CN106800520B - A kind of betaine type amphoteric surfac-tant and preparation method thereof - Google Patents
A kind of betaine type amphoteric surfac-tant and preparation method thereof Download PDFInfo
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- CN106800520B CN106800520B CN201611140819.3A CN201611140819A CN106800520B CN 106800520 B CN106800520 B CN 106800520B CN 201611140819 A CN201611140819 A CN 201611140819A CN 106800520 B CN106800520 B CN 106800520B
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- 239000002280 amphoteric surfactant Substances 0.000 title claims abstract description 36
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 title claims abstract description 32
- 229960003237 betaine Drugs 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000011938 amidation process Methods 0.000 claims abstract description 32
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 25
- 239000002808 molecular sieve Substances 0.000 claims abstract description 24
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 24
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 propyl dimethyl tertiary amine Chemical class 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 70
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000004094 surface-active agent Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000006260 foam Substances 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 2
- YBEFXFBAXWUBNQ-UHFFFAOYSA-N n-methylmethanamine;propan-1-amine Chemical class CNC.CCCN YBEFXFBAXWUBNQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 description 63
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 40
- 235000021314 Palmitic acid Nutrition 0.000 description 20
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 20
- HLERILKGMXJNBU-UHFFFAOYSA-N norvaline betaine Chemical compound CCCC(C([O-])=O)[N+](C)(C)C HLERILKGMXJNBU-UHFFFAOYSA-N 0.000 description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 239000012043 crude product Substances 0.000 description 14
- 238000010792 warming Methods 0.000 description 13
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- 238000002390 rotary evaporation Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 239000002585 base Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 208000012839 conversion disease Diseases 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005292 vacuum distillation Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000003512 tertiary amines Chemical class 0.000 description 5
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 4
- 235000021360 Myristic acid Nutrition 0.000 description 4
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 0 CN(C)CCC* Chemical compound CN(C)CCC* 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000001293 FEMA 3089 Substances 0.000 description 2
- 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 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QEALYLRSRQDCRA-UHFFFAOYSA-N myristamide Chemical compound CCCCCCCCCCCCCC(N)=O QEALYLRSRQDCRA-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical group [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QHJABUZHRJTCAR-UHFFFAOYSA-N n'-methylpropane-1,3-diamine Chemical compound CNCCCN QHJABUZHRJTCAR-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- SNWQKAWITMVCQW-UHFFFAOYSA-N phthalylsulfacetamide Chemical group C1=CC(S(=O)(=O)NC(=O)C)=CC=C1NC(=O)C1=CC=CC=C1C(O)=O SNWQKAWITMVCQW-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
- C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
- C07C233/36—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Cosmetics (AREA)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of betaine type amphoteric surfac-tant and preparation method thereof, the preparation method of the betaine type amphoteric surfac-tant includes the following steps：1）Amidation process：Natural oil resin acid and 3 dimethylamine propylamines carry out amidation process under the effect of the catalyst, and remove the water of dereaction generation in time using 4A molecular sieves, obtain alkylamide propyl dimethyl tertiary amine；2）Quaternary ammonium reaction：Alkylamide propyl dimethyl tertiary amine carries out quaternary ammonium reaction in a solvent with sodium chloroacetate, obtains betaine type amphoteric surfac-tant.Contain amido bond in the amphoteric surfactant group of the present invention, change the performance of molecule, there is better foam stability, performance is mild, and emulsifiability is substantially better than empgen BB surfactant.The preparation method of the present invention is simple for process, and production cost is low, raw material green natural, and absorbs the water generated during amidation process by 4A molecular sieves, improves yield.
Description
Technical field
The present invention relates to a kind of betaine type amphoteric surfac-tants and preparation method thereof.
Background technology
Amphoteric surfactant refers to being existed simultaneously in same molecular structure by bridge chain (hydrocarbon chain, carbon fluorine chain etc.) even
The surfactant of the positive and negative charge-site (or dipole center) of one or more connect, biodegradability are good, less toxic, anti-
Electrostatic.Amphoteric surfactant is appeared in earliest in the 1930s, being gradually developed application later, and China is in both sexes table
Research and development in terms of the activating agent of face are started late, and there is a big difference compared with other developed countries for kind and yield.
Domestic surfactant is based on anionic surfactant and nonionic surfactant, this two classes surface
Activating agent pollutes the environment, it is difficult to biodegradable.Alkylamide propyl-betaine is a kind of new and effective amphoteric surface's work
Property agent there is performance is mild, decontamination is strong, frothing capacity is good, conditioning performance is superior etc. containing amide group and quaternary amines
Advantage is widely used in articles for washing, especially shampoo, hair cream etc. in recent years.Currently, personal care articles industry alkane
The annual consumption of base amide betaine amphoteric surfactant is about ten tens of thousands of tons, wide market.
The preparation process of alkylamide propyl-betaine is broadly divided into following two step：1) amidation process：With aliphatic acid and
3- dimethylamine propylamines are that raw material prepares alkylamide propyl dimethyl tertiary amine；2) quaternary ammonium reaction：With alkylamide propyl two
Methyl tertiary amine and sodium chloroacetate are raw material, water and isopropanol as reaction dissolvent, prepare alkylamide propyl-betaine.Mainly deposit
In problems with：1) acid value of amidation process is difficult to decrease, and to which yield is relatively low, production cost is higher；2) mostly with mixing
Fatty acid is raw materials for production, but this kind of fatty acid contains more impurity, and property is unstable, and it is production also to have with fatty acid methyl esters
Raw material, but further increase production cost；3) purifying technique is fairly simple, and obtained Product Activity content of material is low.
Invention content
The purpose of the present invention is to provide a kind of betaine type amphoteric surfac-tants and preparation method thereof.
The technical solution used in the present invention is：
A kind of betaine type amphoteric surfac-tant, structural formula are：
Wherein n is 12 or 14 or 16.
The preparation method of above-mentioned betaine type amphoteric surfac-tant includes the following steps：
1) amidation process：Natural oil resin acid is melted, 3- dimethylamine propylamines are added, mix well, catalyst is added
Amidation process is carried out, 4A molecular sieves are added after reacting 5~7h, the reaction was continued, removes unreacted 3- diformazans after completion of the reaction
Amido propylamine and natural oil resin acid, obtain alkylamide propyl dimethyl tertiary amine；
2) quaternary ammonium reaction：Reactor is added in alkylamide propyl dimethyl tertiary amine and sodium chloroacetate, adds water to chloroethene
The dissolving of sour sodium is complete, adds isopropanol, adjusts pH value to 7~8, carries out quaternary ammonium reaction, remove after completion of the reaction isopropanol,
Water and unreacted sodium chloroacetate, obtain betaine type amphoteric surfac-tant.
The structural formula of natural oil resin acid described in step 1) is：Wherein n be 12 or 14 or
16。
Catalyst described in step 1) is KOH, NaOH, NaF, CH3One kind in ONa, additive amount are natural oil resin acid matter
The 0.3%~0.7% of amount.
The molar ratio of natural oil resin acid, 3- dimethylamine propylamines described in step 1) is 1：(1.05~1.08).
The mass ratio of natural oil resin acid, 4A molecular sieves described in step 1) is 1：(0.33~0.46).
The reaction temperature of amidation process described in step 1) is 160~180 DEG C, and the reaction time is 9~11 hours.
The molar ratio of alkylamide propyl dimethyl tertiary amine, sodium chloroacetate described in step 2) is 1：(1.05~1.15).
The volume ratio of water, isopropanol described in step 2) is (1.5~2)：1.
The reaction temperature of quaternary ammonium reaction described in step 2) is 80~95 DEG C, and the reaction time is 4~6 hours.
The present invention relates to reaction it is as follows：
1) amidation process：
2) quaternary ammonium reaction：
The beneficial effects of the invention are as follows：
1) contain amido bond in amphoteric surfactant group of the invention, change the performance of molecule, have better
Foam stability, performance is mild, and emulsifiability is substantially better than empgen BB surfactant；
2) preparation method of the invention is simple for process, and production cost is low, and selected reaction raw materials are natural oil resin acid,
Source is wide, green safe, degradable, and absorbs the water generated during amidation process by 4A molecular sieves, can be effective
Promote reaction to be carried out to positive direction, improves yield.
Description of the drawings
Fig. 1 is the infrared spectrogram of betaine type amphoteric surfac-tant prepared by embodiment 1.
Fig. 2 is the nuclear magnetic resonance spectroscopy of betaine type amphoteric surfac-tant prepared by embodiment 1.
Fig. 3 is the surface tension test result figure of betaine type amphoteric surfac-tant prepared by embodiment 1.
Fig. 4 is solubilising test result figure of the betaine type amphoteric surfac-tant to benzene of the preparation of embodiment 1.
Fig. 5 is influence test result figure of the 4A molecular sieves to amidation process conversion ratio.
Specific implementation mode
A kind of betaine type amphoteric surfac-tant, structural formula are：
Wherein n is 12 or 14 or 16.
The preparation method of above-mentioned betaine type amphoteric surfac-tant includes the following steps：
1) amidation process：Natural oil resin acid is melted, 3- dimethylamine propylamines are added, mix well, catalyst is added
It carries out
4A molecular sieves are added after reacting 5~7h in amidation process, and the reaction was continued, removes after completion of the reaction unreacted
3- dimethylamine propylamines and natural oil resin acid, obtain alkylamide propyl dimethyl tertiary amine；
2) quaternary ammonium reaction：Reactor is added in alkylamide propyl dimethyl tertiary amine and sodium chloroacetate, adds water to chloroethene
Sour sodium is molten
Solution is complete, adds isopropanol, adjusts pH value to 7~8, carries out quaternary ammonium reaction, remove after completion of the reaction different
Propyl alcohol, water and unreacted sodium chloroacetate, obtain betaine type amphoteric surfac-tant.
Preferably, the structural formula of the natural oil resin acid described in step 1) is：Wherein n is
12 or 14 or 16.
Preferably, the catalyst described in step 1) is KOH, NaOH, NaF, CH3One kind in ONa, additive amount are natural oil
The 0.3%~0.7% of resin acid quality.
Preferably, the natural oil resin acid described in step 1), 3- dimethylamine propylamines molar ratio be 1：(1.05~1.08).
Preferably, the natural oil resin acid described in step 1), 4A molecular sieves mass ratio be 1：(0.33~0.46).
Preferably, the reaction temperature of the amidation process described in step 1) is 160~180 DEG C, and the reaction time is 9~11 small
When.
Preferably, the alkylamide propyl dimethyl tertiary amine described in step 2), sodium chloroacetate molar ratio be 1：(1.05~
1.15)。
Preferably, the water described in step 2), isopropanol volume ratio be (1.5~2)：1.
Preferably, the reaction temperature of the quaternary ammonium reaction described in step 2) is 80~95 DEG C, and the reaction time is 4~6 hours.
The present invention is made further explanation and description with reference to specific embodiment.
Embodiment 1：
A kind of preparation method of betaine type amphoteric surfac-tant includes the following steps：
1) amidation process：The palmitic acid of 25.6475g is added in the three-necked flask equipped with reflux condenser, is warming up to
80 DEG C so that palmitic acid slowly melts, then 3- dimethylamine propylamines (palmitic acid and the 3- dimethylamine of 10.728g are added dropwise while stirring
The molar ratio of base propylamine is 1:1.05), 30min is dripped off, and is added the KOH of 0.177g as catalyst, is warming up to 160 DEG C, into
Row amidation process, reacts the 4A molecular sieves that 10g is added after 6h, the reaction was continued 5h, and first vacuum distillation after completion of the reaction removes thick
Unreacted 3- dimethylamine propylamines and by-product water in product, then the Na with mass fraction 1%2CO3Solution washing removes not anti-
The palmitic acid answered obtains palmitamide propyl-dimethyl tertiary amine, yield 93.42%；
2) quaternary ammonium reaction：The palmitamide dimethylamine of 34.06g is added in the three-necked flask equipped with reflux condenser
(molar ratio of palmitamide propyl-dimethyl tertiary amine and sodium chloroacetate is 1 to the sodium chloroacetate of base tertiary amine and 13.40g:1.15), then
The water of 30.5g, which is added, makes sodium chloroacetate dissolve just completely, adds the isopropanol of 15.25g, adjusts pH between 7~8, rises
Temperature measures once free amine value to 80 DEG C of progress quaternary ammonium reactions, every a hour, and after reacting 6h, conversion ratio is not further added by,
Stop reaction, obtain crude product, rotary evaporation removes the isopropyl alcohol and water in crude product, and the isopropanol for adding 3 times of volumes is molten
Solution filtering, removes unreacted sodium chloroacetate, and last rotary evaporation recycles isopropanol, obtains palmitamide propyl betaine, i.e.,
The betaine type amphoteric surfac-tant of the present invention, yield 95.32%.
The infrared spectrogram of palmitamide propyl betaine manufactured in the present embodiment is as shown in Figure 1, its nuclear magnetic resonance spectroscopy
(500MHz, DMSO) as shown in Figure 2.
As shown in Figure 1：3311.58cm-1Place is the stretching vibration absworption peak of hydrogen bound to nitrogen N-H；2918.13cm-1、
2850.62cm-1And 1467.74cm-1Place is the stretching vibration absworption peak of C-H bond C-H；1641.33cm-1Place is amido bond-
The characteristic absorption peak of CONH-；1552.61cm-1Place is the antisymmetric stretching vibration absorption peak of carboxylate, and 1398.31cm-1Place
For its symmetrical stretching vibration absorption peak；1232.44cm-1Place is the vibration absorption peak of carbonnitrogen bond-C-N-；721.33cm-1Place for-
(CH2)nRocking vibration absorption peak.
As shown in Figure 2：δ=7.75-7.72 (s, 1H ,-CONH-), δ=4.43-4.09 (s, 2H, N+-CH2COO-), δ=
3.37-3.34 (s, 6H, CH3-N+-CH3), δ=3.11-2.94 (s, 4H ,-NH-CH2-CH2-CH2-N+), δ=2.17-2.12
(s, 2H ,-CH2-CO-), δ=2.09-2.08 (m, 2H ,-CH2-CH2-CH2-N+), δ=1.47-1.44 (s, 2H ,-CH2-CH2-
CONH-), δ=1.24-1.19 (s, 22H ,-(CH2)11), δ=1.12-1.03 (s, 2H ,-CH2-CH3), δ=0.85 (s, 3H ,-
CH3)。
Complex chart 1 and Fig. 2 are understood：Palmitamide propyl betaine product impurity prepared by above-mentioned technological process is few, purity
It is higher.
Embodiment 2：
A kind of preparation method of betaine type amphoteric surfac-tant includes the following steps：
1) amidation process：The myristic acid of 22.84g is added in the three-necked flask equipped with reflux condenser, is warming up to
80 DEG C so that myristic acid slowly melts, then 3- dimethylamine propylamines (myristic acid and the 3- bis- of 10.73g are added dropwise while stirring
The molar ratio of methylamino propylamine is 1:1.05), 30min is dripped off, and is added the NaOH of 0.17g as catalyst, is warming up to 160
DEG C, amidation process is carried out, reacts the 4A molecular sieves that 10g is added after 6h, the reaction was continued 5h, first vacuum distillation removes after completion of the reaction
Go unreacted 3- dimethylamine propylamines and by-product water in crude product, then the Na with mass fraction 1%2CO3Solution washing removes
Unreacted myristic acid obtains myristamide propyl-dimethyl tertiary amine, yield 92.31%；
2) quaternary ammonium reaction：The myristamide propyl two of 31.26g is added in the three-necked flask equipped with reflux condenser
(molar ratio of myristamide propyl-dimethyl tertiary amine and sodium chloroacetate is 1 to the sodium chloroacetate of methyl tertiary amine and 13.40g:
1.15), adding the water of 30.50g makes sodium chloroacetate dissolve just completely, adds the isopropanol of 15.25g, adjust pH 7~
Between 8,80 DEG C of progress quaternary ammonium reactions are warming up to, measure once free amine value every a hour, after reacting 6h, conversion ratio is not
It is further added by, stops reaction, obtain crude product, rotary evaporation removes the isopropyl alcohol and water in crude product, adds the different of 3 times of volumes
Propyl alcohol dissolution filter, removes unreacted sodium chloroacetate, and last rotary evaporation recycles isopropanol, obtains myristamide propyl sweet tea
Dish alkali, i.e. betaine type amphoteric surfac-tant of the invention, yield 94.86%.
Embodiment 3：
A kind of preparation method of betaine type amphoteric surfac-tant includes the following steps：
1) amidation process：The palmitic acid of 25.64g is added in the three-necked flask equipped with reflux condenser, is warming up to 80
DEG C so that palmitic acid slowly melts, then 3- dimethylamine propylamines (palmitic acid and the 3- dimethylamine of 11.1169g are added dropwise while stirring
The molar ratio of base propylamine is 1:1.08), 30min is dripped off, and is added the NaF of 0.18g as catalyst, is warming up to 160 DEG C, carries out
Amidation process reacts the 4A molecular sieves of addition 10g after 6h, the reaction was continued 5h, the after completion of the reaction thick production of first vacuum distillation removing
Unreacted 3- dimethylamine propylamines and by-product water in object, then the Na with mass fraction 1%2CO3Solution washing removes unreacted
Palmitic acid, obtain palmitamide propyl-dimethyl tertiary amine, yield 89.46%；
2) quaternary ammonium reaction：The palmitamide dimethylamine of 34.16g is added in the three-necked flask equipped with reflux condenser
(molar ratio of palmitamide propyl-dimethyl tertiary amine and sodium chloroacetate is 1 to the sodium chloroacetate of base tertiary amine and 12.40g:1.06), then
The water of 31g, which is added, makes sodium chloroacetate dissolve just completely, adds the isopropanol of 15.25g, adjusts pH between 7~8, heating
To 80 DEG C of progress quaternary ammonium reactions, free amine value being measured once every a hour, reacts and continues 6h, conversion ratio is not further added by,
Stop reaction, obtain crude product, rotary evaporation removes the isopropyl alcohol and water in crude product, and the isopropanol for adding 3 times of volumes is molten
Solution filtering, removes unreacted sodium chloroacetate, and last rotary evaporation recycles isopropanol, obtains palmitamide propyl betaine, i.e.,
The betaine type amphoteric surfac-tant of the present invention, yield 76.22%.
Embodiment 4：
A kind of preparation method of betaine type amphoteric surfac-tant includes the following steps：
1) amidation process：The palmitic acid of 25.67g is added in the three-necked flask equipped with reflux condenser, is warming up to 80
DEG C so that palmitic acid slowly melts, then 3- dimethylamine propylamines (palmitic acid and the 3- dimethylamino of 11.43g are added dropwise while stirring
The molar ratio of propylamine is 1:1.06), 30min is dripped off, and adds the CH of 0.190g3ONa is warming up to 160 DEG C as catalyst, into
Row amidation process, reacts the 4A molecular sieves that 10g is added after 6h, the reaction was continued 5h, and first vacuum distillation after completion of the reaction removes thick
Unreacted 3- dimethylamine propylamines and by-product water in product, then the Na with mass fraction 1%2CO3Solution washing removes not anti-
The palmitic acid answered obtains palmitamide propyl-dimethyl tertiary amine, yield 89.60%；
2) quaternary ammonium reaction：The palmitamide dimethylamine of 34.01g is added in the three-necked flask equipped with reflux condenser
(molar ratio of palmitamide propyl-dimethyl tertiary amine and sodium chloroacetate is 1 to the sodium chloroacetate of base tertiary amine and 12.2g:1.05), then
The water of 30g, which is added, makes sodium chloroacetate dissolve just completely, adds the isopropanol of 11.80g, adjusts pH between 7~8, heating
To 95 DEG C of progress quaternary ammonium reactions, free amine value is measured once every a hour, after reacting 6h, conversion ratio is not further added by, and is stopped
It only reacts, obtains crude product, rotary evaporation removes the isopropyl alcohol and water in crude product, adds the isopropanol dissolving of 3 times of volumes
Filtering removes unreacted sodium chloroacetate, and last rotary evaporation recycles isopropanol, obtains palmitamide propyl betaine, i.e., originally
The betaine type amphoteric surfac-tant of invention, yield 84.31%.
Embodiment 5：
A kind of preparation method of betaine type amphoteric surfac-tant includes the following steps：
1) amidation process：The palmitic acid of 25.63g is added in the three-necked flask equipped with reflux condenser, is warming up to 80
DEG C so that palmitic acid slowly melts, then 3- dimethylamine propylamines (palmitic acid and the 3- dimethylamino of 10.78g are added dropwise while stirring
The molar ratio of propylamine is 1:1.05), 30min is dripped off, and is added the NaOH of 0.190g as catalyst, is warming up to 160 DEG C, carries out
Amidation process reacts the 4A molecular sieves of addition 10g after 6h, the reaction was continued 5h, the after completion of the reaction thick production of first vacuum distillation removing
Unreacted 3- dimethylamine propylamines and by-product water in object, then the Na with mass fraction 1%2CO3Solution washing removes unreacted
Palmitic acid, obtain palmitamide propyl-dimethyl tertiary amine, yield 89.31%；
2) quaternary ammonium reaction：The palmitamide dimethylamine of 34.39g is added in the three-necked flask equipped with reflux condenser
(molar ratio of palmitamide propyl-dimethyl tertiary amine and sodium chloroacetate is 1 to the sodium chloroacetate of base tertiary amine and 13.08g:1.11), then
The water of 27g, which is added, makes sodium chloroacetate dissolve just completely, adds the isopropanol of 16.12g, adjusts pH between 7~8, heating
To 85 DEG C of progress quaternary ammonium reactions, free amine value is measured once every a hour, after reacting 6h, conversion ratio is not further added by, and is stopped
It only reacts, obtains crude product, rotary evaporation removes the isopropyl alcohol and water in crude product, adds the isopropanol dissolving of 3 times of volumes
Filtering removes unreacted sodium chloroacetate, and last rotary evaporation recycles isopropanol, obtains palmitamide propyl betaine, i.e., originally
The betaine type amphoteric surfac-tant of invention, yield 88.28%.
Embodiment 6：
A kind of preparation method of betaine type amphoteric surfac-tant includes the following steps：
1) amidation process：The palmitic acid of 25.65g is added in the three-necked flask equipped with reflux condenser, is warming up to 80
DEG C so that palmitic acid slowly melts, then 3- dimethylamine propylamines (palmitic acid and the 3- dimethylamino of 10.83g are added dropwise while stirring
The molar ratio of propylamine is 1:1.06), 30min is dripped off, and is added the KOH of 0.19g as catalyst, is warming up to 160 DEG C, carries out acyl
Aminating reaction reacts the 4A molecular sieves that 10g is added after 6h, and the reaction was continued 5h, first vacuum distillation removes crude product after completion of the reaction
In unreacted 3- dimethylamine propylamines and by-product water, then the Na with mass fraction 1%2CO3Solution washing removes unreacted
Palmitic acid obtains palmitamide propyl-dimethyl tertiary amine, yield 89.31%；
2) quaternary ammonium reaction：The palmitamide dimethylamine of 34.39g is added in the three-necked flask equipped with reflux condenser
(molar ratio of palmitamide propyl-dimethyl tertiary amine and sodium chloroacetate is 1 to the sodium chloroacetate of base tertiary amine and 12.71g:1.10), then
The water of 27g, which is added, makes sodium chloroacetate dissolve just completely, adds the isopropanol of 16.12g, adjusts pH between 7~8, heating
To 85 DEG C of progress quaternary ammonium reactions, free amine value is measured once every a hour, after reacting 6h, conversion ratio is not further added by, and is stopped
It only reacts, obtains crude product, rotary evaporation removes the isopropyl alcohol and water in crude product, adds the isopropanol dissolving of 3 times of volumes
Filtering removes unreacted sodium chloroacetate, and last rotary evaporation recycles isopropanol, obtains palmitamide propyl betaine, i.e., originally
The betaine type amphoteric surfac-tant of invention, yield 84.62%.
Test case：
1) surface tension is tested
Surface tension test is carried out to palmitamide propyl betaine prepared by embodiment 1 at 24 DEG C, test result is such as
Shown in Fig. 3.
As shown in Figure 3：With being continuously increased for surfactant concentration, the surface tension of solution continuously decreases, until going out
The variation of existing inflection point rear surface tension tends towards stability, and the critical micelle concentration cmc for thus obtaining palmitamide propyl betaine is
1.12×10-4Mol/L, corresponding γcmcFor 31.63mN/m, there is the performance of the preferable surface tension for reducing water, this benefit
In the chain hydrophobic alkyl that palmitamide propyl betaine possesses.
2) solubilising of benzene is tested
Solubilising test to benzene, test result such as Fig. 4 institutes are carried out to palmitamide propyl betaine prepared by embodiment 1
Show.
As shown in Figure 4：The solubilized limit A of palmitamide propyl betainePAPB=0.498ml, is calculated palmitamide
The solubilising power X=4980ml/mol of propyl betaine, because the palmitamide propyl betaine of synthesis has chain hydrophobic end,
So the aggregation number of the surfactant is bigger, so that the solubilizing amount for being solubilized into the non-polar hydrocarbon of micelle inner core increases
Add, there is preferable characteristic of solubilizing.
3) emulsifiability is tested
The palmitamide propyl betaine and empgen BB prepared to embodiment 1 carries out emulsifiability test, surveys
Test result is as shown in table 1：
The emulsifiability of 1 palmitamide propyl betaine of table and empgen BB in different oil phases
As shown in Table 1：Palmitamide propyl betaine prepared by embodiment 1 is suitable to the emulsifying capacity sizes of different oil phases
Sequence is as follows：Benzene ＞ turpentine oil ＞ atoleine ＞ tetrafluoroethene, and it is bright to the emulsifiability of benzene, turpentine oil and tetrafluoroethene
It is aobvious to be better than empgen BB.It is primarily due to draw in the alkylamide propyl-betaine type surfactant group of the present invention
Enter amide group, changed the performance of molecule, made it have better foam stability, mildness, plays increasing in formula
Add the effect of viscosity, compatibility and solubility property can be substantially improved, expands its application range, and contain in the long-chain of synthetic product
16 atomicities and the ability with the surface tension for reducing water well so that its emulsion process median surface film strength increases
By force, emulsibility also improves therewith.
4) influence of the 4A molecular sieves to amidation process conversion ratio
At 160 DEG C, acid is 1 with amine molar ratio:1.05 ω(KOH)Under conditions of=0.5%, amidation process process is compared
Middle to add and do not add 4A molecular sieves, reaction conversion ratio changes with time, and test results are shown in figure 5.
As shown in Figure 5：Before 5h, addition and not add 4A molecular sieves reaction conversion ratio be all rapid growth at any time
, the reaction conversion ratio for not adding that group of 4A molecular sieves after 5h is basicly stable, increases unobvious, but adds 4A molecular sieves
That group reaction conversion ratio continue to increase, final reaction conversion ratio is apparently higher than that group for not adding 4A molecular sieves, reaction
What is carried out is more thorough, and the water of amidation process generation can be absorbed by being primarily due to 4A molecular sieves, to promote reaction forward
It carries out, reaction conversion ratio also improves therewith.Therefore, selection is added 4A molecular sieves after amidation process carries out 5~7h and more closes
It is suitable.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (6)
1. a kind of preparation method of betaine type amphoteric surfac-tant, it is characterised in that：Include the following steps：
1) amidation process：Natural oil resin acid is melted, 3- dimethylamine propylamines are added, mix well, catalyst is added and carries out
4A molecular sieves are added after reacting 5~7h in amidation process, and the reaction was continued, removes unreacted 3- dimethylamino after completion of the reaction
Propylamine and natural oil resin acid, obtain alkylamide propyl dimethyl tertiary amine；
2) quaternary ammonium reaction：Reactor is added in alkylamide propyl dimethyl tertiary amine and sodium chloroacetate, adds water to sodium chloroacetate
Dissolving is complete, adds isopropanol, adjusts pH value to 7~8, carries out quaternary ammonium reaction, remove after completion of the reaction isopropanol, water and
Unreacted sodium chloroacetate, obtains betaine type amphoteric surfac-tant；
The molar ratio of natural oil resin acid, 3- dimethylamine propylamines described in step 1) is 1：(1.05~1.08)；
The mass ratio of natural oil resin acid, 4A molecular sieves described in step 1) is 1：(0.33~0.46)；
The reaction temperature of amidation process described in step 1) is 160~180 DEG C, and the reaction time is 9~11 hours.
2. preparation method according to claim 1, it is characterised in that：The structural formula of natural oil resin acid described in step 1)
For：
Wherein n is 12 or 14 or 16.
3. preparation method according to claim 1, it is characterised in that：Catalyst described in step 1) be KOH, NaOH,
NaF、CH3One kind in ONa, additive amount are the 0.3%~0.7% of natural oil resin acid quality.
4. preparation method according to claim 1, it is characterised in that：Alkylamide propyl dimethyl uncle described in step 2)
Amine, sodium chloroacetate molar ratio be 1：(1.05~1.15).
5. preparation method according to claim 1, it is characterised in that：The volume ratio of water, isopropanol described in step 2) is
(1.5~2)：1.
6. preparation method according to claim 1, it is characterised in that：The reaction temperature of quaternary ammonium reaction described in step 2)
It it is 80~95 DEG C, the reaction time is 4~6 hours.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3113026A (en) * | 1959-01-19 | 1963-12-03 | Gen Aniline & Film Corp | Polyvinyl alcohol photographic silver halide emulsions |
| CN101406433A (en) * | 2007-10-09 | 2009-04-15 | 戈尔德施米特有限公司 | Mild water-bearing surfactant preparing article for cosmetics and washing agent |
| CN102344793A (en) * | 2011-08-16 | 2012-02-08 | 中国石油化工股份有限公司 | Thickener and preparation method thereof |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3113026A (en) * | 1959-01-19 | 1963-12-03 | Gen Aniline & Film Corp | Polyvinyl alcohol photographic silver halide emulsions |
| CN101406433A (en) * | 2007-10-09 | 2009-04-15 | 戈尔德施米特有限公司 | Mild water-bearing surfactant preparing article for cosmetics and washing agent |
| CN102344793A (en) * | 2011-08-16 | 2012-02-08 | 中国石油化工股份有限公司 | Thickener and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Synthesis and Evaluation of acid self-diverting agent";Jigang Wang et al.;《Applied Mechanics and Materials》;20130715;第333-335卷;1824-1827 * |
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