CN101173034B - Polyacrylamide polyurethane urea and method for producing the same - Google Patents
Polyacrylamide polyurethane urea and method for producing the same Download PDFInfo
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- CN101173034B CN101173034B CN200710181744.8A CN200710181744A CN101173034B CN 101173034 B CN101173034 B CN 101173034B CN 200710181744 A CN200710181744 A CN 200710181744A CN 101173034 B CN101173034 B CN 101173034B
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- polyurethane urea
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- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 19
- 229920003226 polyurethane urea Polymers 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title 1
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 210000000988 bone and bone Anatomy 0.000 claims abstract description 4
- 210000000845 cartilage Anatomy 0.000 claims abstract description 3
- 239000007822 coupling agent Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- -1 amino, hydroxyl Chemical group 0.000 claims description 19
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- NPSSWQJHYLDCNV-UHFFFAOYSA-N prop-2-enoic acid;hydrochloride Chemical compound Cl.OC(=O)C=C NPSSWQJHYLDCNV-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004472 Lysine Substances 0.000 claims description 3
- 150000001414 amino alcohols Chemical class 0.000 claims description 3
- 239000001273 butane Substances 0.000 claims description 3
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 238000001679 laser desorption electrospray ionisation Methods 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 3
- VPSSPAXIFBTOHY-LURJTMIESA-N (2s)-2-amino-4-methylpentan-1-ol Chemical compound CC(C)C[C@H](N)CO VPSSPAXIFBTOHY-LURJTMIESA-N 0.000 claims description 2
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- STVVMTBJNDTZBF-VIFPVBQESA-N L-phenylalaninol Chemical compound OC[C@@H](N)CC1=CC=CC=C1 STVVMTBJNDTZBF-VIFPVBQESA-N 0.000 claims description 2
- 125000004494 ethyl ester group Chemical group 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 230000008439 repair process Effects 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims 1
- AGPKZVBTJJNPAG-WHFBIAKZSA-N L-isoleucine Chemical compound CC[C@H](C)[C@H](N)C(O)=O AGPKZVBTJJNPAG-WHFBIAKZSA-N 0.000 claims 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims 1
- 235000013832 Valeriana officinalis Nutrition 0.000 claims 1
- 244000126014 Valeriana officinalis Species 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 125000005442 diisocyanate group Chemical group 0.000 claims 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims 1
- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 claims 1
- 229960000310 isoleucine Drugs 0.000 claims 1
- KPNBUPJZFJCCIQ-LURJTMIESA-N methyl L-lysinate Chemical compound COC(=O)[C@@H](N)CCCCN KPNBUPJZFJCCIQ-LURJTMIESA-N 0.000 claims 1
- 235000016788 valerian Nutrition 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004202 carbamide Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 36
- 239000007787 solid Substances 0.000 description 28
- 238000009413 insulation Methods 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 238000010792 warming Methods 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 11
- 238000004821 distillation Methods 0.000 description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 7
- 239000004160 Ammonium persulphate Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 7
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 7
- 238000013019 agitation Methods 0.000 description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 7
- 235000019395 ammonium persulphate Nutrition 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000004900 laundering Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000001953 recrystallisation Methods 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 210000001519 tissue Anatomy 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- IOGKLTAKFFMNQR-UHFFFAOYSA-N n-(2-aminopropyl)prop-2-enamide Chemical compound CC(N)CNC(=O)C=C IOGKLTAKFFMNQR-UHFFFAOYSA-N 0.000 description 3
- HXJGFDIZSMWOGY-UHFFFAOYSA-N n-(2-azaniumylethyl)prop-2-enimidate Chemical compound NCCNC(=O)C=C HXJGFDIZSMWOGY-UHFFFAOYSA-N 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- 206010002198 Anaphylactic reaction Diseases 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000036783 anaphylactic response Effects 0.000 description 1
- 208000003455 anaphylaxis Diseases 0.000 description 1
- 230000010100 anticoagulation Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000000747 cardiac effect Effects 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N dimethylbutene Natural products CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- YBWQZBVPWXXJKQ-UHFFFAOYSA-N n-(4-hydroxybutyl)prop-2-enamide Chemical compound OCCCCNC(=O)C=C YBWQZBVPWXXJKQ-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000017074 necrotic cell death Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- SESSOVUNEZQNBV-UHFFFAOYSA-M sodium;2-bromoacetate Chemical compound [Na+].[O-]C(=O)CBr SESSOVUNEZQNBV-UHFFFAOYSA-M 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
Abstract
The invention discloses polyacrylamide/urea with netted texture and a preparation method and use thereof. The polymer with netted texture is formed by connecting the polyacrylamide with a linear structure and the ramification by using aliphatics diisocyanate as coupling agent and has good biocompatibility and mechanical property, and the invention can be used for preparing the bracket material of repairing damaged bone or cartilage tissue project.
Description
Technical field
The invention belongs to the preparing technical field of high-molecular biologic medical engineering material, be specifically related to a kind of Biodegradable reticular structure polyacrylamide polyurethane urea with biocompatibility.
Background technology
The application of biodegradable synthetic polymer in medical tissue engineering compared with other materials, and its outstanding advantage is to regulate mechanical property, size shape and aperture, degradation property according to application need.In addition, polymkeric substance can be designed to have the chemical functional group, but the for example induced tissue cell growth or be used for making polymkeric substance to be suitable for required application of these functional groups.The modal synthetic polymer that is used to make grown cell support and biodegradable inner support is a polyester; For example POLYACTIC ACID, Sodium bromoacetate homopolymer, SRU, polylactide and multipolymer thereof etc. are because its relatively easily degraded and degraded product absorbed in the body again under hydrolysising condition.Yet these polymkeric substance have a lot of shortcomings, comprise that the low acidity of losing mechanical property, processing difficulties and degraded product in vivo fast that reaches of mechanical property intensity causes inflammation and tissue necrosis etc.Urethane (PU) has excellent physical and mechanical performance and excellent biological compatibility and degradability; Be widely used in and made various medical equipments; And in many artificial organs and tissue repair, play an important role, such as interposing catheter, artificial cardiac pacemaker and TAH, bone tissue engineering stent material etc.Urethane is compared with other as bio-medical material, has following outstanding advantage: excellent biological compatibility, no aberration inducing effect, no anaphylaxis; Good anticoagulation function; The physical and mechanical properties wide ranges, the hardness of material and intensity can be regulated as required; Has good toughness and elasticity, good processability; Have excellent abrasive, soft sense of touch, wet fastness, the medicine of anti-number of chemical performance; Can adopt usual method sterilization, it is constant etc. to be exposed under the gamma-rays performance.Therefore, through having become a present research focus with the urethane that obtains property to polyurethane-modified.There are some researches show, at surface grafting polyoxyethylene glycol, the SEPIGEL 305 (PMMA) of polyurethane material, gather (2-hydroxyethyl methyl acrylate), can significantly improve their blood compatibility.
The present invention is coupling agent with the vulcabond, prepares a kind of Biodegradable reticular structure polyacrylamide polyurethane urea with biocompatibility, can in medical tissue engineering, be applied.
Summary of the invention
The polyacrylamide polyurethane urea that the purpose of this invention is to provide a kind of novel inierpeneirating network structure.
The polyacrylamide polyurethane urea structure of inventing following graphic shown in:
Wherein: R
1Being straight or branched alkane, the aromatic hydrocarbons of 2～6 carbon, can be identical, also can be different; R
2From isocyanic ester, be aliphatics alkane or naphthenic hydrocarbon, can be identical, also can be different.
Preparing method's key step is following:
(1) by acrylate chloride and diamines or amino alcohol reaction generation acrylamide deriv monomer;
(2) in the presence of chain initiator, the acrylamide deriv monomer carries out polymerization, generates polyacrylamide derivative;
(3) the adding vulcabond is crosslinked, generates cancellated polyacrylamide polyurethane urea.
Advantage of the present invention and positively effect: reticulated structure polyurethane/urea polymkeric substance of the present invention; Have the characteristics of SEPIGEL 305 and polyurethane/urea concurrently; The good mechanical performance is arranged; Have excellent biological compatibility and biodegradability; Degraded product is nonacid being absorbed or the nontoxic small molecules of excretory, and the advantage of this method is to change polyacrylamide monomer and linking agent kind, consumption according to different needs, thereby synthesizes the high molecular polymer with different mechanical properties and degradation property.The preparation method is simple, for preparation be applied to repair damaged bone or cartilage tissue engineered in timbering material one type of new artificial-synthetic copolymer is provided.
Embodiment
Embodiment 1:
(1) in the 100mL there-necked flask, add 1,2-tn 8.2g (0.11mol), 20mL zero(ppm) water connects whipping appts, places low temperature thermostat bath.After treating that temperature drops to-5 ℃, and slow simultaneously dropping acrylate chloride 9.0g (0.1mol) of beginning and 16mL aqueous sodium hydroxide solution (25%, w/w).Temperature is controlled in 0～5 ℃ in the dropping process, keeps the pH value 8～9.After dropwising, continue stir about 30min, slowly rise to room temperature reaction 2h, be warming up to 50 ℃ then and continue reaction 2h, stopped reaction.It is unreacted 1 that underpressure distillation goes out, and 2-tn and water obtain pale brown look thick liquid.Add absolute ethyl alcohol 50mL, stirring and dissolving, solids removed by filtration sodium-chlor.Filtrating boils off absolute ethyl alcohol, obtains N-(2-aminopropyl)-thick product of acrylic amide.Use acetic acid ethyl dissolution, place refrigerator and cooled to freeze recrystallization and go out white solid.Filter, vacuum-drying gets N-(2-aminopropyl)-acrylic amide 9.7g.
(2) 25.6g (0.2mol) N-(2-aminopropyl)-acrylic amide is joined in the 250mL there-necked flask adding distil water 100mL.Join in the there-necked flask after the 0.2g ammonium persulphate is dissolved in a small amount of zero(ppm) water.There-necked flask is placed thermostat water bath, connect reaction unit, logical nitrogen excluding air under agitation slowly is warming up to 60 ℃, insulation reaction 2h.Isophorone diisocyanate (IPDI) 11.2g (0.05mol) is placed constant pressure funnel, in 30min, drip, have a large amount of solids to separate out in the solution.Continue insulation reaction 6 h, stopped reaction.Suction filtration is washed with massive laundering, washs after drying with small amount of ethanol again, obtains white granular solid IPDI cross-linked N-(2-aminopropyl)-acrylic amide 34.0g.
Embodiment 2:
(1) in the 100mL there-necked flask, add quadrol 6.6g (0.11mol), the 30mL THF connects whipping appts, puts into low temperature thermostat bath.After treating that temperature drops to-5 ℃, and slow simultaneously adding acrylate chloride 9.0g (0.1mol) of beginning and 16mL aqueous sodium hydroxide solution (25%, w/w).Temperature all is controlled at below 0 ℃ in the dropping process, keeps the pH value 8～9.After dropwising, continue stir about 30min, slowly rise to room temperature reaction 2h, be warming up to 40 ℃ then and continue reaction 1h, stopped reaction.Underpressure distillation goes out unreacted quadrol, THF and water, obtains little yellow thick liquid.Add absolute ethyl alcohol 50mL, stirring and dissolving, solids removed by filtration sodium-chlor.Filtrating boils off absolute ethyl alcohol, obtains N-(2-amino-ethyl)-thick product of acrylic amide.Use acetic acid ethyl dissolution, place refrigerator and cooled to freeze recrystallization and go out white solid.Filter, vacuum-drying gets N-(2-amino-ethyl)-acrylic amide 9.5g.
(2) 22.8g (0.2mol) N-(2-amino-ethyl)-acrylic amide is joined in the 250mL there-necked flask adding distil water 100mL.Join in the there-necked flask after the 0.2g ammonium persulphate is dissolved in a small amount of zero(ppm) water.There-necked flask is placed thermostat water bath, connect reaction unit, logical nitrogen excluding air under agitation slowly is warming up to 60 ℃, insulation reaction 2h.Isophorone diisocyanate (IPDI) 11.2g (0.025mol) and hexamethylene diisocyanate (HDI) 3.4g (0.025mol) are placed constant pressure funnel, in 30min, drip, have a large amount of solids to separate out in the solution.Continue insulation reaction 6h, stopped reaction.Suction filtration is washed with massive laundering, washs after drying with small amount of ethanol again, obtains white granular solid IPDI and HDI cross-linked N-(2-amino-ethyl)-acrylic amide 35.0g.
Embodiment 3:
(1) in the 250mL there-necked flask, add 1,6-hexanediamine 24.4g (0.21mol), 50mL zero(ppm) water connects whipping appts, places low temperature thermostat bath.After treating that temperature drops to-5 ℃, and slow simultaneously dropping acrylate chloride 18.0g (0.2mol) of beginning and 30mL aqueous sodium hydroxide solution (25%, w/w).Temperature is controlled in 0～5 ℃ in the dropping process, keeps the pH value 8～9.After dropwising, continue stir about 30min, slowly rise to room temperature reaction 2h, be warming up to 50 ℃ then and continue reaction 2h, stopped reaction.Underpressure distillation goes out unreacted reactant and water, obtains pale brown look thick liquid.Add absolute ethyl alcohol 50mL, stirring and dissolving, solids removed by filtration sodium-chlor.Filtrating boils off absolute ethyl alcohol, obtains N-(the amino hexyl of 6-)-thick product of acrylic amide.Use acetic acid ethyl dissolution, place refrigerator and cooled to freeze recrystallization and go out white solid.Filter, vacuum-drying gets N-(the amino hexyl of 6-)-acrylic amide 29.0g.
(2) 34.0g (0.2mol) N-(the amino hexyl of 6-)-acrylic amide is added in the 250mL there-necked flask adding distil water 100mL.Join in the there-necked flask after the 0.2g ammonium persulphate is dissolved in a small amount of zero(ppm) water.There-necked flask is placed thermostat water bath, connect reaction unit, logical nitrogen excluding air under agitation slowly is warming up to 70 ℃, insulation reaction 2h.Isophorone diisocyanate (IPDI) 11.2g (0.025mol) is placed constant pressure funnel, in 30min, drip, have a large amount of solids to separate out in the solution.Continue insulation reaction 4h, stopped reaction.Suction filtration is washed with massive laundering, washs after drying with small amount of ethanol again, obtains white granular solid IPDI cross-linked N-(the amino hexyl of 6-)-acrylic amide 33.5g.
Embodiment 4:
(1) in the 250mL there-necked flask, add 4-amino butanol 18.7g (0.21mol), 50mL zero(ppm) water connects whipping appts, places low temperature thermostat bath.After treating that temperature drops to-5 ℃, and slow simultaneously dropping acrylate chloride 18.0g (0.2mol) of beginning and 30mL aqueous sodium hydroxide solution (25%, w/w).Temperature is controlled in 0～5 ℃ in the dropping process, keeps the pH value 8～9.After dropwising, continue stir about 30min, slowly rise to room temperature reaction 2h, be warming up to 50 ℃ then and continue reaction 2h, stopped reaction.Underpressure distillation goes out unreacted reactant and water, obtains pale brown look thick liquid.Add absolute ethyl alcohol 50mL, stirring and dissolving, solids removed by filtration sodium-chlor.Filtrating boils off absolute ethyl alcohol, obtains N-(4-hydroxybutyl)-acrylic amide and the thick product of the amino butyl ester mixture of a small amount of vinylformic acid 4-.Use acetic acid ethyl dissolution, place refrigerator and cooled to freeze recrystallization and go out white solid.Filter, vacuum-drying gets smart product 24.0g.
(2) 28.6g (0.2mol) N-(4-the hydroxybutyl)-acrylic amide that will go up method preparation joins in the 250mL there-necked flask adding distil water 100mL with the amino butyl ester mixture of a small amount of vinylformic acid 4-.Join in the there-necked flask after the 0.2g ammonium persulphate is dissolved in a small amount of zero(ppm) water.There-necked flask is placed thermostat water bath, connect reaction unit, logical nitrogen excluding air under agitation slowly is warming up to 80 ℃, insulation reaction 2h.With 4,4 '-vulcabond dicyclohexyl methyl hydride (H
12MDI) 13.1g (0.05mol) places constant pressure funnel, in 30min, drips, and has a large amount of solids to separate out in the solution.Continue insulation reaction 4h, stopped reaction.Suction filtration is washed with massive laundering, washs after drying with small amount of ethanol again, obtains white granular solid 4,4 '-vulcabond dicyclohexyl methyl hydride (H
12MDI) the amino butyl ester multipolymer of cross-linked N-(4-hydroxybutyl)-acrylic amide-ROHM 4-40.0g.
Embodiment 5:
(1) in the 250mL there-necked flask, add L-leucinol 24.6g (0.21mol), 50mL zero(ppm) water connects whipping appts, places low temperature thermostat bath.After treating that temperature drops to-5 ℃, and slow simultaneously dropping acrylate chloride 18.0g (0.2mol) of beginning and 30mL aqueous sodium hydroxide solution (25%, w/w).Temperature is controlled in 0～5 ℃ in the dropping process, keeps the pH value 8～9.After dropwising, continue stir about 30min, slowly rise to room temperature reaction 2h, be warming up to 60 ℃ then and continue reaction 2h, stopped reaction.Underpressure distillation goes out unreacted reactant and water.Add absolute ethyl alcohol 50mL, stirring and dissolving, solids removed by filtration sodium-chlor.Filtrating boils off absolute ethyl alcohol, obtains N-(4-methyl isophthalic acid-hydroxyl-2-amyl group)-acrylic amide and a small amount of vinylformic acid 2-amino-thick product of 4-methyl-1-pentene alcohol ester mixture.Use acetic acid ethyl dissolution, place refrigerator and cooled to freeze recrystallization and go out white solid.Filter, vacuum-drying gets smart product 29.5g.
(2) 34.2g (0.2mol) N-(4-methyl isophthalic acid-hydroxyl-2-the amyl group)-acrylic amide that will go up method preparation joins in the 250mL there-necked flask adding distil water 100mL with a small amount of vinylformic acid 2-amino-4-methyl-1-pentene alcohol ester mixture.Join in the there-necked flask after the 0.2g ammonium persulphate is dissolved in a small amount of zero(ppm) water.There-necked flask is placed thermostat water bath, connect reaction unit, logical nitrogen excluding air under agitation slowly is warming up to 80 ℃, insulation reaction 2h.11.3g (0.05mol) L-ethyl ester of lysine vulcabond (ELDI) is placed constant pressure funnel, in 30min, drip, have a large amount of solids to separate out in the solution.Continue insulation reaction 4h, stopped reaction.Suction filtration; Wash with massive laundering; Wash after drying with small amount of ethanol again, obtain white solid ethyl ester of lysine vulcabond (ELDI) cross-linked N-(4-methyl isophthalic acid-hydroxyl-2-amyl group)-acrylic amide-ROHM 2-amino-4-methyl-1-pentene alcohol ester copolymer 40.5g.
Embodiment 6:
(1) in the 250mL there-necked flask, add 1,6-hexanediamine 17.4g (0.15mol) and L-phenylalaninol 7.55g (0.05mol), 50mL zero(ppm) water connects whipping appts, places low temperature thermostat bath.After treating that temperature drops to-5 ℃, and slow simultaneously dropping acrylate chloride 18.0g (0.2mol) of beginning and 30mL aqueous sodium hydroxide solution (25%, w/w).Temperature is controlled in 0～5 ℃ in the dropping process, keeps the pH value 8～9.After dropwising, continue stir about 30min, slowly rise to room temperature reaction 2h, be warming up to 50 ℃ then and continue reaction 2h, stopped reaction.Underpressure distillation goes out unreacted reactant and water, obtains pale brown look thick liquid.Add absolute ethyl alcohol 50mL, stirring and dissolving, solids removed by filtration sodium-chlor.Filtrating boils off absolute ethyl alcohol, obtains N-(the amino hexyl of 6-)-acrylic amide and N-(3-hydroxyl-2-hydrocinnamyl)-acrylic amide, a small amount of thick product of vinylformic acid L-phenylalaninol ester mixture.Use acetic acid ethyl dissolution, place refrigerator and cooled to freeze recrystallization and go out white solid.Filter, vacuum-drying gets smart product 30.5g.
(2) above-mentioned purified 30.5g N-(the amino hexyl of 6-)-acrylic amide and N-(3-hydroxyl-2-hydrocinnamyl)-acrylic amide, a small amount of vinylformic acid L-phenylalaninol ester mixture are joined in the 250mL there-necked flask adding distil water 100mL.Join in the there-necked flask after the 0.2g ammonium persulphate is dissolved in a small amount of zero(ppm) water.There-necked flask is placed thermostat water bath, connect reaction unit, logical nitrogen excluding air under agitation slowly is warming up to 80 ℃, insulation reaction 2h.7.0g (0.05mol) butane vulcabond (BDI) is placed constant pressure funnel, in 30min, drip, have a large amount of solids to separate out in the solution.Continue insulation reaction 4h, stopped reaction.Suction filtration; Wash with massive laundering; Wash after drying with small amount of ethanol again, obtain white solid butane vulcabond (BDI) crosslinked gather N-(6-amino hexyl)-acrylic amide-gather N-(3-hydroxyl-2-hydrocinnamyl)-acrylic amide-ROHM L-phenylalaninol ester copolymer 33.5g.
Embodiment 7:
(1) 16.75mL (0.25mol) glycol chlorohydrin is joined in the 100mL there-necked flask, will join in the there-necked flask by the NaOH solution (about 4mol/L) that 5.0gNaOH and 30ml water are made into again, connect spherical condensation tube, load onto the machine whisking appliance.At bath temperature is under 30 ℃, stirs about 0.5h, drips quadrol 17mL (0.255mol) then, is warmed up to 60 ℃ after dripping, insulation reaction 14h.After having reacted, remove unreacted reactant and water with the underpressure distillation of rotary distillation appearance.In product, add absolute ethyl alcohol, remove by filter NaCl.Ethanol is removed in underpressure distillation again, remaining yellow oily liquid.
(2) in the 250mL there-necked flask, add the N-hydroxyethyl-ethylenediamine (H that method prepares
2NCH
2CH
2NHCH
2CH
2OH) 20.80g (0.20mol), 50mL zero(ppm) water connects whipping appts, places low temperature thermostat bath.After treating that temperature drops to-5 ℃, and slow simultaneously dropping acrylate chloride 18.0g (0.20mol) of beginning and 16mL aqueous sodium hydroxide solution (25%, w/w).Temperature is controlled in 0～5 ℃ in the dropping process, keeps the pH value 8～9.After dropwising, continue stir about 30min, slowly rise to room temperature reaction 2h, be warming up to 50 ℃ then and continue reaction 2h, stopped reaction.It is unreacted 1 that underpressure distillation goes out, and 2-tn and water obtain pale brown look thick liquid.Add absolute ethyl alcohol 50mL, stirring and dissolving, solids removed by filtration sodium-chlor.Filtrating boils off absolute ethyl alcohol, obtains acrylic amide
and a small amount of propenoate
thick product of mixture of N-hydroxyethyl-ethylenediamine.Use acetic acid ethyl dissolution, place refrigerator and cooled to freeze recrystallization and go out white solid.Filter, vacuum-drying gets smart product 27.5g.
(3) acrylic amide with aforesaid method purified 31.6g (0.20mol) N-hydroxyethyl-ethylenediamine joins in the 250mL there-necked flask adding distil water 100mL with a small amount of propenoate mixture.Join in the there-necked flask after the 0.2g ammonium persulphate is dissolved in a small amount of zero(ppm) water.There-necked flask is placed thermostat water bath, connect reaction unit, logical nitrogen excluding air under agitation slowly is warming up to 80 ℃, insulation reaction 2h.Isophorone diisocyanate (IPDI) 8.96g (0.04mol) is placed constant pressure funnel, in 30min, drip, have a large amount of solids to separate out in the solution.Continue insulation reaction 4h, stopped reaction.Suction filtration is washed with massive laundering, washs after drying with small amount of ethanol again, obtains the crosslinked SEPIGEL 305 of white solid isophorone diisocyanate (IPDI)-acrylate copolymer 36.5g.
Claims (4)
1. reticulated structure polyacrylamide polyurethane urea; It is characterized in that with the aliphatic diisocyanate being that the polyacrylamide derivative that coupling agent will contain the linear structure of amino, hydroxyl reactive functional group is connected into the biodegradable superpolymer of reticulated structure, its structure is:
Wherein: R
1Being straight or branched alkane, the aromatic hydrocarbons of 2～6 carbon, can be identical, also can be different; R
2From isocyanic ester, be aliphatics alkane or naphthenic hydrocarbon, can be identical, also can be different;
Wherein said polyacrylamide derivative has following two kinds of substructions:
Wherein: R
1Being straight or branched alkane, the aromatic hydrocarbons of 2～6 carbon, can be identical, also can be different.
2. reticulated structure polyacrylamide polyurethane urea as claimed in claim 1 is characterized in that:
(1) wherein said isocyanic ester is an aliphatic diisocyanate, is isophorone diisocyanate (IPDI) hexamethylene diisocyanate (HDI), butane vulcabond (BDI), 4,4 '-vulcabond dicyclohexyl methyl hydride (H
12MDI), ethyl ester of lysine vulcabond (ELDI) and lysine methyl ester vulcabond (MLDI);
(2) wherein said polyacrylamide derivative has following two kinds of substructions:
Wherein: R
1Being straight or branched alkane, the aromatic hydrocarbons of 2～6 carbon, can be identical, also can be different;
(3) wherein said polyacrylamide derivative is homopolymer or multipolymer;
(4) used vulcabond is single vulcabond or two kinds and above different mixtures of diisocyanates.
3. the preparation method of the described polyacrylamide derivative of claim 2 is characterized in that: aliphatie diamine, amino alcohol and the acrylate chloride by 1～6 carbon reacts generation under sodium hydroxide catalysis earlier, and used aliphatie diamine is a quadrol; Tetramethylenediamine; Hexanediamine, 1, the 2-tn; Amino alcohol is a monoethanolamine, 4-amino butanol, Propanolamine, L-phenylalaninol, L-leucinol, isoleucine alcohol, valerian ammonia alcohol.
4. the purposes of the described reticulated structure polyacrylamide polyurethane urea of claim 1 is characterized in that: as preparation repair damaged bone and cartilage tissue engineered in support.
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| 郝冈岭.二异氰酸酯与二元醇反应化学.《皮革化工》.1994,(第2期),p38-42和p11. * |
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