CN108794721A - 一种聚氨酯中空微球的制备方法 - Google Patents
一种聚氨酯中空微球的制备方法 Download PDFInfo
- Publication number
- CN108794721A CN108794721A CN201810714232.1A CN201810714232A CN108794721A CN 108794721 A CN108794721 A CN 108794721A CN 201810714232 A CN201810714232 A CN 201810714232A CN 108794721 A CN108794721 A CN 108794721A
- Authority
- CN
- China
- Prior art keywords
- diisocyanate
- preparation
- polyurethane prepolymer
- polyurethane
- miniemulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004005 microsphere Substances 0.000 title claims abstract description 52
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 46
- 239000004814 polyurethane Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- -1 papermaking Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 230000001804 emulsifying effect Effects 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000004970 Chain extender Substances 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 239000003995 emulsifying agent Substances 0.000 claims description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 230000002209 hydrophobic effect Effects 0.000 claims description 8
- 239000012948 isocyanate Substances 0.000 claims description 8
- 239000005056 polyisocyanate Substances 0.000 claims description 8
- 229920001228 polyisocyanate Polymers 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000008236 heating water Substances 0.000 claims description 7
- 150000002513 isocyanates Chemical class 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 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 claims description 7
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 claims description 4
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- 238000007872 degassing Methods 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 4
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 4
- 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 4
- 230000004224 protection Effects 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims 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 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical class OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- 239000012875 nonionic emulsifier Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- IAPSIVOHAUJHLF-UHFFFAOYSA-N 1,1-diisocyanato-2-methylcyclohexane Chemical compound CC1CCCCC1(N=C=O)N=C=O IAPSIVOHAUJHLF-UHFFFAOYSA-N 0.000 claims description 2
- WOGVOIWHWZWYOZ-UHFFFAOYSA-N 1,1-diisocyanatoethane Chemical compound O=C=NC(C)N=C=O WOGVOIWHWZWYOZ-UHFFFAOYSA-N 0.000 claims description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical class OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 210000000481 breast Anatomy 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043237 diethanolamine Drugs 0.000 claims description 2
- 238000004945 emulsification Methods 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 2
- 238000000265 homogenisation Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims 2
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 claims 1
- NDHCTLYYXSMJMI-UHFFFAOYSA-N 2-phenoxyethane-1,1-diol Chemical compound OC(O)COC1=CC=CC=C1 NDHCTLYYXSMJMI-UHFFFAOYSA-N 0.000 claims 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 claims 1
- COQACEIOFNTHKM-UHFFFAOYSA-N C(N)(OC)=O.C(CCCCCN=C=O)N=C=O Chemical compound C(N)(OC)=O.C(CCCCCN=C=O)N=C=O COQACEIOFNTHKM-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims 1
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 claims 1
- 235000019260 propionic acid Nutrition 0.000 claims 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 10
- 238000000576 coating method Methods 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 3
- 238000009413 insulation Methods 0.000 abstract description 3
- 239000010985 leather Substances 0.000 abstract description 3
- 239000000049 pigment Substances 0.000 abstract description 3
- 239000003607 modifier Substances 0.000 abstract 1
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000011806 microball Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- QAQSNXHKHKONNS-UHFFFAOYSA-N 1-ethyl-2-hydroxy-4-methyl-6-oxopyridine-3-carboxamide Chemical compound CCN1C(O)=C(C(N)=O)C(C)=CC1=O QAQSNXHKHKONNS-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- GTCAXTIRRLKXRU-UHFFFAOYSA-N methyl carbamate Chemical compound COC(N)=O GTCAXTIRRLKXRU-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- BJEJEBOUUCXCRZ-UHFFFAOYSA-N 2-(2-hydroxyphenoxy)ethane-1,1-diol Chemical compound OC(COC=1C(=CC=CC=1)O)O BJEJEBOUUCXCRZ-UHFFFAOYSA-N 0.000 description 1
- DBXBTMSZEOQQDU-UHFFFAOYSA-N 3-hydroxyisobutyric acid Chemical compound OCC(C)C(O)=O DBXBTMSZEOQQDU-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 102400000830 Saposin-B Human genes 0.000 description 1
- 101800001697 Saposin-B Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 1
- XIWFQDBQMCDYJT-UHFFFAOYSA-M benzyl-dimethyl-tridecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 XIWFQDBQMCDYJT-UHFFFAOYSA-M 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- TWFQJFPTTMIETC-UHFFFAOYSA-N dodecan-1-amine;hydron;chloride Chemical group [Cl-].CCCCCCCCCCCC[NH3+] TWFQJFPTTMIETC-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000002421 finishing Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical group CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- 229940032912 zephiran Drugs 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3212—Polyhydroxy compounds containing cycloaliphatic groups
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明公开了一种聚氨酯中空微球的制备方法,首先合成聚氨酯预聚体,再使用细乳液聚合将聚氨酯预聚体、疏水溶剂和水的混合物均质乳化制备获得聚氨酯中空微球。本发明采用细乳液工艺,制得的聚氨酯中空微球尺寸大小可调,壁厚可控,稳定性好,具有优异的水分散性。聚氨酯中空微球具有优异的遮盖性能,中空结构又可以提高涂层的隔热保温性能,可用作遮盖性颜料、抗紫外添加剂和手感改性剂等,广泛地应用于涂料、造纸、皮革等行业。
Description
技术领域
本发明属于材料技术领域,特别涉及一种聚氨酯中空微球的制备方法。
背景技术
近年来,聚氨酯一直是众多领域研究的热点。因聚氨酯具有很多优异的性能,如较高的机械强度和氧化稳定性、优良的耐油性、较高的柔曲性和回弹性,因而在胶粘剂、涂料、弹性体、泡沫和纤维等众多领域有广泛的应用前景。中国专利CN1793192A公开了一种交联聚氨酯微球的制备方法,通过将含有异氰酸基化合物在水中分散聚合,制备聚氨酯微球,制备的聚氨酯微球虽然分散性好,但性能单一,应用领域受限。
中空微球具有独特的结构以及完好的形貌外观,使得中空微球具有某些特殊的功能,如内部空间大、稳定性较好、尺寸和组成易控制以及优良的渗透性等特性。聚合物中空微球具有的多功能性,在填料、消光剂、涂料、粘合剂等众多领域有良好的应用价值;特别是细乳液的单体液滴可以实现对各种纳米粒子和活性物质的有效包封。中国专利CN102153747B公开了一种聚苯胺中空微球的制备方法,通过将苯胺与氧化剂在水中混合反应,干燥后制得聚苯胺中空微球,制备方法虽然简单,但制备的中空微球表面褶皱较大,形貌不规整,中空并不明显,在一定程度上影响其应用。中国专利CN104226275B公开了一种基于甲基丙烯酰氧基笼型倍半硅氧烷中空微球的制备方法,采用丙酮和环己烷的混合溶液作为刻蚀剂以除去核,制备中空微球,但制备的中空微球产生了一定的交联,且中空不明显。中国专利CN108047420A公开了一种聚氨酯抛光层及其制备方法,将异氰酸酯预聚物、固化剂、中空微球体三者混合,形成掺混中空微球体的液体聚合混合物,该方法制得的聚合物工艺复杂,且不是自形成的含中空的聚氨酯微球。
细乳液聚合是一种以液滴成核为主的聚合方法,细乳液的每个液滴都是一个微小的反应容器,操作简单易行且制备的粒子稳定性好、尺寸在纳米级别,因而成为制备特殊结构的聚合物纳米粒子的新型方法。
目前,还没有使用细乳液聚合法合成聚氨酯中空微球相关文献的报道。
发明内容
本发明为了解决现有的聚氨酯材料难以一步法合成聚氨酯中空微球材料的技术问题,旨在提供一种聚氨酯中空微球的制备方法。本发明方法制备的聚氨酯中空微球产率高、稳定性好、壁厚可控且环境友好,大大扩展了聚氨酯材料的应用范围。
本发明聚氨酯中空微球的制备方法,首先合成聚氨酯预聚体,再使用细乳液聚合将聚氨酯预聚体、疏水溶剂和水的混合物均质乳化制备获得聚氨酯中空微球。本发明聚氨酯中空微球的壳层聚合物与中空部分的空气之间存在较大的折光指数差,具有优异的遮盖性能,中空结构又可以提高涂层的隔热保温性能,可用作遮盖性颜料、抗紫外添加剂和手感改性剂等,广泛地应用于涂料、造纸、皮革等行业。本发明聚氨酯中空微球密度低且熔融温度高,耐压性优良,在各种树脂基体中的分散性良好,能够满足高档涂料如汽车涂料、航空涂料等很高的轻量化要求。同时,微球的空腔结构作为活性物质包覆和缓释的载体,在微胶囊材料、化妆品、医药保健等领域也有广阔的应用前景。
本发明聚氨酯中空微球的制备方法,包括如下步骤:
步骤1:将聚多元醇进行脱水脱气处理,随后降温至30-50℃后加入多异氰酸酯、催化剂和亲水扩链剂,然后在70-100℃下反应2-6h,制得聚氨酯预聚体;
步骤2:将所述聚氨酯预聚体和疏水溶剂加入到乳化剂水溶液中形成预乳液,在冰水浴下通过均质乳化机高速均质分散,获得稳定的细乳液;
步骤3:将所述细乳液在氮气保护下机械搅拌30min,水浴加热至恒温,向细乳液中加入交联剂使聚氨酯预聚体发生交联反应,制得聚氨酯中空微球。
步骤1中,所述聚多元醇为聚四亚甲基醚二醇、聚四氢呋喃醚二醇、聚氧化丙烯二醇、聚己二酸丁二醇酯二醇、聚己二酸己二醇酯二醇、聚碳酸酯二元醇中的一种或多种,聚多元醇的分子量在1000-3000。
步骤1中,所述多异氰酸酯包括脂肪族、脂环族、芳香族的多异氰酸酯,优选为甲苯二异氰酸酯、二苯甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、环己基二异氰酸酯、六亚甲基二异氰酸酯、亚丙基-1,2-二异氰酸酯、异佛尔酮二异氰酸酯、四亚甲基-1,4-二异氰酸酯、1,6-六亚甲基-二异氰酸酯、十二烷-1,12-二异氰酸酯、环丁烷-1,3-二异氰酸酯、环己烷-1,3-二异氰酸酯、环己烷-1,4-二异氰酸酯、甲基亚环己基二异氰酸酯、六亚甲基二异氰酸酯的三异氰酸酯、六亚甲基二异氰酸酯的氨基甲酸甲酯、亚乙基二异氰酸酯、2,4,4-三甲基六亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯中的一种或多种。
步骤1中,所述催化剂为辛酸亚锡、二月桂二丁基锡、N,N-二甲基环己胺、N-乙基吗啉、N-甲基吗啉、N,N-二甲基吡啶、N,N-二乙基哌嗪中的一种或多种。
步骤1中,所述亲水扩链剂包括多元醇类、脂环醇类、芳醇类、醇胺类亲水扩链剂,优选为1,4-丁二醇、1,6-己二醇、1,2-丙二醇、1,4-环己二醇、二亚甲基苯基二醇、2,2-二羟甲基丙酸、2,2-二羟甲基丁酸、2-[(2-氨乙基)氨基]磺酸钠、乙二醇、二乙醇胺、乙二胺、对苯二酚二羟乙基醚、N-甲基二乙醇胺中的一种或多种。
步骤1中,所述脱水脱气处理是升温至100-120℃处理1-3h。
步骤1中,聚多元醇的质量为所述聚氨酯预聚体质量的40-65%;多异氰酸酯的质量为所述聚氨酯预聚体质量的20-40%;催化剂的质量为所述聚氨酯预聚体质量的0.02-0.05%;亲水扩链剂的质量为所述聚氨酯预聚体质量的3-8%。
步骤2中,所述疏水溶剂为异辛烷、异庚烷、正壬烷、十二烷、乙酸乙酯、甲苯中的一种。
步骤2中,所述乳化剂包括阳离子型、阴离子型和非离子型乳化剂;优选阳离子型乳化剂为烷基季铵盐、含杂原子的季铵盐、含有苯环的季铵盐、含杂环的季铵盐、胺盐型等阳离子乳化剂中的一种;优选阴离子型乳化剂为羧酸盐型、磺酸盐型、硫酸盐型等阴离子乳化剂中的一种;优选非离子型乳化剂为聚氧乙烯型、多元醇型等非离子乳化剂中的一种;进一步优选乳化剂为十二烷基氯化铵、十六烷基三甲基氯化铵、十六烷基三甲基溴化铵、十二烷基二甲基苄基氯化铵、十六烷基溴化吡啶、十二烷基硫酸钠、十二烷基苯磺酸钠、十二烷基磺酸钠、脂肪醇聚氧乙烯醚中的一种或多种。
步骤2中,聚氨酯预聚体的质量为所述细乳液总质量的10-40%;所述疏水溶剂的质量为所述细乳液总质量的5-50%;所述乳化剂的质量为所述细乳液总质量的0.1-1%。
步骤2中,所述均质乳化机的剪切速率为10000-23000rpm,乳化时间为2-10min。
步骤3中,所述交联剂为乙二胺、三乙胺、三乙醇胺、四乙烯五胺、二乙烯三胺、三乙烯四胺、氨水、三羟甲基氨基甲烷中的一种或多种;交联剂的质量为所述聚氨酯预聚体质量的0.3-3%。
步骤3中,交联反应的温度为30-80℃,反应时间为3-24h。
本发明制得的聚氨酯中空微球平均粒径在50-1000nm;所述聚合物杂化中空微球的壳层壁厚是由所加入的有机溶剂的量所决定,壳层壁厚在10-200nm;制备的细乳液固含量在15-35%。
本发明的有益技术效果体现在以下方面:
1、本发明制备的聚氨酯中空微球稳定性好、中空结构较好且壁厚可控,具有优异的遮盖性能,可以提高涂层的隔热保温性能,可用作遮盖性颜料、抗紫外添加剂和手感改性剂等,广泛地应用于隔热涂料、消光剂、粘合剂、整理剂、造纸、皮革等众多领域。
2、本发明所使用的原料成本低,操作工艺简单,中空聚合物微球密度低,能够满足高档涂料如汽车涂料、航空涂料等很高的轻量化要求。
3、本发明制备的聚氨酯中空微球,可以包覆各种纳米粒子和活性物质,作为活性物质包覆和缓释的载体,在微胶囊材料、化妆品、医药保健等领域也有广阔的应用前景。
附图说明
图1为本发明聚氨酯中空微球的制备反应机理示意图。
图2为实施例1中聚氨酯中空微球的粒径图。从图2中可以看出,制备的聚氨酯中空微球分布均匀,平均粒径在500nm左右。
图3为实施例1中聚氨酯中空微球的红外光谱图。从图3的红外光谱图可以看出,产物出现了明显的聚氨酯各种官能团的特征吸收峰,说明已成功制备出聚氨酯中空微球。
图4为实施例1中聚氨酯中空微球的热失重曲线图。从图4中可以看出,制备的聚氨酯中空微球热稳定性较好,在特定的两个不同温度范围内才进行热分解。
图5为实施例1中聚氨酯中空微球的的透射电镜图。从图5中可以看出,制备的聚氨酯中空微球稳定性好,中空明显,壳层壁厚在30nm左右。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明。
实施例1:
1、称量30g聚己二酸己二醇酯二醇在110℃下抽真空干燥脱水2.5h,降温至50℃后投入反应容器中,再加入15g甲苯二异氰酸酯、0.02g辛酸亚锡催化剂和1.9g扩链剂1,4-丁二醇,控制温度在85℃反应2h,用二正丁胺法测定剩余异氰酸酯量,当-NCO基团的剩余含量达到理论上剩余量的92-98%时,加热反应即可停止,制得聚氨酯预聚体。
2、称量35g上述制得的聚氨酯预聚体和30g异辛烷混合均匀,加入100ml质量浓度为1.0%十二烷基硫酸钠水溶液中搅拌混合,然后在冰水浴下使用均质乳化机以16000rpm转速均质乳化5min,制得稳定的细乳液。
3、将制得的细乳液加入到装有搅拌器、温度计和回流冷凝管的三口烧瓶中,开启电动搅拌并通氮气30min,打开水浴加热快速升温至预设聚合温度65℃,再向细乳液中加入0.3g交联剂二乙烯三胺溶液,而后恒温反应8h后,降温至室温得到聚氨酯中空微球。
本实施例制得的聚氨酯中空微球形貌规整,中空结构明显,平均粒径在500nm左右,壳层壁厚在30nm左右,固含量为21%。
实施例2:
1、称量30g聚己二酸己二醇酯二醇在110℃下抽真空干燥脱水2.5h,降温至50℃后投入反应容器中,再加入15g二苯甲烷二异氰酸酯、0.02g辛酸亚锡催化剂和2.5g扩链剂1,6-己二醇,控制温度在85℃反应2h,用二正丁胺法测定剩余异氰酸酯量,当-NCO基团的剩余含量达到理论上剩余量的92-98%时,加热反应即可停止,制得聚氨酯预聚体。
2、称量35g上述制得的聚氨酯预聚体和25g异辛烷混合均匀,加入100ml质量浓度为1.5%十六烷基三甲基溴化铵水溶液中搅拌混合,然后在冰水浴下使用均质乳化机以16000rpm转速均质乳化5min,制得稳定的细乳液。
3、将制得的细乳液加入到装有搅拌器、温度计和回流冷凝管的三口烧瓶中,开启电动搅拌并通氮气30min,打开水浴加热快速升温至预设聚合温度65℃,再向细乳液中加入0.3g交联剂乙二胺溶液,而后恒温反应8h后,降温至室温得到聚氨酯中空微球。
本实施例制得的聚氨酯中空微球形貌规整,中空结构明显,平均粒径在400nm左右,壳层壁厚在40nm左右,固含量为22%。
实施例3:
1、称量25g聚四亚甲基醚二醇在110℃下抽真空干燥脱水2.5h,降温至50℃后投入反应容器中,再加入12g二苯甲烷二异氰酸酯、0.01g辛酸亚锡催化剂和1.9g扩链剂1,4-环己二醇,控制温度在85℃反应2h,用二正丁胺法测定剩余异氰酸酯量,当-NCO的剩余含量达到理论上剩余量的92-98%时,加热反应即可停止,制得聚氨酯预聚体。
2、称量30g上述制得的聚氨酯预聚体和25g乙酸乙酯混合均匀,加入100ml质量浓度为1.5%十二烷基二甲基苄基氯化铵水溶液中搅拌混合,然后在冰水浴下使用均质乳化机以16000rpm转速均质乳化5min,制得稳定的细乳液。
3、将制得的细乳液加入到装有搅拌器、温度计和回流冷凝管的三口烧瓶中,开启电动搅拌并通氮气30min,打开水浴加热快速升温至预设聚合温度65℃,再向细乳液中加入0.5g交联剂三乙烯四胺溶液,而后恒温反应8h后,降温至室温得到聚氨酯中空微球。
本实施例制得的聚氨酯中空微球形貌规整,中空结构明显,平均粒径在400nm左右,壳层壁厚在40nm左右,固含量为19%。
实施例4:
1、称量25g聚四亚甲基醚二醇在110℃下抽真空干燥脱水2.5h,降温至50℃后投入反应容器中,再加入12g异佛尔酮二异氰酸酯、0.01g辛酸亚锡催化剂和1.9g扩链剂2,2-二羟甲基丙酸,控制温度在85℃反应2h,用二正丁胺法测定剩余异氰酸酯量,当-NCO基团的剩余含量达到理论上剩余量的92-98%时,加热反应即可停止,制得聚氨酯预聚体。
2、称量30g上述制得的聚氨酯预聚体和30g乙酸乙酯混合均匀,加入100ml质量浓度为1.0%十六烷基溴化吡啶水溶液中搅拌混合,然后在冰水浴下使用均质乳化机以16000rpm转速均质乳化5min,制得稳定的细乳液。
3、将制得的细乳液加入到装有搅拌器、温度计和回流冷凝管的三口烧瓶中,开启电动搅拌并通氮气30min,打开水浴加热快速升温至预设聚合温度65℃,再向细乳液中加入0.5g交联剂氨水溶液,而后恒温反应8h后,降温至室温得到聚氨酯中空微球。
本实施例制得的聚氨酯中空微球形貌规整,中空结构明显,平均粒径在550nm左右,壳层壁厚在40nm左右,固含量为19%。
实施例5:
1、称量25g聚己二酸丁二醇酯二醇在110℃下抽真空干燥脱水2.5h,降温至50℃后投入反应容器中,再加入15g异佛尔酮二异氰酸酯、0.01g辛酸亚锡催化剂和2.8g扩链剂二亚甲基苯基二醇,控制温度在85℃反应2h,用二正丁胺法测定剩余异氰酸酯量,当-NCO基团的剩余含量达到理论上剩余量的92-98%时,加热反应即可停止,制得聚氨酯预聚体。
2、称量30g上述制得的聚氨酯预聚体和20g乙酸乙酯混合均匀,加入100ml质量浓度为1.2%十二烷基苯磺酸钠水溶液中搅拌混合,然后在冰水浴下使用均质乳化机以16000rpm转速均质乳化5min,制得稳定的细乳液。
3、将制得的细乳液加入到装有搅拌器、温度计和回流冷凝管的三口烧瓶中,开启电动搅拌并通氮气30min,打开水浴加热快速升温至预设聚合温度65℃,再向细乳液中加入0.3g交联剂三乙醇胺溶液,而后恒温反应8h后,降温至室温得到聚氨酯中空微球。
本实施例制得的聚氨酯中空微球形貌规整,中空结构明显,平均粒径在500nm左右,壳层壁厚在40nm左右,固含量为20%。
Claims (10)
1.一种聚氨酯中空微球的制备方法,其特征在于:首先合成聚氨酯预聚体,再使用细乳液聚合将聚氨酯预聚体、疏水溶剂和水的混合物均质乳化制备获得聚氨酯中空微球。
2.根据权利要求1所述的制备方法,其特征在于包括如下步骤:
步骤1:将聚多元醇进行脱水脱气处理,随后降温至30-50℃后加入多异氰酸酯、催化剂和亲水扩链剂,然后在70-100℃下反应2-6h,制得聚氨酯预聚体;
步骤2:将所述聚氨酯预聚体和疏水溶剂加入到乳化剂水溶液中形成预乳液,在冰水浴下通过均质乳化机高速均质分散,获得稳定的细乳液;
步骤3:将所述细乳液在氮气保护下机械搅拌30min,水浴加热至恒温,向细乳液中加入交联剂使聚氨酯预聚体发生交联反应,制得聚氨酯中空微球。
3.根据权利要求2所述的制备方法,其特征在于:
步骤1中,所述聚多元醇为聚四亚甲基醚二醇、聚四氢呋喃醚二醇、聚氧化丙烯二醇、聚己二酸丁二醇酯二醇、聚己二酸己二醇酯二醇、聚碳酸酯二元醇中的一种或多种,聚多元醇的分子量在1000-3000;
步骤1中,所述多异氰酸酯包括脂肪族、脂环族、芳香族的多异氰酸酯,优选为甲苯二异氰酸酯、二苯甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、环己基二异氰酸酯、六亚甲基二异氰酸酯、亚丙基-1,2-二异氰酸酯、异佛尔酮二异氰酸酯、四亚甲基-1,4-二异氰酸酯、1,6-六亚甲基-二异氰酸酯、十二烷-1,12-二异氰酸酯、环丁烷-1,3-二异氰酸酯、环己烷-1,3-二异氰酸酯、环己烷-1,4-二异氰酸酯、甲基亚环己基二异氰酸酯、六亚甲基二异氰酸酯的三异氰酸酯、六亚甲基二异氰酸酯的氨基甲酸甲酯、亚乙基二异氰酸酯、2,4,4-三甲基六亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯中的一种或多种;
步骤1中,所述催化剂为辛酸亚锡、二月桂二丁基锡、N,N-二甲基环己胺、N-乙基吗啉、N-甲基吗啉、N,N-二甲基吡啶、N,N-二乙基哌嗪中的一种或多种;
步骤1中,所述亲水扩链剂包括多元醇类、脂环醇类、芳醇类、醇胺类亲水扩链剂,优选为1,4-丁二醇、1,6-己二醇、1,2-丙二醇、1,4-环己二醇、二亚甲基苯基二醇、2,2-二羟甲基丙酸、2,2-二羟甲基丁酸、2-[(2-氨乙基)氨基]磺酸钠、乙二醇、二乙醇胺、乙二胺、对苯二酚二羟乙基醚、N-甲基二乙醇胺中的一种或多种。
4.根据权利要求2所述的制备方法,其特征在于:
步骤1中,所述脱水脱气处理是升温至100-120℃处理1-3h。
5.根据权利要求2或3所述的制备方法,其特征在于:
步骤1中,聚多元醇的质量为所述聚氨酯预聚体质量的40-65%;多异氰酸酯的质量为所述聚氨酯预聚体质量的20-40%;催化剂的质量为所述聚氨酯预聚体质量的0.02-0.05%;亲水扩链剂的质量为所述聚氨酯预聚体质量的3-8%。
6.根据权利要求2所述的制备方法,其特征在于:
步骤2中,所述疏水溶剂为异辛烷、异庚烷、正壬烷、十二烷、乙酸乙酯、甲苯中的一种;
步骤2中,所述乳化剂包括阳离子型、阴离子型、非离子型乳化剂。
7.根据权利要求2或6所述的制备方法,其特征在于:
步骤2中,聚氨酯预聚体的质量为所述细乳液总质量的10-40%;所述疏水溶剂的质量为所述细乳液总质量的5-50%;所述乳化剂的质量为所述细乳液总质量的0.1-1%。
8.根据权利要求2所述的制备方法,其特征在于:
步骤2中,所述均质乳化机的剪切速率为10000-23000rpm,乳化时间为2-10min。
9.根据权利要求2所述的制备方法,其特征在于:
步骤3中,所述交联剂为乙二胺、三乙胺、三乙醇胺、四乙烯五胺、二乙烯三胺、三乙烯四胺、氨水、三羟甲基氨基甲烷中的一种或多种;交联剂的质量为所述聚氨酯预聚体质量的0.3-3%。
10.根据权利要求2所述的制备方法,其特征在于:
步骤3中,交联反应的温度为30-80℃,反应时间为3-24h。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810714232.1A CN108794721A (zh) | 2018-07-03 | 2018-07-03 | 一种聚氨酯中空微球的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810714232.1A CN108794721A (zh) | 2018-07-03 | 2018-07-03 | 一种聚氨酯中空微球的制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN108794721A true CN108794721A (zh) | 2018-11-13 |
Family
ID=64074074
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810714232.1A Pending CN108794721A (zh) | 2018-07-03 | 2018-07-03 | 一种聚氨酯中空微球的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108794721A (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111359554A (zh) * | 2020-03-27 | 2020-07-03 | 华南理工大学 | 一种大粒径聚氨酯相变微胶囊及其制备方法 |
CN112794978A (zh) * | 2021-01-20 | 2021-05-14 | 重庆中科力泰高分子材料股份有限公司 | 一种大粒径水性聚氨酯分散体及其制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20100107328A (ko) * | 2009-03-25 | 2010-10-05 | (주)다락 | 미소구체가 분산된 수분산 폴리우레탄 및 이의 제조방법 |
CN105694699A (zh) * | 2016-01-27 | 2016-06-22 | 优美特(北京)环境材料科技股份公司 | 一种消光型水性聚氨酯乳液及其制备方法 |
CN105801898A (zh) * | 2016-03-14 | 2016-07-27 | 华南理工大学 | 一种交联聚脲中空微球及其制备方法与应用 |
CN106582463A (zh) * | 2016-12-15 | 2017-04-26 | 上海雅运纺织助剂有限公司 | 一种聚氨酯微胶囊分散液的制备方法及其产物 |
CN108192074A (zh) * | 2016-12-08 | 2018-06-22 | 万华化学集团股份有限公司 | 一种交联聚氨酯微球和/或聚氨酯空心微球的制备方法 |
-
2018
- 2018-07-03 CN CN201810714232.1A patent/CN108794721A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20100107328A (ko) * | 2009-03-25 | 2010-10-05 | (주)다락 | 미소구체가 분산된 수분산 폴리우레탄 및 이의 제조방법 |
CN105694699A (zh) * | 2016-01-27 | 2016-06-22 | 优美特(北京)环境材料科技股份公司 | 一种消光型水性聚氨酯乳液及其制备方法 |
CN105801898A (zh) * | 2016-03-14 | 2016-07-27 | 华南理工大学 | 一种交联聚脲中空微球及其制备方法与应用 |
CN108192074A (zh) * | 2016-12-08 | 2018-06-22 | 万华化学集团股份有限公司 | 一种交联聚氨酯微球和/或聚氨酯空心微球的制备方法 |
CN106582463A (zh) * | 2016-12-15 | 2017-04-26 | 上海雅运纺织助剂有限公司 | 一种聚氨酯微胶囊分散液的制备方法及其产物 |
Non-Patent Citations (3)
Title |
---|
MENG LI等: "Facile Route to Synthesize Polyurethane Hollow Microspheres with Size-Tunable Single Holes", 《LANGMUIR》 * |
周其凤: "《高分子化学》", 31 May 2001 * |
梁志武: "聚氨酯微胶囊的制备及其性能研究", 《南开大学 硕士学位论文》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111359554A (zh) * | 2020-03-27 | 2020-07-03 | 华南理工大学 | 一种大粒径聚氨酯相变微胶囊及其制备方法 |
CN111359554B (zh) * | 2020-03-27 | 2021-08-10 | 华南理工大学 | 一种大粒径聚氨酯相变微胶囊及其制备方法 |
CN112794978A (zh) * | 2021-01-20 | 2021-05-14 | 重庆中科力泰高分子材料股份有限公司 | 一种大粒径水性聚氨酯分散体及其制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR101424551B1 (ko) | 비-섬유 중합체 조성물 및 방법 | |
CN110382580B (zh) | 制备复合元件的聚氨酯制剂 | |
US4307004A (en) | Polyurethane urea heat seal adhesive for the preparation of heat sealable padding material | |
CN109679584B (zh) | 一种多组分网状壳体相变微胶囊及其制备方法 | |
US20070185003A1 (en) | Non-textile polymer compositions and methods | |
US4321173A (en) | Method for the preparation of finely dispersed polyurethane ureas | |
CN108794721A (zh) | 一种聚氨酯中空微球的制备方法 | |
CN108192074B (zh) | 一种交联聚氨酯微球和/或聚氨酯空心微球的制备方法 | |
CN105381767B (zh) | 一种聚氨酯微胶囊包封相变材料及其制备方法 | |
CN1245445A (zh) | 涂敷的多孔材料 | |
CN101851463B (zh) | 特黑特雾皮革表面处理剂及其制备方法 | |
JP3042950B2 (ja) | ポリウレタンゲル微粒子及びその製造方法 | |
Abdelkader et al. | New microcapsules based on isosorbide for cosmetotextile: Preparation and characterization | |
CN101591420A (zh) | 一种喷塑聚氨酯组合物、其制备方法及其应用 | |
CN109369884A (zh) | 一种软质聚氨酯多孔复合材料的制备方法 | |
CN101109151A (zh) | 嵌段聚氨酯微胶囊复合整理剂的制备方法 | |
CN109554935A (zh) | 一种抗菌防霉合成革生产工艺 | |
JPH0660260B2 (ja) | ポリウレタン発泡体の製造方法 | |
CN109369872A (zh) | 一种添加中空微球水性聚氨酯消光树脂及制备方法 | |
CN114736349B (zh) | 一种自消光水性聚氨酯及其制备方法和应用 | |
KR100812635B1 (ko) | 수분산 폴리카보네이트 폴리우레탄 수지 | |
JP2000297211A (ja) | 多孔質形成用水系ウレタン樹脂組成物 | |
CN112030567A (zh) | 一种多重绒感羊巴的表面涂层剂及其制备方法和应用 | |
JP4204711B2 (ja) | 皮革様シートの製造方法 | |
CN109337083A (zh) | 一种自消光水性聚氨酯隔热保温树脂的制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181113 |
|
RJ01 | Rejection of invention patent application after publication |