CN105732953B - A kind of amphoteric ion aqueous polyurethane of anti-albumen and microorganism adsorption - Google Patents
A kind of amphoteric ion aqueous polyurethane of anti-albumen and microorganism adsorption Download PDFInfo
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Abstract
The present invention provides a kind of anti-albumen and microorganism adsorption amphoteric ion aqueous polyurethanes.Preparation method is to first pass through Eschweiler Clarke methylation reactions to prepare monomer-dimethylamino 1 with double hydroxyls and tertiary amino, 3 propylene glycol (PEDA), then PEDA is introduced on aqueous polyurethane main chain by polyaddition reaction, obtain the polyurethane (NPU) with tertiary amino, amphoteric ion polyurethane is obtained by the reaction by NPU and ester type compound again, it is eventually adding neutralizer neutralization, emulsification in water obtains amphoteric ion aqueous polyurethane.Zwitterionic presence can assign polyurethane material automatic emulsifying performance and anti-protein adsorption performance, prevent the formation of biodeterioration.In terms of bio-medical, zwitterionic presence can improve the biocompatibility of polyurethane material, and the adherency that can reduce albumen and blood platelet etc., so that coating has anticoagulant property.This amphoteric ion polyurethane has preferable application prospect in terms of aqueous leather coating material and bio-medical coating.
Description
Technical field
The present invention relates to waterborne polyurethane resin field, and in particular to a kind of anti-albumen and microorganism adsorption amphoteric ion are aqueous
Polyurethane and preparation method thereof.
Background technology
Polyurethane (PU) is one of high molecular material with fastest developing speed, but since there are inherent defects for the system.
Under the driving of environmental requirement, with the enhancing of the establishment and people's environmental consciousness of various countries' environmental regulation, traditional solvent based coating
In the discharge of volatile-type organic compound (VOC) be more and more restricted.Aqueous polyurethane not only inherits general polyurethane
The excellent properties of intrinsic high intensity, rub resistance, flexibility and fatigue durability etc. be free of or only and using water as decentralized medium
It is free from environmental pollution containing a small amount of organic solvent, safe to use, the adjustability bigger of properties of product.Microorganisms are in different materials
The surface of matter（Cotton, 60% cotton and 40% polyester, polyester and polyurethane）Growing state, find microorganism in polyurethane surface
Time-to-live longest, therefore polyurethane is that a kind of be highly desirable to has the anti-biological high molecular material for being stained performance.Numerous studies
It has been shown that, from molecular level, biodeterioration starts from the absorption of albumen and microorganism on surface.Amphoteric ion polymer is such as
Sulphur-amine（) and carboxylic-amine SBMA（CBMA）Show that good anti-protein adsorption performance, polyurethane material have adherency well
Amphoteric ion and polyurethane are combined the mechanical property for being expected to polyurethane can be utilized excellent by power and preferable biocompatibility
And adhesive capacity, and the anti-albumen and microorganism adsorption performance of amphoteric ion polymer can be utilized, obtain having anti-albumen and micro-
The polyurethane material of biological adsorption performance.Zwitterionic presence can assign polyurethane material automatic emulsifying performance and anti-albumen and
Microorganism adsorption performance can improve the biocompatibility of material in terms of bio-medical, and reduce the formation of thrombus so that apply
Layer has anticoagulant property.Therefore the poly- ammonia of amphoteric ion is before water paint and bio-medical coating etc. have a wide range of applications
Scape.
By amphoteric ion be introduced into polymeric groups presently, there are one of critical issue be dissolving in organic solvent
Sex chromosome mosaicism.This be primarily due to it is zwitterionic highly polar, it is difficult to which amphoteric ion polymer can both be dissolved by finding a kind of solvent
The polyurethane of relative hydrophobic is dissolved again.Research report points out in the way of interpenetrating networks (IPN) though can be combined SBMA with PU,
But distribution of the SBMA monomers in PU network structures is unstable, is easy migration, anti-protein adsorption is by temperature, the pole of solvent
The restriction of the various conditions such as property and concentration；And its film performance is difficult control.DMAEMA and 1,3- third are utilized studies have reported that waiting
Sultones ring-opening reaction will produce amphoteric ion this property, will first contain PDMAEMA side chains and introduce polyurethane, then again plus
Enter 1,3-propane sultone and carries out sulfonating reaction generation amphoteric ion, to obtain containing zwitterionic polyurethane material, but
Since side chain is too long, film hydrophily is too strong, and mechanical strength is relatively low, is not suitable for being used as coating.Known to investigation, it is most of
The amphoteric ion polyurethane material of report, there are still prepare complicated and be not easy to mass produce, cost is higher the shortcomings of.
It is applied to bio-medical field and surfactant about the patent report of amphoteric ion aqueous polyurethane at present more
Field and cosmetic field.As to disclose a kind of amphoteric ion polymer surface modification with bio-medical poly- by CN103772731A
The method of urethane is to carry out modification to polyurethane surface by click reactions, but there are grafting densities to be not easy for surface modification
The shortcomings that control.ZL02128235.8 report a kind of preparation method of amphoteric urethane resin and obtained by this method two
Property polyurethane resin and resin combination, it is steady to improve its storage comprising two kinds of groups of carboxyl and tertiary amino in the polyurethane structural
It is qualitative, it is mainly used as hair fixative agent and cosmetic field.
The purpose of the present invention is in view of the shortcomings of the prior art and defect, provide a kind of anti-albumen and microorganism to inhale
Attached amphoteric ion type aqueous polyurethane and preparation method thereof.Cheap 2- amino-1,3-propanediols are selected, are passed through
Monomer-dimethylamino -1,3-PD (PEDA) of double hydroxyls and tertiary amino is prepared in Eschweiler-Clarke reactions, so
It regard PEDA as small molecule chain extender by polyaddition reaction afterwards to be introduced on aqueous polyurethane main chain, synthesizes with tertiary ammonia
Polyurethane (the NPU of base group）, react to obtain containing amphoteric ion polyurethane finally by NPU and ester type compound.
According to literature survey, document and patent report yet there are no about amphoteric ion polyurethane is prepared using such method.
Invention content
The present invention provides a kind of anti-albumen and the amphoteric ion aqueous polyurethanes of microorganism adsorption, it is characterised in for preparing
Method is to first pass through Clarke methylation reaction (Eschweiler-Clarke) to prepare the list with double hydroxyls and tertiary amine groups
Body-dimethylamino -1,3-PD (PEDA) is then regard PEDA as small molecule chain extender by polyaddition reaction and is introduced
Onto aqueous polyurethane main chain, the polyurethane (NPU) with tertiary amino is obtained, then be obtained by the reaction by NPU and ester type compound
Amphoteric ion polyurethane is eventually adding neutralizer, and high speed emulsification in water obtains the amphoteric ion of anti-albumen and microorganism adsorption
Aqueous polyurethane；
Described dimethylamino -1,3- propylene glycol (PEDA) preparation method is as follows：
(1) 2- amino-1,3-propanediols is taken to be dissolved in a certain amount of formic acid, addition volume fraction is 37% formalin,
Wherein 2- amino -1,3- propylene glycol:Formic acid:The molar ratio of formaldehyde is (2 ~ 5):2:1, it is dispersed with stirring 2h ~ 4h, stirring speed at room temperature
Degree is 200 ~ 1000rpm, is warming up to 40 DEG C ~ 90 DEG C and carries out 8 ~ 12h of reaction, and vacuum distillation removes extra formic acid and formaldehyde,
The reaction equation of preparation route is as follows:
(2) hydrochloric acid solution that volume fraction is 37 % is added into reaction solution and carries out acidification, is 25 DEG C ~ 40 in temperature
Under the conditions of react 1 ~ 3h, the wherein molar ratio of hydrochloric acid and 2- amino-1,3-propanediols is (1 ~ 1.5:1)；Appropriate NaOH is added,
Adjust pH to 9 ~ 12；It is eventually adding the salt Precipitation that excessive methanol generates reaction, filtrate is concentrated under reduced pressure for filtering,
It is PEDA to obtain white crystal;
The preparation method of the amphoteric ion aqueous polyurethane is as follows：
（1）According to molar ratio it is (1.5~3) by diisocyanate and polymer diatomic alcohol:1 is added in reactor, temperature
Degree is 60~100 DEG C, and 500~2000rpm of mixing speed is stirred to react 0.5 ~ 2h；
（2）The molar ratio of small molecule chain extender PEDA, PEDA and diisocyanate that preparation is added into reactor is
(0.3~0.7):1；The viscosity of appropriate solvent adjustment system is added, temperature is 70~90 DEG C, 500~2000rpm of mixing speed,
1~4h is reacted, the polyurethane (NPU) with tertiary amino is obtained；
（3）A certain amount of ester type compound is added into reactor, 12 ~ 48h is reacted under the conditions of temperature is 25 ~ 40 DEG C,
Obtain amphoteric ion polyurethane (ZPU);
（4）It is (0.2 ~ 1) according to the molar ratio of neutralizer and esters:1 neutralizer is added into reactor, is in temperature
20 ~ 40min of neutralization reaction is carried out under the conditions of 20 ~ 40 DEG C, reaction solution is concentrated, and deionized water is added, in 7000 ~ 10000 rpm
Lower high-speed stirred 0.2 ~ 1h, 1000 ~ 3000rpm 0.5 ~ 1h of stirring at low speed, obtains amphoteric ion aqueous polyurethane emulsion, is concentrated into
Solid content is 20%~40%.
The amphoteric ion aqueous polyurethane of a kind of described anti-albumen and microorganism adsorption, it is characterised in that the esters
Compound and the molar ratio of PEDA are (1.2 ~ 1.5):1.
The amphoteric ion aqueous polyurethane of a kind of described anti-albumen and microorganism adsorption, it is characterised in that the esters
Compound is 1,3- propane sultones, bromoacetate, 3- ethyl bromides, 4- bromobutyrates and 5- bromine valeric acid ethyl esters
In one kind.
The amphoteric ion aqueous polyurethane of a kind of described anti-albumen and microorganism adsorption, it is characterised in that the polymerization
Object dihydric alcohol is the polycaprolactone glycol of molecular weight 1000~8000, polycarbonate glycol, polytetrahydrofuran ether glycol, poly- the third two
The mixture of one or more of alcohol.
The amphoteric ion aqueous polyurethane of a kind of described anti-albumen and microorganism adsorption, it is characterised in that described two are different
Cyanate is isophorone diisocyanate (IPDI), toluene di-isocyanate(TDI), methyl diphenylene diisocyanate (MDI), six
One or more of mixtures of methylene diisocyanate (HDI).
The amphoteric ion aqueous polyurethane of a kind of described anti-albumen and microorganism adsorption, it is characterised in that this aqueous poly- ammonia
Ester can be used as coating material for leather and the coating of biomedical material surface.
The present invention provides a kind of anti-albumen and microorganism adsorption amphoteric ion aqueous polyurethanes.Preparation method is first logical
It crosses Eschweiler-Clarke methylation reactions and prepares monomer-dimethylamino -1,3- third with double hydroxyls and tertiary amino
Then PEDA is introduced on aqueous polyurethane main chain by polyaddition reaction, obtains having tertiary amino by glycol (PEDA)
Polyurethane (NPU), then amphoteric ion polyurethane is obtained by the reaction by NPU and ester type compound, it is eventually adding neutralizer neutralization,
Emulsification obtains amphoteric ion aqueous polyurethane in water.Zwitterionic presence can assign polyurethane material automatic emulsifying performance and resist
Protein adsorption performance prevents the formation of biodeterioration.In terms of bio-medical, zwitterionic presence can improve polyurethane material
The biocompatibility of material, and the adherency that albumen and blood platelet can be reduced etc., so that coating has anticoagulant property.This two
Property ion polyurethane has preferable application prospect in terms of aqueous leather coating material and bio-medical coating.
Specific implementation mode
Four embodiments of the present invention are given below, to illustrate sulfanilamide (SN) amphoteric ion type aqueous polyurethane leather finish
The preparation method of agent.
Embodiment 1
The detailed process that PEDA prepares reaction is as follows：Weigh 2- amino-1,3-propanediols 0.5mol (45.6g), Mn=
91.11 in the three-necked flask of 250ml, after 153ml formic acid is added, 37% formalin 70ml is added immediately, mixes at room temperature
After stirring 2h, it is warming up to 80 DEG C of reaction 8h (in the process, can constantly have gas releasing).25 DEG C are cooled to, is added 37%
HCl 90ml, are stirred to react 1h.Then appropriate NaOH is added, adjusts pH to 12, mixed liquor vacuum distillation, concentration removes solvent.
Excessive methanol is added, is filtered to remove salt, filtrate is concentrated under reduced pressure, and it is white crystal to obtain pure substance；
Weigh 20.00 g polyoxypropyleneglycols（Mn=2000）, it is added in the three-necked flask of 250ml, 110 degree
2h is dried in vacuum dehydration, and temperature is down to 70 DEG C, 3.48g toluene di-isocyanate(TDI)s and 100ml tetrahydrofuran solvents is added, in nitrogen
Mechanic whirl-nett reaction 1h under gas shielded.1.2gPEDA is added, 80 DEG C of stirrings expand even reaction 2h, cooling discharge and obtain NPU, will
Product is put into 50 DEG C of vacuum drying chambers for 24 hours.By NPU tetrahydrofurans（THF）It is dissolved in 100ml flasks, 1.8g bromines is added
Ethyl acetate reacts at 35 DEG C for 24 hours, and neutralizer sodium hydroxide is added and obtains bisexual ion purification polyurethane solutions.By amphoteric ion
Change polyurethane solutions rotary evaporation to concentrate, lower under the conditions of high-speed stirred that deionized water is added, high speed emulsifies 0.5h, and spin concentration is extremely
Solid content is 40%.
Embodiment 2
The detailed process that PEDA prepares reaction is as follows：Weigh 2- amino-1,3-propanediols 0.5mol (45.6g), Mn=
91.11 in the three-necked flask of 250ml, after 153ml formic acid is added, 37% formalin 70ml is added immediately, mixes at room temperature
After stirring 2h, it is warming up to 80 DEG C of reaction 8h (in the process, can constantly have gas releasing).25 DEG C are cooled to, is added 37%
HCl 90ml, are stirred to react 1h.Then appropriate NaOH is added, adjusts pH to 12, mixed liquor vacuum distillation, concentration removes solvent.
Excessive methanol is added, is filtered to remove salt, filtrate is concentrated under reduced pressure, and it is white crystal to obtain pure substance；
Weigh 20.00 g PolyTHFs（Mn=2000）, it is added in the three-necked flask of 250ml, 110 degree of vacuum
2h is dehydrated, temperature is down to 60 DEG C, and 5g methyl diphenylene diisocyanates are added（It is dissolved in THF）With 100ml tetrahydrochysene furans
It mutters solvent, under nitrogen protection mechanic whirl-nett reaction 1h.1.2gPEDA is added, 70 DEG C of stirrings expand even reaction 2h, cool down and
Material obtains NPU, and product is put into 50 DEG C of vacuum drying chambers for 24 hours.By NPU tetrahydrofurans（THF）It is dissolved in 100ml flasks
In, 1.6g1 is added, 3 propane sultones react at 35 DEG C for 24 hours, neutralizer sodium hydroxide is added, obtains the poly- ammonia of bisexual ion purification
Ester solution.Bisexual ion purification polyurethane solutions rotary evaporation is concentrated, it is lower under the conditions of high-speed stirred that deionized water, high speed breast is added
Change 0.5h, spin concentration to solid content is 40%.
Embodiment 3
The detailed process that PEDA prepares reaction is as follows：Weigh 2- amino-1,3-propanediols 0.5mol (45.6g), Mn=
91.11 in the three-necked flask of 250ml, after 153ml formic acid is added, 37% formalin 70ml is added immediately, mixes at room temperature
After stirring 2h, it is warming up to 80 DEG C of reaction 8h (in the process, can constantly have gas releasing).25 DEG C are cooled to, is added 37%
HCl 90ml, are stirred to react 1h.Then appropriate NaOH is added, adjusts pH to 12, mixed liquor vacuum distillation, concentration removes solvent.
Excessive methanol is added, is filtered to remove salt, filtrate is concentrated under reduced pressure, and it is white crystal to obtain pure substance；
Weigh 10.00 g PolyTHFs（Mn=1000）, it is added in the three-necked flask of 250ml, 110 degree of vacuum
2h is dehydrated, temperature is down to 60 DEG C, 4.5g isophorone diisocyanate and 100ml tetrahydrofuran solvents is added, in nitrogen
The lower mechanic whirl-nett reaction 1h of protection.1.2gPEDA is added, 70 DEG C of stirrings, which expand, even reacts 2h, and cooling discharge obtains NPU, will produce
Object is put into 50 DEG C of vacuum drying chambers for 24 hours.By NPU tetrahydrofurans（THF）It is dissolved in 100ml flasks, 1.46g1 is added,
3- propane sultones react at 35 DEG C for 24 hours, neutralizer triethylamine is added carries out neutralization reaction 40min and obtain bisexual ion purification
Polyurethane solutions.Bisexual ion purification polyurethane solutions rotary evaporation is concentrated, it is lower under the conditions of high-speed stirred that deionized water, height is added
Speed emulsification 0.5h, spin concentration to solid content are 40%.
Embodiment 4
The detailed process that PEDA prepares reaction is as follows：Weigh 2- amino-1,3-propanediols 0.5mol (45.6g), Mn=
91.11 in the three-necked flask of 250ml, after 153ml formic acid is added, 37% formalin 70ml is added immediately, mixes at room temperature
After stirring 2h, it is warming up to 80 DEG C of reaction 8h (in the process, can constantly have gas releasing).25 DEG C are cooled to, is added 37%
HCl 90ml, are stirred to react 1h.Then appropriate NaOH is added, adjusts pH to 12, mixed liquor vacuum distillation, concentration removes solvent.
Excessive methanol is added, is filtered to remove salt, filtrate is concentrated under reduced pressure, and it is white crystal to obtain pure substance；
Weigh 20.00 g polycarbonate glycol（Mn=2000）, it is added in the three-necked flask of 250ml, 110 degree true
Sky dehydration and drying 2h, temperature are down to 60 DEG C, 3.36g hexamethylene diisocyanates and 100ml tetrahydrofuran solvents are added, in nitrogen
Mechanic whirl-nett reaction 1h under gas shielded.1.2gPEDA is added, 70 DEG C expand even reaction 2h, and cooling discharge obtains NPU, by product
It is put into 50 DEG C of vacuum drying chambers for 24 hours.By NPU tetrahydrofurans（THF）It is dissolved in 100ml flasks, 1.5g bromoacetic acids is added
Ethyl ester reacts at 35 DEG C for 24 hours, and neutralizer triethylamine is added and carries out neutralization reaction 40min, it is molten to obtain bisexual ion purification polyurethane
Liquid.Bisexual ion purification polyurethane solutions rotary evaporation is concentrated, lower under the conditions of high-speed stirred that deionized water is added, high speed emulsifies
0.5h, spin concentration to solid content are 40%.
Claims (4)
1. the amphoteric ion aqueous polyurethane of a kind of anti-albumen and microorganism adsorption, it is characterised in that preparation method is to first pass through gram
Clarke methylation reaction prepares monomer -2- dimethylaminos -1,3-PD PEDA with double hydroxyls and tertiary amine groups, then
It regard PEDA as small molecule chain extender by polyaddition reaction to be introduced on aqueous polyurethane main chain, obtains that there is tertiary amino
Polyurethane NPU, then amphoteric ion polyurethane is obtained by the reaction by NPU and ester type compound, it is eventually adding neutralizer, it is newborn in water
Change obtains the amphoteric ion aqueous polyurethane of anti-albumen and microorganism adsorption；
2- dimethylamino -1,3- propylene glycol PEDA the preparation methods are as follows：
(1) 2- amino-1,3-propanediols is taken to be dissolved in a certain amount of formic acid, addition volume fraction is 37 % formalins,
Middle 2- amino -1,3- propylene glycol:Formic acid:The molar ratio of formaldehyde is (2 ~ 5):2:1, it is dispersed with stirring 2h ~ 4h, mixing speed at room temperature
For 200 ~ 1000rpm, it is warming up to 40 DEG C ~ 90 DEG C and carries out 8 ~ 12h of reaction, vacuum distillation removes extra formic acid and formaldehyde, system
The reaction equation of standby route is as follows：
(2) hydrochloric acid solution that volume fraction is 37 % is added into reaction solution and carries out acidification, is 25 DEG C ~ 40 in temperature
1 ~ 3h is reacted under part, the molar ratio of wherein hydrochloric acid and 2- amino-1,3-propanediols is (1 ~ 1.5:1)；Appropriate NaOH is added, is adjusted
Save pH to 9 ~ 12；It is eventually adding the salt Precipitation that excessive methanol generates reaction, filtrate is concentrated under reduced pressure, obtains by filtering
It is PEDA to white crystal；
The preparation method of the amphoteric ion aqueous polyurethane is as follows：
（1）According to molar ratio it is (1.5~3) by diisocyanate and polymer diatomic alcohol:1 is added in reactor, and temperature is
60~100 DEG C, 500~2000rpm of mixing speed is stirred to react 0.5 ~ 2h；
（2）Be added into reactor preparation small molecule chain extender PEDA, PEDA and diisocyanate molar ratio be (0.3~
0.7):1；The viscosity of appropriate solvent adjustment system is added, temperature is 70~90 DEG C, 500~2000rpm of mixing speed, reaction 1~
4h obtains the polyurethane NPU with tertiary amino；
（3）A certain amount of ester type compound is added into reactor, 12 ~ 48h is reacted under the conditions of temperature is 25 ~ 40 DEG C, is obtained
Amphoteric ion polyurethane ZPU；
（4）It is (0.2 ~ 1) according to the molar ratio of neutralizer and esters:1 neutralizer is added into reactor, is 20 ~ 40 in temperature
20 ~ 40min of neutralization reaction is carried out under the conditions of DEG C, reaction solution is concentrated, and deionized water is added, the high speed at 7000 ~ 10000 rpm
0.2 ~ 1h is stirred, 1000 ~ 3000rpm, 0.5 ~ 1h of stirring at low speed obtain amphoteric ion aqueous polyurethane emulsion, are concentrated into solid content
It is 20%~40%；
Wherein, the molar ratio of the ester type compound and PEDA are (1.2 ~ 1.5):1；The ester type compound is 1,3-
One kind in propane sultone, bromoacetate, 3- ethyl bromides, 4- bromobutyrates and 5- bromine valeric acid ethyl esters.
2. the amphoteric ion aqueous polyurethane of a kind of anti-albumen according to claim 1 and microorganism adsorption, feature exist
In polycaprolactone glycol, polycarbonate glycol, PolyTHF that the polymer diatomic alcohol is molecular weight 1000~8000
The mixture of one or more of ether glycol, polypropylene glycol.
3. the amphoteric ion aqueous polyurethane of a kind of anti-albumen according to claim 1 and microorganism adsorption, feature exist
In the diisocyanate be isophorone diisocyanate (IPDI), toluene di-isocyanate(TDI), two isocyanide of diphenyl methane
One or more of mixtures of acid esters (MDI), hexamethylene diisocyanate (HDI).
4. the amphoteric ion aqueous polyurethane of a kind of anti-albumen according to claim 1 and microorganism adsorption, feature exist
Coating material for leather and the coating of biomedical material surface are can be used as in this aqueous polyurethane.
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| CN107286355B (en) * | 2017-07-21 | 2020-07-03 | 天津大学 | Cation-zwitterion copolymer and polycaprolactone blended membrane and preparation method and application thereof |
| CN107988197B (en) * | 2017-12-25 | 2019-02-12 | 桑德生态科技有限公司 | Using plant fiber as Microorganism-embeddcarrier carrier of supporter and preparation method thereof |
| CN112760023B (en) * | 2021-01-25 | 2022-04-26 | 四川大学 | Mixed-charge polyurethane coating material and preparation method and application thereof |
| CN113121790B (en) * | 2021-04-27 | 2022-04-15 | 苏州大学 | Wet rubbing fastness improver for acid dye and preparation method thereof |
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