CN104945564A - Method for preparing block cationic water-borne polyurethane iron (III) chelates - Google Patents
Method for preparing block cationic water-borne polyurethane iron (III) chelates Download PDFInfo
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Abstract
The invention discloses a method for preparing block cationic water-borne polyurethane iron (III) chelates. The method comprises reacting diisocyanate with macromolecular dibasic alcohol, micromolecular dibasic alcohol and a hydrophilic chain extender, adding an end-capping reagent to obtain double bond end-capped polyurethane prepolymer, adding glycidyl methacrylate to carry out the copolymerization reaction, adding amino-containing 3-hydroxyl-4-pyridone derivatives to carry out the ring-opening reaction with epoxy groups, and performing covalent linkage to the two ends of polyurethane to obtain the block cationic water-borne polyurethane iron (III) chelates. The method avoids the side reaction between 3 hydroxyl groups and isocyanate, the reaction conditions are mild, the aftertreatment is simple, the obtained micromolecular chelates are located on side chains at the two ends of a chain of polyurethane, the content is adjustable (0.1-15wt%); and the obtained macromolecular chelates can be dissolved in water, acetone, butanone, N,N-dimethylformamide and dimethylsulfoxide.
Description
One, technical field
The present invention relates to a kind of preparation method of block cation-type water-thinned polyurethane iron (III) inner complex, belong to water-base polyurethane material technical field.
Two, background technology
At present, polymer iron chelate more and more receives publicity, and polymer iron chelate is widely used in water treatment, Environmental capacity, and metal ion reclaims, the field such as active packing and analytical chemistry.Because the pyranone derivatives such as kojic acid, voitol and 3-hydroxyl-4-pyridinone derivatives have good iron sequestering power, raw material is easy to get, low price, through being commonly used to synthesis polymer iron chelate.
U.S.'s " journal of applied " (Journal of Applied Polymer Science, 52 volumes the 1st phase 21-28 page in 1994) use 1-(β-acryloyl ethyl)-3-hydroxy-2-methyl-4-(1H)-pyridone (AHMP), N that reports, N-DMAA, N, N'-vinyl bisacrylamide obtains a kind of polymkeric substance containing 3-hydroxyl-4-pyridinone, and this polymkeric substance is insoluble not to be melted.Equally, Britain's " European polymkeric substance magazine " (European Polymer Journal, 30th volume the 8th phase in 1994,941 – 947 pages) use AHMP, hydroxyethyl methylacrylate and the Ethylene glycol dimethacrylate reported also obtain a kind ofly having crosslinking structure, the insoluble molten polymkeric substance containing-hydroxyl-4-pyridinone.The U.S. " biomacromolecule " (Biomacromolecules, 9th volume the 5th phase 1372 – 1380 pages in 2008) a kind of chelate polymer material of crosslinking structure based on the synthesis of 3-hydroxyl-4-pyridinone sexadentate ligand of reporting, also be a kind of insoluble not molten material, limit the application of this type of inner complex, and above report do not belong to polyurethane material field, above method is not suitable for the polyurethane material of synthesis with 3-hydroxyl-4-pyridine compounds.
The U.S.'s " polymer science magazine, A collects: polymer chemistry " (Journal of Polymer Science Part A:Polymer Chemistry, 50th volume 3493 – 3498 pages in 2012) report a kind ofly obtain having the method for the urethane of chelating ability based on 2 methylols and isocyanate reaction in kojic acid derivative, but on pyranoid ring, 5 hydroxyls also can react in kojic acid, not only form crosslinking structure, and consume the hydroxyl moieties much doing chelating.Raw material due to polyurethane reaction is generally isocyanic ester and diatomic alcohol compounds, isocyanic ester and hydroxyl reaction activity very high, pyranone derivatives (as kojic acid, voitol etc.), 3-hydroxyl-4-pyridinone derivatives are (as the compound of trade(brand)name Ferriprox, chemical name is 3-hydroxyl-1,2-dimethyl-4-(1H)-pyridone, can be used for general Fe supply disease, also can be used for treating the excessive distribution of some local ferro element) in hydroxyl containing coordination inevitable must with isocyanate reaction.3-hydroxyl-4-pyridinone derivatives has higher iron affinity ability compared with pyranone derivatives, according to Holland " coordination chemistry comment " (Coordination Chemistry Reviews, 232nd volume 151-171 page in 2002) report the pFe of kojic acid, voitol and 3-hydroxyl-1,2-dimethyl-4-(1H)-pyridone
iIIvalue is respectively 14.93,15 and 19, wherein pFe
iIIvalue is [part]
always=10
-5m, [Fe]
always=10
-5when M, pH=7.4, the negative logarithm of free iron (III) ionic concn, value shows that more greatly sequestrant is stronger to ferric ion affinity ability, and the stability of iron (III) chelating agent complexes of formation is higher.
So, if synthesize water miscible urethane iron (III) inner complex based on 3-hydroxyl-4-pyridinone derivatives will greatly to expand its application in iron overload, sewage disposal, wound healing, food product pack etc.The raw material of polyurethane reaction is generally isocyanic ester, macromolecule dihydric alcohol, small molecules dibasic alcohol, binary amine compound, introducing functional group generally uses dibasic alcohol, binary amine functional compounds as chainextender (binary chainextender), partly or entirely substitute small molecule chain extender, but due to 3 hydroxyls and isocyanate reaction in 3-hydroxyl-4-ketone pyridine derivatives, become the method for glycol chain extender to be incorporated in urethane its modification to there will be the problem such as side reaction is many, introducing rate is low and product structure is uncontrollable.
At present, to when introducing the hydroxy kind compound having and need protection in urethane synthesis, easily there is the problems such as side reaction is many, hydroxyl retains difficulty, structure is uncontrollable as being directly used in reaction.If but by protecting hydroxyl in advance, again macromole solution is protected after introducing urethane, also there will be complex steps, separate the problems such as protective efficacy is low.
Three, summary of the invention
The object of the present invention is to provide a kind of preparation method of block cation-type water-thinned polyurethane iron (III) inner complex based on 3-hydroxyl-4-ketone pyridine derivatives, methyl propenoic acid glycidyl ether-ether containing epoxide group is passed through radical polymerization, the two ends of introducing polyurethane chain obtain the controlled block cation-type water-thinned polyurethane of epoxy group content, then by upper amido and the epoxy generation ring-opening reaction of 3-hydroxyl-4-pyridinone derivatives, be grafted on polyurethane molecular chain, obtaining two ends is 3-hydroxyl-4-pyridinone derivatives, centre is block cation-type water-thinned polyurethane iron (III) inner complex of aqueous polyurethane structure, to avoid 3 hydroxyls and isocyanic ester generation side reaction in 3-hydroxyl-4-pyridinone derivatives, solve that current polymer iron (III) inner complex is insoluble not to be melted, during formation urethane inner complex, side reaction is many, 3 hydroxyls are difficult to the problems such as reservation.
The preparation method of a kind of block cation-type water-thinned polyurethane iron (III) inner complex of the present invention, reacted by vulcabond and macromolecule dihydric alcohol, small molecules dibasic alcohol, hydrophilic chain extender, then the base polyurethane prepolymer for use as that end-capping reagent obtains double bond end-blocking is added, it is characterized in that: add glycidyl methacrylate again and carry out copolyreaction, then add the 3-hydroxyl-4-pyridinone derivatives containing amido and epoxide group generation ring-opening reaction, be covalently attached to urethane two ends and obtain block cation-type water-thinned polyurethane iron (III) inner complex; Comprise the following steps:
By macromolecule dihydric alcohol at 100-120 DEG C of dehydration 0.5-1.5 hour, add vulcabond again, in 80-90 DEG C of reaction 2-4 hour, add glycol chain extender subsequently, dibutyl tin laurate (DBTDL) and solvent butanone, in 70-80 DEG C of reaction 1-4 hour, then 40-50 DEG C is cooled to, in reaction solution, dripping the butanone solution of hydrophilic chain extender, (mass percent concentration of hydrophilic chain extender is 20-50%, butanone is not herein within the addition of each raw material calculates), control time for adding is 0.5-1 hour, drip off rear maintenance 50-70 DEG C reaction 2-5 hour, add end-capping reagent and stopper again, at 50-70 DEG C of reaction 2-4 hour, obtain the base polyurethane prepolymer for use as of double bond end-blocking, initiator and glycidyl methacrylate are joined in the base polyurethane prepolymer for use as of double bond end-blocking, 60-75 DEG C of reaction 2-4 hour, add the 3-hydroxyl-4-pyridinone derivatives containing amido again, 60-75 DEG C is kept to react 2-4 hour, be cooled to 0-40 DEG C subsequently, add acetic acid, react and under agitation add water again after 1-5 minute, stirring reaction 5 – removed desolventizing butanone after 30 minutes under 40 – 50 DEG C, 0.01MPa vacuum condition, obtained block cation-type water-thinned polyurethane iron (III) inner complex.
Each raw material is constructed as follows by mass parts:
Macromolecule dihydric alcohol 30-70 part, vulcabond 15-50 part, hydrophilic chain extender 6-15 part, glycol chain extender 1.5-11 part, 0-1 part trivalent alcohol linking agent, dibutyl tin laurate 0.01-0.08 part, butanone 20-200 part, end-capping reagent 2-6 part, stopper 0.1-0.5 part, initiator 0.1-0.6 part, glycidyl methacrylate 0.1-15 part, acetic acid 4-11 part, the 3-hydroxyl-4-pyridinone derivatives 0.1-15 part containing amido, water 200-400 part.
Also can add trivalent alcohol linking agent when adding glycol chain extender simultaneously.
Described macromolecule dihydric alcohol is selected from PTMG (PTMG), poly-hexanodioic acid-BDO ester dibasic alcohol (PBA), polyethylene glycol adipate dibasic alcohol (PEA), polycaprolactone diols (PCL), polypropylene glycol (PPG) or PCDL (PCDL).
Described vulcabond is selected from isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI) or hexamethylene diisocyanate (HDI).
Described hydrophilic chain extender is N methyldiethanol amine (MDEA).
Described glycol chain extender is selected from BDO (BDO), ethylene glycol (EG), 1,6-hexylene glycol (HDO) or glycol ether (DEG).
Described end-capping reagent is selected from Hydroxyethyl acrylate (HEA), hydroxyethyl methylacrylate (HEMA), Propylene glycol monoacrylate (HPA) or Rocryl 410 (HPMA).
Described stopper is selected from 2,6 ditertiary butyl p cresol (BHT), Isosorbide-5-Nitrae-benzoquinones (BQ) or 1, 4-benzenediol (HQ).
Described initiator is Diisopropyl azodicarboxylate (AIBN).
Described trivalent alcohol linking agent is selected from trolamine (NTA) or tri-isopropanolamine (TIPA).
The described 3-hydroxyl-4-pyridinone derivatives containing amido is 1-amino-ethyl-2-methyl-3-hydroxyl-4-(1H)-pyridone, and its structural formula is:
The present invention compared with prior art has the following advantages:
Preparation method of the present invention utilizes the amido generation ring-opening reaction on epoxide group and 3-hydroxyl-4-pyridinone derivatives, avoids 3 hydroxyls and isocyanic ester generation side reaction when covalent linkage introduces small molecules inner complex, and reaction conditions is gentle, and aftertreatment is simple.
Adopt aqueous polyurethane iron (III) inner complex that the present invention obtains, 3-hydroxyl-4-pyridinone derivatives is positioned on the side chain at chain two ends of urethane, and can control the content of small molecules inner complex in urethane is as required 0.1-15wt%.
Adopt aqueous polyurethane iron (III) inner complex that obtains of the present invention, be dissolvable in water in water and acetone, butanone, DMF, methyl-sulphoxide, greatly extend its application in the aqueous solution, organic solvent system.
Present invention incorporates aqueous polyurethane environmental protection, pollution-free, structure properties can be in harmonious proportion high iron (III) the affinity ability of 3-hydroxyl-4-pyridinone derivatives.
The invention solves the hydroxy kind compound (hydroxyl and isocyanic ester have the problem of side reaction) introduced at present and have and need protection, the method is also applicable to synthesize other functional type block cation-type water-thinned polyurethanes.
Four, embodiment
Embodiment 1:
By 33.9 grams of PPG (M
n=2000) at 110 DEG C of dehydration 0.5-1.5 hour, add the IPDI of 26.4 grams again, 3.5 grams of DEG are added after 2 hours 90 DEG C of reactions, 70 DEG C of reactions 2 hours, then at 50 DEG C, drip the mixing solutions of 7.6 grams of MDEA and 40mL butanone, drip off in 0.5-1 hour, drip off rear maintenance 65 DEG C reaction 3 hours, add 0.045 gram of BHT and 1.2 gram HEA in 60 DEG C of reactions 1 hour, obtain the base polyurethane prepolymer for use as of double bond end-blocking, 0.05 gram of AIBN is added in the base polyurethane prepolymer for use as of double bond end-blocking, 2.1 grams of glycidyl methacrylate, add 100mL butanone 75 DEG C of reactions 2 hours, add 2.8 grams of 1-amino-ethyl-2-methyl-3-hydroxyl-4-(1H)-pyridones react 75 DEG C reaction 2 hours after be cooled to 30 DEG C, under high speed shear, 181mL water is added after adding 3.98 grams of acetic acidreaction 1-5 minutes, to stir reaction product after 5-30 minute at 45 DEG C, solvent butanone is sloughed under 0.01MPa vacuum condition, namely obtain solid containing being 30wt%, 1-amino-ethyl-2-methyl-3-hydroxyl-4-(1H)-pyridone content is block cation-type water-thinned polyurethane iron (III) the inner complex emulsion Chelating-CWPU of 3.6wt%.
Embodiment 2:
By 50.0 grams of PBA (M
n=2000) at 110 DEG C of dehydration 0.5-1.5 hour, add the TDI of 24.1 grams again, 2.8 grams of BDO are added after 2 hours 80 DEG C of reactions, 70 DEG C of reactions 2 hours, then at 50 DEG C, drip the mixing solutions of 9.0 grams of MDEA and 40mL butanone, drip off in 0.5-1 hour, drip off rear maintenance 60 DEG C reaction 3 hours, add 0.025 gram of HQ and 1.7 gram HEMA in 60 DEG C of reactions 1 hour, obtain the base polyurethane prepolymer for use as of double bond end-blocking, 0.08 gram of AIBN is added in the base polyurethane prepolymer for use as of double bond end-blocking, 2.0 grams of glycidyl methacrylate, add 100mL butanone 65 DEG C of reactions 2 hours, add again 2.37 grams of 1-amino-ethyl-2-methyl-3-hydroxyl-4-(1H)-pyridones react 75 DEG C reaction 2 hours after be cooled to 30 DEG C, under high speed shear, 215mL water is added after adding 4.9 grams of acetic acidreaction 1-5 minutes, to stir reaction product after 5-30 minute at 45 DEG C, solvent butanone is sloughed under 0.01MPa vacuum condition, namely obtain solid containing being 30wt%, 1-amino-ethyl-2-methyl-3-hydroxyl-4-(1H)-pyridone content is block cation-type water-thinned polyurethane iron (III) the inner complex emulsion Chelating-CWPU2 of 2.6wt%.
Embodiment 3:
By 50.0 grams of PPG (M
n=2000) at 110 DEG C of dehydration 0.5-1.5 hour, add the IPDI of 38.87 grams again, 2.6 grams of EG are added after 2 hours 90 DEG C of reactions, 70 DEG C of reactions 2 hours, then at 50 DEG C, drip the mixing solutions of 12.0 grams of MDEA and 40mL butanone, drip off in 0.5-1 hour, drip off rear maintenance 65 DEG C reaction 3 hours, add 0.07 gram of BQ and 1.8 gram HEMA in 60 DEG C of reactions 1 hour, obtain the base polyurethane prepolymer for use as of double bond end-blocking, 0.056 gram of AIBN is added in the base polyurethane prepolymer for use as of double bond end-blocking, 5.6 grams of glycidyl methacrylate, add 100mL butanone 65 DEG C of reactions 2 hours, add 6.6 grams of 1-amino-ethyl-2-methyl-3-hydroxyl-4-(1H)-pyridones again and be cooled to 30 DEG C in 75 DEG C of reactions after 2 hours, under high speed shear, 274mL water is added after adding 7.2 grams of acetic acidreaction 1-5 minutes, to stir reaction product after 5-30 minute at 45 DEG C, solvent butanone is sloughed under 0.01MPa vacuum condition, namely obtain solid containing being 30wt%, 1-amino-ethyl-2-methyl-3-hydroxyl-4-(1H)-pyridone content is the block Cationic Aqueous Polyurethane Emulsion Epoxy-CWPU3 of 5.6wt%.
If keep other conditions of the present embodiment constant, change the content of AIBN and methyl propenoic acid glycidyl ether-ether, 1-amino-ethyl-2-methyl-3-hydroxyl-4-(1H)-pyridone content can be obtained between 0.1-15wt%, block cation-type water-thinned polyurethane iron (III) the inner complex emulsion of different small molecules chelate content.
If other condition of the present embodiment is constant, and IPDI is changed into HDI, block cation-type water-thinned polyurethane iron (III) inner complex emulsion also can be obtained.
If other condition of the present embodiment is constant, and PPG is changed into PTMG, PCDL, PEA, PCL or PCDL, block cation-type water-thinned polyurethane iron (III) inner complex emulsion all can be obtained.
If other condition of the present embodiment is constant, and EG is changed into HDO, block cation-type water-thinned polyurethane iron (III) inner complex emulsion also can be obtained.
If other condition of the present embodiment is constant, and HEMA is changed into HPA or HPMA, block cation-type water-thinned polyurethane iron (III) inner complex emulsion all can be obtained.
If other condition of the present embodiment is constant, after prepolymerization reaction (90 DEG C stirring reaction 2 hours), adds NTA or TIPA, all can obtain block cation-type water-thinned polyurethane iron (III) inner complex emulsion.
Claims (9)
1. the preparation method of block cation-type water-thinned polyurethane iron (III) inner complex, it is characterized in that: reacted by vulcabond and macromolecule dihydric alcohol, small molecules dibasic alcohol, hydrophilic chain extender, then the base polyurethane prepolymer for use as that end-capping reagent obtains double bond end-blocking is added, add glycidyl methacrylate again and carry out copolyreaction, then add the 3-hydroxyl-4-pyridinone derivatives containing amido and epoxide group generation ring-opening reaction, be covalently attached to urethane two ends and obtain block cation-type water-thinned polyurethane iron (III) inner complex.
2. preparation method according to claim 1, is characterized in that comprising the following steps:
By macromolecule dihydric alcohol at 100-120 DEG C of dehydration 0.5-1.5 hour, add vulcabond again, in 80-90 DEG C of reaction 2-4 hour, add glycol chain extender, dibutyl tin laurate and solvent butanone subsequently, in 70-80 DEG C of reaction 1-4 hour, be then cooled to 40-50 DEG C, in reaction solution, drip the butanone solution of hydrophilic chain extender, control time for adding is 0.5-1 hour, drips off rear maintenance 50-70 DEG C reaction 2-5 hour; Add end-capping reagent and stopper again, at 50-70 DEG C of reaction 2-4 hour, obtain the base polyurethane prepolymer for use as of double bond end-blocking; Initiator and glycidyl methacrylate are joined in the base polyurethane prepolymer for use as of double bond end-blocking, 60-75 DEG C of reaction 2-4 hour, add the 3-hydroxyl-4-pyridinone derivatives containing amido again, 60-75 DEG C is kept to react 2-4 hour, be cooled to 0-40 DEG C subsequently, add acetic acid, react and under agitation add water after 1-5 minute, stirring reaction 5 – removed desolventizing butanone after 30 minutes under 40 – 50 DEG C, 0.01MPa vacuum condition, obtained block cation-type water-thinned polyurethane iron (III) inner complex.
3. preparation method according to claim 2, is characterized in that:
Trivalent alcohol linking agent is added while adding glycol chain extender.
4. the preparation method according to Claims 2 or 3, is characterized in that each raw material is constructed as follows by mass parts:
Macromolecule dihydric alcohol 30-70 part, vulcabond 15-50 part, hydrophilic chain extender 6-15 part, glycol chain extender 1.5-11 part, 0-1 part trivalent alcohol linking agent, dibutyl tin laurate 0.01-0.08 part, butanone 20-200 part, end-capping reagent 2-6 part, stopper 0.1-0.5 part, initiator 0.1-0.6 part, glycidyl methacrylate 0.1-15 part, acetic acid 4-11 part, the 3-hydroxyl-4-pyridinone derivatives 0.1-15 part containing amido, water 200-400 part.
5. preparation method according to claim 2, is characterized in that:
Described macromolecule dihydric alcohol is selected from PTMG, poly-hexanodioic acid-BDO ester dibasic alcohol, polyethylene glycol adipate dibasic alcohol, polycaprolactone diols, polypropylene glycol or PCDL;
Described vulcabond is selected from isophorone diisocyanate, tolylene diisocyanate or hexamethylene diisocyanate.
6. preparation method according to claim 2, is characterized in that:
Described hydrophilic chain extender is N methyldiethanol amine;
Described glycol chain extender is selected from BDO, ethylene glycol, 1,6-hexylene glycol or glycol ether.
7. preparation method according to claim 2, is characterized in that:
Described end-capping reagent is selected from Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate or Rocryl 410;
Described stopper is selected from 2,6 ditertiary butyl p cresol, Isosorbide-5-Nitrae-benzoquinones or 1, 4-benzenediol;
Described initiator is Diisopropyl azodicarboxylate.
8. preparation method according to claim 3, is characterized in that:
Described trivalent alcohol linking agent is selected from trolamine or tri-isopropanolamine.
9. preparation method according to claim 2, is characterized in that:
The described 3-hydroxyl-4-pyridinone derivatives containing amido is 1-amino-ethyl-2-methyl-3-hydroxyl-4-(1H)-pyridone, and its structural formula is:
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110965086A (en) * | 2019-11-21 | 2020-04-07 | 武汉奥邦表面技术有限公司 | Acidic zinc plating impurity removing agent and application thereof |
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| CN110965086A (en) * | 2019-11-21 | 2020-04-07 | 武汉奥邦表面技术有限公司 | Acidic zinc plating impurity removing agent and application thereof |
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