CN105732953A - Zwitter-ion waterborne polyurethane resisting protein and microorganism adsorption - Google Patents
Zwitter-ion waterborne polyurethane resisting protein and microorganism adsorption Download PDFInfo
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- CN105732953A CN105732953A CN201610261043.4A CN201610261043A CN105732953A CN 105732953 A CN105732953 A CN 105732953A CN 201610261043 A CN201610261043 A CN 201610261043A CN 105732953 A CN105732953 A CN 105732953A
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- polyurethane
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Abstract
The invention provides zwitter-ion waterborne polyurethane resisting protein and microorganism adsorption.According to the preparing method, monomer-dimethylamino-1,3-propylene glycol (PEDA) with di-hydroxy and tertiary amino is prepared through the Eschweiler-Clarke methylation, then PEDA is introduced to a waterborne polyurethane main chain through the addition polymerization reaction to obtain polyurethane (NPU) with tertiary amino, NPU reacts with an ester compound to obtain zwitter-ion polyurethane, finally, a neutralizing agent is added for neutralizing, and the mixture is emulsified in water to obtain zwitter-ion waterborne polyurethane.A polyurethane material can be endowed with the self-emulsifying performance and the protein adsorption resisting performance due to existence of zwitter-ions, and formation of biology defiling is prevented.In the aspect of biomedical application, due to existence of the zwitter-ions, the biocompatibility of the polyurethane material can be improved, adsorption of protein, blood platelet and the like can be reduced, and therefore a coating has anticoagulation performance.Zwitter-ion waterborne polyurethane has a good application prospect in the aspects of water-based paint for leather and biomedical coatings.
Description
Technical field
The present invention relates to waterborne polyurethane resin field, is specifically related to a kind of anti-albumen and microorganism adsorption amphion aqueous
Polyurethane and preparation method thereof.
Background technology
Polyurethane (PU) is one of macromolecular material with fastest developing speed, but owing to this system exists inherent defects.?
Under the driving of environmental requirement, along with establishment and the enhancing of 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, pliability and fatigue durability etc., and with water as disperse medium, without or only
Containing a small amount of organic solvent, free from environmental pollution, use safety, the adjustability of properties of product is bigger.Microorganisms is at different materials
The growing state on the surface (cotton, 60% cotton and the polyester of 40%, polyester and polyurethane) of matter, finds that microorganism is at polyurethane surface
Time-to-live is the longest, and therefore polyurethane is that a kind of being highly desirable to possesses the anti-biological macromolecular material being stained performance.Numerous studies
Display, from molecular level, biodeterioration starts from albumen and the microorganism absorption on surface.Amphoteric ion polymer is such as
Sulphur-amine (SBMA) and carboxylic-amine (CBMA) demonstrate good anti-protein adsorption performance, and polyurethane material has and adheres well to
Power and preferably biocompatibility, combine, by amphion and polyurethane, the mechanical property being expected to utilize polyurethane excellent
And adhesive capacity, anti-albumen and the microorganism adsorption performance of amphoteric ion polymer can be utilized again, obtain having anti-albumen and micro-
The polyurethane material of biological adsorption performance.Zwitterionic existence can give 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 thrombosis so that be coated with
Layer has anticoagulant property.Therefore the poly-ammonia of amphion is before the aspects such as water paint and bio-medical coating have a wide range of applications
Scape.
It is dissolving in organic solvent that amphion introduces one of key issue of presently, there are in polymeric groups
Sex chromosome mosaicism.This is primarily due to zwitterionic highly polar, is difficult to find a kind of solvent can both dissolve amphoteric ion polymer
Dissolve again the polyurethane of relative hydrophobic.Research report point out the mode (IPN) utilizing interpenetrating networks though SBMA with PU can be combined,
But the distribution that SBMA monomer is in PU network structure is unstable, easily migrates, and its 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 to control.Studies have reported that etc. and to utilize DMAEMA Yu 1,3-third
Sultones ring-opening reaction can produce this character of amphion, first will introduce polyurethane containing PDMAEMA side chain, and add
Enter PS and carry out sulfonating reaction generation amphion, thus obtain containing zwitterionic polyurethane material, but
Owing to side chain is oversize, film hydrophilic is too strong, and mechanical strength is relatively low, is not suitable for as coating.Known according to investigation, great majority are
The amphion polyurethane material of report, still suffers from preparation complicated and be difficult to large-scale production, the shortcoming such as relatively costly.
Patent report about amphion aqueous polyurethane is applied to bio-medical field and surfactant more at present
Field and cosmetic field.Modify poly-as CN103772731A discloses the amphoteric ion polymer surface of a kind of bio-medical
The method of urethane, is to be reacted by click polyurethane surface carries out modification, but surface modification exists grafting density and is difficult to
The shortcoming controlled.ZL02128235.8 reports the preparation method of a kind of amphoteric urethane resin and obtained two by the method
Property polyurethane resin and resin combination, this polyurethane structural comprises carboxyl and two kinds of groups of tertiary amino and stores steady to improve it
Qualitative, it is mainly used as hair fixative agent and cosmetic field.
It is an object of the invention to deficiency and the defect existed for prior art, it is provided that a kind of anti-albumen and microorganism are inhaled
Attached amphoteric ion type aqueous polyurethane and preparation method thereof.Select cheap 2-amino-1,3-propanediol, pass through
Double hydroxyl and the monomer dimethylamino-1,3-PD (PEDA) of tertiary amino are prepared in Eschweiler-Clarke reaction, so
By polyaddition reaction, PEDA is incorporated on aqueous polyurethane main chain as small molecule chain extender afterwards, synthesizes and there is tertiary ammonia
The polyurethane (NPU) of base group, obtains containing amphion polyurethane with reacting of ester type compound finally by NPU.
According to literature survey, yet there are no document and patent report about utilizing this kind of method to prepare amphion polyurethane.
Summary of the invention
The invention provides the amphion aqueous polyurethane of a kind of anti-albumen and microorganism adsorption, it is characterised in that preparation
Method is to first pass through Clarke methylation reaction (Eschweiler-Clarke) to prepare the list with double hydroxyl and tertiary amine groups
Body dimethylamino-1,3-PD (PEDA), is then introduced PEDA as small molecule chain extender by polyaddition reaction
On aqueous polyurethane main chain, obtain the polyurethane (NPU) with tertiary amino, then reacted with ester type compound by NPU and obtain
Amphion polyurethane, is eventually adding nertralizer, obtains the amphion of anti-albumen and microorganism adsorption in water high speed emulsifying
Aqueous polyurethane；
Described dimethylamino-1,3-propylene glycol (PEDA) preparation method is as follows:
(1) taking 2-amino-1,3-propanediol to be dissolved in a certain amount of formic acid, adding volume fraction is 37% formalin, wherein
2-amino-1,3-propanediol: formic acid: the mol ratio of formaldehyde is (2 ~ 5): 2:1, dispersed with stirring 2h ~ 4h under room temperature, mixing speed is
200 ~ 1000rpm, is warming up to 40 DEG C ~ 90 DEG C and carries out reacting 8 ~ 12h, and decompression is distilled off unnecessary formic acid and formaldehyde, and it is prepared
The reaction equation of route is as follows:
(2) in reactant liquor, add the hydrochloric acid solution that volume fraction is 37 % and carry out acidification, be 25 DEG C ~ 40 conditions in temperature
Lower reaction 1 ~ 3h, wherein hydrochloric acid is (1 ~ 1.5:1) with the mol ratio of 2-amino-1,3-propanediol；Add appropriate NaOH, regulation
PH to 9 ~ 12；It is eventually adding the salt Precipitation that reaction is produced by excessive methanol, filters, filtrate is carried out concentrating under reduced pressure, obtains
White crystal is PEDA;
The preparation method of described amphion aqueous polyurethane is as follows:
(1) diisocyanate and polymer diatomic alcohol are (1.5～3) according to mol ratio: 1 joins in reactor, and temperature is
60～100 DEG C, mixing speed 500～2000rpm, stirs reaction 0.5 ~ 2h；
(2) mol ratio of the small molecule chain extender PEDA, PEDA and diisocyanate that add preparation in reactor be (0.3～
0.7):1；Adding the viscosity of appropriate solvent adjustment system, temperature is 70～90 DEG C, mixing speed 500～2000rpm, reaction 1～
4h, obtains the polyurethane (NPU) with tertiary amino；
(3) in reactor, add a certain amount of ester type compound, under the conditions of temperature is 25 ~ 40 DEG C, reacts 12 ~ 48h, obtains
Amphion polyurethane (ZPU);
(4) it is (0.2 ~ 1) according to the mol ratio of nertralizer Yu esters: 1 adds nertralizer in reactor, is 20 ~ 40 in temperature
It is neutralized reaction 20 ~ 40min under the conditions of DEG C, reactant liquor is concentrated, add deionized water, under 7000 ~ 10000 rpm at a high speed
Stirring 0.2 ~ 1h, 1000 ~ 3000rpm stirring at low speed 0.5 ~ 1h, obtains amphion aqueous polyurethane emulsion, is concentrated into solid content
It is 20%～40%.
Described a kind of anti-albumen and the amphion aqueous polyurethane of microorganism adsorption, it is characterised in that described esters
Compound is (1.2 ~ 1.5) with the mol ratio of PEDA: 1.
Described a kind of anti-albumen and the amphion aqueous polyurethane of microorganism adsorption, it is characterised in that described esters
Compound is 1,3-propane sultone, bromoacetate, 3-ethyl bromide, 4-bromobutyrate and 5-bromine ethyl valerate
In one.
Described a kind of anti-albumen and the amphion aqueous polyurethane of microorganism adsorption, it is characterised in that described polymerization
Thing dihydroxylic alcohols be the polycaprolactone glycol of molecular weight 1000～8000, PCDL, PTMG, poly-the third two
The mixture of one or more in alcohol.
Described a kind of anti-albumen and the amphion aqueous polyurethane of microorganism adsorption, it is characterised in that described two are different
Cyanate be isophorone diisocyanate (IPDI), toluene di-isocyanate(TDI), methyl diphenylene diisocyanate (MDI), six
The mixture of one or more of methylene diisocyanate (HDI).
Described a kind of anti-albumen and the amphion aqueous polyurethane of microorganism adsorption, it is characterised in that the poly-ammonia of this aqueous
Ester can be as coating material for leather and the coating of biomedical material surface.
The invention provides a kind of anti-albumen and microorganism adsorption amphion aqueous polyurethane.Its preparation method is first to lead to
Cross Eschweiler-Clarke methylation reaction and prepare the monomer dimethylamino-1,3-third with double hydroxyl and tertiary amino
Glycol (PEDA), is then incorporated into PEDA on aqueous polyurethane main chain by polyaddition reaction, obtains having tertiary amino
Polyurethane (NPU), then react with ester type compound obtain amphion polyurethane by NPU, it is eventually adding nertralizer neutralization,
In water, emulsifying obtains amphion aqueous polyurethane.Zwitterionic existence can give polyurethane material automatic emulsifying performance and resist
Protein adsorption performance, prevents the formation of biodeterioration.In terms of bio-medical, zwitterionic existence can improve polyurethane material
The biocompatibility of material, and the adhesion of albumen and platelet etc. can be reduced, so that coating has anticoagulant property.These are two years old
Property ion polyurethane has preferable application prospect in terms of leather water paint and bio-medical coating.
Detailed description of the invention
Four embodiments of the present invention are given below, to illustrate sulfanilamide amphoteric ion type aqueous polyurethane leather finish
The preparation method of agent.
Embodiment 1
PEDA preparation reaction detailed process as follows: weigh 2-amino-1,3-propanediol 0.5mol (45.6g), Mn=91.11 in
In the there-necked flask of 250ml, after adding 153ml formic acid, add 37% formalin 70ml immediately, mix and blend 2h under room temperature
After, it is warming up to 80 DEG C of reactions 8h (in the process, can constantly have gas to release).It is cooled to 25 DEG C, adds the HCl of 37%
90ml, stirring reaction 1h.It is subsequently adding appropriate NaOH, regulates pH to 12, mixed liquor decompression distillation, concentrate, remove solvent.Add
Excessive methanol, is filtered to remove salt, and filtrate carries out concentrating under reduced pressure, and obtaining pure substance is white crystal；
Weigh 20.00 g polyoxypropyleneglycol (Mn=2000), join in the there-necked flask of 250ml, 110 degree of vacuum
Dehydrate 2h, temperature is down to 70 DEG C, is added 3.48g toluene di-isocyanate(TDI) and 100ml tetrahydrofuran solvent, protects at nitrogen
Protect lower mechanic whirl-nett reaction 1h.Adding 1.2gPEDA, 80 DEG C of stirrings carry out expanding even reaction 2h, and cooling discharge obtains NPU, by product
Put into 24h in 50 DEG C of vacuum drying ovens.NPU oxolane (THF) is dissolved in 100ml flask, adds 1.8g bromoacetic acid
Ethyl ester, reacts 24h at 35 DEG C, add nertralizer sodium hydroxide and obtain bisexual ion purification polyurethane solutions.Bisexual ion purification is gathered
Urethane solution rotating evaporation and concentration, under the conditions of high-speed stirred under add deionized water, high speed emulsifying 0.5h, spin concentration is to admittedly containing
Amount is 40%.
Embodiment 2
PEDA preparation reaction detailed process as follows: weigh 2-amino-1,3-propanediol 0.5mol (45.6g), Mn=91.11 in
In the there-necked flask of 250ml, after adding 153ml formic acid, add 37% formalin 70ml immediately, mix and blend 2h under room temperature
After, it is warming up to 80 DEG C of reactions 8h (in the process, can constantly have gas to release).It is cooled to 25 DEG C, adds the HCl of 37%
90ml, stirring reaction 1h.It is subsequently adding appropriate NaOH, regulates pH to 12, mixed liquor decompression distillation, concentrate, remove solvent.Add
Excessive methanol, is filtered to remove salt, and filtrate carries out concentrating under reduced pressure, and obtaining pure substance is white crystal；
Weigh 20.00 g PolyTHF (Mn=2000), join in the there-necked flask of 250ml, 110 degree of vacuum dehydrations
Being dried 2h, temperature is down to 60 DEG C, adds 5g methyl diphenylene diisocyanate (being dissolved in THF) and 100ml oxolane is molten
Agent, under nitrogen protection mechanic whirl-nett reaction 1h.Adding 1.2gPEDA, 70 DEG C of stirrings carry out expanding even reaction 2h, and cooling discharge obtains
To NPU, product is put into 24h in 50 DEG C of vacuum drying ovens.NPU oxolane (THF) is dissolved in 100ml flask, adds
Enter 1.6g1,3 propane sultones, react 24h, add nertralizer sodium hydroxide, obtain bisexual ion purification polyurethane molten at 35 DEG C
Liquid.By bisexual ion purification polyurethane solutions rotary evaporation concentrate, under the conditions of high-speed stirred under add deionized water, high speed emulsifying
0.5h, spin concentration to solid content is 40%.
Embodiment 3
PEDA preparation reaction detailed process as follows: weigh 2-amino-1,3-propanediol 0.5mol (45.6g), Mn=91.11 in
In the there-necked flask of 250ml, after adding 153ml formic acid, add 37% formalin 70ml immediately, mix and blend 2h under room temperature
After, it is warming up to 80 DEG C of reactions 8h (in the process, can constantly have gas to release).It is cooled to 25 DEG C, adds the HCl of 37%
90ml, stirring reaction 1h.It is subsequently adding appropriate NaOH, regulates pH to 12, mixed liquor decompression distillation, concentrate, remove solvent.Add
Excessive methanol, is filtered to remove salt, and filtrate carries out concentrating under reduced pressure, and obtaining pure substance is white crystal；
Weigh 10.00 g PolyTHF (Mn=1000), join in the there-necked flask of 250ml, 110 degree of vacuum dehydrations
Being dried 2h, temperature is down to 60 DEG C, adds 4.5g isophorone diisocyanate and 100ml tetrahydrofuran solvent, protects at nitrogen
Lower mechanic whirl-nett reaction 1h.Adding 1.2gPEDA, 70 DEG C of stirrings carry out expanding even reaction 2h, and cooling discharge obtains NPU, is put by product
Enter 24h in 50 DEG C of vacuum drying ovens.NPU oxolane (THF) is dissolved in 100ml flask, adds 1.46g1,3-third
Sultone, reacts 24h at 35 DEG C, addition nertralizer triethylamine is neutralized reaction 40min and obtains the poly-ammonia of bisexual ion purification
Ester solution.Bisexual ion purification polyurethane solutions rotary evaporation is concentrated, under the conditions of high-speed stirred under add deionized water, breast at a high speed
Changing 0.5h, spin concentration to solid content is 40%.
Embodiment 4
PEDA preparation reaction detailed process as follows: weigh 2-amino-1,3-propanediol 0.5mol (45.6g), Mn=91.11 in
In the there-necked flask of 250ml, after adding 153ml formic acid, add 37% formalin 70ml immediately, mix and blend 2h under room temperature
After, it is warming up to 80 DEG C of reactions 8h (in the process, can constantly have gas to release).It is cooled to 25 DEG C, adds the HCl of 37%
90ml, stirring reaction 1h.It is subsequently adding appropriate NaOH, regulates pH to 12, mixed liquor decompression distillation, concentrate, remove solvent.Add
Excessive methanol, is filtered to remove salt, and filtrate carries out concentrating under reduced pressure, and obtaining pure substance is white crystal；
Weigh 20.00 g PCDL (Mn=2000), joining in the there-necked flask of 250ml, 110 degree of vacuum take off
Water is dried 2h, and temperature is down to 60 DEG C, adds 3.36g hexamethylene diisocyanate and 100ml tetrahydrofuran solvent, protects at nitrogen
Protect lower mechanic whirl-nett reaction 1h.Adding 1.2gPEDA, 70 DEG C carry out expanding even reaction 2h, and cooling discharge obtains NPU, is put into by product
24h in 50 DEG C of vacuum drying ovens.NPU oxolane (THF) is dissolved in 100ml flask, adds 1.5g bromoacetate,
React 24h at 35 DEG C, add nertralizer triethylamine and be neutralized reaction 40min, obtain bisexual ion purification polyurethane solutions.Will
Bisexual ion purification polyurethane solutions rotary evaporation concentrates, under the conditions of high-speed stirred under add deionized water, high speed emulsifying 0.5h, rotation
Turn that to be concentrated into solid content be 40%.
Claims (6)
1. an anti-albumen and the amphion aqueous polyurethane of microorganism adsorption, it is characterised in that preparation method is to first pass through gram
Clarke methylation reaction (Eschweiler-Clarke) prepares monomer dimethylamino-1 with double hydroxyl and tertiary amine groups,
Ammediol (PEDA), is then incorporated into aqueous polyurethane main chain using PEDA as small molecule chain extender by polyaddition reaction
On, obtain the polyurethane (NPU) with tertiary amino, then reacted with ester type compound by NPU and obtain amphion polyurethane,
Rear addition nertralizer, in water, emulsifying obtains the amphion aqueous polyurethane of anti-albumen and microorganism adsorption；
Described dimethylamino-1,3-propylene glycol (PEDA) preparation method is as follows:
(1) taking 2-amino-1,3-propanediol to be dissolved in a certain amount of formic acid, adding volume fraction is 37 % formalins, its
Middle 2-amino-1,3-propanediol: formic acid: the mol ratio of formaldehyde is (2 ~ 5): 2:1, dispersed with stirring 2h ~ 4h, mixing speed under room temperature
Being 200 ~ 1000rpm, be warming up to 40 DEG C ~ 90 DEG C and carry out reacting 8 ~ 12h, decompression is distilled off unnecessary formic acid and formaldehyde, its system
The reaction equation of standby route is as follows:
(2) in reactant liquor, add the hydrochloric acid solution that volume fraction is 37 % and carry out acidification, be 25 DEG C ~ 40 in temperature
Reacting 1 ~ 3h under part, wherein hydrochloric acid is (1 ~ 1.5:1) with the mol ratio of 2-amino-1,3-propanediol；Add appropriate NaOH, adjust
Joint pH to 9 ~ 12；It is eventually adding the salt Precipitation that reaction is produced by excessive methanol, filters, filtrate is carried out concentrating under reduced pressure,
It is PEDA to white crystal；
The preparation method of described amphion aqueous polyurethane is as follows:
(1) diisocyanate and polymer diatomic alcohol are (1.5～3) according to mol ratio: 1 joins in reactor, and temperature is
60～100 DEG C, mixing speed 500～2000rpm, stirs reaction 0.5 ~ 2h；
(2) mol ratio of the small molecule chain extender PEDA, PEDA and diisocyanate that add preparation in reactor be (0.3～
0.7):1；Adding the viscosity of appropriate solvent adjustment system, temperature is 70～90 DEG C, mixing speed 500～2000rpm, reaction 1～
4h, obtains the polyurethane (NPU) with tertiary amino；
(3) in reactor, add a certain amount of ester type compound, under the conditions of temperature is 25 ~ 40 DEG C, reacts 12 ~ 48h, obtains
Amphion polyurethane (ZPU)；
(4) it is (0.2 ~ 1) according to the mol ratio of nertralizer Yu esters: 1 adds nertralizer in reactor, is 20 ~ 40 in temperature
It is neutralized reaction 20 ~ 40min under the conditions of DEG C, reactant liquor is concentrated, add deionized water, under 7000 ~ 10000 rpm at a high speed
Stirring 0.2 ~ 1h, 1000 ~ 3000rpm stirring at low speed 0.5 ~ 1h, obtains amphion aqueous polyurethane emulsion, is concentrated into solid content
It is 20%～40%.
A kind of anti-albumen the most according to claim 1 and the amphion aqueous polyurethane of microorganism adsorption, its feature exists
Mol ratio in described ester type compound Yu PEDA is (1.2 ~ 1.5): 1.
A kind of anti-albumen the most according to claim 1 and the amphion aqueous polyurethane of microorganism adsorption, its feature exists
It is 1,3-propane sultone, bromoacetate, 3-ethyl bromide, 4-bromobutyrate and 5-in described ester type compound
One in bromine ethyl valerate.
A kind of anti-albumen the most according to claim 1 and the amphion aqueous polyurethane of microorganism adsorption, its feature exists
It is the polycaprolactone glycol of molecular weight 1000～8000, PCDL, PolyTHF in described polymer diatomic alcohol
The mixture of one or more in ether glycol, polypropylene glycol.
A kind of anti-albumen the most according to claim 1 and the amphion aqueous polyurethane of microorganism adsorption, its feature exists
It is isophorone diisocyanate (IPDI), toluene di-isocyanate(TDI), diphenyl methane two isocyanide in described diisocyanate
Acid esters (MDI), the mixture of one or more of hexamethylene diisocyanate (HDI).
A kind of anti-albumen the most according to claim 1 and the amphion aqueous polyurethane of microorganism adsorption, its feature exists
Can be as coating material for leather and the coating of biomedical material surface in this aqueous polyurethane.
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| CN112760023A (en) * | 2021-01-25 | 2021-05-07 | 四川大学 | Mixed-charge polyurethane coating material and preparation method and application thereof |
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