CN105384899B - A kind of preparation method of Y types three block nonionic polyurethane Bola surfactants - Google Patents
A kind of preparation method of Y types three block nonionic polyurethane Bola surfactants Download PDFInfo
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- CN105384899B CN105384899B CN201510889084.3A CN201510889084A CN105384899B CN 105384899 B CN105384899 B CN 105384899B CN 201510889084 A CN201510889084 A CN 201510889084A CN 105384899 B CN105384899 B CN 105384899B
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- bola
- surfactants
- monomethyl ether
- diisocyanate
- nonionic polyurethane
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- 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
- C08G18/4833—Polyethers containing oxyethylene units
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- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
- C09K23/16—Amines or polyamines
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- Chemical Kinetics & Catalysis (AREA)
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- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of Y types three block nonionic polyurethane Bola surfactants and preparation method thereof.The surfactant that the invention is stated is copolymerized by glycerin monostearate and diisocyanate, is then generated with polyoxyethylene monomethyl ether through block polymerization.The building-up process is simple to operate, environmentally friendly without using organic solvent.Synthesized surfactant is polyurethane structural, good water solubility, and biocompatibility is good.Y type molecular structures make its absorption surface absorbed layer in solution surface be made up of methyl, and the surface absorbed layer of common Bola surfactants is made up of methylene.The ability that surface tension is reduced due to methyl is higher than methylene, therefore the Y type surfactants have the ability of stronger reduction surface tension, available for the displacement of reservoir oil, sewage disposal, the thin preparation of supermolecule etc..
Description
Technical field
The present invention relates to a kind of preparation method of surfactant, particularly Y types three block nonionic polyurethane Bola
The preparation of surfactant.
Background technology
Surfactant is that hydrophilic group is contained in a kind of one end, and hydrophobic group is contained in one end, and adding minimal amount can significantly reduce
Solvent surface tension, change system surface state, so as to produce moistening, emulsification, bubble, the material of solubilization.And Bola types
The structure of surfactant is different from classical surfactant, and it is hydrophobic group among hydrophilic group that its both ends, which are, Gemini type
Surfactant is the surfactant for being linked up two identical or different amphiphilic moieties with chemical bond.
Nonionic polyurethane Bola surfactants are a kind of surfactants non-ionizing in water, and such surface is lived
Although property agent using later, has the performance more more excellent than ionic surfactant, its stability is more in many aspects
Height, it is not easy to be influenceed by soda acid, MOLECULE DESIGN cutting property is strong, has good compatibility with other types surfactant, so as to
In biomaterial, drug delivery, emulsion dispersion agent and coating etc. have a wide range of applications.
But compared with low-molecular-weight surfactant and Gemini surface active, because Bola type surfactants are molten
The adsorption layer on liquid surface is made up of methylene, and the ability that methylene reduces surface tension is not so good as methyl, therefore Bola tables
The ability that face activating agent reduces solution surface tension is relatively low, it is generally difficult to reaches low-molecular-weight surfactant and Gemini surfaces are lived
The decreasing value of property agent, so find a kind of Bola type surfactants with more high surface has become everybody in recent years
Study the focus of surfactant.But the research of ionic surfactant is more at this stage, for nonionic polyurethane
The research report of Bola surfactants is few.
Such as Chinese patent（CN102731773A）Disclose a kind of preparation of triblock cross-linkable nonionic surfactant
Method, it is dissolved in heating response in solvent by maleic anhydride and equimolar long aliphatic chain, with doing after the solvent of product is removed
Dry polyethylene glycol is in solvent is dissolved in, then adds dicyclohexylcarbodiimide solution reaction to obtain.The patent claims the surface to live
Property agent stability is good, and accessory substance is few, high conversion rate, but needs constantly to dissolve and except molten during the synthesis of surfactant
Agent, make operating process complicated, and the solvent added has certain toxicity, potential security risk to environmental and biological materials be present, no
Meet the principle of Green Chemistry.
Such as Chinese patent（CN1810846）Disclose a kind of system of the polymerizable type polyurethane molecular surface active agent of three block
Preparation Method, it is formed by polyvinylether, polyethenoxy ether and the poly- sudden reaction of diisocyanate.The patent claims the surfactant
It is good to solution ion strength and pH value change tolerance, there is polymerization, crosslinking function, but this kind of surfactant is inhaled
When being attached to solution surface, adsorption layer is made up of methylene, and the ability that methylene reduces surface tension is not so good as methyl, therefore, the table
Face activating agent reduces the indifferent of surface-active.
The present invention is using glycerin monostearate and IPDI copolymer as raw material, with polyethylene monomethyl ether
Block copolymer generates a kind of Y types three block nonionic polyurethane Bola surfactants.The surface-active that the present invention generates
In Adsorption at surface of solution, adsorption layer is made up of methyl for agent, and common three block Bola surfactants are in Adsorption at surface of solution
When adsorption layer be made up of methylene, the ability that methyl reduces surface-active be higher than methylene, so the surfactant is with more
The ability of high reduction surface tension.In addition Y types three block nonionic polyurethane Bola surfactants are in preparation process
Any organic solvent is not added with, there is the advantages of green, and it is simple to operate, it is polyurethane structural, there is preferably biology
Compatibility.
The content of the invention
It is an object of the invention to provide the nonionic polyurethane Bola surfactants that a kind of Y types have high surface
Preparation method, be first to be copolymerized diisocyanate and glycerin monostearate, then with polyethylene monomethyl ether block copolymerization
Generation.
Y types three block nonionic polyurethane Bola surfactants provided by the present invention are characterised by：
（1）Preparation method provided by the present invention is in synthesis Y type three block nonionic polyurethane Bola surfactants
When, because reaction temperature is higher than reactant fusing point, reactant can dissolve each other at the reaction temperatures, thus be not required to make in building-up process
With any organic solvent, meet green chemistry demand.
（2）Y type three block nonionic polyurethane Bola surfactants synthesized by the present invention are polyurethane structural, point
Minor structure is easy to regulate and control, and hydrophily is strong, and solubility is high, there is more preferable biocompatibility.
（3）The synthesized Y type three block nonionic polyurethane Bola SURFACTANT ADSORPTIONs of this hair in solution surface,
Adsorption layer is constituted by methyl, improving former polyurethane nonionic Bola surfactants reduces solution surface tension deficiency
Defect, it is improved the surface-active of Bola surfactants.
The purpose of the present invention is achieved through the following technical solutions：
The preparation of Y type three block nonionic polyurethane Bola surfactants described in this patent is first by two isocyanic acids
Ester and glycerin monostearate copolymerization, then add polyoxyethylene monomethyl ether, are obtained through block polymerization, wherein the matter of each component
Measuring proportioning is：
Diisocyanate 15.7 ~ 40.1
Glycerin monostearate 15.4 ~ 32.7
Polyoxyethylene monomethyl ether 31.7 ~ 67.8
Catalyst 0.1 ~ 0.3
Distilled water 100 ~ 500
Wherein Y types three block nonionic polyurethane Bola surfactants are synthesized by following special process：
（1）At 100 ~ 120 DEG C, vacuum carries out vacuum distillation 5 ~ 8 under conditions of being 0.09MPa to polyoxyethylene monomethyl ether
Hour, remove moisture.
（2）The instruments such as four-necked bottle, agitator, charge pipe are dried 2 ~ 4 hours in 100 ~ 120 DEG C, taking-up is placed in drier
Middle cooling.
（3）To with agitator, thermometer four-necked bottle in add glycerin monostearate, be heated to 80 ~ 90 under stirring
℃。
（4）Catalyst dibutyltin dilaurylate is added, diisocyanate is then added dropwise, is reacted 1.5 ~ 2 hours.
（5）Polyoxyethylene monomethyl ether is added, continues reaction 1.5 ~ 2 hours.
（6）30 DEG C are cooled to, distilled water is added and stirs 30 ~ 60 minutes, that is, nonionic three block polyurethane is made.
Wherein：Diisocyanate is IPDI, toluene di-isocyanate(TDI), diphenylmethane diisocyanate
One kind in ester；Polyoxyethylene monomethyl ether be number average molecular weight be 200,350,550,750 in one kind.
The advantage of the invention is that：Y type three block nonionic polyurethane Bola surfactants form absorption by methyl
Layer, it can preferably reduce the surface tension of solution；It, without any organic solvent is added, meets green in building-up process
Trend；The molecular structure of its polyurethane causes the surfactant to have more preferable biocompatibility, and molecular structure
It is easy to regulate and control.
Embodiment：
Embodiment one：It it is 120 DEG C in temperature, vacuum subtracts under conditions of being 0.09MPa to polyoxyethylene monomethyl ether
Pressure distillation 8 hours, removes moisture.The instruments such as four-necked bottle, agitator, charge pipe are dried 2 hours in 120 DEG C, taking-up is placed in dry
Cooled down in dry device.To with agitator, thermometer four-necked bottle in add 8.7g glycerin monostearates, be heated to 80 under stirring
℃.0.02g dibutyl tin laurates are added, 11.2g IPDIs are then added dropwise, are reacted 2 hours.Add
10g number average molecular weights are 200 polyoxyethylene monomethyl ether, continue reaction 2 hours.30 DEG C are subsequently cooled to, adds 120g
Distilled water is stirred 30 minutes and discharged, you can obtains the Y type three block nonionic polyurethane Bola surface-actives that solid content is 20%
Agent.
Embodiment two：It it is 120 DEG C in temperature, vacuum subtracts under conditions of being 0.09MPa to polyoxyethylene monomethyl ether
Pressure distillation 8 hours, removes moisture.The instruments such as four-necked bottle, agitator, charge pipe are dried 2 hours in 120 DEG C, taking-up is placed in dry
Cooled down in dry device.To with agitator, thermometer four-necked bottle in add 8.7g glycerin monostearates, be heated to 80 under stirring
℃.0.02g dibutyl tin laurates are added, 11.2g IPDIs are then added dropwise, are reacted 2 hours.Add
17.5g number average molecular weights are 350 polyoxyethylene monomethyl ether, continue reaction 2 hours.30 DEG C are subsequently cooled to, is added
150g distilled water is stirred 30 minutes and discharged, you can is obtained the Y type three block nonionic polyurethane Bola surfaces that solid content is 20% and is lived
Property agent.
Embodiment three：It it is 100 DEG C in temperature, vacuum subtracts under conditions of being 0.09MPa to polyoxyethylene monomethyl ether
Pressure distillation 8 hours, removes moisture.The instruments such as four-necked bottle, agitator, charge pipe are dried 2 hours in 120 DEG C, taking-up is placed in dry
Cooled down in dry device.To with agitator, thermometer four-necked bottle in add 8.7g glycerin monostearates, be heated to 80 under stirring
℃.0.02g dibutyl tin laurates are added, 11.2g IPDIs are then added dropwise, are reacted 2 hours.Add
27.5g number average molecular weights are 550 polyoxyethylene monomethyl ether, continue reaction 2 hours.30 DEG C are subsequently cooled to, is added
142.5g distilled water is stirred 30 minutes and discharged, you can obtains the Y type three block nonionic polyurethane Bola surfaces that solid content is 25%
Activating agent.
Example IV：It it is 120 DEG C in temperature, vacuum subtracts under conditions of being 0.09MPa to polyoxyethylene monomethyl ether
Pressure distillation 5 hours, removes moisture.The instruments such as four-necked bottle, agitator, charge pipe are dried 2 hours in 120 DEG C, taking-up is placed in dry
Cooled down in dry device.To with agitator, thermometer four-necked bottle in add 8.7g glycerin monostearates, be heated to 80 under stirring
℃.0.02g dibutyl tin laurates are added, 11.2g IPDIs are then added dropwise, are reacted 2 hours.Add
37.5g number average molecular weights are 750 polyoxyethylene monomethyl ether, continue reaction 2 hours.30 DEG C are subsequently cooled to, is added
172.5g distilled water is stirred 30 minutes and discharged, you can obtains the Y type three block nonionic polyurethane Bola surfaces that solid content is 25%
Activating agent.
Claims (2)
1. a kind of preparation method of Y types three block nonionic polyurethane Bola surfactants, it is characterised in that live on the surface
Property agent is formed by diisocyanate, glycerin monostearate and polyoxyethylene monomethyl ether by block polymerization；Wherein, each component
Quality proportioning is：
Diisocyanate 15.7 ~ 40.1
Glycerin monostearate 15.4 ~ 32.7
Polyoxyethylene monomethyl ether 31.7 ~ 67.8
Catalyst 0.1 ~ 0.3
Distilled water 100 ~ 500
The catalyst is dibutyl tin laurate；
Y type three block nonionic polyurethane Bola surfactants are synthesized by following special process：
（1）At 100 ~ 120 DEG C, it is small that vacuum carries out vacuum distillation 5 ~ 8 under conditions of being 0.09MPa to polyoxyethylene monomethyl ether
When, remove moisture；
（2）The instruments such as four-necked bottle, agitator, charge pipe are dried 2 ~ 4 hours in 100 ~ 120 DEG C, taking-up is placed in cold in drier
But；
（3）To with agitator, thermometer four-necked bottle in add glycerin monostearate, 80 ~ 90 DEG C are heated under stirring；
（4）Dibutyl tin laurate is added, diisocyanate is then added dropwise, it is 80 ~ 90 DEG C to keep reaction temperature, reaction 1.5 ~
2 hours；
（5）Polyoxyethylene monomethyl ether is added, it is 80 ~ 90 DEG C to keep reaction temperature, is reacted 1.5 ~ 2 hours；
（6）30 DEG C are cooled to, distilled water is added and stirs 30 ~ 60 minutes, that is, three block nonionic polyurethane Bola surfaces are made
Activating agent.
2. a kind of preparation method of Y types three block nonionic polyurethane Bola surfactants according to claim 1,
It is characterized in that polyoxyethylene monomethyl ether used be number average molecular weight be 200,350,550,750 in one kind, it is used
Diisocyanate be IPDI, toluene di-isocyanate(TDI), one kind in methyl diphenylene diisocyanate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105797643B (en) * | 2016-03-30 | 2017-08-04 | 四川大学 | A kind of preparation method of nonionic polyurethane Gemini surface active |
| CN108579611B (en) * | 2018-03-26 | 2020-11-03 | 四川大学 | Preparation method of triblock nonionic polyurethane fluorine-containing short-chain surfactant |
| CN114917847B (en) * | 2022-05-23 | 2023-06-30 | 华南理工大学 | Silica microsphere and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810846A (en) * | 2006-02-21 | 2006-08-02 | 中国科学院成都有机化学有限公司 | Prepn of polymerisable non-ionic block polyurethane surfactant |
| CN101058063A (en) * | 2007-05-09 | 2007-10-24 | 中国科学院成都有机化学有限公司 | Method for preparing Bola type high molecular surfactant |
| CN104498649A (en) * | 2015-01-12 | 2015-04-08 | 四川大学 | Aldehydic high polymer retanning agent with self-assembly function for free-chrome leather |
| CN104645877A (en) * | 2015-02-02 | 2015-05-27 | 常熟理工学院 | Bola type polyether modified organic silicon surfactant and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE19943681A1 (en) * | 1999-09-13 | 2001-03-15 | Rwe Dea Ag | Surfactant composition containing gemini surfactants and their use for skin and hair cleaning |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810846A (en) * | 2006-02-21 | 2006-08-02 | 中国科学院成都有机化学有限公司 | Prepn of polymerisable non-ionic block polyurethane surfactant |
| CN101058063A (en) * | 2007-05-09 | 2007-10-24 | 中国科学院成都有机化学有限公司 | Method for preparing Bola type high molecular surfactant |
| CN104498649A (en) * | 2015-01-12 | 2015-04-08 | 四川大学 | Aldehydic high polymer retanning agent with self-assembly function for free-chrome leather |
| CN104645877A (en) * | 2015-02-02 | 2015-05-27 | 常熟理工学院 | Bola type polyether modified organic silicon surfactant and preparation method thereof |
Non-Patent Citations (2)
| Title |
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| "一种非离子型水性聚氨酯表面活性剂的合成及性能";曾小君等;《日用化学工业》;20070430;第37卷(第2期);第77页左侧栏和右侧栏第1段，第78页右侧栏第1段及表2，第79页左侧栏第2段 * |
| "新型非离子性嵌段型聚氨酯表面活性剂的合成及其表面活性研究";苗青等;《合成化学》;20101231;第126-136页 * |
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