CN1033169C - Polyurethane polymer metal super-fine microparticle composite material and preparation method thereof - Google Patents
Polyurethane polymer metal super-fine microparticle composite material and preparation method thereof Download PDFInfo
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- CN1033169C CN1033169C CN93111576.0A CN93111576A CN1033169C CN 1033169 C CN1033169 C CN 1033169C CN 93111576 A CN93111576 A CN 93111576A CN 1033169 C CN1033169 C CN 1033169C
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 66
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 66
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 60
- 239000002184 metal Substances 0.000 title claims abstract description 60
- 229920000642 polymer Polymers 0.000 title claims abstract description 58
- 239000011859 microparticle Substances 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 14
- 125000000524 functional group Chemical group 0.000 claims abstract description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 229920000554 ionomer Polymers 0.000 claims description 12
- 230000002829 reductive effect Effects 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 11
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 8
- 229920000768 polyamine Polymers 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910001510 metal chloride Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 150000001455 metallic ions Chemical class 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 150000001735 carboxylic acids Chemical group 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 8
- 230000002776 aggregation Effects 0.000 abstract 1
- 238000004220 aggregation Methods 0.000 abstract 1
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 150000004696 coordination complex Chemical class 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 23
- 229920003224 poly(trimethylene oxide) Polymers 0.000 description 18
- 239000004970 Chain extender Substances 0.000 description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- -1 poly(propylene oxide) Polymers 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- DBXBTMSZEOQQDU-UHFFFAOYSA-N 3-hydroxyisobutyric acid Chemical compound OCC(C)C(O)=O DBXBTMSZEOQQDU-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 101100202428 Neopyropia yezoensis atps gene Proteins 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- ANJPRQPHZGHVQB-UHFFFAOYSA-N hexyl isocyanate Chemical class CCCCCCN=C=O ANJPRQPHZGHVQB-UHFFFAOYSA-N 0.000 description 3
- QVPWDPDVDVVXIB-UHFFFAOYSA-N n-(2-hydroxyethyl)pyridine-4-carboxamide Chemical compound OCCNC(=O)C1=CC=NC=C1 QVPWDPDVDVVXIB-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- QDDZXPJEJCHUGE-UHFFFAOYSA-N 2,3-dihydroxypropane-1-sulfonic acid;sodium Chemical compound [Na].OCC(O)CS(O)(=O)=O QDDZXPJEJCHUGE-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- YDNLNVZZTACNJX-UHFFFAOYSA-N isocyanatomethylbenzene Chemical compound O=C=NCC1=CC=CC=C1 YDNLNVZZTACNJX-UHFFFAOYSA-N 0.000 description 2
- XYUOTGCKNKRHHX-UHFFFAOYSA-N isocyanatooxybenzene Chemical compound O=C=NOC1=CC=CC=C1 XYUOTGCKNKRHHX-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920003225 polyurethane elastomer Polymers 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 229960003080 taurine Drugs 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- YPFUJZAAZJXMIP-UHFFFAOYSA-N 3-sulfopropanediol Chemical group OCC(O)CS(O)(=O)=O YPFUJZAAZJXMIP-UHFFFAOYSA-N 0.000 description 1
- 241000345998 Calamus manan Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000012675 alcoholic extract Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000015927 pasta Nutrition 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 235000012950 rattan cane Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/83—Chemically modified polymers
- C08G18/838—Chemically modified polymers by compounds containing heteroatoms other than oxygen, halogens, nitrogen, sulfur, phosphorus or silicon
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention relates to a polyurethane polymer metal superfine microparticle composite material. Polyurethane polymer which has a polyphase structure and functional groups capable of the coordination or action with metal ions is used as macromolecular complex to form a multiphase polyurethane polymer metal complex (or non-polymer) with the metal ions, and the metal ions are restored into zero valent metal in domains by reducing agents to obtain polyurethane polymer metal superfine microparticle composite material. The composite material of the present invention has the advantages of difficult aggregation of metal superfine microparticles, easy control of particle diameters of particles, difficult oxidation of surfaces and even dispersion of particles in the polymer.
Description
The present invention relates to metal super-fine microparticle and technical field of polymer, specifically, is to belong to a kind of polymer metal super-fine microparticle composite material.
At present, though metal super-fine microparticle has different method for makings, as the pasta method of evaporation (referring to the numerous tree of eight paddy " chemistry is always said ", 1984,48), vacuum vapor deposition method (referring to: grand " chemistry is always said " 1985 in Xiao Gong mountain, 48), chemical gas phase sink the filter method (referring to: add the clear husband of rattan " Surface Science " 1987,18 (5), 20) the metallo-organic complex hydrolysis method is (referring to K.Haneda etc. " IEEE Trans On Magns ", 1987,23 (5), 3134) and alkoxide hydrolysis (referring to Jing Xiaoyan etc. " Chinese rare-earth journal " 1989,7 (2), 47) but mostly there is the preparation difficulty, shortcomings such as particle is assembled easily, and particle diameter is wayward, and the metallic surface is easily oxidized.Polymer metal super-fine microparticle composite material generally also is to make metal super-fine microparticle earlier, and then adds in the polymkeric substance.Zhi Bei polymer metal super-fine microparticle composite material metal super-fine microparticle disperses inhomogeneously in polymkeric substance in this way, and not reaching to have performance and effect.
The purpose of this invention is to provide that a kind of metal super-fine microparticle particle diameter is controlled easily, the surface is difficult for oxidized, metal super-fine microparticle is finely dispersed polyurethane polymer metal super-fine microparticle composite material in polyurethane polymer, and a kind of simple and convenient preparation method is provided.
Polyurethane polymer metal super-fine microparticle composite material of the present invention be utilize have heterogeneous structure, contain and can be macromolecular ligand with the polyurethane polymer of metallic ion coordination or effect functional group, form heterogeneous polyurethanes metal complexes (or ionomer) with metal ion, with reductive agent metal ion branch farmland is reduced into zero-valent metal and polyurethane polymer metal super-fine microparticle composite material.
Polyurethane polymer among the present invention can be a carboxylic acid type urethane, sulfonic acid type urethane, pyridine type urethane or Polyamine Type urethane, they are by isocyanic ester, soft section oligomer, the polyurethane polymer with heterogeneous structure of chainextender preparation, the carboxyl on the urethane section (hard section) wherein, sulfonic group, functional group such as pyridyl or amino can form ion pair or title complex with metal ion, soft section existence, make them form metal ion and assemble microdomain, it is (hard to regulate the polyurethane polymer matrix, soft section) composition, the kind of ratio and metal ion and content, metal ion be can control effectively and the form and the size of microdomain assembled, use reductive agent, metal ion branch farmland is reduced into zero-valent metal, promptly gets polyurethane polymer metal super-fine microparticle composite material.Since zero-valent metal be macromolecular chain separate and the microdomain that coats in, so neither can assemble, be difficult for oxidizedly again, and in polymkeric substance, be uniformly dispersed.
The isocyanic ester of preparation polyurethane polymer can be 4,4 '-two isocyanato ditanes, 2,4-two isocyanato toluene, 4,4 '-two isocyanato phenyl ether or 1,6-two isocyanato hexanes, soft section oligomer can be polytetrahydrofuran, polyethylene oxide, poly(propylene oxide), polydimethylsiloxane or with the end capped polyester of alcoholic extract hydroxyl group.When chainextender is 2, during 2-two (methylol) propionic acid, what obtain is carboxylic acid type urethane, chainextender is 2,3-dihydroxyl propanesulfonic acid or N, N-two (hydroxyethyl) taurine, obtain sulfonic acid type urethane, chainextender is N, and N-two (hydroxyethyl) Isonicotinamide then obtains pyridine type urethane.
Polyamine Type urethane can be with above-mentioned isocyanic ester, above-mentioned soft section oligomer and N, N-dihydroxy ethyl-2, and 4-dinitraniline reactive polymeric becomes amino to make nitroreduction then.
In addition, polyurethane polymer also can directly be prepared by polyurethane elastomer: handle polyurethane elastomer with highly basic (as sodium hydride), making wherein, part＞NH group is transformed into＞N
-, make itself and γ-propane sultone reaction promptly obtain sulfonic acid type urethane then; Perhaps make and 2, the 4-DNCB reaction becomes amino with nitroreduction again, then obtains Polyamine Type urethane.
Its metal of polyurethane polymer metal super-fine microparticle composite material of the present invention can be silver, iron, cobalt, nickel, zinc, copper etc.
Polyurethane polymer metal super-fine microparticle composite material of the present invention can prepare with following method:
The metal chloride or the acetate of stoichiometric quantity are dissolved in solvent, as dimethyl formamide, be added to then in the solution of polyurethane polymer macromolecular ligand, heating, obtain the metal complexes (or ionomer) of polyurethane polymer, become zero-valent metal with reductive agent reducing metal ion, promptly obtain polyurethane polymer metal super-fine microparticle composite material.
With metal complexes (or ionomer) reduction of polyurethane polymer, can use hydrazine hydrate, sodium borohydride (NaBH
4) or reductive agent such as hydrogen.
In addition, also can earlier the metal complexes (or ionomer) of polyurethane polymer be made film, with sodium borohydride or hydrogen reducing, make polyurethane polymer metal super-fine microparticle composite material of the present invention then.
Its advantage of polyurethane polymer metal super-fine microparticle composite material of the present invention is that the particle diameter of metal super-fine microparticle is controlled easily, median size can easily be controlled at below the 100nm, particle diameter ratio is more even, the surface is difficult for oxidized, metal super-fine microparticle is uniformly dispersed in matrix material, and its preparation method is easier.
Polyurethane polymer metal super-fine microparticle composite material of the present invention can be used as electro-conductive material or as catalyzer, good performance and effect is arranged.
Below be embodiment.
A. carboxylic acid type urethane.
Embodiment 1, with 4,4 '-two isocyanato ditanes, 25 grams place dry four-necked bottle, add N, dinethylformamide (DMF) 100 grams, feed argon gas, after being warming up to 50 ℃, with molecular weight is 1000, hydroxy-end capped polytetrahydrofuran (soft section) 50 grams (being made into the DMF solution of 25% (WT)) splash into four-necked bottle, react after one hour temperature to be risen to 70-80 ℃, splash into chainextender 2,2-two (methylol) propionic acid 6.7 gram and several (0.1-0.4ml) stannous octoate catalysts, continue reaction four hours, add depositing in water and fold product, filter and be placed on drying in the vacuum drying oven, obtain 73.5 gram carboxylic acid type urethane, productive rate 88.7%.
Embodiment 2, change 4,4 '-two isocyanato ditanes among the embodiment 1 into 17.4 grams 2,4-two isocyanato toluene, and other steps are constant, obtain the corresponding carboxylic acid type polyurethane, and productive rate is 90%.
Embodiment 3, change 4,4 '-two isocyanato ditanes among the embodiment 1 into 16.8 grams 1,6-two isocyanato hexanes, and the constant corresponding carboxylic acid type polyurethane that obtains of other steps, productive rate is 80%.
Embodiment 4, and changing the soft segment molecule amount 1000 among the embodiment 1 into molecular weight is 2000 polytetrahydrofuran 100g, and other steps are constant, obtain the corresponding carboxylic acid type polyurethane.
Embodiment 5, and changing molecular weight into soft section among the embodiment 1 is 2000 polysiloxane 100g, and other steps are constant, obtain the corresponding carboxylic acid type polyurethane.
Embodiment 6, and in embodiment 1, vulcabond: soft section: chainextender=mol ratio changed over 4: 1: 3 in 2: 1: 1, and other steps are constant, obtained the corresponding carboxylic acid type polyurethane.
B. sulfonic acid type urethane
Synthetic method is with the embodiment 1-6 among the A, just chainextender is changed into 8.9 grams 2,3-dihydroxyl propanesulfonic acid sodium, obtain the sodium sulfonate type polyurethane, the sodium sulfonate type polyurethane is dissolved among the DMF, by strong acid ion exchange resin (Amberlyst 15 ion-exchange) post, and use a large amount of solvent washings, obtain sulfonic acid type urethane.
Embodiment 7, with 4,4 '-two isocyanato ditanes, 25 grams place dry four-necked bottle, add the DMF100 gram,, feed argon gas, after being warming up to 50 ℃, with molecular weight be 1000, hydroxy-end capped polytetrahydrofuran 50 grams (being made into the DMF solution of 25% (WT)) splash into four-necked bottle, react and after one hour temperature is risen to 70-80 ℃, splash into 1.4-butyleneglycol 4.5 gram and several stannous octoate catalysts, continue reaction four hours, add depositing in water evolution reaction product, dry in vacuum drying oven, get 75 gram urethane segmented copolymers.Then it is dissolved among the 300 gram DMF, feed argon gas, in cryosel is molten, be cooled to-5 ℃, the careful suspension liquid that adds 4.5 gram sodium hydrides and DMF composition reacted after 30 minutes, added γ-propane sultone 22.9 grams, be warming up to 50 ℃, react to make in 2 hours and react completely, product is poured in the toluene, separate out the sodium sulfonate type polyurethane.This sodium sulfonate type polyurethane is dissolved among the DMF, slowly, uses solvent washing, obtain sulfonic acid type urethane by the strong acid ion exchange resin post.
C. pyridine type urethane:
Synthetic method just changes chainextender into 10.5 gram N with the embodiment 1-6 among the A, and N-two (hydroxyethyl) Isonicotinamide obtains pyridine type urethane.
D. Polyamine Type urethane:
Implement 8, change the chainextender among the embodiment 1 into 13.6 gram N, N-dihydroxy ethyl-2,4-dinitraniline.Other steps are constant, obtain the nitro type polyurethane, the nitro type polyurethane is dissolved among the DMF, add hydrazine hydrate, Ranny nickel, and in 60 ℃ of backflows 12 hours, it is amino that nitroreduction becomes, and obtains Polyamine Type urethane.
Embodiment 9. changes the γ-propane sultone among the embodiment 7 into 2, and 4-dinitrochlorobenzene 40.3 grams are warming up to 50 ℃, react 2 hours, obtain the nitro type polyurethane.The nitro type polyurethane with the step reduction that is same as embodiment 8, is obtained Polyamine Type urethane.
E. the preparation of polyurethane polymer metal title complex (or ionomer):
Embodiment 10: after the metal chloride of stoichiometric quantity or acetate (consumption sees Table 1) are dissolved in DMF, be added in the DMF solution of four kinds of polyurethane polymers of above-mentioned A.B.C.D., reflux and promptly obtain corresponding polyurethane polymer metal title complex (or ionomer) after 2 hours.
F. the preparation of polyurethane polymer metal super-fine microparticle composite material:
Embodiment 11, take by weighing the polyurethane polymer metal title complex (or polymkeric substance) that 3 gram embodiment 10 produce, put into the 100ml round-bottomed bottle, after the adding 30mlDMF dissolving, the hydrazine hydrate aqueous solution and the 0.1ml formalin that add 0.1ml 30% (WT) again, be heated to 60 ℃, reacted 12 hours, solution is scarlet, the stop reaction, take out and desolvate and micromolecular compound, obtain the polyurethane polymer metal super-fine microparticle composite material film, it the results are shown in Table 1.
Embodiment 12, take by weighing the 3 polyurethane polymer metal title complexs (or ionomer) produced of gram embodiment 10 and put into the 100ml round-bottomed flask, add the 30mlDMF dissolving, add the solution that is made into by 0.1 gram sodium borohydride and 50ml water then, be heated to 60 ℃, reacted 2 hours, add depositing in water and separate out product, oven dry obtains polyurethane polymer metal super-fine microparticle composite material.
Embodiment 13, and polyurethane polymer metal title complex (or ionomer) solution is poured in the tetrafluoroethylene mould, and evaporation removes and desolvates, and makes the film of the following thickness of 0.03mm, and this film is immersed by 0.5 gram NaBH
4In the solution of forming with 50ml water, add tensio-active agent (as tween 80) several, refluxed 48 hours, promptly obtain polyurethane polymer metal super-fine microparticle composite material.
Embodiment 14, and polyurethane polymer metal title complex (or ionomer) film with making among the embodiment 13 places H
2In the atmosphere.Be heated to 160 ℃, reaction is 24 hours under 380Torr pressure, obtains polyurethane polymer metal super-fine microparticle composite material.
Table 1 polyurethane polymer metal ultra-fine ultra micron Composite Preparation raw material and material characteristics
| Urethane | Form | Metal-salt (mole number) | Reductive agent | XPS bound energy (EV) | Electronic Speculum TEM metal particle diameter | ||||||
| Isocyanic ester | Mole number | Soft section | Mole number | Chainextender | Mole number | 2P3/2 | 2P1/2 | ||||
| Sulfonic acid type urethane | MDI | 2 | PTMO (1000) | 1 | B | 1 | Cu(OAC) 2(1.5) | NaBH 4 | 933.15 | 952.95 | |
| MDI | 4 | PTMO (1000) | 1 | B | 3 | Cu(OAC) 2(1.5) | NaBH 4 | 933.15 | 952.95 | ||
| MDI | 2 | PTMO (1000) | 1 | A | 1 | Ni(OAC) 2(0.5) | Hydrazine hydrate | 853.25 | 870.63 | ||
| MDI | 3 | PTMO (1000) | 1 | C | 2 | Ni(OAC) 2(1.0) | Hydrazine hydrate | 853.25 | 870.65 | 30nm | |
| MDI | 3 | PTMO (2000) | 1 | A | 2 | Cu(OAC) 2(1.0) | NaBH 4 | 933.15 | 952.95 | ||
| MDI | 2 | ATPS (1000) | 1 | A | 1 | Cu(OAC) 2(0.5) | BaBH 4 | 933.15 | 952.95 | ||
| Carboxylic acid type urethane | MDI | 3 | PTMO (1000) | 1 | D | 2 | Cu(OAC) 2(1.0) | NaBH 4 | 933.15 | 952.95 | |
| MDI | 2 | PTMO (1000) | 1 | D | 1 | Cu(OAC) 2(0.5) | NaBH 4 | 933.15 | 952.95 | ||
| MDI | 3 | PTMO (1000) | 1 | D | 2 | Ni(OAX) 2(1.0) | NaBH 4 | 853.25 | 870.65 | 30nm | |
| MDI | 2 | PTMO (1000) | 1 | D | 1 | Ni(OAX) 2(0.5) | NaBH 4 | 853.25 | 870.65 | 10nm | |
| ODI | 3 | PTMO (1000) | 1 | D | 2 | Ni(OAX) 2(0.5) | NaBH 4 | 853.25 | 870.65 | ||
Continuous table 1:
| Urethane | Form | Metal-salt (mole number) | Reductive agent | XPS bound energy (EV) | Electronic Speculum TEM metal particle diameter | ||||||
| Isocyanic ester | Mole number | Soft section | Mole number | Chainextender | Mole number | 2P3/2 | 2P1/2 | ||||
| Pyridine type urethane | MDI | 2 | PTMO (1000) | 1 | E | 1 | Ni(OAC) 2(0.5) | Hydrazine hydrate | 853.25 | 870.65 | ～10nm |
| MDI | 3 | PTMO (1000) | 1 | E | 2 | Ni(OAC) 2(1.0) | Hydrazine hydrate | 853.25 | 870.65 | 10nm | |
| MDI | 4 | PTMO (1000) | 1 | E | 3 | Ni(OAC) 2(1.5) | NaBH 4 | 853.25 | 870.65 | ||
| MDI | 3 | PTMO (1000) | 1 | E | 2 | Cu(OAC) 2(1.0) | Hydrazine hydrate | 933.15 | 952.95 | 10nm | |
| MDI | 2 | ATPS (680) | 1 | E | 1 | Ni(OAC) 2(0.5) | NaBH 4 | 853.25 | 870.65 | ||
| HDI | 2 | PTMO (1000) | 1 | E | 1 | Ni(OAC) 2(0.5) | NaBH 4 | 853.25 | 870.65 | ||
| Polyamine Type urethane | MDI | 3 | PTMO (1000) | 1 | F | 2 | NiCl 2(1.0) | NaBH 4 | 853.25 | 870.65 | 8nm |
| MDI | 4 | PTMO (1000) | 1 | F | 3 | NiCl 2(1.5) | NaBH 4 | 863.25 | 870.65 | 15nm | |
A is 2,3-dihydroxyl propanesulfonic acid sodium,
B is N, N-two (hydroxyethyl) taurine;
C is to be to react with γ-propane sultone after chainextender is handled with NaH then with the butyleneglycol again;
D is 2,2-two (methylol) propionic acid; E is N, N-two (hydroxyethyl) Isonicotinamide;
F is N, N-dihydroxy ethyl-2,4-dinitraniline; MDI is 4,4 '-two isocyanato ditanes;
ODI is 4,4 '-two isocyanato phenyl ether; HDI is 1.6-two isocyanato hexanes;
PTMO is a polytetrahydrofuran; ATPS is amino-terminated dimethyl siloxane.
Claims (6)
1, a kind of polyurethane polymer metal super-fine microparticle composite material, it is characterized in that utilizing have heterogeneous structure, contain can with metallic ion coordination or the effect functional group polyurethane polymer be macromolecular ligand, form heterogeneous polyurethane polymer metal title complex (or ionomer) with metal ion, with reductive agent metal ion branch farmland is reduced into zero-valent metal and polyurethane polymer metal super-fine microparticle composite material.
2, polyurethane polymer metal super-fine microparticle composite material according to claim 1 is characterized in that polyurethane polymer can be carboxylic acid type urethane, sulfonic acid type urethane, pyridine type urethane or Polyamine Type urethane.
3, polyurethane polymer metal super-fine microparticle composite material according to claim 1, its feature metal super-fine microparticle can be the ultrafine particulates of silver, iron, cobalt, nickel, zinc or copper.
4, a kind of preparation method of polyurethane polymer metal super-fine microparticle composite material, it is characterized in that the metal chloride or the acetate of stoichiometric quantity are dissolved in solvent, be added to then in the solution of polyurethane polymer macromolecular ligand, heating, obtain the metal complexes (or ionomer) of polyurethane polymer, become zero-valent metal with reductive agent reducing metal ion, promptly get polyurethane polymer metal super-fine microparticle composite material.
5, preparation method according to claim 4 is characterized in that reductive agent can be hydrazine hydrate, sodium borohydride (NaBH
4), or hydrogen.
6, preparation method according to claim 4 is characterized in that and the metal complexes or the ionomer of polyurethane polymer can be made film earlier, then with sodium borohydride or hydrogen reducing.
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| CN93111576.0A CN1033169C (en) | 1993-07-07 | 1993-07-07 | Polyurethane polymer metal super-fine microparticle composite material and preparation method thereof |
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| CN93111576.0A CN1033169C (en) | 1993-07-07 | 1993-07-07 | Polyurethane polymer metal super-fine microparticle composite material and preparation method thereof |
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| CN1033169C true CN1033169C (en) | 1996-10-30 |
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