vacuum for 2 to 4 hours, then cool down to 50°C to 60°C to generate fatty alcohol Sodium ether (Ⅱ); its main chemical reaction is:
2)．脂肪醇醚（Ⅰ）与卤代烷基羧酸钠（Ⅲ）事先以质量比1﹕1进行混合，其混合物与脂肪醇醚钠（Ⅱ）于50℃～60℃温度和搅拌条件下，继续进行反应3～5小时，生成脂肪醇醚烷基羧酸钠（Ⅳ）；其主要化学反应为： 2). Fatty alcohol ether (I) and sodium haloalkyl carboxylate (III) are mixed in advance at a mass ratio of 1:1, and the mixture is reacted with fatty alcohol ether sodium (II) at a temperature of 50°C to 60°C under stirring conditions After 3 to 5 hours, fatty alcohol ether alkyl carboxylate sodium (Ⅳ) is generated; its main chemical reaction is:
3)．反应生成物脂肪醇醚烷基羧酸钠（Ⅳ）用水进行稀释，缓慢加入酸液酸化，调PH至1～2，酸化后用乙酸乙酯提取酸化产物，用水洗涤酸化产物至中性，无水硫酸钠干燥，得脂肪醇醚烷基羧酸（Ⅴ）；其主要化学反应为： 3). The reaction product fatty alcohol ether alkyl carboxylate sodium (Ⅳ) is diluted with water, slowly added acid solution to acidify, adjust the pH to 1-2, after acidification, extract the acidified product with ethyl acetate, wash the acidified product with water until neutral, no Water and sodium sulfate are dried to obtain fatty alcohol ether alkyl carboxylic acid (Ⅴ); the main chemical reaction is:
4)．干燥的脂肪醇醚烷基羧酸（Ⅴ）与氯化亚砜（Ⅵ），加热升温至65℃～75℃，进行反应2～3小时，尾气用碱液吸收，之后常压蒸去过量的氯化亚砜，得到的黄色液体脂肪醇醚烷基酰氯（Ⅵ），用干燥的四氢呋喃溶解脂肪醇醚烷基酰氯（Ⅵ），备用；其主要化学反应为： 4). Dried fatty alcohol ether alkyl carboxylic acid (Ⅴ) and thionyl chloride (Ⅵ) are heated to 65°C to 75°C and reacted for 2 to 3 hours. The tail gas is absorbed by lye, and then the excess Thionyl chloride, obtained yellow liquid fatty alcohol ether alkyl acid chloride (VI), dissolved fatty alcohol ether alkyl acid chloride (VI) with dry tetrahydrofuran, and set aside; its main chemical reaction is:
5)．向氨基酸（Ⅶ）中加入20%的氢氧化钠溶液，调节PH=9～10，进行反应1小时，制得氨基酸钠（Ⅷ）溶液，备用；其主要化学反应为： 5). Add 20% sodium hydroxide solution to the amino acid (Ⅶ), adjust the pH=9 to 10, and react for 1 hour to prepare the amino acid sodium (Ⅷ) solution for later use; the main chemical reaction is:
6)．于0～5℃温度下，向氨基酸钠（Ⅷ）溶液中以3～4毫升/分的速度滴加肪醇醚烷基酰氯（Ⅵ）的四氢呋喃溶液，边滴加边充分搅拌，同时滴加20%的氢氧化钠溶液，以保持反应体系PH=9～10，滴加完毕后，保持反应体系温度0～5℃，进行反应3～5小时，蒸去四氢呋喃溶剂，生成脂肪醇醚烷酰基氨基酸钠（Ⅸ）。其主要化学反应为： 6). Add the THF solution of fatty alcohol ether alkyl acid chloride (VI) dropwise to the amino acid sodium (VIII) solution at a rate of 3-4 ml/min at a temperature of 0-5°C, stir fully while adding, and add dropwise at the same time 20% sodium hydroxide solution to keep the pH of the reaction system at 9~10. After the dropwise addition, keep the temperature of the reaction system at 0~5°C and carry out the reaction for 3~5 hours. The tetrahydrofuran solvent is evaporated to generate fatty alcohol ether alkanoyl Sodium amino acid (IX). Its main chemical reaction is:
其中，反应式中的R1是碳原子数为C12～C18的伯醇或仲醇；n是3～9的整数；R2是碳原子数为C1～C5的亚烷基；X是氯元素或溴元素； R3是的碳原子数为C1～C6的烷基或氢。 Wherein, R in the reaction formula is a primary or secondary alcohol with carbon atoms of C 12 to C 18 ; n is an integer of 3 to 9; R 2 is an alkylene group with carbon atoms of C 1 to C 5 ; X is chlorine or bromine; R 3 is an alkyl group with C 1 to C 6 carbon atoms or hydrogen.
进一步的是，所述的脂肪醇醚优选仲-十二碳脂肪醇醚、仲-十四碳脂肪醇醚和仲-十六碳脂肪醇醚和仲-十八碳脂肪醇醚及其混合醇醚。 Further, the fatty alcohol ether is preferably secondary-dodecanal fatty alcohol ether, secondary-tetradecyl fatty alcohol ether, secondary-hexadecyl fatty alcohol ether and secondary-octadecanic fatty alcohol ether and their mixed alcohols ether.
所述的卤代烷基羧酸钠优选3-氯丙酸钠和4-溴丁酸钠。 The sodium haloalkyl carboxylate is preferably sodium 3-chloropropionate and sodium 4-bromobutyrate.
所述的脂肪醇醚、氢氧化钠和卤代烷基羧酸钠的摩尔比为1﹕1.2～1.3﹕1.1～1.2。 The molar ratio of the fatty alcohol ether, sodium hydroxide and sodium halogenated alkyl carboxylate is 1:1.2-1.3:1.1-1.2.
所述的脂肪醇醚烷基羧酸与氯化亚砜的摩尔比为1﹕2.5～3.0。 The molar ratio of the fatty alcohol ether alkyl carboxylic acid to the thionyl chloride is 1:2.5-3.0.
所述的氨基酸优选甘氨酸、丙氨酸、缬氨酸、亮氨酸和异亮氨酸。 The amino acids are preferably glycine, alanine, valine, leucine and isoleucine.
所述的脂肪醇醚烷基酰氯与氨基酸钠摩尔比为1﹕1.6～1.8。 The molar ratio of fatty alcohol ether alkyl acid chloride to amino acid sodium is 1:1.6-1.8.
所述的酸液是4摩尔/升的稀硫酸溶液或稀盐酸溶液。 The acid solution is 4 mol/liter of dilute sulfuric acid solution or dilute hydrochloric acid solution.
本发明一种脂肪醇醚烷酰基氨基酸钠的合成方法，其特点和优点是：合成物是一种烷基酚醚乙酰基氨基酸，对头发和皮肤作用温和，刺激性小、低毒，而且还有其他各种表面活性剂良好的相容性，以及良好的抑菌和杀菌性能，具有耐硬水性能。 A kind of synthetic method of fatty alcohol ether alkanoyl amino acid sodium of the present invention, its characteristic and advantage are: synthetic is a kind of alkylphenol ether acetyl amino acid, has mild effect on hair and skin, little irritation, low toxicity, and also It has good compatibility with various other surfactants, good antibacterial and bactericidal properties, and has hard water resistance.
具体实施方式 detailed description
实施例1 Example 1
在装有搅拌器和温度计的四口瓶中，加入35.8克仲-十四碳脂肪醇醚（平均分子量508.4）和4.8克氢氧化钠，通氮气保护，加热升温至105℃～110℃，搅拌条件下，进行减压真空条件下的碱处理反应4小时后，降温至60℃，生成仲-十四碳脂肪醇醚钠，将事先已经混合好的仲-十四碳脂肪醇醚15克与3-氯丙酸钠15克，加入到四口瓶中，于54℃～58℃温度和搅拌条件下，继续进行反应5小时，生成仲-十四碳脂肪醇醚烷基羧酸钠；向四口瓶中80克水进行稀释，缓慢加入4摩尔/升的稀硫酸溶液，调PH至1～2，酸化后用150克乙酸乙酯提取酸化产物，用水洗涤酸化产物至中性，无水硫酸钠干燥，得仲-十四碳脂肪醇醚丙酸，干燥的仲-十四碳脂肪醇醚丙酸加入到装有搅拌器、温度计，回流冷凝器和干燥管的四颈中，再加入355克氯化亚砜，加热升温至65℃～70℃，进行反应2.5小时，尾气用碱液吸收，之后常压蒸去过量的氯化亚砜，得到的黄色液体仲-十四碳脂肪醇醚丙酰氯用干燥的四氢呋喃200毫升溶解，备用；向22克亮氨酸中加入20%的氢氧化钠溶液，调节PH=9～10，进行反应1小时，制得亮氨酸钠溶液，然后将此溶液加入到装有搅拌器、温度计，回流冷凝器的四颈中，将溶液用低温反应浴冷却至0～5℃，于0～5℃温度下，向四颈中以5毫升/分的速度滴加仲-十四碳脂肪醇醚丙酰氯的四氢呋喃溶液，边滴加边充分搅拌，同时滴加20%的氢氧化钠溶液，以保持反应体系PH=9～10，滴加完毕后，保持反应体系温度0～5℃，进行反应5小时，蒸去四氢呋喃溶剂，生成仲-十四碳脂肪醇醚丙酰基亮氨酸钠。 In a four-neck flask equipped with a stirrer and a thermometer, add 35.8 grams of sec-tetradecyl fatty alcohol ether (average molecular weight 508.4) and 4.8 grams of sodium hydroxide, protect with nitrogen, heat up to 105 ° C ~ 110 ° C, stir Under the conditions, after carrying out the alkali treatment reaction under reduced pressure and vacuum conditions for 4 hours, the temperature was lowered to 60° C. to generate secondary-tetradecyl fatty alcohol ether sodium, and 15 grams of secondary-tetradecyl fatty alcohol ethers that had been mixed in advance were mixed with Add 15 grams of sodium 3-chloropropionate into a four-necked bottle, and continue to react for 5 hours at a temperature of 54°C to 58°C under stirring conditions to generate secondary-tetradecyl fatty alcohol ether sodium alkyl carboxylate; Dilute with 80 grams of water in a four-necked bottle, slowly add 4 mol/liter of dilute sulfuric acid solution, adjust the pH to 1~2, extract the acidified product with 150 grams of ethyl acetate after acidification, wash the acidified product with water until neutral, anhydrous Sodium sulfate is dried to obtain secondary-tetradecyl fatty alcohol ether propionic acid, and the dry secondary-tetradecyl fatty alcohol ether propionic acid is added to the four necks equipped with agitator, thermometer, reflux condenser and drying pipe, and then added 355 grams of thionyl chloride, heated to 65 ℃ ~ 70 ℃, reacted for 2.5 hours, the tail gas was absorbed with lye, and then the excess thionyl chloride was evaporated under normal pressure to obtain a yellow liquid secondary-tetradecyl fatty alcohol Ether propionyl chloride was dissolved in 200 ml of dry tetrahydrofuran and set aside; 20% sodium hydroxide solution was added to 22 grams of leucine to adjust the pH=9 to 10, and the reaction was carried out for 1 hour to obtain a sodium leucine solution, and then Add this solution to the four necks equipped with a stirrer, thermometer, and reflux condenser, cool the solution to 0-5°C with a low-temperature reaction bath, and pour it into the four necks at 5 ml/min at a temperature of 0-5°C. Add the tetrahydrofuran solution of sec-tetradecyl fatty alcohol ether propionyl chloride dropwise at a high speed, stir fully while adding dropwise, and at the same time add 20% sodium hydroxide solution dropwise to keep the pH of the reaction system = 9 ~ 10, after the dropwise addition , keeping the temperature of the reaction system at 0-5° C., reacting for 5 hours, distilling off the tetrahydrofuran solvent to generate secondary-tetradecyl fatty alcohol ether propionyl leucine sodium.
实施例2 Example 2
在装有搅拌器和温度计的四口瓶中，加入15克十六碳脂肪醇醚（平均分子量374.5）和5.2克氢氧化钠，通氮气保护，加热升温至110℃～115℃，搅拌条件下，进行减压真空条件下的碱处理反应3小时后，降温至55℃，生成十六碳脂肪醇醚钠，将事先混合好的十六碳脂肪醇醚22.6克与4-溴丁酸钠22.6克，加入到四口瓶中，于55℃～60℃温度和搅拌条件下，继续进行反应3小时，生成十六碳脂肪醇醚丁酸钠；向四口瓶中100克水进行稀释，缓慢加入4摩尔/升的稀盐酸溶液，调PH至1～2，酸化后用190克乙酸乙酯提取酸化产物，用水洗涤酸化产物至中性，无水硫酸钠干燥，得十六碳脂肪醇醚丁酸，干燥的十六碳脂肪醇醚丁酸加入到装有搅拌器、温度计，回流冷凝器和干燥管的四颈中，再加入330克氯化亚砜，加热升温至60℃～70℃，进行反应3小时，尾气用碱液吸收，之后常压蒸去过量的氯化亚砜，得到的黄色液体十六碳脂肪醇醚丁酰氯用干燥的四氢呋喃240毫升溶解，备用；向142.5克丙氨酸中加入20%的氢氧化钠溶液，调节PH=9～10，进行反应1小时，制得丙氨酸钠溶液，然后将此溶液加入到装有搅拌器、温度计，回流冷凝器的四颈中，将溶液用低温反应浴冷却至0～5℃， In a four-neck flask equipped with a stirrer and a thermometer, add 15 grams of hexadecyl fatty alcohol ether (average molecular weight 374.5) and 5.2 grams of sodium hydroxide, protect it with nitrogen, heat up to 110 ° C ~ 115 ° C, and stir , after carrying out the alkali treatment reaction under reduced pressure and vacuum for 3 hours, the temperature was lowered to 55 ° C to generate sodium cetyl fatty alcohol ether, and 22.6 grams of cetyl fatty alcohol ether mixed in advance with 22.6 grams of sodium 4-bromobutyrate gram, was added to a four-necked bottle, and continued to react for 3 hours at a temperature of 55°C to 60°C under stirring conditions to generate cetyl fatty alcohol ether sodium butyrate; to dilute with 100 grams of water in a four-necked bottle, slowly Add 4 mol/liter of dilute hydrochloric acid solution, adjust the pH to 1~2, extract the acidified product with 190 g of ethyl acetate after acidification, wash the acidified product with water until neutral, dry it with anhydrous sodium sulfate, and obtain hexadecyl fatty alcohol ether Butyric acid, dry hexadecyl fatty alcohol ether butyric acid is added to the four necks equipped with agitator, thermometer, reflux condenser and drying tube, then add 330 grams of thionyl chloride, and heat up to 60 ° C ~ 70 ° C , reacted for 3 hours, the tail gas was absorbed with lye, and then the excess thionyl chloride was evaporated at normal pressure, and the obtained yellow liquid hexadecyl fatty alcohol ether butyryl chloride was dissolved in 240 milliliters of dry tetrahydrofuran for subsequent use; Add 20% sodium hydroxide solution to the acid, adjust the pH=9 to 10, and carry out the reaction for 1 hour to obtain the sodium alanine solution, and then add this solution to a four-way tank equipped with a stirrer, a thermometer, and a reflux condenser. In the neck, cool the solution to 0-5°C with a low-temperature reaction bath,
于0～5℃温度下，向四颈中以4毫升/分的速度滴加十六碳脂肪醇醚丁酰氯的四氢呋喃溶液，边滴加边充分搅拌，同时滴加20%的氢氧化钠溶液，以保持反应体系PH=9～10，滴加完毕后，保持反应体系温度0～5℃，进行反应4小时，蒸去四氢呋喃溶剂，生成十六碳脂肪醇醚丁酰基丙氨酸钠。 At a temperature of 0-5°C, add cetyl fatty alcohol ether butyryl chloride tetrahydrofuran solution dropwise to the four necks at a rate of 4 ml/min, stir well while adding dropwise, and add 20% sodium hydroxide solution dropwise at the same time , to keep the pH of the reaction system at 9-10, after the dropwise addition, keep the temperature of the reaction system at 0-5°C, carry out the reaction for 4 hours, evaporate the tetrahydrofuran solvent, and generate hexadecyl fatty alcohol ether butyrylalanine sodium.
实施例3 Example 3
在装有搅拌器和温度计的四口瓶中，加入40.6克仲-十二碳～仲-十八碳脂肪醇醚（平均分子量605）和5克氢氧化钠，通氮气保护，加热升温至108℃～112℃，搅拌条件下，进行减压真空条件下的碱处理反应2小时后，降温至50℃，生成仲-十二碳脂肪醇醚钠，将事先混合好的仲-十二碳脂肪醇醚14.4克与3-氯丙酸钠14.4克，加入到四口瓶中，于50℃～55℃温度和搅拌条件下，继续进行反应4小时，生成仲-十二碳脂肪醇醚烷基丙酸钠；向四口瓶中90克水进行稀释，缓慢加入4摩尔/升的稀硫酸溶液，调PH至1～2，酸化后用170克乙酸乙酯提取酸化产物，用水洗涤酸化产物至中性，无水硫酸钠干燥，得仲-十二碳脂肪醇醚丙酸，干燥的仲-十二碳脂肪醇醚丙酸加入到装有搅拌器、温度计，回流冷凝器和干燥管的四颈中，再加入300克氯化亚砜，加热升温至70℃～80℃，进行反应2小时，尾气用碱液吸收，之后常压蒸去过量的氯化亚砜，得到的黄色液体用干燥的四氢呋喃220毫升溶解，备用；向135克甘氨酸中加入20%的氢氧化钠溶液，调节PH=9～10，进行反应1小时，制得甘氨酸钠溶液，然后将此溶液加入到装有搅拌器、温度计，回流冷凝器的四颈中，将溶液用低温反应浴冷却至0～5℃，于0～5℃温度下，向四颈中以4毫升/分的速度滴加仲-十二碳脂肪醇醚丙酰氯的四氢呋喃溶液，边滴加边充分搅拌，同时滴加20%的氢氧化钠溶液，以保持反应体系PH=9～10，滴加完毕后，保持反应体系温度0～5℃，进行反应3小时，蒸去四氢呋喃溶剂，生成仲-十二碳～仲-十八碳脂肪醇醚丙酰基甘氨酸钠。 In a four-necked flask equipped with a stirrer and a thermometer, add 40.6 grams of sec-dodeca to sec-octadecan fatty alcohol ether (average molecular weight 605) and 5 grams of sodium hydroxide, protect it with nitrogen, and heat up to 108 ℃～112℃, under the condition of stirring, carry out alkali treatment reaction under reduced pressure and vacuum condition for 2 hours, then lower the temperature to 50℃, generate secondary-dodecyl fatty alcohol ether sodium, and mix the pre-mixed secondary-dodecyl fatty alcohol Add 14.4 grams of alcohol ether and 14.4 grams of sodium 3-chloropropionate into a four-necked bottle, and continue to react for 4 hours at a temperature of 50 ° C to 55 ° C under stirring conditions to generate secondary-dodecyl fatty alcohol ether alkyl Sodium propionate; dilute with 90 grams of water in a four-necked bottle, slowly add 4 mol/liter of dilute sulfuric acid solution, adjust the pH to 1-2, extract the acidified product with 170 grams of ethyl acetate after acidification, wash the acidified product with water to Neutral, dry over anhydrous sodium sulfate to obtain secondary-dodecanal fatty alcohol ether propionic acid, dry secondary-dodecanalic fatty alcohol ether propionic acid is added to the four-way tank equipped with agitator, thermometer, reflux condenser and drying tube In the neck, add 300 grams of thionyl chloride, heat up to 70°C to 80°C, and react for 2 hours. The tail gas is absorbed with lye, and then the excess thionyl chloride is evaporated at normal pressure, and the obtained yellow liquid is dried with 220 ml of tetrahydrofuran was dissolved and set aside; 20% sodium hydroxide solution was added to 135 grams of glycine to adjust the pH=9 to 10, and the reaction was carried out for 1 hour to obtain a sodium glycinate solution, which was then added to a tank equipped with a stirrer. , Thermometer, in the four necks of the reflux condenser, cool the solution to 0-5°C with a low-temperature reaction bath, and at a temperature of 0-5°C, add secondary-dodecacarbon dropwise to the four necks at a rate of 4 ml/min The tetrahydrofuran solution of fatty alcohol ether propionyl chloride is fully stirred while adding dropwise, and at the same time, 20% sodium hydroxide solution is added dropwise to keep the pH of the reaction system at 9~10. After the dropwise addition, keep the temperature of the reaction system at 0~5°C , reacted for 3 hours, evaporated the tetrahydrofuran solvent, and generated sec-dodecyl to sec-octadecyl fatty alcohol ether propionyl glycinate sodium.
以上所述，实施方式仅仅是对本发明的优选实施方式进行描述，并非对本发明的范围进行限定，在不脱离本发明技术的精神的前提下，本领域工程技术人员对本发明的技术方案作出的各种变形和改进，均应落入本发明的权利要求书确定的保护范围内。 As mentioned above, the embodiment is only a description of the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. On the premise of not departing from the spirit of the technology of the present invention, engineers and technicians in the field make various technical solutions of the present invention All such modifications and improvements should fall within the scope of protection defined by the claims of the present invention.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410144752.5A CN103980150B (en) | 2014-04-12 | 2014-04-12 | A kind of synthetic method of fatty alcohol ether alkanoylamino acid sodium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410144752.5A CN103980150B (en) | 2014-04-12 | 2014-04-12 | A kind of synthetic method of fatty alcohol ether alkanoylamino acid sodium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103980150A CN103980150A (en) | 2014-08-13 |
| CN103980150B true CN103980150B (en) | 2016-08-17 |
Family
ID=51272351
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410144752.5A Expired - Fee Related CN103980150B (en) | 2014-04-12 | 2014-04-12 | A kind of synthetic method of fatty alcohol ether alkanoylamino acid sodium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103980150B (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH059869A (en) * | 1991-02-08 | 1993-01-19 | Kanebo Ltd | Animal hair processed yarn and continuous manufacturing method thereof |
| JPH09309869A (en) * | 1996-05-22 | 1997-12-02 | Lion Corp | N-alkylamide ether acetic acid or salt thereof, production thereof and detergent containing the same |
| CN100543143C (en) * | 2001-01-19 | 2009-09-23 | 巴斯福股份公司 | Ways to Increase Pantothenic Acid Production |
| JP2002348264A (en) * | 2001-03-22 | 2002-12-04 | Marine Biotechnol Inst Co Ltd | Novel hydroxy fatty acid analogs exhibiting selective algicidal activity |
| CN102875409B (en) * | 2012-09-05 | 2016-03-30 | 长沙普济生物科技有限公司 | A kind of synthetic method of laurel acyl amino acid sodium |
-
2014
- 2014-04-12 CN CN201410144752.5A patent/CN103980150B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103980150A (en) | 2014-08-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105983370B (en) | Saturated cardanol betaine surfactant, and preparation method and application thereof | |
| CN105152957B (en) | The synthetic method of laurel acyl amino acid sodium | |
| CN103894105A (en) | N-long-chain acyl hydroxy amino acid surfactant and preparation method | |
| BRPI0906451B1 (en) | method to produce arginine bicarbonate | |
| CN103752210B (en) | Monomester succinate amino acid surfactant of functional amino groups and preparation method thereof | |
| CN108927073A (en) | A kind of cardanol amino acid surfactant and preparation method thereof | |
| CN103193835B (en) | Novel method for synthesizing and purifying sucrose octasulphonate sodium salt | |
| CN103980150B (en) | A kind of synthetic method of fatty alcohol ether alkanoylamino acid sodium | |
| CN103611471A (en) | Carboxylate surfactant containing aryl groups and preparation method thereof | |
| CN104163848A (en) | Synthetic method of dipeptide Fmoc-Ser(tBu)-Cys-OH | |
| CN100404117C (en) | A kind of preparation method of α-alkyl betaine amphoteric surfactant | |
| CN103073449A (en) | Method for synthesizing N, O-dimethylhydroxylamine hydrochloride | |
| CN102391139B (en) | Energy-saving and environmentally-friendly process for synthesizing alkyl betaine | |
| CN101016377A (en) | Method of synthesizing polyethylene glycol perfluoroolefin ether | |
| CN104649927B (en) | A kind of glutamic acid triethanolamine salt of n-undecane diacyl two and preparation method thereof | |
| CN114380710A (en) | A kind of preparation method of salt-free imidazoline amphoteric surfactant | |
| CN101254441A (en) | Lauric acid amide surfactant and its synthesis method | |
| US8207376B2 (en) | Method for producing amino acid phosphates | |
| CN102527292A (en) | Coupling link-free carboxylate Genmini surfactant and synthesis method thereof | |
| CN101139310A (en) | A kind of synthetic method of bleaching activator alkanoyloxybenzenesulfonate | |
| US3892802A (en) | Processes for making benzamide compounds | |
| CN105198825B (en) | A kind of preparation method of D seromycins | |
| JP6523897B2 (en) | Fluorine-containing carboxylic acid compound | |
| CN118406497B (en) | ITO etching solution | |
| CN118005541B (en) | Di-taurine salt and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170607 Address after: 226500 Rugao, Jiangsu Shi Shi Zhuang Town, Suijiang Road, No. 8, No. Patentee after: JIANGSU TAICANG AGRICULTURAL CHEMICALS CO.,LTD. Address before: 510000 unit 2414-2416, building, No. five, No. 371, Tianhe District, Guangdong, China Patentee before: GUANGDONG GAOHANG INTELLECTUAL PROPERTY OPERATION Co.,Ltd. Effective date of registration: 20170607 Address after: 510000 unit 2414-2416, building, No. five, No. 371, Tianhe District, Guangdong, China Patentee after: GUANGDONG GAOHANG INTELLECTUAL PROPERTY OPERATION Co.,Ltd. Address before: 264760, Yantai City, Yantai province high tech Zone, No. 101, aerospace Road, university students park C-109 Patentee before: YANTAI HENGDIKE ENERGY TECHNOLOGY Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20191204 Address after: Haiyan County of Jiaxing City, Zhejiang province 314311 Shendang Town Industrial Park Patentee after: JIAXING RIFENG METAL PRODUCTS Co.,Ltd. Address before: 226500, No. 8, Suijiang Road, Shi Zhuang Town, Nantong City, Jiangsu Province, Rugao Patentee before: JIANGSU TAICANG AGRICULTURAL CHEMICALS CO.,LTD. |
|
| TR01 | Transfer of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160817 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |