CN113135846A - Preparation method of sulfobetaine type waterborne polyurethane chain extender - Google Patents
Preparation method of sulfobetaine type waterborne polyurethane chain extender Download PDFInfo
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- CN113135846A CN113135846A CN202110372354.9A CN202110372354A CN113135846A CN 113135846 A CN113135846 A CN 113135846A CN 202110372354 A CN202110372354 A CN 202110372354A CN 113135846 A CN113135846 A CN 113135846A
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- chain extender
- sulfobetaine
- solvent
- aqueous polyurethane
- polyurethane chain
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 27
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 27
- 239000004970 Chain extender Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 229940117986 sulfobetaine Drugs 0.000 title claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 26
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims abstract description 18
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012043 crude product Substances 0.000 claims abstract description 17
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000002386 leaching Methods 0.000 claims abstract description 9
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000005070 sampling Methods 0.000 claims abstract description 8
- 239000000725 suspension Substances 0.000 claims abstract description 8
- 239000013068 control sample Substances 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims abstract description 7
- 238000005507 spraying Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 9
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 10
- 239000000839 emulsion Substances 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000004945 emulsification Methods 0.000 abstract description 3
- 108010025899 gelatin film Proteins 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 28
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- -1 coatings Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005580 one pot reaction Methods 0.000 description 3
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid group Chemical group S(N)(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000003799 water insoluble solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
Abstract
The invention discloses a preparation method of a sulfobetaine type aqueous polyurethane chain extender, which comprises the following steps: (1) dissolving N-methyldiethanolamine in a solvent, adding a catalyst, uniformly stirring, dropwise adding 1, 3-propane sultone, controlling the reaction temperature at 30-50 ℃, controlling the dropwise adding time at 1-3 h, controlling the aging time at 1-2 h, separating out a product in the reaction process, carrying out central control sampling to monitor the mixed suspension, and filtering to obtain a crude product after the content of tertiary amine is unchanged; (2) and (3) spraying and leaching the crude product in a filtering device by using a newly prepared solvent which is the same as that in the step (1) until a central control sample is sampled and monitored to have no tertiary amine content, filtering, and drying under reduced pressure to obtain the high-purity N, N-bis (2-hydroxyethyl) -N-methyl-3-sulfonate-1-propylamine. When the method is used for synthesizing the waterborne polyurethane, the emulsification process is convenient to control, the emulsion stability is good, the relevant mechanical property and water resistance of the emulsion after the emulsion is formed into a gel film can be improved, and the waterborne polyurethane with high solid content can be synthesized.
Description
Technical Field
The invention belongs to the technical field of organic compound synthesis, and particularly relates to a preparation method of a sulfobetaine type aqueous polyurethane chain extender.
Technical Field
The waterborne polyurethane can use water as a dispersion medium, abandons the traditional mode of adopting volatile solvent, has the characteristics of less pollution, no toxicity, no harm and the like, and has no great difference in application performance. The method is mainly applied to the fields of coatings, leather, coatings, adhesives and the like. The hydrophilic chain extender plays a critical role in the waterborne polyurethane, and the currently used types mainly comprise a carboxylic acid type and a sulfonic acid type.
N, N-bis (2-hydroxyethyl) -N-methyl-3-sulfonate-1-propylamine, MDAPS for short, is a double-end hydroxyl sulfobetaine type aqueous polyurethane chain extender. After the hydrophilic chain extender is introduced into a polyurethane molecular chain, the polyurethane has better emulsion dispersion stability. Compared with a carboxylic acid type chain extender, when the aqueous polyurethane chain extender is used for the chain extension of aqueous polyurethane, the thermosetting content and the thermal stability of the prepared aqueous polyurethane are high. Compared with a double-end sulfamic acid chain extender, the double-end sulfamic acid chain extender has low reaction activity and has great advantage in the aspect of controlling the viscosity of a reaction system. The betaine type waterborne polyurethane belongs to an amphoteric type and has better stability in a wider pH range. Meanwhile, the cationic quaternary ammonium salt contained in the sulfobetaine structure has excellent protein adsorption resistance and antifouling performance, and can have antimicrobial, sterilization and antifouling effects after being introduced into the molecular structure of the waterborne polyurethane.
The existing MDAPS synthesis process mainly adopts a one-pot method for synthesis under the reflux state of a solvent, and then adopts a recrystallization mode for purification (patent CN 103665291A). The method has long time consumption, the temperature is difficult to control when the one-pot method is adopted for synthesis, the safety problem is easy to occur in the actual production process, the one-pot method is easy to agglomerate, in addition, the solubility of MDAPS in most solvents is small, when the MDAPS is purified by adopting a recrystallization or extraction mode, the solvent consumption is very large, the yield of the final product is low, different solvents are used in the product purification process, the treatment difficulty is high after the solvents are mixed, and the recycling is difficult.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of the sulfobetaine type waterborne polyurethane chain extender, which has the advantages of high efficiency, low cost, environmental protection, high yield and easy industrial production.
In order to achieve the purpose, the invention is implemented by the following technical scheme: a preparation method of a sulfobetaine type aqueous polyurethane chain extender comprises the following steps:
(1) dissolving N-methyldiethanolamine in a solvent, adding a catalyst, uniformly stirring, dropwise adding 1, 3-propane sultone, controlling the reaction temperature at 30-50 ℃, the dropwise adding time at 1-3 h, and the aging time at 1-2 h, separating out a product in the reaction process, carrying out central control sampling to monitor the mixed suspension, and filtering to obtain a crude product after the tertiary amine content is unchanged.
(2) And (3) spraying and leaching the crude product in a filtering device by using the same solvent as the solvent in the step (1) until no tertiary amine content is monitored, filtering, and drying under reduced pressure to obtain the high-purity MDAPS. The solvent part can be directly reused or recycled after simple treatment.
As a preferable scheme: in the step (1), the solvent is one of methanol, isopropanol, n-hexane, cyclohexane, pentane and octane.
As a preferable scheme: in the step (1), the catalyst is one of potassium hydroxide, sodium methoxide, potassium tert-butoxide and morpholine.
As a preferable scheme: the molar weight ratio of the reaction raw material N-methyldiethanolamine to 1, 3-propane sultone in the step (1) is 1.05-1.3: 1.
As a preferable scheme: the mass fraction of the catalyst used in the step (1) is 0.1-3% of the total mass of the raw materials (the sum of the mass of the N-methyldiethanolamine and the mass of the 1, 3-propane sultone).
As a preferable scheme: the mass and the dosage of the solvent in the step (1) are 0.5-10 times of the total mass of the raw materials (the sum of the mass of the N-methyldiethanolamine and the mass of the 1, 3-propane sultone).
As a preferable scheme: the crude product is purified by adopting a spray leaching mode with less solvent consumption.
As a preferable scheme: and the sample is dried under reduced pressure, so that the time consumption of the preparation period is reduced.
The reaction principle of the invention is as follows:
compared with the prior art, the invention has the following advantages:
(1) the reaction of the invention adopts a dropwise addition type reaction, the system is not easy to agglomerate, no blockage is caused to a production device, the reaction temperature is easy to control, and the sample yield is more than 93 percent.
(2) The invention adopts the catalyst to reduce the ring-opening activity of the 1, 3-propane sultone, completes the reaction at lower temperature and in shorter time, reduces the time cost and has more efficient preparation process.
(3) The product adopts a solvent spraying crude product purification mode, so that the solvent consumption is greatly reduced, and the purification progress is judged by the difference of the values of N-methyldiethanolamine and MDAPS tertiary amine as raw materials; and the sample is subjected to reduced pressure drying treatment, so that the time consumption of the preparation period is reduced.
(4) The solvents used in the single preparation process of the product are the same, and the product is convenient to use either mechanically or after treatment.
(5) Part of the solvent is a water-insoluble solvent, and can be recycled after being washed and dried after being used for multiple times, so that the solvent has high recycling rate, is environment-friendly and reduces the production cost.
(6) When the sulfobetaine type chain extender prepared by the invention is used for synthesizing waterborne polyurethane, the emulsification process is convenient to control, the emulsion stability is good, the relevant mechanical property and water resistance of the emulsion after the emulsion is formed into a gel film can be improved, and the waterborne polyurethane with high solid content can be synthesized.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood, the present invention may be implemented in accordance with the contents of the description, and in order to make the above and other objects, features, and advantages of the present invention more clearly understood, the following detailed description is given in conjunction with the preferred embodiments.
Detailed Description
In order to make the aforementioned features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below, without limiting the present invention in any way.
Example 1:
a preparation method of N, N-bis (2-hydroxyethyl) -N-methyl-3-sulfonate-1-propylamine comprises the following steps:
(1) 107.4g N-methyldiethanolamine was charged in a 1000ml four-necked flask equipped with a thermometer and a tetrafluoro stirrer, and 280g of anhydrous methanol was added and dissolved with stirring. After complete dissolution, 1g of powdered potassium hydroxide solid was added. And (3) dropwise adding 100g of 1, 3-propane sultone at the temperature of 30-50 ℃, wherein the dropwise adding time is 1-3 h, and the aging time is 1-2 h. Sampling is carried out for two times continuously, the content of the tertiary amine of the central control sample is calculated to be 2.83 percent and 2.81 percent respectively of the residue of the raw material N-methyldiethanolamine, the suspension is cooled to be below 20 ℃, and 247.6g of crude MDAPS is obtained by filtering.
(2) And (3) leaching the MDAPS crude product by using 50ml of methanol, repeating for 2-3 times, detecting that the sample basically has no tertiary amine content, and drying the sample under reduced pressure by using a rotary evaporator until the weight of the sample is not obviously changed to obtain 188.5g of the MDAPS sample, wherein the yield is 95.93% by using 1, 3-propane sultone, the solid content of the sample is 99.87%, and the melting range is 136-.
Example 2:
a preparation method of N, N-bis (2-hydroxyethyl) -N-methyl-3-sulfonate-1-propylamine comprises the following steps:
(1) 102.4g N-methyldiethanolamine was charged in a 1000ml four-necked flask equipped with a thermometer and a tetrafluoro stirrer, and 280g of methanol recovered in example 1 was added and dissolved with stirring. After complete dissolution, 1g of powdered potassium hydroxide solid was added. And (3) dropwise adding 100g of 1, 3-propane sultone at the temperature of 30-50 ℃, wherein the dropwise adding time is 1-3 h, and the aging time is 1-2 h. Sampling is carried out for two times continuously, the content of the tertiary amine of the central control sample is calculated to be 3.51 percent and 3.49 percent respectively of the residual N-methyldiethanolamine of the raw material, the temperature of the suspension is reduced to be below 20 ℃, and 253.1g of MDAPS crude product is obtained by filtering.
(2) And (3) leaching the MDAPS crude product by using 50ml of fresh methanol, repeating for 2-3 times, detecting that the sample basically has no tertiary amine content, and drying the sample under reduced pressure by using a rotary evaporator until the weight of the sample is not obviously changed to obtain 184.7g of the MDAPS sample, wherein the yield is 93.50% by using 1, 3-propane sultone, the solid content of the sample is 99.81%, and the melting range is 135-137 ℃.
Example 3:
a preparation method of N, N-bis (2-hydroxyethyl) -N-methyl-3-sulfonate-1-propylamine comprises the following steps:
(1) 356.2g N-methyldiethanolamine was charged into a 3000ml four-necked flask equipped with a thermometer and a tetrafluoro stirrer, and 800g of cyclohexane was added and dissolved with stirring. After completely dispersed and dissolved, 5.3g of potassium methoxide was added. Dropping 304.3g of 1, 3-propane sultone at the temperature of 30-50 ℃, wherein the dropping time is 1-3 h, and the aging time is 1-2 h. Sampling is carried out for two times continuously, the content of the tertiary amine of the central control sample is calculated to be 4.70 percent and 4.68 percent respectively of the residue of the raw material N-methyldiethanolamine, the suspension is cooled to be below 20 ℃, and 732.7g of MDAPS crude product is obtained by filtering.
(2) And (3) leaching the MDAPS crude product by using 160ml of fresh cyclohexane, repeating for 2-3 times, detecting that the sample basically has no tertiary amine content, and drying the sample under reduced pressure by using a rotary evaporator until the weight of the sample is not obviously changed to obtain 581.4g of the MDAPS sample, wherein the yield is 96.72% by using 1, 3-propane sultone, the solid content of the sample is 99.91%, and the melting range is 137-138 ℃.
Example 4:
a preparation method of N, N-bis (2-hydroxyethyl) -N-methyl-3-sulfonate-1-propylamine comprises the following steps:
(1) 372.3g N-methyldiethanolamine was charged in a 3000ml four-necked flask equipped with a thermometer and a tetrafluoro stirrer, and 900g of cyclohexane recovered in example 3 was added and dissolved with stirring. After completely dispersed and dissolved, 5.3g of potassium methoxide was added. 347.0g of 1, 3-propane sultone is dripped at the temperature of 30-50 ℃, the dripping time is 1-3 hours, and the aging time is 1-2 hours. Sampling is carried out for two times continuously, the content of the tertiary amine of the central control sample is calculated to be 3.15 percent and 3.14 percent respectively of the residue of the raw material N-methyldiethanolamine, the suspension is cooled to be below 20 ℃, and 768.3g of MDAPS crude product is obtained by filtering.
(2) And (3) leaching the MDAPS crude product by using 160ml of fresh cyclohexane, repeating for 2-3 times, detecting that the sample basically has no tertiary amine content, and drying the sample under reduced pressure by adopting rotary evaporation until the weight of the sample is not obviously changed to obtain 655.2g of the MDAPS sample, wherein the yield is 95.59% by taking 1, 3-propane sultone as a reference, the solid content of the sample is 99.88%, and the melting range is 137-138 ℃.
Example 5:
a preparation method of N, N-bis (2-hydroxyethyl) -N-methyl-3-sulfonate-1-propylamine comprises the following steps:
(1) the cyclohexane solvent recovered in example 4 was washed with water, and the mixture was allowed to stand for separation, and then the solvent water was adsorbed by anhydrous sodium sulfate.
(2) 383.0g N-methyldiethanolamine was charged in a 3000ml four-necked flask equipped with a thermometer and a tetrafluoro stirrer, and 900g of cyclohexane recovered in the step (1) was added and dissolved with stirring. After complete dispersion and dissolution, 1.8g of morpholine were added. 356.9g of 1, 3-propane sultone is dripped at the temperature of 30-50 ℃, the dripping time is 1-3 hours, and the aging time is 1-2 hours. Sampling is carried out for two times continuously, the content of the tertiary amine of the central control sample is calculated to be 2.78 percent and 2.76 percent respectively of the residue of the raw material N-methyldiethanolamine, the temperature of the suspension is reduced to be below 20 ℃, and 793.7g of MDAPS crude product is obtained by filtering.
(3) And (3) leaching the MDAPS crude product by using 160ml of fresh cyclohexane, repeating for 2-3 times, detecting that the sample basically has no tertiary amine content, and drying the sample under reduced pressure by using a rotary evaporation rotary evaporator until the weight of the sample has no obvious change to obtain 682.9g of the MDAPS sample, wherein the yield is 96.85% by using 1, 3-propane sultone, the solid content of the sample is 99.93%, and the melting range is 138-139 ℃.
Example 6:
(1) the powdery MDAPS obtained in example 3 is dried in a drying oven at 100 ℃ for more than 24h, and the polypropylene glycol (PPG-2000) is dehydrated under vacuum at 100 ℃ for 3 h.
(2) Adding the treated MDAPS and PPG-2000 into a four-neck flask, uniformly mixing and stirring, adding isophorone diisocyanate (IPDI), continuously stirring, keeping the reaction temperature at 60-70 ℃, dropwise adding 2-5 drops of dibutyltin dilaurate until NCO reaches a theoretical value, wherein the molar weight ratio of the MDAPS, the PPG-2000 and the IPDI is 0.4-1.1: 0.5: 1.
(3) And deionized water is added into the solution for emulsification under high-speed stirring, the emulsion has good stability, the mechanical property and the water resistance of a glue film are good, and the solid content of the obtained waterborne polyurethane can reach more than 50%.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (6)
1. A preparation method of a sulfobetaine type aqueous polyurethane chain extender is characterized by comprising the following steps:
(1) dissolving N-methyldiethanolamine in a solvent, adding a catalyst, uniformly stirring, dropwise adding 1, 3-propane sultone, controlling the reaction temperature at 30-50 ℃, the dropwise adding time at 1-3 h, and the aging time at 1-2 h, separating out a product in the reaction process, carrying out central control sampling to monitor the mixed suspension, and filtering to obtain a crude product after the content of tertiary amine is unchanged;
(2) spraying and leaching the crude product in a filtering device by using a newly prepared solvent which is the same as that in the step (1) until a central control sample is obtained and no tertiary amine content is monitored, filtering, and drying under reduced pressure to obtain high-purity N, N-bis (2-hydroxyethyl) -N-methyl-3-sulfonate-1-propylamine;
the reaction equation is as follows:
2. the method for preparing the sulfobetaine-type aqueous polyurethane chain extender as claimed in claim 1, wherein the solvent used in the step (1) is one of methanol, isopropanol, n-hexane, cyclohexane, pentane and octane.
3. The method for preparing the sulfobetaine-type aqueous polyurethane chain extender as claimed in claim 1, wherein the catalyst used in the step (1) is one of potassium hydroxide, sodium methoxide, potassium tert-butoxide, and morpholine.
4. The method for preparing the sulfobetaine-type aqueous polyurethane chain extender as claimed in claim 1, wherein the molar weight ratio of the raw materials N-methyldiethanolamine and 1, 3-propane sultone in the step (1) is 1.05-1.3: 1.
5. The preparation method of the sulfobetaine-type aqueous polyurethane chain extender as claimed in claim 1, wherein the amount of the catalyst used in the step (1) is 0.1-3% by mass of the total mass of the raw materials.
6. The method for preparing the sulfobetaine-type aqueous polyurethane chain extender as claimed in claim 1, wherein the mass amount of the solvent in the step (1) is 0.5-10 times of the total mass of the raw materials.
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|---|---|---|---|---|
| CN113999147A (en) * | 2021-12-01 | 2022-02-01 | 中科华宇(福建)科技发展有限公司 | Preparation process of sulfonate polyurethane aqueous chain extender |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2166035A1 (en) * | 1970-12-26 | 1973-02-15 | Lion Fat Oil Co Ltd | PROCESS FOR THE PREPARATION OF AMINO ALKANE SULFONATES OR HYDROXYAMMONIUM ALKANE SULFONATES WITH OMEGA-HYDROXYPOLYOXYALKYLENE RESIDUES ON THE NITROGEN ATOM |
| CN101058552A (en) * | 2006-04-18 | 2007-10-24 | 上海师范大学 | Double-functional group ionic liquid and preparation method |
| CN102863948A (en) * | 2012-10-14 | 2013-01-09 | 东北石油大学 | Hydroxysulfobetaine amphoteric surfactant for flooding and preparation method of hydroxysulfobetaine amphoteric surfactant |
| CN103665291A (en) * | 2013-11-29 | 2014-03-26 | 陕西科技大学 | Zwitterionic hydrophilic chain extender and preparation method thereof |
| CN104262597A (en) * | 2014-10-10 | 2015-01-07 | 泉州三欣新材料科技有限公司 | Zwitterionic polyester diol and preparation method thereof |
| WO2015199100A1 (en) * | 2014-06-23 | 2015-12-30 | リンテック株式会社 | Zwitterionic compound and ion conductor |
| CN105474015A (en) * | 2013-07-04 | 2016-04-06 | 斯特拉斯堡大学 | 3-aryl propiolonitrile compounds for thiol labeling |
| US20170081277A1 (en) * | 2015-09-17 | 2017-03-23 | Eastman Chemical Company | Amphoteric compounds |
| CN106866470A (en) * | 2017-01-16 | 2017-06-20 | 广州理文科技有限公司 | A kind of fluorine-containing alkyl sulfonic acid type surfactant and its synthetic method |
| WO2018174304A1 (en) * | 2017-03-20 | 2018-09-27 | 한국과학기술연구원 | Antithrombotic or antimicrobial polymer compound, method for manufacturing same, and medical substance comprising same |
| CN109160890A (en) * | 2018-10-22 | 2019-01-08 | 湖北吉和昌化工科技有限公司 | A kind of synthetic method of SPE |
| CN109336790A (en) * | 2018-10-31 | 2019-02-15 | 湖北吉和昌化工科技有限公司 | The synthetic method of (3- (methacrylamido) propyl) dimethyl (3- sulfopropyl) ammonium hydroxide inner salt |
| CN109836397A (en) * | 2017-11-27 | 2019-06-04 | 荆楚理工学院 | A kind of preparation method of biological buffer-morpholinopropane sulfonic acid (MOPS) |
| CN110358044A (en) * | 2019-05-17 | 2019-10-22 | 中国科学院化学研究所 | A kind of polyurethane and its preparation method and application |
| CN110358039A (en) * | 2019-08-28 | 2019-10-22 | 盐城工学院 | It is a kind of from preparation method of coloured polyurethanes and products thereof and to be applied based on amphoteric ion |
| CN111100041A (en) * | 2018-10-25 | 2020-05-05 | 栾福海 | Preparation method of ethylenediamine ethanesulfonic acid sodium salt |
-
2021
- 2021-04-07 CN CN202110372354.9A patent/CN113135846A/en active Pending
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2166035A1 (en) * | 1970-12-26 | 1973-02-15 | Lion Fat Oil Co Ltd | PROCESS FOR THE PREPARATION OF AMINO ALKANE SULFONATES OR HYDROXYAMMONIUM ALKANE SULFONATES WITH OMEGA-HYDROXYPOLYOXYALKYLENE RESIDUES ON THE NITROGEN ATOM |
| CN101058552A (en) * | 2006-04-18 | 2007-10-24 | 上海师范大学 | Double-functional group ionic liquid and preparation method |
| CN102863948A (en) * | 2012-10-14 | 2013-01-09 | 东北石油大学 | Hydroxysulfobetaine amphoteric surfactant for flooding and preparation method of hydroxysulfobetaine amphoteric surfactant |
| CN105474015A (en) * | 2013-07-04 | 2016-04-06 | 斯特拉斯堡大学 | 3-aryl propiolonitrile compounds for thiol labeling |
| CN103665291A (en) * | 2013-11-29 | 2014-03-26 | 陕西科技大学 | Zwitterionic hydrophilic chain extender and preparation method thereof |
| WO2015199100A1 (en) * | 2014-06-23 | 2015-12-30 | リンテック株式会社 | Zwitterionic compound and ion conductor |
| CN104262597A (en) * | 2014-10-10 | 2015-01-07 | 泉州三欣新材料科技有限公司 | Zwitterionic polyester diol and preparation method thereof |
| US20170081277A1 (en) * | 2015-09-17 | 2017-03-23 | Eastman Chemical Company | Amphoteric compounds |
| CN106866470A (en) * | 2017-01-16 | 2017-06-20 | 广州理文科技有限公司 | A kind of fluorine-containing alkyl sulfonic acid type surfactant and its synthetic method |
| WO2018174304A1 (en) * | 2017-03-20 | 2018-09-27 | 한국과학기술연구원 | Antithrombotic or antimicrobial polymer compound, method for manufacturing same, and medical substance comprising same |
| CN109836397A (en) * | 2017-11-27 | 2019-06-04 | 荆楚理工学院 | A kind of preparation method of biological buffer-morpholinopropane sulfonic acid (MOPS) |
| CN109160890A (en) * | 2018-10-22 | 2019-01-08 | 湖北吉和昌化工科技有限公司 | A kind of synthetic method of SPE |
| CN111100041A (en) * | 2018-10-25 | 2020-05-05 | 栾福海 | Preparation method of ethylenediamine ethanesulfonic acid sodium salt |
| CN109336790A (en) * | 2018-10-31 | 2019-02-15 | 湖北吉和昌化工科技有限公司 | The synthetic method of (3- (methacrylamido) propyl) dimethyl (3- sulfopropyl) ammonium hydroxide inner salt |
| CN110358044A (en) * | 2019-05-17 | 2019-10-22 | 中国科学院化学研究所 | A kind of polyurethane and its preparation method and application |
| CN110358039A (en) * | 2019-08-28 | 2019-10-22 | 盐城工学院 | It is a kind of from preparation method of coloured polyurethanes and products thereof and to be applied based on amphoteric ion |
Non-Patent Citations (1)
| Title |
|---|
| SAYYED ASIM ALI SHAH ET AL.: "Thermo-mechanically improved curcumin and zwitterions incorporated polyurethane-urea elastomers", 《POLYMER DEGRADATION AND STABILITY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113999147A (en) * | 2021-12-01 | 2022-02-01 | 中科华宇(福建)科技发展有限公司 | Preparation process of sulfonate polyurethane aqueous chain extender |
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