CN1371927A - Fluorine containing polyurethane material and preparation method thereof - Google Patents
Fluorine containing polyurethane material and preparation method thereof Download PDFInfo
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- CN1371927A CN1371927A CN 01107200 CN01107200A CN1371927A CN 1371927 A CN1371927 A CN 1371927A CN 01107200 CN01107200 CN 01107200 CN 01107200 A CN01107200 A CN 01107200A CN 1371927 A CN1371927 A CN 1371927A
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Abstract
The present invention relates to a fluorinated polyurethane material which is made up by means of alternative copolymerization of flexible chain segment formed from polycarbonate dibasic alcohol and/or polyether dibasic alcohol and perfluoropolyether dibasic alcohol and rigid chain segment formed from diisocyanate and small molecule chain extender under a certain condition, and in the course of heat treatment or film formation the perfluoropolyether dibasic alcohol can be enriched in the surface of material so as to make the material possess high strength, good elasticity, resistance to oxidation and resistance to hydrolysis, and possess good bio-stability, so that said material can be used for making various medical products capable of being implanted into human body for a long period.
Description
The invention belongs to high-molecular biologic medical engineering material and preparing technical field thereof, is a kind of fluorochemical urethane thermoplastic elastic material with high strength, snappiness and good body internal stability and preparation method thereof.
The material that implants for long-term (〉=30 days), require it to have excellent biological compatibility, good processibility and high strength, snappiness and good in vivo biologically stable, promptly good physics and chemical stability do not take place or rare degraded.Though polyurethane material has high strength, snappiness, excellent biological compatibility and processibility have obtained to use widely in the material field that implants, as insulated wire as the heart heartstart lead, artificial blood vessel and various medical catheters etc., but be polyester type or polyether(poly)urethane owing to make the material of said products, and PAUR is owing to exist ester bond to be easy to hydrolysis, after the hydrolysis with release fat acid, produce acid catalysis Degradation [L.Pinchuk, Journal of Biomaterials Science:Polymer Edition, 1994,6 (3): 225～267]; Though and polyether(poly)urethane has stability to hydrolysis, but produced oxidative degradation when using in vivo, when using as the insulated wire of making the heart heartstart lead of it, find that crackle appears in material, after body fluid entered, short circuit appearred in the heart heartstart power supply, cause life danger [K.Stokes to patient, Journal of Biomaterials Sci-ence:Polymer Edition, 1990,1 (3): 207～230].
In order to solve the problem that polyester type or polyether(poly)urethane exist, U.S. Pat 5,133,742 disclose a kind of polycarbonate polyurethane material, the PCDL that this material adopts US 4,131,731 described methods to generate, aliphatics or aromatic diisocyanate and low molecule chainextender are synthesized into, and wherein PCDL has following structure:
Wherein x is 2～35, and y is 0,1,2, and R is the aliphatics of carbon containing 4～40, alicyclic or aromatic inferior hydrocarbon, and R ' is the inferior hydrocarbon of the aliphatics of carbon containing 2～4.U.S. Pat 5,254,662 disclose another kind of polycarbonate polyurethane material, and it is 1000～2000 aliphatic polycarbonate dibasic alcohol that this material has adopted molecular weight, and its structure is as follows:
HOR ' O (CO) OR '
nOHR ' is the inferior hydrocarbon of the aliphatics of linear carbon containing 2～20.It is said these two kinds of materials owing to adopted the aliphatic polycarbonate dibasic alcohol that does not contain or seldom contain ehter bond as soft section material, thereby can prevent the oxidative degradation of material, be suitable for implanting for a long time.But Ze Zhang[sees Biomaterials in recent years, 1997,18:113～124] etc. research show that again the polycarbonate polyurethane artificial blood vessel is after human body is implanted into 358 days, hydrolytic deterioration has taken place in material, tiny crack occurred.Therefore, the polycarbonate polyurethane material still can not be satisfied the demand to implant and be reached above service requirements of several years.
In addition, U.S. Pat 5,589,563 have also disclosed a kind of the employing at the polyurethane macromolecular two ends has the biologically stable that the end capped technology of surface-active molecule improves urethane, and the single alkane hydroxyl polysiloxane of wherein main employing carries out end-blocking.Because silicon surfactants is low, is enriched in material surface in material processing, can hinder the degraded to bulk material of oxidizing medium and acidic substance, therefore improved the material biologically stable.But polysiloxane has lipophilicity, the adsorbent inner lipid, makes the material swelling set, so still there is certain defective.
One of purpose of the present invention is in order to solve the problem that prior art exists, provide a kind of can resistance to oxidation, the medical polyurethane material with good biological stability of hydrolysis.
Two of purpose of the present invention provides the method that a kind of preparation has the polyurethane material of above-mentioned performance.
Three of purpose of the present invention provides another kind of preparation and has the method for the polyurethane material of above-mentioned performance.
In order to reach first purpose, the inventor has carried out research screening extensively and profoundly to existing various medical materials, think over-all properties, comprise mechanical property, biocompatibility, what workability etc. were best is the Polyurethane Thermoplastic Elastomer material, and biologically stable the best is fluoroplastics or fluoroelastomer, and fluorine material also has oil-proofness, can not adsorb lipid material in vivo, therefore in conjunction with the two advantage, a kind of like this technical solution has been proposed: by PCDL, polyether Glycols, the PFPE dibasic alcohol constitutes elastomeric soft segment and by vulcabond, the material that the rigid chain segment alternating copolymerization that small molecule chain extender constitutes forms, its molecular weight is 25000～250000.Because PFPE dibasic alcohol surface energy is low, but in hot-work or film forming process enrichment material surface just, prevent oxidizing medium and hydrolysis medium purpose thereby reach to the bulk material degraded.
The PFPE dibasic alcohol that adopts in the such scheme is following any structure or the mixture of appointing two or more structure:
1. HO CH
2 zCF
2O C
2F
4O
m CF
2O
nCF
2 CH
2 zOH is z=1 wherein, and 2, m/n=0.2～2 are preferably 0.5～1.2, and the concrete numerical value of m, n will make its molecular weight reach 500～3000;
2. HO CH
2CH
2O
zCH
2-CF
2O C
2F
4O
m CF
2O
nCH
2 OCH
2CH
2 zOH is z=1 wherein, and 2,3, m/n=0.2～2 are preferably 0.5～1.2, and the concrete numerical value of m, n will make its molecular weight reach 500～3000;
3. HOCH
2CF
2 C
3F
6O
r C
2F
4O
a CFXO
tCF
2CH
2OH is x=F or CF wherein
3, r, s, t are respectively 0～100, and r+s ≠ 0, and molecular weight will reach 500～3000 simultaneously;
④??????????????????RC
2F
4O
nR
⑤??????????????????RCF
2CF
2CF
2O
nR
6. R CFCF
3CF
2O
n4.～6. middle R=CH of R
2OH or CH
2 OCH
2CH
2 zOH, z=1,2,3; The value of n will make its molecular weight reach 500～3000.
PCDL that adopts in the such scheme and polyether Glycols, can enumerate as concrete kind: polypropylene glycol, polyoxyethylene glycol, PTMG, poly-(1,4-butyleneglycol carbonic ether) glycol, poly-(1,6-hexylene glycol carbonic ether) glycol, poly-(1,6-hexylene glycol 1 carbonic ether) glycol etc.In addition, also can adopt copolymerization polycarbonate for PCDL with following structure:
R=R wherein
1Or R
2, R
1For containing the stable hydrocarbon of even number of carbon atoms, R
2For containing the stable hydrocarbon of odd number carbon atom.X/y=0.5～2, and the concrete numerical value of x, y will make its molecular weight reach 500～3000.
The vulcabond that adopts in the such scheme can be aromatic diisocyanate or aliphatic diisocyanate.Can enumerate as aromatic diisocyanate: 4,4 '-diphenylmethanediisocyanate (MDI), 2,4-or 2,6-tolylene diisocyanate (TDI), 1,4-phenylene diisocyanate, 1,5-naphthalene diisocyanate, tetramethyl-PPDI etc.Can enumerate as aliphatic diisocyanate: hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4 '-dicyclohexyl methane diisocyanate (HMDI), 1,4-cyclohexyl diisocyanate etc.
The small molecule chain extender that adopts in the such scheme or for the aliphatic dihydroxy alcohol of carbon containing 2～10 or be the aliphatics or the aromatic diamine of carbon containing 2～10.Aliphatic dihydroxy alcohol specifically can be listed: ethylene glycol, glycol ether, 1,4-butyleneglycol, neopentyl glycol, 1,6-hexylene glycol, 1,8-ethohexadiol, 1,2-propylene glycol, 1, ammediol and 1,5-pentanediols etc., they can use separately also and can use both above mixing.Aliphatics or aromatic diamine specifically can be listed: quadrol, 1,3-propylene diamine, 1,4-butanediamine, 1,5-pentamethylene diamine, 1,6-hexanediamine, 1,7-heptamethylene diamine, 1, the 8-octamethylenediamine, O-Phenylene Diamine, Ursol D, 1,4-cyclohexyl diamines etc., they can use separately also and can use both above mixing.
Two of the object of the invention is to be reached by a kind of like this technical solution: the composition of raw materials that this programme adopted (weight percent) is:
PFPE dibasic alcohol 1～10%
Polycarbonate is or/and polyether Glycols 30～70%
Vulcabond 20～50%
Small molecule chain extender 3～25% its preparation technologies that adopt can be described as " mixing macromolecular diol " technology, and concrete steps and condition are:
1. with PFPE dibasic alcohol, polycarbonate or/and polyether Glycols, small molecule chain extender join in the reactor and mix, and be warming up to 90～100 ℃, vacuum outgas is 30～60 minutes then;
2. again vulcabond is added polyreaction 5～20 minutes;
3. reaction mixture is continued 100～130 ℃ of following slakings 3～6 hours.This processing method is called " solventless one-step method ".
Perhaps divide two step polyreactions in the presence of solvent-free, its step and condition are:
1. earlier with the PFPE dibasic alcohol with polycarbonate or/and mix in the polyether Glycols adding reactor, and be warming up to 70～100 ℃, vacuum outgas is 30～60 minutes then;
2. be cooled to 60～70 ℃ and add down vulcabond, and prepolymerization reaction 20～60 minutes;
3. add small molecule chain extender again, and be warming up to 100～130 ℃ of polyreactions 5～20 minutes;
4. reaction mixture is continued 100～130 ℃ of following slakings 3～6 hours.
In above-mentioned preparation scheme, when vulcabond is selected aliphatic diisocyanate for use, need to add amine or the tin class catalyzer of 200～400ppm, appropriate catalyst has stannous octoate, dibutyl tin laurate, triethylenediamine etc.
When small molecule chain extender is selected amine chain extender for use, need in solvent, to carry out polyreaction, its processing step and condition are:
1. in being placed with the reactor of solvent, add PFPE dibasic alcohol, polycarbonate or/and polyether Glycols, small molecules amine chainextender mix, and be warming up to 100～120 ℃;
2. add vulcabond again, continue promptly to get solution-type fluorochemical urethane material in 3～6 hours 100～120 ℃ of following polyreactions.This processing method can be described as " the solvent single stage method is arranged ".Perhaps two step of branch polyreactions in the presence of the solvent are being arranged, its step and condition are:
1. in being placed with the reactor of solvent, add earlier PFPE dibasic alcohol, polycarbonate or/and polyether Glycols mixes, and be warming up to 50～100 ℃;
2. add vulcabond, and 70～100 ℃ of following prepolymerization reactions 40～60 minutes;
3. add small molecules amine chainextender again, and be warming up to 100～130 ℃ of polyreactions 3～6 hours.
In above-mentioned preparation scheme no matter be single stage method or the two step method polyreaction that solvent is arranged, its used solvent all is a mixed solvent, be specially N, dinethylformamide, N, at least aly in the N-N,N-DIMETHYLACETAMIDE mix with the difluoro tetrachloroethane, its volume ratio is 1～3: 1, and it is 30～50% that usage quantity should make the solid content of product.
Three the technical solution that reaches the object of the invention is synthetic respectively earlier PFPE urethane and polycarbonate or polyether-polyurethane, and then its melt blending or cosolvent dissolving blend made the fluorochemical urethane material, so be called " blending technology ", its concrete prescription, processing step and condition are as follows:
The prescription (weight percent) of 1. synthetic PFPE urethane and polycarbonate or polyether-polyurethane is respectively:
A) the PFPE dibasic alcohol 30～70%
Vulcabond 20～55%
Small molecule chain extender 3～25%
B) polycarbonate or polyether Glycols 30～70%
Vulcabond 20～55%
Small molecule chain extender 3～25% its step of preparation process and condition are:
A) PFPE dibasic alcohol or polycarbonate or polyether Glycols and small molecule chain extender are joined mix in the reactor, and be warming up to 90～100 ℃, vacuum outgas is 30～60 minutes then;
B) again vulcabond is added polyreaction 5～20 minutes;
C) reaction mixture is continued 100～130 ℃ of following slakings 3～6 hours.This processing method is called " solventless one-step method ".
Perhaps divide two step polyreactions in the presence of solvent-free, its step and condition are:
A) earlier with in PFPE dibasic alcohol or polycarbonate or the polyether Glycols adding reactor, and be warming up to 70～100 ℃, vacuum outgas is 30～60 minutes then;
B) be cooled to 60～70 ℃ and add down vulcabond, and prepolymerization reaction 20～60 minutes;
C) add small molecule chain extender again, and be warming up to 100～130 ℃ of polyreactions 5～20 minutes;
D) with reaction mixture 100～130 ℃ of following slakings 3～6 hours.
2. melt blending or the cosolvent dissolving blend prescription (weight percent) for preparing the fluorochemical urethane material is:
PFPE urethane 5～20%
Polycarbonate or polyether-polyurethane 80～95%
Its melt blending is to carry out on twin screw extruder.Forcing machine melt zone temperature is controlled to be 180～200 ℃, and the extrusion neck ring mold temperature is controlled to be 160～190 ℃, and 3～15 minutes melting mixing time, extruding pelletization gets the fluorochemical urethane pellet then.
The cosolvent that cosolvent dissolving blend is adopted is difluoro tetrachloroethane/N, dinethylformamide or N, N-N,N-DIMETHYLACETAMIDE or tetrahydrofuran (THF), its both volume ratio is 1: 1～3, and to make the PFPE urethane that joins in the solvent and the solid content of polycarbonate or polyether-polyurethane be 10～30%, after the stirring and dissolving.If make the film material, then can earlier it be dried by the fire 10～15 hours down at 60～80 ℃, and then 80～100 ℃ of temperature, vacuum tightness 50～100mmHg dried by the fire 24～72 hours down, promptly got fluorochemical urethane film material.
In above-mentioned preparation scheme, when vulcabond is selected aliphatic diisocyanate for use, need to add amine or the tin class catalyzer of 200～400ppm, appropriate catalyst has stannous octoate, dibutyl tin laurate, triethylenediamine etc.
When small molecule chain extender is selected amine chain extender for use, need in solvent, to carry out polyreaction, its processing step and condition are:
1. in being placed with the reactor of solvent, add PFPE dibasic alcohol or polycarbonate or polyether Glycols and small molecules amine chainextender and mix, and be warming up to 100～120 ℃;
2. add vulcabond again, continue promptly to get solution-type fluorochemical urethane material in 3～6 hours 100～120 ℃ of following polyreactions.This processing method can be described as " the solvent single stage method is arranged ".Perhaps two step of branch polyreactions in the presence of the solvent are being arranged, its step and condition are:
1. in being placed with the reactor of solvent, add PFPE dibasic alcohol or polycarbonate or polyether Glycols earlier and mix, and be warming up to 50～100 ℃;
2. add vulcabond, and 70～100 ℃ of following prepolymerization reactions 40～60 minutes;
3. add small molecules amine chainextender again, and be warming up to 100～130 ℃ of polyreactions 3～6 hours.
In above-mentioned preparation scheme no matter be single stage method or the two step method polyreaction that solvent is arranged, its used solvent is a mixed solvent when synthesizing PFPE urethane, be specially N, dinethylformamide, N, at least aly in the N-N,N-DIMETHYLACETAMIDE mix with the difluoro tetrachloroethane, its volume ratio is 1～3: 1, and it is 30～50% that usage quantity should make the solid content of product.When polycarbonate synthesis or polyether-polyurethane, the solvent of employing is N, and dinethylformamide is at least a in the N,N-dimethylacetamide, and it is 30～50% that usage quantity should make the product solid content.
Provide embodiment below being described in more detail the present invention, but it is worthy of note that the present invention is not limited to these embodiment.
Adopted following code name in an embodiment, hereby explanation.
FDOL=is the perfluoropolyethers dibasic alcohol 1., z=1, m/n=1/2.
FDOL EP=is the perfluoropolyethers dibasic alcohol 2., z=2, m/n=1/2.
FDOL C=is the perfluoropolyethers dibasic alcohol 3., wherein x=CF
3, r: s: t=2: 1: 1.
FDOL D=is the perfluoropolyethers dibasic alcohol 4., R=CH
2OH
FDOL E=is the perfluoropolyethers dibasic alcohol 5., R=CH
2OCH
2CH
2OH
FDOL F=is the perfluoropolyethers dibasic alcohol 6., R=CH
2OH
PTMG=PTMG dibasic alcohol.
PHC=gathers (1,6-hexylene glycol carbonic ether) dibasic alcohol.
Copolymerization carbonic ether dibasic alcohol, wherein R
1=contain the stable hydrocarbon of 6 carbon atoms, R
2=contain the stable hydrocarbon of 5 carbon atoms, x: y=3: 2.
MDI=4,4 '-ditan two different hydrogen acid ether HMDI=4,4 '-dicyclohexyl methane diisocyanate
HDI=1, hexamethylene-diisocyanate IPDI=isophorone diisocyanate
The TDI=tolylene diisocyanate (2,4-and 2, two kinds of isomer weight ratios of 6-are 20: 80)
DMF=N, dinethylformamide THF=tetrahydrofuran (THF)
DMAc=N, the N-N,N-DIMETHYLACETAMIDE
Embodiment one, two, five～eight, ten:
What this group embodiment adopted is " mixing the solvent-free two step method of macromole technology ".They are PFPE dibasic alcohol and polycarbonate or the polyether Glycols that add corresponding molecular weight in a reactor that agitator, thermometer, vacuum unit be housed, and fully mix, and the limit are warming up to relevant temperature, then the vacuum outgas certain hour; Add vulcabond and prepolymerization reaction certain hour after being cooled to relevant temperature; Add small molecule chain extender again, vigorous stirring, and the limit is warming up to relevant temperature polyreaction certain hour; At last reaction mixture is moved in the polytetrafluoroethyldisk disk of preheating, the slaking certain hour promptly gets the fluorochemical urethane material under relevant temperature.Concrete component kind, proportioning and processing condition see Table 1.
Embodiment three, nine:
What these two embodiment adopted is " mix macromole technology the solvent two step method is arranged ".Specifically be in a reactor that agitator, thermometer, reflux be housed, to add difluoro tetrachloroethane/DMAc (volume ratio 1: 2) 5000 grams (embodiment three) or 8000 grams (embodiment nine) respectively, the PFPE dibasic alcohol of corresponding molecular weight and PCDL or polyether Glycols, fully mix, and be warming up to relevant temperature; Add vulcabond prepolymerization reaction certain hour then, embodiment nine belongs to aliphatic diisocyanate because of the vulcabond that adds, so also added dibutyl tin laurate; Adding amine small molecule chain extender vigorous stirring and limit again is warming up to relevant temperature polyreaction certain hour and promptly gets the fluorochemical urethane material.Concrete component kind, proportioning and processing condition see Table 1.Recording embodiment three solid contents is 43%, and embodiment nine is 35%.
Embodiment four, 11:
What these two embodiment adopted is " mix macromole technology the solvent single stage method is arranged ".Specifically be PFPE dibasic alcohol, PCDL and the amine small molecule chain extender that in a reactor that agitator, thermometer, reflux be housed, adds difluoro tetrachloroethane/DMF (volume ratio 1: 3) 5000 grams (embodiment four) or 7000 grams (embodiment 11), corresponding molecular weight respectively, fully mix, and the limit is warming up to corresponding temperature; Add vulcabond again, continuation polyreaction certain hour under relevant temperature promptly gets the fluorochemical urethane material.Concrete component kind, proportioning and processing condition see Table 1.Recording embodiment four solid contents is 39%, and embodiment 11 solid contents are 31%.
Embodiment 12,13:
What these two embodiment adopted is " mixing macromole technology solventless one-step method ".Concrete also is the PFPE dibasic alcohol that adds corresponding molecular weight in a reactor that agitator, thermometer, vacuum unit be housed, PCDL or/and polyether Glycols, small molecule chain extender fully mix, and the limit is warming up to relevant temperature, then the vacuum outgas certain hour; Add the vulcabond vigorous stirring again, and be warming up to relevant temperature polyreaction certain hour and since embodiment 13 added be aliphatic diisocyanate, so also need add a certain amount of dibutyltin dilaurate catalyst; At last reaction mixture is moved in the polytetrafluoroethyldisk disk of preheating, the slaking certain hour promptly under relevant temperature.Concrete component kind, proportioning and processing condition see Table 1.
Comparative example one:
Add molecular weight and be 2000 PHPC2000 gram in a reactor that agitator, thermometer, vacuum unit be housed, the limit is warming up to 90 ℃, and the limit fully mixes, and vacuum outgas is 30 minutes then; Added MDI750 gram prepolymerization reaction after being cooled to 70 ℃ again 40 minutes; Add 1,4 again---butyleneglycol 180 gram vigorous stirring, and be warming up to 100 ℃ of reactions 15 minutes; At last reaction mixture is moved in the polytetrafluoroethyldisk disk of 100 ℃ of preheatings, slaking promptly got the polycarbonate polyurethane material in 4 hours under 100 ℃ of conditions.
Comparative example two:
This comparative example is except that changing component PHPC the PTMG into, and its component and proportioning thereof and processing step condition are not stated so omit with comparative example 1, gets the polyether(poly)urethane material at last.
Comparative example three:
Add mixed solvent 4000 grams of difluoro tetrachloroethane/DMF (volume ratio 1: 1) and molecular weight and be 2000 FDOL2000 in a reactor that agitator, thermometer, reflux condensing tube be housed and restrain, heated and stirred is all dissolved it and is warming up to 70 ℃; 750 gram MDI are added in the reaction system, and keep this temperature of reaction to reach about 8.4% theoretical value until the weight percentage of NCO; And then adding 1,4 of 180 grams---butyleneglycol, 100 ℃ of reactions promptly got PFPE polyurethane solution (solid content about 44%) in 4 hours.
Following examples are " blending technology ".
Embodiment 14,20:
These two embodiment prepare fluorochemical polyether urethane I and polycarbonate polyurethane or polyether-polyurethane II by " solvent-free two step method " processing step respectively earlier, and its processing condition and prescription see Table 2; Adopt cosolvent difluoro tetrachloroethane/THF (1: 3) 1330 gram dissolving blend respectively by corresponding proportioning then, or melt blending (processing condition see Table 2) promptly makes the fluorochemical urethane material on twin screw extruder.
Embodiment 15,18:
These two embodiment prepare fluorochemical polyether urethane I and polyether-polyurethane or polycarbonate polyurethane II by " solventless one-step method " processing step respectively earlier, and its processing condition and prescription see Table 2; On twin screw extruder, carry out melt blending respectively by corresponding proportioning then and promptly get the fluorochemical urethane material by the listed processing condition of table 2.
Embodiment 16,19:
These two embodiment prepare fluorochemical polyether urethane I (solvent difluoro tetrachloroethane/DMAc by " the solvent two step method is arranged " processing step respectively earlier, volume ratio 1: 1,3500 gram or difluoro tetrachloroethane/DMF, volume ratio 1: 1,4300 restrain) and polycarbonate polyurethane or polyether-polyurethane II (solvent DMAc2900 gram or DMF4400 gram), its prescription and processing condition see Table 2.Record solid content embodiment 16: I.50%, II.50%; Embodiment 19: I.40%, and II.38%.Then according to used prescription (dry weight) in the table 2 and above-mentioned solid content data, calculate actual required component I and component II, in component II, add the difluoro tetrachloroethane then, making difluoro tetrachloroethane/DMAc among the component II (embodiment 16) or difluoro tetrachloroethane/DMF (embodiment 19) reach volume ratio is 1: 1, under agitation condition that component I and II is fully mixed then, being diluted to solid content for embodiment 16 usefulness difluoro tetrachloroethane/DMAc (volume ratio 1: 2) at last is 30%, and perhaps being diluted to solid content for embodiment 19 usefulness difluoro tetrachloroethane/DMF (volume ratio 1: 2) is 10%.
Embodiment 17,21:
These two embodiment prepare fluorochemical polyether urethane I (solvent difluoro tetrachloroethane/DMF by " the solvent single stage method is arranged " processing step respectively earlier, volume ratio 1: 2,7400 gram or difluoro tetrachloroethane/DMAc, volume ratio 1: 3,12 kilograms) and polycarbonate polyurethane II (DMF10 kilogram or DMAc10 kilogram), its prescription and processing condition see Table 2.Recording solid content is: embodiment 17 I are 35%, and II is 34%; Embodiment 21 I are 32%, and II is 35%.Then according to used prescription (dry weight) in the table 2 and above-mentioned solid content data, calculate actual required component I and component II, in component II, add the difluoro tetrachloroethane then, make that difluoro tetrachloroethane/DMF volume ratio reaches 1: 2 (embodiment 17) among the component II, make perhaps that difluoro tetrachloro/DMAc volume ratio reaches 1: 3 among the component II, under agitation condition that component I and II is fully mixed then, be that to be diluted to solid content be 20% (embodiment 17) or be that to be diluted to solid content be 15% (embodiment 21) for difluoro tetrachloroethane/DMAc of 1: 3 with volume ratio for 1: 2 difluoro tetrachloroethane DMF with volume ratio at last.
In order to contrast the mechanical property and the ageing-resistant performance of simple polycarbonate polyurethane, polyether-polyurethane and PFPE urethane and fluorochemical urethane material of the present invention, the present invention partly material that embodiment obtains and material that comparative example obtains all to be mixed with solid content be 10% solution, make thick about 1 millimeter film then, make print with dumb-bell shape standard cutter, each 12 of every kind of materials.Wherein 4 be used for aging before Mechanics Performance Testings, 4 are immersed among the 0.1MNaAc/HAc (pH=3.3～3.5,37 ℃) hydrolysising aging and test its mechanical property after half a year, other 4 are immersed in 3%H
2O
2/ 0.1MCoCl
2Test (seeing Journal of Biomedical Mate-rials Research, Vol.29,467～475,1995) after aging half a year in (37 ℃) oxidizing medium.All aging mediums change weekly 2 times.The back sample that worn out was removed institute in dry 2 days at 60 ℃ of vacuum drying ovens and is absorbed water after part, tested on XLL-100 type tension testing machine.Test result sees Table 3 (data are the mean value of four tests in the table).
As can be seen from the table, polycarbonate polyurethane mechanics strength degradation under NaAc/HAc (pH=3.3～3.5) condition is very big, and the not hydrolysis (comparative example 1) under the acid resistance condition of this material is described.Polyether-polyurethane is at H
2O
2/ CoCl
2Mechanical properties decrease is also very big under the condition, and not resistance to oxidation (comparative example 2) of this material is described.Though and pure PFPE urethane has good biologically stable, mechanical strength is than the former much lower again (comparative example 3).Fluorochemical urethane material of the present invention not only itself has mechanical property preferably, and under acidic hydrolysis or oxidizing condition, mechanical property changes little, this material not only hydrolysis but also resistance to oxidation are described, has good biologically stable, therefore, the present invention introduces soft section of PFPE in the building-up process of polycarbonate polyurethane and polyether-polyurethane, make fluorine-containing soft section of gained material surface enrichment by courses of processing such as solution-cast or thermal treatments, improved biologically stable greatly, and its synthesis technique maturation, simple is easy to control, and implementation is strong.
Mechanical property relatively before and after table 3 embodiment and the comparative example gained material aging
The aging back of NaAc/HAc H before aging
2O
2/ CoCl
2Aging back material
Hot strength MPa elongation at break % hot strength MPa elongation at break % aging intensity MPa elongation at break % embodiment 1 42.3 230 42.3 300 42.1 300 embodiment 2 30.4 250 30.3 260 30.2 240 embodiment 3 55.4 300 55.5 300 55.4 310 embodiment 4 60.3 320 60.2 320 60.1 320 embodiment 5 37.4 570 37.1 580 37.2 570 embodiment 6 25.7 560 25.8 560 25.4 550 embodiment 12 45.2 350 45.1 350 45.0 370 comparative examples 1 45.7 310 20.5 430 39.1 300 comparative examples 2 37.5 580 35.8 580 15.4 300 comparative examples 3 12.4 800 12.5 800 12.4 800 embodiment 14 40.0 320 40.1 320 40.0 320 embodiment 15 33.8 600 33.7 600 33.9 600
Table 1 mixes macromolecular diol process implementing example proportioning and processing condition table look-up
(continuous table)
Table 2 blending technology embodiment proportioning and processing condition table look-up
(continuous table)
| Poly-(1,6-hexylene glycol-1,2-ethylene carbonate) glycol | ??1000 | ?1600 | |||||||||||||||
| MDI | ?1000 | ?1250 | ??1625 | ?2250 | ?1250 | ?750 | ??750 | ?750 | |||||||||
| HMDI | ?1310 | ??1310 | ?2620 | ?2358 | |||||||||||||
| TDI | ??696 | ?696 | |||||||||||||||
| IPDI | ?621.6 | ?621.6 | |||||||||||||||
| 1, the 4-butyleneglycol | ?180 | ?270 | ?360 | ?180 | |||||||||||||
| 1, the 6-hexylene glycol | ?472 | ??472 | |||||||||||||||
| 1, the 5-pentanediol | ??229 | ?208 | |||||||||||||||
| 1, the 3-propylene diamine | ??222 | ?222 | |||||||||||||||
| 1, the 5-pentamethylene diamine | ??561 | ?836.4 | |||||||||||||||
| Quadrol | ?120 | ?120 | |||||||||||||||
| 1, the 7-heptamethylene diamine | ?1040 | ?962 | |||||||||||||||
| Stannous octoate | ?0.66 | ??0.56 | |||||||||||||||
| Triethylenediamine | ?0.70 | ?0.94 | |||||||||||||||
| Dibutyl tin laurate | ?2.10 | ?1.72 |
(continuous table)
Claims (11)
1. fluorochemical urethane material, the soft segment that constitutes by PCDL, polyether Glycols and form by the rigid chain segment alternating copolymerization that vulcabond, small molecule chain extender constitute, its molecular weight is 25000～250000, it is characterized in that in soft segment, also containing the PFPE dibasic alcohol, and be enriched in material surface.
2. fluorochemical urethane material according to claim 1 is characterized in that the PFPE dibasic alcohol adopts the mixture with following any structure or its wantonly two kinds or three kinds structures:
1. HO CH
2 zCF
2O C
2F
4O
m CF
2O
nCF
2 CH
2 zOH is z=1 wherein, and 2, m/n=0.2～2 are preferably 0.5～1.2, and the concrete numerical value of m, n will make its molecular weight reach 500～3000;
2. HO CH
2CH
2O
zCH
2-CF
2O C
2F
4O
m CF
2O
nCH
2 OCH
2CH
2 zOH is z=1 wherein, and 2,3, m/n=0.2～2 are preferably 0.5～1.2, and the concrete numerical value of m, n will make its molecular weight reach 500～3000;
3. HOCH
2CF
2 C
3F
6O
r C
2F
4O
s CFXO
tCF
2CH
2OH is x=F or CF wherein
3, r, s, t are respectively 0～100, and r+s ≠ 0, and molecular weight will reach 500～3000 simultaneously;
④??????????????????RC
2F
4O
nR
⑤????????????????RCF
2CF
2CF
2O
nR
⑥????????????????RCFCF
3CF
2O
nR
4.～6. R=CH in
2OH or CH
2 OCH
2CH
2 zOH, z=1,2, the value of n makes its molecular weight reach 500～3000.
3. fluorochemical urethane material according to claim 1 and 2 is characterized in that PCDL can also have following structure:
R=R wherein
1Or R
2, R
1For containing the stable hydrocarbon of even number of carbon atoms, R
2For containing the stable hydrocarbon of odd number carbon atom, x/y=0.5～2, and the concrete numerical value of x, y will make its molecular weight reach 500～3000.
4. method for preparing above-mentioned fluorochemical urethane material is characterized in that the composition of raw materials (weight percent) that is adopted is:
PFPE dibasic alcohol 1～10%
Polycarbonate is or/and polyether Glycols 30～70%
Vulcabond 20～50%
Small molecule chain extender 3～25% its step of preparation process that adopt and condition are:
1. with PFPE dibasic alcohol, polycarbonate or/and polyether Glycols, small molecule chain extender join in the reactor and mix, and be warming up to 90～100 ℃, vacuum outgas is 30～60 minutes then;
2. again vulcabond is added polyreaction 5～20 minutes;
3. with reaction mixture 100～130 ℃ of following slakings 3～6 hours, or be:
1. earlier with the PFPE dibasic alcohol with polycarbonate or/and mix in the polyether Glycols adding reactor, and be warming up to 70～100 ℃, vacuum outgas is 30～60 minutes then;
2. be cooled to 60～70 ℃ and add down vulcabond, and prepolymerization reaction 20～60 minutes;
3. add small molecule chain extender again, and be warming up to 100～130 ℃ of polyreactions 5～20 minutes;
4. with reaction mixture 100～130 ℃ of following slakings 3～6 hours.
5. the method for preparing the fluorochemical urethane material according to claim 4, when it is characterized in that vulcabond is selected aliphatic diisocyanate for use, need to add amine or the tin class catalyzer of 200-400ppm, appropriate catalyst has stannous octoate, dibutyl tin laurate, triethylenediamine etc.
6. according to claim 4 or the 5 described methods that prepare the fluorochemical urethane material, when it is characterized in that small molecule chain extender is selected amine chain extender for use, need to carry out polyreaction in solvent, its processing step and condition are:
1. in being placed with the reactor of solvent, add PFPE dibasic alcohol, polycarbonate or/and polyether Glycols, small molecules amine chainextender mix, and be warming up to 100～120 ℃;
2. add vulcabond again, continue 100～120 ℃ of following polyreactions 3～6 hours, or be:
1. in being placed with the reactor of solvent, add earlier PFPE dibasic alcohol, polycarbonate or/and polyether Glycols mixes, and be warming up to 50～100 ℃;
2. add vulcabond, and 70～100 ℃ of following prepolymerization reactions 40～60 minutes;
3. add small molecules amine chainextender again, and be warming up to 100～130 ℃ of polyreactions 3～6 hours.
7. the method for preparing the fluorochemical urethane material according to claim 6, it is characterized in that used solvent is a mixed solvent, be specially N, dinethylformamide, N, at least aly in the N-N,N-DIMETHYLACETAMIDE mix with the difluoro tetrachloroethane, its volume ratio is 1～3: 1, and it is 30～50% that usage quantity should make the solid content of product.
8. method for preparing above-mentioned fluorochemical urethane material, it is characterized in that synthetic respectively earlier PFPE urethane and polycarbonate or polyether-polyurethane, and then its melt blending or cosolvent dissolving blend made the fluorochemical urethane material, its concrete prescription, processing step and condition are as follows:
The prescription (weight percent) of 1. synthetic PFPE urethane and polycarbonate or polyether-polyurethane is respectively:
A) the PFPE dibasic alcohol 30～70%
Vulcabond 20～55%
Small molecule chain extender 3～25%
B) polycarbonate or polyether Glycols 30～70%
Vulcabond 20～55%
Small molecule chain extender 3～25% its processing steps and condition are:
A) PFPE dibasic alcohol or polycarbonate or polyether Glycols and small molecule chain extender are joined mix in the reactor, and be warming up to 90～100 ℃, vacuum outgas is 30～60 minutes then;
B) again vulcabond is added polyreaction 5～20 minutes;
C) with reaction mixture 100～130 ℃ of following slakings 3～6 hours, or be:
A) earlier add PFPE dibasic alcohol or polycarbonate or polyether Glycols in the reactor and be warming up to 70～100 ℃, vacuum outgas is 30～60 minutes then;
B) add vulcabond down 60～70 ℃ of temperature, and prepolymerization reaction 20～60 minutes;
C) add small molecule chain extender again, and be warming up to 100～130 ℃ of polyreactions 5～20 minutes;
D) with reaction mixture 100～130 ℃ of following slakings 3～6 hours;
2. melt blending or the cosolvent dissolving blend prescription (weight percent) for preparing the fluorochemical urethane material is:
PFPE urethane 5～20%
Polycarbonate or polyether-polyurethane 80～95%
Its melt blending is to carry out on twin screw extruder, and the melt zone temperature is 180～200 ℃, and the extrusion neck ring mold temperature is 160～190 ℃, and 3～15 minutes melting mixing time, extruding pelletization gets the fluorochemical urethane pellet;
The cosolvent that cosolvent dissolving blend is adopted is difluoro tetrachloroethane/N, dinethylformamide or N, N-N,N-DIMETHYLACETAMIDE or tetrahydrofuran (THF), its volume ratio is 1: 1～3, and to make the PFPE urethane that joins in the solvent and the solid content of polycarbonate or polyether-polyurethane be 10～30%, after the stirring and dissolving earlier 60～80 ℃ of bakings 10～15 hours down, and then 80～100 ℃ of temperature, vacuum tightness 50～100mmHg dried by the fire 24～72 hours down, promptly got fluorochemical urethane film material.
9. the method for preparing the fluorochemical urethane material according to claim 8, when it is characterized in that vulcabond is selected aliphatic diisocyanate for use, need to add amine or the tin class catalyzer of 200～400ppm, appropriate catalyst has stannous octoate, dibutyl tin laurate, triethylenediamine etc.
10. according to Claim 8 or the 9 described methods that prepare the fluorochemical urethane material, when it is characterized in that small molecule chain extender is selected amine chain extender for use, need carry out polyreaction in solvent, its processing step and condition are:
1. in being placed with the reactor of solvent, add PFPE dibasic alcohol or PCDL or polyether Glycols and small molecules amine chainextender and mix, and be warming up to 100～120 ℃;
2. add vulcabond again, continue 100～120 ℃ of following polyreactions 3～6 hours, or be:
1. in being placed with the reactor of solvent, add PFPE dibasic alcohol or PCDL or polyether Glycols earlier and mix, and be warming up to 50～70 ℃;
2. add vulcabond, and 70～100 ℃ of following prepolymerization reactions 40～60 minutes;
3. add small molecules amine chainextender again, and be warming up to 100～130 ℃ of polyreactions 3～6 hours.
11. the method for preparing the fluorochemical urethane material according to claim 10, it is characterized in that used solvent is a mixed solvent when synthesizing PFPE urethane, be specially N, dinethylformamide, N, at least aly in the N-N,N-DIMETHYLACETAMIDE mix with the difluoro tetrachloroethane, its volume ratio is 1～3: 1, and it is 30～50% that usage quantity should make the solid content of product; When polycarbonate synthesis or polyether-polyurethane, solvent for use is N, at least a in dinethylformamide and the N,N-dimethylacetamide, and it is 30～50% that usage quantity should make the solid content of product.
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|---|---|---|---|
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