CN113825781A - 水性聚氨酯分散体及其制备方法 - Google Patents
水性聚氨酯分散体及其制备方法 Download PDFInfo
- Publication number
- CN113825781A CN113825781A CN202080035429.8A CN202080035429A CN113825781A CN 113825781 A CN113825781 A CN 113825781A CN 202080035429 A CN202080035429 A CN 202080035429A CN 113825781 A CN113825781 A CN 113825781A
- Authority
- CN
- China
- Prior art keywords
- isocyanate
- groups
- group
- hydroxyl
- aqueous polyurethane
- 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
- 229920003009 polyurethane dispersion Polymers 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000008569 process Effects 0.000 title claims description 11
- -1 siloxane compound Chemical class 0.000 claims abstract description 83
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 54
- 239000002649 leather substitute Substances 0.000 claims abstract description 40
- 239000012948 isocyanate Substances 0.000 claims description 65
- 150000002513 isocyanates Chemical class 0.000 claims description 64
- 239000004814 polyurethane Substances 0.000 claims description 50
- 229920002635 polyurethane Polymers 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 43
- 229920005862 polyol Polymers 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 28
- 150000003077 polyols Chemical class 0.000 claims description 24
- 239000004970 Chain extender Substances 0.000 claims description 22
- 239000005056 polyisocyanate Substances 0.000 claims description 22
- 229920001228 polyisocyanate Polymers 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 21
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 20
- 239000003995 emulsifying agent Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229920005906 polyester polyol Polymers 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 14
- 150000002009 diols Chemical class 0.000 claims description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 11
- 150000001412 amines Chemical class 0.000 claims description 11
- 229920000570 polyether Polymers 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- 229920000768 polyamine Polymers 0.000 claims description 7
- 150000003512 tertiary amines Chemical class 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 150000007942 carboxylates Chemical group 0.000 claims description 3
- 150000002780 morpholines Chemical class 0.000 claims description 3
- 150000004885 piperazines Chemical class 0.000 claims description 3
- 229920006264 polyurethane film Polymers 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical class 0.000 claims description 2
- 238000005956 quaternization reaction Methods 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims 2
- 239000004417 polycarbonate Substances 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims 1
- 125000000542 sulfonic acid group Chemical group 0.000 claims 1
- 229940066771 systemic antihistamines piperazine derivative Drugs 0.000 claims 1
- 235000015112 vegetable and seed oil Nutrition 0.000 claims 1
- 239000008158 vegetable oil Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 description 56
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 24
- 229920005830 Polyurethane Foam Polymers 0.000 description 22
- 150000003254 radicals Chemical class 0.000 description 18
- 239000010985 leather Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 11
- 125000002947 alkylene group Chemical group 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 11
- 239000004744 fabric Substances 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 9
- 239000002562 thickening agent Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 230000000903 blocking effect Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000004604 Blowing Agent Substances 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000002657 fibrous material Substances 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 239000006254 rheological additive Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 150000002596 lactones Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000001419 dependent effect Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 229960004063 propylene glycol Drugs 0.000 description 4
- 235000013772 propylene glycol Nutrition 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- UDVRROYKHLBOPZ-UHFFFAOYSA-N 3,3-dihydroxy-2-methylpropanoic acid Chemical compound OC(O)C(C)C(O)=O UDVRROYKHLBOPZ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 125000001302 tertiary amino group Chemical group 0.000 description 3
- 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 3
- 150000004072 triols Chemical class 0.000 description 3
- 229940043375 1,5-pentanediol Drugs 0.000 description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-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
- CZSSKBQAJULWPY-UHFFFAOYSA-N 2-undecylsulfanylacetic acid Chemical compound CCCCCCCCCCCSCC(O)=O CZSSKBQAJULWPY-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 241000282421 Canidae Species 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical class OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000004103 aminoalkyl group Chemical group 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 150000003863 ammonium salts Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Polymers C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 125000005702 oxyalkylene group Chemical group 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 150000003141 primary amines Chemical group 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical class [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- SHXHPUAKLCCLDV-UHFFFAOYSA-N 1,1,1-trifluoropentane-2,4-dione Chemical compound CC(=O)CC(=O)C(F)(F)F SHXHPUAKLCCLDV-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 1
- NFDXQGNDWIPXQL-UHFFFAOYSA-N 1-cyclooctyldiazocane Chemical compound C1CCCCCCC1N1NCCCCCC1 NFDXQGNDWIPXQL-UHFFFAOYSA-N 0.000 description 1
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 description 1
- BFXXDIVBYMHSMP-UHFFFAOYSA-L 2,2-diethylhexanoate;tin(2+) Chemical compound [Sn+2].CCCCC(CC)(CC)C([O-])=O.CCCCC(CC)(CC)C([O-])=O BFXXDIVBYMHSMP-UHFFFAOYSA-L 0.000 description 1
- CVFRFSNPBJUQMG-UHFFFAOYSA-N 2,3-bis(2-hydroxyethyl)benzene-1,4-diol Chemical compound OCCC1=C(O)C=CC(O)=C1CCO CVFRFSNPBJUQMG-UHFFFAOYSA-N 0.000 description 1
- SWFYIOVXCUTUOB-UHFFFAOYSA-N 2,3-dihydroxypropylphosphonic acid Chemical compound OCC(O)CP(O)(O)=O SWFYIOVXCUTUOB-UHFFFAOYSA-N 0.000 description 1
- VZDIRINETBAVAV-UHFFFAOYSA-N 2,4-diisocyanato-1-methylcyclohexane Chemical compound CC1CCC(N=C=O)CC1N=C=O VZDIRINETBAVAV-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- IYBOGQYZTIIPNI-UHFFFAOYSA-N 2-methylhexano-6-lactone Chemical compound CC1CCCCOC1=O IYBOGQYZTIIPNI-UHFFFAOYSA-N 0.000 description 1
- RJOFSHRKXGENSO-UHFFFAOYSA-N 2-methylpropane-1,1-diamine Chemical compound CC(C)C(N)N RJOFSHRKXGENSO-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 244000198134 Agave sisalana Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 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 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- VDVJBLBBQLHKKM-UHFFFAOYSA-N OOP(=O)OO Chemical compound OOP(=O)OO VDVJBLBBQLHKKM-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920000974 Poly(dimethylsiloxane-ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- CQQXCSFSYHAZOO-UHFFFAOYSA-L [acetyloxy(dioctyl)stannyl] acetate Chemical compound CCCCCCCC[Sn](OC(C)=O)(OC(C)=O)CCCCCCCC CQQXCSFSYHAZOO-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 229920013822 aminosilicone Polymers 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004653 carbonic acids Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000012971 dimethylpiperazine Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 150000002332 glycine derivatives Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- SAMYCKUDTNLASP-UHFFFAOYSA-N hexane-2,2-diol Chemical compound CCCCC(C)(O)O SAMYCKUDTNLASP-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- YLGXILFCIXHCMC-JHGZEJCSSA-N methyl cellulose Chemical group COC1C(OC)C(OC)C(COC)O[C@H]1O[C@H]1C(OC)C(OC)C(OC)OC1COC YLGXILFCIXHCMC-JHGZEJCSSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002557 mineral fiber Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003003 phosphines Chemical group 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical group 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 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
- 229920003987 resole Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000003655 tactile properties Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
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
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- 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
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- 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
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
- C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
-
- 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
-
- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
-
- 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
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/20—Heterocyclic amines; Salts thereof
- C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
- C08G18/2063—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having two nitrogen atoms in the condensed ring system
-
- 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
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
- C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
-
- 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
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
-
- 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
-
- 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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
- C08G18/485—Polyethers containing oxyethylene units and other oxyalkylene units containing mixed oxyethylene-oxypropylene or oxyethylene-higher oxyalkylene end 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
- C08G18/40—High-molecular-weight compounds
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
-
- 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
- C08G18/6541—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/34
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/128—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with silicon polymers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/147—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the isocyanates used
-
- 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
- C08G2101/00—Manufacture of cellular products
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
-
- 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
- C08G2150/00—Compositions for coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Abstract
提供了一种水性聚氨酯分散体。所述水性聚氨酯分散体包含主链的羟基封端硅氧烷化合物的残留部分，并且在保持优异机械性能时表现出良好抗粘性和/或湿色牢度。还提供了一种用所述水性聚氨酯分散体制备的层压合成皮革制品以及用于制备所述合成皮革制品的方法。
Description
技术领域
本公开涉及一种水性聚氨酯分散体及其制备方法、一种包含衍生自水性聚氨酯分散体的皮膜的层压合成皮革制品及其制备方法。由水性聚氨酯分散体所制备的层压合成皮革制品表现出优异抗粘性、机械性质和湿色牢度。
背景技术
合成皮革在人们的日常生活中得到了广泛的应用，从衣服、鞋类、袋子和行李箱、家庭装饰品到汽车座椅。合成皮革提供了与天然皮革类似的性能和手感，具有更好的成本优势。合成皮革通过将聚合物涂覆于织物基材上或将聚合物浸渍到织物基材中来制造，并且最通常所用的聚合物为聚氨酯(PU)。目前，大部分的PU皮革由溶剂型PU制成，但溶剂在加工期间的蒸发和皮革中的残留物产生了关于环境和工人健康的问题。由于来自政府和法规的压力，行业路线图表明需要环保型PU皮革，并且将极其快速地增长。作为市场上环保解决方案之一，作为合成皮革应用的皮层，水性聚氨酯分散体(PUD)将发挥越来越重要的作用。然而，据报道，使用水性聚氨酯分散体所制造的合成皮革具有许多问题，例如粘性。不粘性为PUD皮层的一项非常关键性能，并且进行了大量创新努力来改善这种性质。据报道，一些添加剂(诸如填料或手感添加剂)可用于改善PUD皮层的粘性，但仍存在对于无溶剂PUD的持续需求，该无溶剂PUD表现出优异粘性和/或湿色牢度，同时保持相当于溶剂型PUD的机械性质的良好PUD膜机械性质。
在不断探索之后，已意外地发现了一种水性聚氨酯分散体，该水性聚氨酯分散体可实现上述目标的一者或多者。
发明内容
本公开提供了一种独特的水性聚氨酯分散体以及一种使用水性聚氨酯分散体制备的层压合成皮革制品。
在本公开的第一方面，本公开提供了一种水性聚氨酯分散体，该水性聚氨酯分散体包含分散在水中的聚氨酯颗粒，其中水性聚氨酯分散体衍生自：
(A)包含一种或多种具有至少两个异氰酸酯基团的化合物的异氰酸酯组分；
(B)包含一种或多种具有至少两个异氰酸酯反应性基团的化合物的异氰酸酯反应性组分；
(C)由式I表示的亲水性氨基硅氧烷化合物：
其中R1和R4的每一者独立地表示由选自由以下项组成的组的一个或两个取代基所任选取代的亚甲基：C1-C5烷基、C1-C5烷氧基、C6-C12芳基、C6-C12芳氧基和卤素；
R2和R3的每一者独立地表示由选自由以下项组成的组的一个或两个取代基所任选取代的C1-C6氧化烯基团：C1-C5烷基、C1-C5烷氧基、C6-C12芳基、C6-C12芳氧基和卤素；
R5、R6、R7、R8、R9和R10的每一者独立地表示由选自由以下项组成的组的一个或两个取代基所任选取代的C1-C5烷基：C1-C5烷基、C1-C5烷氧基、C6-C12芳基、C6-C12芳氧基和卤素；
其中a和e的每一者独立地为0至30的整数；b和d的每一者独立地为5至30的整数，并且c为3至100的整数；
a和e的每一者独立地为1至30的整数；b和d的每一者独立地为0的整数；并且c为3至100的整数；
(D)催化剂；
(E)乳化剂；
(F)扩链剂；和
(G)水。
在本公开的第二方面，本公开提供了一种用于生产第一方面的水性聚氨酯分散体的方法，该方法包括(i)在存在催化剂(D)的情况下使异氰酸酯组分(A)与异氰酸酯反应性组分(B)和羟基封端硅氧烷化合物(C)反应以形成第一预聚合中间体；(ii)使第一预聚中间体与乳化剂(E)反应以形成第二预聚合中间体；(iii)使预聚合中间体与扩链剂(F)反应以形成水性聚氨酯分散体。优选地，步骤(ii)中所形成的第二预聚合中间体在步骤(iii)中与扩链剂(F)反应之前以中和剂进行中和。
在本发明的第三方面，本公开提供了一种合成皮革制品，该合成皮革制品从上到下包括：衍生自第一方面的水性聚氨酯分散体的聚氨酯皮膜；衍生自2k PU复合组合物的基层；和可选的背衬基材。
在本公开的第四方面，本公开提供了一种用于制备如第三方面所述的合成皮革制品的方法，该方法包括：
a)提供如第一方面所述的水性聚氨酯分散体；
b)用水性聚氨酯分散体形成聚氨酯皮膜；
c)将2k PU复合组合物施加到聚氨酯皮膜的一侧上以形成基层；以及
d)任选地将背衬基材施加到基层的与聚氨酯皮膜相反的一侧上。
应理解，前面的一般性描述和以下的详细描述均仅为示例性和解释性的，而非对如所要求保护的本发明的限制。
附图说明
图1为本文所述的合成皮革制品的一个实施例的横截面的示意图；
图2为用于制备本文所述的合成皮革制品的工艺的示意图；
图3示出了实例1至5中所制备的五种PUD的TEM显微照片；和
图4示出了五种合成皮革在抗粘性测试之后的显微照片。
具体实施方式
除非另外定义，否则本文所用的所有技术和科学术语具有与本发明所属领域中的普通技术人员通常所理解相同的含义。此外，本文所提及的所有公开案、专利申请、专利以及其它参考文献均以引用的方式并入。
如本文所公开，术语“组合物”、“制剂”或“混合物”是指不同组分的物理共混物，其是通过用物理方式简单地混合不同组分来获得。
如本文所公开，“和/或”意指“以及，或作为替代方案”。除非另外指示，否则所有范围都包括端点。
异氰酸酯组分
在各种实施例中，异氰酸酯组分(A)所具有的平均官能度为至少约2.0、优选地约2至10、更优选地约2至约8，和最优选地约2至约6。在一些实施例中，异氰酸酯组分包括含有至少两个异氰酸酯基团的一种或多种聚异氰酸酯化合物。合适的聚异氰酸酯化合物包括具有两个或更多个异氰酸酯基团的芳香族、脂肪族、环脂族和芳脂族聚异氰酸酯。在优选的实施例中，聚异氰酸酯组分包含选自由以下项组成的组的聚异氰酸酯化合物：包含至少两个异氰酸酯基团的C4-C12脂肪族聚异氰酸酯、包含至少两个异氰酸酯基团的C6-C15环脂族或芳香族聚异氰酸酯、包含至少两个异氰酸酯基团的C7-C15芳脂族聚异氰酸酯，以及它们的组合。在另一个优选的实施例中，合适的聚异氰酸酯化合物包括间苯二异氰酸酯、2,4-甲苯二异氰酸酯和/或2,6-甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)的各种异构体、碳化二亚胺改性的MDI产物、六亚甲基-1,6-二异氰酸酯、四亚甲基-1,4-二异氰酸酯、环己烷-1,4-二异氰酸酯、六氢甲苯二异氰酸酯、氢化MDI、萘基-1,5-二异氰酸酯、异佛尔酮二异氰酸酯(IPDI)，或它们的混合物。
替代地或另外，聚异氰酸酯组分还可包含异氰酸酯官能度在2至10、优选地2至8、更优选地2至6的范围内的异氰酸酯预聚物。可通过使上述单体异氰酸酯组分与选自由以下项组成的组的一种或多种异氰酸酯反应性化合物反应来获得异氰酸酯预聚物：乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,4-丁炔二醇、1,5-戊二醇、新戊二醇、双(羟甲基)环己烷诸如1,4-双(羟甲基)环己烷、2-甲基丙烷-1,3-二醇、甲基戊二醇、二甘醇、三甘醇、四甘醇、聚乙二醇、二丙二醇、聚丙二醇、二丁二醇和聚丁二醇。用作聚异氰酸酯组分的合适的预聚物为NCO基团含量为2至40重量百分比、更优选地4至30重量百分比的预聚物。优选地通过二异氰酸酯和/或聚异氰酸酯与包括较低分子量的二醇和三醇的材料的反应来制备这些预聚物。个别实例为含有氨基甲酸酯基团的芳香族聚异氰酸酯，优选地NCO含量为5至40重量百分比，更优选地20至35重量百分比，其通过二异氰酸酯和/或聚异氰酸酯与例如较低分子量的二醇、三醇、氧化烯二醇、二氧化烯二醇或分子量高达约800的聚氧化烯二醇的反应来获得。这些多元醇可单独使用或以二氧化烯二醇和/或聚氧化烯二醇的混合物形式使用。例如，可使用二甘醇、二丙二醇、聚氧乙烯二醇、乙二醇、丙二醇、丁二醇、聚氧丙烯二醇和聚氧丙烯-聚氧乙烯二醇。也可使用聚酯多元醇，以及烷烃二醇，诸如丁二醇。其它也可用的二醇包括双羟乙基-或双羟丙基-双酚A、环己烷二甲醇和双羟乙基氢醌。
也有利地用于异氰酸酯组分的为所谓改性多官能异氰酸酯，即通过上述异氰酸酯化合物的化学反应获得的产物。示例性的是含有酯、脲、缩二脲、脲基甲酸酯并且优选地碳化二亚胺和/或脲酮亚胺的聚异氰酸酯。也可使用含有碳化二亚胺基、脲酮亚胺基和/或异氰脲酸酯环的液体聚异氰酸酯，其异氰酸酯基(NCO)含量为12至40重量百分比，更优选地20至35重量百分比。这些包括例如基于以下项的聚异氰酸酯：4,4'-2,4'-和/或2,2'-二苯基甲烷二异氰酸酯和对应的异构体混合物、2,4-和/或2,6-甲苯二异氰酸酯和对应的异构体混合物；二苯基甲烷二异氰酸酯和PMDI的混合物；以及甲苯二异氰酸酯和PMDI和/或二苯基甲烷二异氰酸酯的混合物。
通常，异氰酸酯组分的量可根据合成皮革制品的实际需要而变化。例如，作为一个例示性实施例，基于异氰酸酯反应性组分(B)和羟基封端硅氧烷化合物(C)的总摩尔含量，异氰酸酯组分的含量可为约101摩尔％至约300摩尔％，优选地约110摩尔％至约280摩尔％，更优选地约150摩尔％至约250摩尔％，更优选地约170摩尔％至240摩尔％，更优选地约180摩尔％至230摩尔％，更优选地190摩尔％至230摩尔％。
异氰酸酯反应性组分
在本公开的各种实施例中，异氰酸酯反应性组分包含选自由以下项组成的组的一种或多种多元醇：包含至少两个羟基的脂族多元醇、包含至少两个羟基的环脂族或芳香族多元醇、包含至少两个羟基的芳脂族多元醇、聚醚多元醇、聚酯多元醇和其混合物。优选地，多元醇选自由以下项组成的组：包含至少两个羟基基团的C2-C16脂族多元醇、包含至少两个羟基基团的C6-C15环脂族或芳香族多元醇、包含至少两个羟基基团的C7-C15芳脂族多元醇、分子量为100至5,000的聚酯多元醇、分子量为1,500至12,000的聚醚多元醇，以及它们的组合。根据一个优选实施例，多元醇包括聚酯多元醇。
在优选实施例中，异氰酸酯反应性组分包含两种或更多种不同多元醇的混合物，诸如两种或更多种聚醚多元醇的混合物、两种或更多种聚酯多元醇的混合物，至少一种聚醚多元醇与至少一种聚酯多元醇的混合物，或聚酯多元醇和单体多元醇的混合物。
在一个优选实施例中，异氰酸酯反应性组分为分子量为500至5,000，优选地1000至3,000g/mol的聚酯多元醇，以实现PUD顶膜的良好成膜性和弹性。聚酯多元醇通常通过使具有2至12个碳原子(优选地2至6个碳原子)的多官能醇与具有2至12个碳原子(优选地2至6个碳原子)的多官能羧酸或其酸酐/酯反应来获得。用于制备聚酯多元醇的典型的多官能醇优选地为二醇或三醇，并且包括乙二醇、丙二醇、丁二醇、戊二醇或己二醇。典型多官能羧酸可为脂肪族的、脂环族的、芳脂族的、芳香族的或杂环的，并且可由例如卤素原子取代，和/或可为饱和的或不饱和的。优选地，多官能羧酸选自由以下项组成的组：辛二酸、壬二酸、邻苯二甲酸、间苯二甲酸、邻苯二甲酸酐、四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、四氯邻苯二甲酸酐、内亚甲基-四氢-邻苯二甲酸酐、戊二酸酐、烯基琥珀酸、马来酸、马来酸酐、富马酸、二聚脂肪酸。优选的是通式HOOC-(CH2)y-COOH表示的二羧酸，其中y是1到20的整数，优选地2到20的偶数。聚酯多元醇优选地用至少两个羟基封端。在优选的实施例中，聚酯多元醇的羟基官能度为2至10，优选地2至6。在另一个实施例中，聚酯多元醇的OH数为80至2,000mgKOH/g，优选地150至1,000mgKOH/g，和更优选地200至500mgKOH/g。设想多种分子量的聚酯多元醇。例如，聚酯多元醇的数均分子量可为约500g/mol至约5,000g/mol，优选地约600g/mol至约4,000g/mol，优选地约500g/mol至约3,000g/mol，优选地约1000g/mol至约2,500g/mol，优选地约1200g/mol至约2.000g/mol，和更优选地约1.500g/mol至约1.800g/mol。
另选地，聚酯多元醇包括基于内酯的聚酯二醇，其为内酯的均聚物或共聚物，优选地为内酯与合适双官能引发剂分子的末端羟基官能加成产物。优选的内酯衍生自由通式HO-(CH2)z-COOH表示的化合物，其中z是1到20的整数并且亚甲基单元的一个氢原子还可由C1到C4烷基代替。示例性基于内酯的聚酯二醇包含ε-己内酯、β-丙内酯、γ-丁内酯、甲基-ε-己内酯或其混合物。
在另一优选实施例中，异氰酸酯反应性组分为聚醚多元醇，其官能度(多元醇分子中异氰酸酯反应性基团，特别是羟基基团的平均数)为1.0至3.0，并且重均分子量(Mw)为1,500至12,000g/mol，优选地2,000至8,000g/mol，更优选地2,000至6,000g/mol。通常通过在存在催化剂的情况下选自环氧丙烷(PO)、环氧乙烷(EO)、环氧丁烷、四氢呋喃和它们的混合物的一种或多种环氧烷与适当的起始剂分子的聚合来制备聚醚多元醇。典型的起始剂分子包括在分子中具有至少2个、优选地4至8个羟基或者具有两个或更多个伯胺基的化合物。合适的起始剂分子例如选自包含以下的组：苯胺、EDA、TDA、MDA和PMDA，更优选地选自包含以下的组：TDA和PMDA，最优选地TDA。当使用TDA时，所有异构体可以单独使用或以任何期望的混合物使用。例如，可使用2,4-TDA、2,6-TDA、2,4-TDA和2,6-TDA的混合物、2,3-TDA、3,4-TDA、3,4-TDA和2,3-TDA的混合物，以及所有上述异构体的混合物。借助于在分子中具有至少2个并且优选地2至8个羟基的起始剂分子，优选的是使用三羟甲基丙烷、甘油、季戊四醇、蓖麻油、糖化合物例如葡萄糖、山梨糖醇、甘露醇和蔗糖、多元酚、甲阶酚醛树脂诸如酚和甲醛的低聚缩合产物以及苯酚、甲醛和二烷醇胺的曼尼希缩合物，以及三聚氰胺。用于制备聚醚多元醇的催化剂可包括用于阴离子聚合的碱性催化剂，诸如氢氧化钾，或用于阳离子聚合的路易斯酸催化剂，诸如三氟化硼。合适的聚合催化剂可包括氢氧化钾、氢氧化铯、三氟化硼或双氰化物络合物(DMC)催化剂，诸如六氰基钴酸锌或季磷腈鎓化合物。在本公开的优选实施例中，聚醚多元醇包括(甲氧基)聚乙二醇(MPEG)、聚乙二醇(PEG)、聚(丙二醇)、或具有伯羟基封端基团和仲羟基封端基团的环氧乙烷和环氧丙烷的共聚物。
一般来讲，基于异氰酸酯反应性组分(B)和羟基封端硅氧烷化合物(C)的总摩尔含量，本文所用的异氰酸酯反应性组分的含量可在约50摩尔％至约98摩尔％，优选地约60摩尔％至约97摩尔％，更优选地约70摩尔％至约96摩尔％，更优选地约80摩尔％至约96摩尔％，更优选地约85摩尔％至约95摩尔％。
在本公开的上下文中，包含可与异氰酸酯基团反应的官能团的其它化合物(诸如羟基封端硅氧烷化合物和扩链剂)未处于所谓“异氰酸酯反应性组分”的定义内。羟基封端硅氧烷化合物和扩链剂可通过分子结构或其添加时间点与异氰酸酯反应性组分清楚地区分。特别地，由式I表示的羟基封端硅氧烷化合物应从异氰酸酯反应性组分的范围排除。此外，可用于扩链剂的化合物也可包含如上所述及的至少两个异氰酸酯反应性基团，但扩链剂在其中PU的主链已形成的稍后阶段添加至反应体系。
羟基封端的硅氧烷化合物
羟基封端硅氧烷化合物为包含由a)硅氧单元、b)氧化烯单元和任选c)亚烷基单元组成的嵌段主链的化合物，或为包含由a)硅氧单元和b)亚烷基单元组成的嵌段主链的化合物。所述羟基封端硅氧烷化合物的主链在两个端部处以羟基基团进行封端。根据本公开的一个实施例，当存在时，末端羟基基团可连接至亚烷基单元；或当存在时，可连接至氧化烯单元。本公开的硅氧烷化合物可视为以氧化烯单元、末端羟基基团和任选亚烷基单元改性的硅氧烷(例如聚二甲基硅氧烷，PDMS)，或可视为以末端羟基基团和亚烷基单元改性的硅氧烷(例如聚二甲基硅氧烷，PDMS)。不受限于任何特定理论，据发现，主链所包含的环氧烷单元对于粘性的改善为至关重要的。不受限于任何特定理论，末端羟基基团可与异氰酸酯组分中的异氰酸酯基团反应以将硅氧烷化合物的链段并入聚氨酯主链，从而显著地改善所得PU皮膜的抗粘性。根据本公开的一个实施例，羟基封端硅氧烷化合物可视为嵌段预聚物，其中聚硅氧烷段、亚烷基段和环氧烷段的关系位置可改变，只要预聚物主链的两个端部以羟基基团进行封端。
根据本公开的实施例，羟基封端硅氧烷化合物的分子结构可由式I表示：
其中R1和R4的每一者独立地表示由选自由以下项组成的组的一个或两个取代基所任选取代的亚甲基：C1-C5烷基、C1-C5烷氧基、C6-C12芳基、C6-C12芳氧基和卤素；R2和R3的每一者独立地表示由选自由以下项组成的组的一个或两个取代基所任选取代的C1-C6氧化烯基团：C1-C5烷基、C1-C5烷氧基、C6-C12芳基、C6-C12芳氧基和卤素；R5、R6、R7、R8、R9和R10的每一者独立地表示由选自由以下项组成的组的一个或两个取代基所任选取代的C1-C5烷基：C1-C5烷基、C1-C5烷氧基、C6-C12芳基、C6-C12芳氧基和卤素；
其中a和e的每一者独立地为0至30的整数，即0,1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30，优选地2至20的整数，即2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20，更优选地3至18的整数，即3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18，更优选地5至10的整数，即5,6,7,8,9,10；b和d的每一者独立地为5至30的整数，即5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30，或7至25的整数，即7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25，或9至20的整数，即9,10,11,12,13,14,15,16,17,18,19,20，或12至12的整数；并且c为3至100的整数，即3,4,5,6,7,8,9,10,11,12,13,…98,99,100，或5至90的整数，即5,6,7,8,9,10,11,12,13,…88,89,90，或7至80的整数，即7,8,9,10,11,12,13,…78,79,80，或9至70的整数，即9,10,11,12,13,…68,69,70，或10至60的整数，即10,11,12,13,…58,59,60，或15至50的整数，即15,16,17,18,…48,49,50，或20至40的整数，即20,21,22,23,…,38,39,40，或30至35的整数，即31,32,33,34,35。
或其中a和e的每一者独立地为1至30的整数，即1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30，优选地2至20的整数，即2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20，更优选地3至18的整数，即3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18，更优选地5至10的整数，即5,6,7,8,9,10；b和d的每一者独立地为0的整数；并且c为3至100的整数，即3,4,5,6,7,8,9,10,11,12,13,…98,99,100，或5至90的整数，即5,6,7,8,9,10,11,12,13,…88,89,90，或7至80的整数，即7,8,9,10,11,12,13,…78,79,80，或9至70的整数，即9,10,11,12,13,…68,69,70，或10至60的整数，即10,11,12,13,…58,59,60，或15至50的整数，即15,16,17,18,…48,49,50，或20至40的整数，即20,21,22,23,…,38,39,40，或30至35的整数，即30,31,32,33,34,35。
根据本公开的一个实施例，羟基封端硅氧烷化合物具有式II所表示的结构：
其中a、b、c、d和e如上文所描述。
根据本公开的一个实施例，羟基封端硅氧烷化合物由式II表示：
其中a和e的每一者独立地为5至10的整数；b和d的每一者独立地为5至7的整数；并且c为20至40的整数。
根据本公开的一个实施例，羟基封端硅氧烷化合物由式II表示：
其中a和e的每一者独立地为1至30的整数；b和d的每一者为0，并且c为3至100的整数。
根据本公开的一个实施例，羟基封端硅氧烷化合物由式II表示：
其中a、b、c、d和e如上文所描述，并且其中羟基封端硅氧烷化合物的EO含量基于重量小于40％，更优选地小于35％。
根据本公开的一个实施例，羟基封端硅氧烷化合物由式II表示：
其中a、b、c、d和e如上文所描述，并且其中羟基封端硅氧烷化合物的EO含量基于重量小于30％，更优选地小于28％。一般来讲，基于异氰酸酯反应性组分(B)和羟基封端硅氧烷化合物(C)的总摩尔含量，本文所用的羟基封端硅氧烷化合物的含量为2摩尔％至50摩尔％，或3摩尔％至40摩尔％，或4摩尔％至30摩尔％，或4摩尔％至20摩尔％，或4摩尔％至15摩尔％，或5摩尔％至13摩尔％。
应当注意，羟基封端硅氧烷化合物可与异氰酸酯组分和异氰酸酯反应性组分直接地混合。另选地，羟基封端硅氧烷化合物可与异氰酸酯反应性组分相组合，并且然后与异氰酸酯组分反应。
催化剂
催化剂可包括能够促进异氰酸酯基团和异氰酸酯反应性基团之间的反应的任何物质。不受理论的限制，催化剂可包括例如：甘氨酸盐；叔胺；叔膦，诸如，三烷基膦和二烷基苄基膦；吗啉衍生物；哌嗪衍生物；各种金属的螯合物，诸如可以从乙酰丙酮、苯甲酰丙酮、三氟乙酰丙酮、乙酰乙酸乙酯等与金属(诸如Be、Mg、Zn、Cd、Pd、Ti、Zr、Sn、As、Bi、Cr、Mo、Mn、Fe、Co和Ni)获得的那些；强酸的酸性金属盐，诸如氯化铁、氯化锡；有机酸与各种金属(诸如，碱金属、碱土金属、Al、Sn、Pb、Mn、Co、Ni和Cu)的盐；有机锡化合物，诸如有机羧酸的锡(II)盐，例如，二乙酸锡(II)、二辛酸锡(II)、二乙基己酸锡(II)和二月桂酸锡(II)，以及有机羧酸的二烷基锡(IV)盐，例如，二乙酸二丁基锡、二月桂酸二丁基锡、马来酸二丁基锡和二乙酸二辛基锡；有机羧酸的铋盐，例如，辛酸铋；三价和五价As、Sb和Bi的有机金属衍生物以及铁和钴的羰基金属；或它们的混合物。
叔胺催化剂包括含有至少一个叔氮原子并且能够催化羟基/异氰酸酯反应的有机化合物。叔胺、吗啉衍生物和哌嗪衍生物催化剂可包括，例如但不限于，三亚乙基二胺、四甲基亚乙基二胺、五甲基二亚乙基三胺、双(2-二甲基氨基乙基)醚、三乙胺、三丙胺、三丁胺、三戊胺、吡啶、喹啉、二甲基哌嗪、哌嗪、N-乙基吗啉、2-甲基丙二胺、甲基三亚乙基二胺、2,4,6-三二甲基氨基-甲基)苯酚、N,N’,N”-三(二甲基氨基-丙基)sym-六氢三嗪或它们的混合物。
一般来讲，基于异氰酸酯组分(A)、异氰酸酯反应性组分(B)和羟基封端硅氧烷化合物(C)的总重量，本文所用的催化剂的含量大于零并且至多为1.0重量％，优选地至多0.5重量％，更优选地至多0.05重量％。可看出，催化剂的含量计算为额外量，同时将异氰酸酯组分(A)、异氰酸酯反应性组分(B)和羟基封端硅氧烷化合物(C)的总量取为100重量％。
乳化剂
根据本公开的一个实施例，乳化剂(E)包含至少一个离子亲水基团或潜在离子亲水基团和至少两个异氰酸酯反应性基团，其中异氰酸酯反应性基团(诸如羟基、胺和巯基基团)可与异氰酸酯基团反应以将具有离子亲水侧基或潜在离子亲水侧基的链段引入所得PU颗粒的聚氨酯-硅氧烷主链中。离子亲水侧基或潜在离子亲水侧基赋予所得聚氨酯颗粒在PUD中的改善自分散性和稳定性。(潜在)离子亲水基团以相比于乳化剂所含有的异氰酸酯基团或异氰酸酯反应性基团的显著较低反应速率与异氰酸酯组分或异氰酸酯反应性组分反应。
在本公开的一个实施例中，(潜在)离子亲水基团包括阴离子基团，诸如其碱金属盐或铵盐形式的磺酸盐、羧酸盐和磷酸盐；以及阳离子基团，诸如铵基团，尤其质子化叔氨基或季铵基团。潜在离子亲水性基团包括可以通过简单的中和、水解或季铵化反应转化成上述离子亲水性基团(例如，羧酸基团、酸酐基团或叔氨基)的那些基团。
在本公开的一个优选实施例中，(潜在)阳离子乳化剂包括具有叔氨基基团的可共聚单体，例如：三(羟烷基)胺、N,N'-双(羟烷基)-烷基胺、N-羟烷基二烷基胺、三(氨基烷基)胺、N,N'-双(氨基烷基)烷基胺、N-氨基烷基二烷基胺，其中这些叔胺的烷基自由基和烷二基单元独立地包括1到6个碳原子。这些叔胺用酸，优选地强无机酸，如磷酸、硫酸、氢卤酸或强有机酸，或者通过与合适的季铵化剂，如C1到C6烷基卤化物或苄基卤化物，例如溴化物或氯化物反应而转化成铵盐。
在本公开的一个优选实施例中，具有(潜在)阴离子基团的乳化剂包括脂肪族、脂环族、芳脂族或芳香族羧酸、碳酸和磺酸，它们承载至少一个醇羟基基团或至少一个伯氨基基团或仲氨基基团。优选的是具有3到10个碳原子的二羟基烷基羧酸，如二羟基甲基丙酸(DMPA)、二羟甲基丁酸(DMBA)、二羟基磺酸、二羟基膦酸(如2,3-二羟基丙烷膦酸)。如果使用具有潜在离子基团的乳化剂，则它们可在异氰酸酯加成聚合之前、期间，但优选地之后转化为离子形式。磺酸根或羧酸根基团特别优选地以其与作为抗衡离子的碱金属离子或铵离子的盐的形式存在。
根据本公开的一个实施例，基于异氰酸酯组分(A)、异氰酸酯反应性组分(B)和羟基封端硅氧烷化合物(C)的总重量，乳化剂(E)的含量为0.01重量％至10重量％，或0.05重量％至8重量％，0.1重量％至7重量％，或0.2重量％至6重量％，或0.5重量％至5重量％，或1重量％至5重量％，或2重量％至5重量％，或3重量％至5重量％，或4重量％至5重量％。可看出，扩链剂的含量计算为额外量，同时将异氰酸酯组分(A)、异氰酸酯反应性组分(B)和羟基封端硅氧烷化合物(C)的总量取为100重量％。
扩链剂
根据本公开的一个实施例，扩链剂可以是二胺或具有另一异氰酸酯反应性基团的胺化合物，但优选地选自由以下项组成的组：胺化聚醚二醇；哌嗪；氨基乙基乙醇胺；包含至少两个胺基团的C2-C16脂肪族多胺，例如乙二胺；包含至少两个胺基团的C4-C15脂环族或芳族多胺，诸如环己二胺和对二甲苯二胺；包含至少两个胺基团的C7-C15芳脂族多胺；胺化的C2-C8醇，例如乙醇胺；以及它们的混合物。根据优选的实施例，扩链剂是具有官能度2并包含伯胺基团或仲胺基团的多胺。优选地，将胺扩链剂溶解在用于制备PU分散体的水中。
根据本公开的一个实施例，基于异氰酸酯组分(A)、异氰酸酯反应性组分(B)和羟基封端硅氧烷化合物(C)的总重量，扩链剂的含量为0.01重量％至10重量％，或0.05重量％至8重量％，0.1重量％至7重量％，或0.2重量％至6重量％，或0.5重量％至5重量％，或1重量％至3重量％。可看出，扩链剂的含量计算为额外量，同时将异氰酸酯组分(A)、异氰酸酯反应性组分(B)和羟基封端硅氧烷化合物(C)的总量取为100重量％。
水性聚氨酯分散体
根据本申请的一个实施例，水性聚氨酯分散体通过三阶段反应来制备。
在第一阶段，在存在催化剂(D)的情况下，异氰酸酯组分(A)中的异氰酸酯基团与异氰酸酯反应性组分(B)中的异氰酸酯反应性基团和羟基封端硅氧烷化合物(C)中的末端羟基基团反应以形成第一预聚合中间体。不受限于任何特定理论，第一预聚合中间体包括异氰酸酯组分(A)和异氰酸酯反应性组分(B)的反应产物I和异氰酸酯组分(A)和羟基封端硅氧烷化合物(C)的反应产物II的混合物。因为异氰酸酯组分(A)以相对于组分(B)中异氰酸酯反应性基团和组分(C)中末端羟基基团的组合量的化学计量上的过量来使用，所以上文所指示反应产物I和II均以游离NCO基团进行封端。
在第二阶段，将乳化剂添加至第一预聚合中间体中并与反应产物I和II反应以形成第二预聚合中间体；该第二预聚合中间体包含衍生自异氰酸酯组分(A)、异氰酸酯反应性组分(B)和羟基封端硅氧烷化合物(C)的聚合物段，以及乳化剂的残留部分。如上所述及，乳化剂(E)包含至少一个离子亲水基团或潜在离子亲水基团和至少两个异氰酸酯反应性基团，其中(潜在)离子亲水基团以相比于乳化剂所含有的异氰酸酯基团或异氰酸酯反应性基团的显著较低速率与异氰酸酯组分或异氰酸酯反应性组分反应。在第二阶段的反应中，乳化剂中的两个异氰酸酯反应性基团与反应产物I和II中的末端游离NCO基团反应，以将反应产物I和II的链段连接在一起并且同时将(潜在)离子亲水依赖性基团引入主链中。
在第三阶段，第二预聚合中间体在剧烈搅拌下与扩链剂反应以形成PUD。根据本公开的一个实施例，第二预聚合中间体包含阴离子依赖性基团，并且在扩链剂的添加之前，添加中和剂以中和阴离子依赖性基团。中和剂可包括任何碱性物质，该碱性物质可中和阴离子依赖性基团而不影响聚氨酯的形成。根据本公开的一个实施例，中和剂为胺，诸如三乙胺。
水性聚氨酯分散体包括分散于水中的聚氨酯颗粒。可以将水性聚氨酯分散体加热和干燥以形成皮膜，该皮膜表现出优异的改进的抗粘性能同时保持良好的PUD膜机械性质。
水性聚氨酯分散体可以具有聚氨酯颗粒的任何合适的固体负载，但是通常固体负载为总分散体重量的约1重量％到约70重量％固体、优选地至少约2重量％、更优选地至少约4重量％、更优选地至少约6重量％、更优选地至少约15重量％、更优选地至少约25重量％、更优选地至少约35重量％、最优选地至少约40重量％到至多约70重量％、优选地至多68重量％、更优选地至多约65重量％、更优选地至多约60重量％并且最优选地至多约50重量％。
水性聚氨酯分散体还可含有流变改性剂，诸如增强分散体的分散性和稳定性的增稠剂。可使用任何合适的流变改性剂，如本领域已知的流变改性剂。优选地，流变改性剂是不会引起分散体变得不稳定的流变改性剂。更优选地，流变改性剂是未离子化的水溶性增稠剂。有用的流变改性剂的实例包括甲基纤维素醚、碱溶胀性增稠剂(例如，钠或铵中和的丙烯酸聚合物)、疏水改性的碱溶胀性增稠剂(例如，疏水改性的丙烯酸共聚物)和缔合性增稠剂(例如，疏水改性的基于环氧乙烷的氨基甲酸酯嵌段共聚物)。优选地，流变改性剂是甲基纤维素醚。增稠剂的量为水性聚氨酯分散体的总重量的至少约0.2重量％到约5重量％、优选地约0.5重量％到约2重量％。
通常，水性聚氨酯分散体所具有的粘度为至少约10cp到至多约10,000cp、优选地至少约20cp到至多约5000cp、更优选地至少约30cp到至多约3000cp。
在本公开的一个实施例中，PU颗粒在水性聚氨酯分散体中的分散可通过表面活性剂和高剪切搅拌作用来促进，其中剪切力和搅拌速度可基于具体需要而适当地调整。
根据本公开的一个实施例，水性聚氨酯分散体还可包含一种或多种颜料、染料和/或着色剂，所有颜料、染料和/或着色剂在本公开中通常被称为“色母料”。例如，可加入色母料，以便对透明或半透明膜赋予期望的颜色。颜料、染料和/或着色剂的实例可包括氧化铁、氧化钛、碳黑以及它们的混合物。按水性聚氨酯分散体的总重量计，颜料、染料和/或着色剂的量可以为0.1重量％到15重量％、优选地0.5-10重量％、更优选地1重量％到5重量％。可用于本发明的合适的可商购获得的黑色颜料可包括例如可从朗盛德国有限责任公司(Lanxess Deutschland GmbH)获得的EUDERMTM黑色B-N碳黑分散体。
层压合成皮革制品
图1是本文所述的合成皮革制品的一个实施例的横截面的示意图。在本发明的一个实施例中，合成皮革制品从上到下包含由水性聚氨酯分散体形成的顶部皮膜、2K PU泡沫基层和背衬基材(例如纺织布)。请注意，皮革制品未必按实际比例示出，并且一层或多层的尺寸可夸大以清楚地示出皮革制品的配置。
本公开所使用的2K PU泡沫优选为非溶剂PU泡沫，并且包含在其中限定多个孔和/或泡孔的连续PU基质。如本文所公开的，术语“无溶剂(solvent free)”、“无溶剂(solventless)”或“非溶剂”可以互换地用于描述PU泡沫或任何其它分散体、混合物等，并且应当解释为按原材料的混合物的总重量计，用于制备PU泡沫或PU分散体的所有原材料的混合物包含小于3重量％、优选地小于2重量％、优选地小于1重量％、更优选地小于0.5重量％、更优选地小于0.2重量％、更优选地小于0.1重量％、更优选地小于100ppm重量份、更优选地小于50ppm重量份、更优选地小于10ppm重量份、更优选地小于1ppm重量份的任何有机溶剂或无机溶剂。如本文所公开的，术语“溶剂”是指其功能是仅溶解一种或多种固体、液体或气体材料而不会引发任何化学反应的有机液体和无机液体。换句话说，尽管在聚合技术中通常视为“溶剂”的一些有机化合物(例如乙二醇和丙二醇以及水)用于制备2k PU泡沫，但是它们均不属于“溶剂”，因为它们通过引发化学反应而主要地作用为异氰酸酯反应性官能物质、扩链剂或发泡剂等。
根据本公开的一个实施例，2k PU泡沫层的厚度在0.01μm至2,000μm的范围内，优选地在0.05μm至1,000μm的范围内，更优选地在0.1μm到750μm的范围内，和更优选地在0.2μm到600μm的范围内。
根据本公开的一个实施例，聚氨酯泡沫层中的2K发泡聚氨酯以无溶剂聚氨酯体系来制备，该无溶剂聚氨酯体系包含：(i)一种或多种第二异氰酸酯组分，(ii)一种或多种第二异氰酸酯反应性组分，(iii)一种或多种发泡剂、第二催化剂和任何其它添加剂。第二异氰酸酯组分(i)包括一种或多种用于异氰酸酯组分(A)的聚异氰酸酯和/或异氰酸酯预聚物。第二异氰酸酯反应性组分(ii)包含具有选自以下的两个或更多个异氰酸酯反应性基团的化合物：OH基团、SH基团、NH基团、NH2基团和碳酸基团，例如β-二酮基团。根据本申请的一个实施例，异氰酸酯反应性组分(ii)包含用于异氰酸酯反应性组分(B)的那些。在本公开的一个优选实施例中，第二异氰酸酯组分(i)和第二异氰酸酯反应性组分(ii)在存在发泡剂/起泡剂的情况下彼此反应，并且发泡剂与异氰酸酯反应性组分组合使用。有用的发泡剂包括通常已知的化学或物理反应性化合物。物理起泡剂可以选自由以下项组成的组中的一种或多种：二氧化碳、氮气、稀有气体、具有4到8个碳原子的(环)脂肪族烃、二烷基醚、酯、酮、缩醛和具有1到8个碳原子的氟代烷烃。化学反应性起泡剂优选地包含水，其优选地作为与异氰酸酯反应性组分(ii)的共混物的成分而被包含在内。按用于制备2k PU泡沫层的所有原材料的总重量计，发泡剂的量在0.05到10重量％的范围内，优选地在0.1到5重量％的范围内，更优选地为0.1到2重量％并且最优选地为0.1到0.5重量％。2K PU层的密度通常为0.3到1.1千克/升，并且密度优选地为0.4到0.9千克/升。
在本公开的一个实施例中，基于用于制备2k PU泡沫层的所有原材料的整体重量，第二异氰酸酯组分(i)在存在选自有机锡化合物(诸如二乙酸锡、二辛酸锡、二月桂酸二丁基锡)和/或强碱性胺(诸如二氮杂双环辛烷、三乙胺、三亚乙基二胺或双(N,N-二甲基氨基乙基)醚)的催化剂的情况下与第二异氰酸酯反应性组分(ii)反应，该催化剂的量为0.01重量％到5重量％，优选地0.05重量％到4重量％，更优选地0.05重量％到3重量％。
在本公开的实施例中，特别选择第二异氰酸酯组分(i)和第二异氰酸酯反应性组分(Bii)的类别和摩尔含量，使得NCO基团与NCO反应性氢原子(例如，羟基中的氢原子)的总当量比在0.9:1到1.8:1的范围内，优选地在0.92:1到1.6:1的范围内，优选地在0.95:1到1.5:1的范围内并且更优选地在1:1到1.45:1的范围内，更优选地在1.05:1到1.4:1的范围内并且更优选地在1.10:1到1.35:1的范围内。
释放层
合适的释放层在现有技术中通常被称为“离型纸”。合适的释放层的实例包括金属箔、塑料箔或纸箔。在本公开的一个优选实施例中，释放层是可选地用塑料膜涂覆的纸层。优选地，用聚烯烃、更优选地用聚丙烯涂覆本文公开的纸层。可替代地，优选地用硅酮涂覆纸层。在另选实施例中，本文所使用的释放层是可选地用塑料膜涂覆的PET层。优选地，可用聚烯烃、更优选地用聚丙烯涂覆PET层。可替代地，优选地用硅酮涂覆PET层。合适的释放层的实例是可商购获得的。本公开中使用的释放层可以具有平坦的、压花的或图案化的表面，使得可以在合成皮革制品的最外表面上形成对应的或互补的表面轮廓。优选地，释放层以皮革纹理的模式纹理化，从而对合成皮革制品赋予与高级天然皮革相当的良好触觉性质。释放层的厚度通常为0.001mm到10mm、优选地0.01mm到5mm并且更优选地0.1mm到2mm。
只要释放层能够耐受在制造过程期间经历的化学反应、机械加工和热处理，并且可容易地从所得到的合成皮革上剥离而不引起皮膜与2k PU泡沫基层之间的分层，可适当地调整释放层的材料和厚度。
助剂和添加剂
PU皮膜和2K PU泡沫基层可独立地且可选地包含用于特定目的的任何附加的助剂和/或添加剂。
在本公开的一个实施例中，助剂和/或添加剂的一者或多者可选自由以下项组成的组：填充剂、泡孔调节剂、释放剂、着色剂/颜料、表面活性化合物、手感剂、消光剂、增稠剂、交联剂和稳定剂。
合适的填充剂的实例包括玻璃纤维、矿物纤维、天然纤维(诸如亚麻、黄麻或剑麻)，例如玻璃鳞片、硅酸盐(诸如云母(mica)或云母(glimmer))、盐(诸如碳酸钙、白垩或石膏)。基于皮膜或2K PU泡沫层的总干重，填充剂通常以0.5重量％到60重量％、优选地3重量％到30重量％并且更优选地3重量％到10重量％的量使用。
背衬基材
在本公开的实施例中，背衬基材所具有的厚度在0.01mm到50mm的范围内，优选地在0.05mm到10mm的范围内并且更特别地在0.1mm到5mm的范围内。背衬基材可包含选自由以下项组成的组中的一种或多种：织物，优选地织造或非织造织物、浸渍织物、针织织物、编织织物或微纤维；金属箔或塑料箔，例如橡胶、PVC或聚酰胺；以及皮革，优选地剖层皮革。
背衬基材可由织造或非织造织物制成。优选地，纺织品是非织造纺织品。纺织品可以通过任何合适的方法制造，如本领域中已知的方法。纺织品可以由任何合适的纤维材料制备。合适的纤维材料包括但不限于合成纤维材料和天然纤维材料或半合成纤维材料及其混合物或共混物。合成纤维材料的实例包括聚酯、聚酰胺、丙烯酸树脂、聚烯烃、聚氯乙烯、聚偏二氯乙烯、聚乙烯醇及其共混物或混合物。天然的半合成纤维材料的实例包括棉、羊毛和大麻。
制造技术
水性聚氨酯分散体可通过常规的涂覆技术，诸如喷涂、刮涂、模涂、铸涂等进行施涂。
在施涂下一层之前，可以将皮膜部分地或完全地干燥。优选地，将皮膜完全地干燥，以便使其中截留的水分最小化，并且然后在其上施涂下一层。在本申请的另选实施例中，仅从释放层上的皮膜去除一部分水分，然后将皮膜与在其上施涂的2K PU泡沫层一起完全地干燥。
根据一个实施例，将用于2K非溶剂PU泡沫的第二异氰酸酯组分(i)和第二异氰酸酯反应性组分(ii)混合在一起，施涂到皮膜，并且通过在例如70℃到120℃、优选地75℃到110℃的温度下在烘箱中加热持续10秒到5分钟、更优选地30秒到2分钟、更优选地45到90秒的短持续时间来预固化。然后在加压辊的辅助下，将背衬基材(例如，纺织品织物)施涂到预固化的2k PU泡沫层，随后在例如100℃到160℃、优选地110℃到150℃的较高温度下后固化持续3到20分钟、优选地3到15分钟、更优选地4到10分钟的较长持续时间。上述两步固化工艺旨在确保预固化的2k PU泡沫与背衬基材之间的高粘附强度。
根据本公开的优选实施例，在2k PU泡沫已经完全固化之后去除释放层。释放层可以经由任何普通技术剥离。
根据本公开的优选实施例，在去除释放层之后，可以将顶部终饰层施涂到合成皮革的表面上(即，皮膜的最外表面上)并且干燥以形成保护膜层。终饰层的存在可以进一步提高多层合成皮革的耐磨性。可以通过使用任何合适的原材料和技术来形成保护膜层。终饰层可以可选地包含添加剂，诸如润湿剂、交联剂、粘合剂、消光剂、手感改性剂、颜料和/或着色剂、增稠剂或用于皮膜的其它添加剂。本文公开的合成皮革还可包含一个或多个任选附加层，诸如皮膜与终饰层之间的颜色层。其它合适的可选的附加层可以选自防水层、UV保护层和触觉(触摸/感觉)改性层。
本发明的工艺可连续地或分批地进行。连续工艺的实例为卷对卷工艺，并且示意性地示于图2中。将一卷的离型纸展开并传送通过两个或多个工作台，其中依次涂覆本申请的PUD和2K PU分散体。本申请的PUD可涂覆一次以上，以获得期望膜厚度或组合物分布。例如，图2示出，第二PUD涂覆于由第一PUD所形成的膜的表面上。第二PU皮膜可具有等同于或不同于第一PU皮膜的厚度和组合物，以满足实际工业需求。加热或照射装置可以布置成在每个涂覆站之后，以促进涂覆层的干燥或固化，并且还可使用辊来增强各层之间的粘附强度。未卷绕的释放层的长度通常为10到20,000米，10到15,000米并且优选地20到10,000米，并且通常以范围为0.1到60米/分钟，优选地3到45米/分钟，更优选地5到15米/分钟的速度传输。在连续技术的最后，释放层被剥离并卷绕在主轴上。卷绕的释放层可以被重复使用，优选地至少2次。
织物背衬基材可以卷对卷模式来提供(即，背衬基材提供为卷)，可展开并涂覆于部分地固化的2K PU泡沫的表面上，然后将2K PU泡沫完全地固化，并且层压合成皮革制品可卷绕于主轴上并且作为卷来储存/销售。
在一个优选的实施例中，合成皮革通过在一个或两个方向(即，单轴或双轴定向)上拉伸来定向。定向的合成皮革的尺寸可以增加1.1到5倍，优选地1.2到2倍。定向的合成皮革表现出改善的透气性。
本文公开的多层结构合成皮革可进行切割或以其它方式成形，从而具有适用于任何期望目的(如鞋子制造)的形状。根据预期应用，可与天然皮革类似地对合成皮革进行进一步处理或后处理，例如通过刷涂、填充、碾磨或熨烫。如果需要，合成皮革(如天然皮革)可以常规终饰组合物进行终饰。这提供了控制其特性的进一步可能性。本文公开的多层结构可以用于特别适合用作合成皮革的各种应用中，例如鞋类、手提包、皮带、钱包、服装、家具装饰品、汽车装饰品和手套。多层结构特别适用于汽车应用。
实例
现将在以下实例中描述本发明的一些实施例，其中除非另外说明，否则所有份数和百分比均以重量计。
下表1中列出了实例中使用的原材料的信息：
表1.实例所用的原材料：
通过将表1所示的异氰酸酯预聚物(VoralastTM GE 143ISO)与表2所列出的多元醇原材料相组，来制备2K非溶剂PU泡沫。
表2. 2K PU复合材料所用的多元醇原材料
在下述实例中，通过下述步骤1)至4)制备了包含衍生自水性聚氨酯分散体的皮膜和2k PU基层的合成皮革制品。
1)水性聚氨酯分散体的制备
将7112T(25.00g)、IPDI(11.11g)和OH封端硅氧烷(如果存在的话)装入1000ml的三颈烧瓶中并在80℃下混合1小时，然后将0.2g的催化剂(DBTDL)添加至烧瓶以开始反应。反应持续两个小时以产生第一预聚合中间体。将DMPA(1.68g)添加至烧瓶并反应2小时。将第一预聚合中间体冷却至40℃，并以TEA(1.26g)中和30分钟。在上述过程期间将少量的丙酮添加至烧瓶，以将反应体系的粘度保持为约500cps。将烧瓶冷却至室温，并在在剧烈搅拌下将EDA(0.83g)的93g水溶液添加至烧瓶以形成PUD。最后，丙酮通过减压蒸馏来从PUD移除。
利用如表3所示的不同配方，制备了六种PU分散体。所有这些PUD具有30重量％的固体含量。
表3.用于制备PUD的羟基封端硅氧烷
| 羟基封端硅氧烷 | 羟基封端硅氧烷的量(克) | |
| PUD A | 无 | 0 |
| PUD B | SF 8427 | 2.50 |
| PUD C | SF 8427 | 5.00 |
| PUD D | BY 16-201 | 2.50 |
| PUD E | Di-10 | 2.50 |
| PUD F | Di-10 | 1.25 |
2)PU膜的制备
称取22.5克的步骤1)所制备的聚氨酯分散体，转移至真空烘箱中并脱气约10分钟。然后，将脱气PUD倾注至塑料表面培养皿中，并且在环境条件下静置过夜。将填充有PUD的培养皿在40℃下的加热平台加热24小时，并且在60℃的空气干燥烘箱中加热24小时。将膜从培养皿剥离，干燥另外24小时，并且冷却至室温以用于测试。使用PUD A至PUD F，分别制备了六种PU膜。
3)合成皮革的制造
将步骤1)所制备的水性聚氨酯分散体与表4所示的色母料和增稠剂在高速(1000至3000rpm)下混合数分钟。将配制的PUD涂覆在离型纸上至湿膜厚度为150μm。将涂覆离型纸在60℃下的烘箱中干燥10分钟，并且然后在130℃下干燥10分钟。将具有干燥PU皮层的离型纸从烘箱中取出并冷却至环境温度。将配制2K PU复合材料涂覆于干燥PU皮膜上至300μm的湿膜厚度。将具有PU皮膜和所涂覆2K PU复合材料的离型纸转移至85℃的烘箱中并预固化45秒。然后，将背衬基材(纺织布)小心地施加至2K PU泡沫层上，并以3.5kg的辊压制2次。将试样放入120℃的烘箱中，并且后固化10分钟，然后取出并冷却。
表4.步骤3)所用原材料的量(重量％)
表征PUD和合成皮革
(a)PUD A至F的平均粒径和稳定性(在不同持续时间之后)通过利用马尔文仪器ZS90粒度仪和Zeta电位分析仪的动态光散射技术在25℃下进行表征，并且表征结果总结于表5中。可看出，所有PUD具有优异稳定性。
表5.PUD A至F的表征结果
(b)PUD A至E的TEM显微照片示出于图3中，其中图(a)至(e)分别对应于PUD A至E。可看出，PUD B至D(通过利用由式I所表示的羟基封端硅氧烷化合物来制备)具有均匀颗粒结构，而PUD E(通过利用不含任何环氧烷段的羟基封端硅氧烷化合物来制备)包括具有核-壳结构的颗粒。不受限于任何特定理论，据推测，PUD E中PU颗粒的组合物和结构的差异可为其劣化抗粘性的原因。
(c)在室温下，在接触角系统(Data Physics，OCA20，德国)上测量PU膜的水接触角，该PU膜通过利用PUD A至PUD D来制备。安装注射器，使得3μl的水滴通过注射器的针头滴落于膜样品的表面上。拍摄液滴的照片，以通过座滴法计算接触角。每个样品进行五次测量，并且利用平均数值来分析。测量结果总结于表6中；从表6可看出，以PUD B至PUD D所制备的PU膜相比于具有对照PUD A的PUD膜表现出较高水接触角(即，更佳疏水性)，该对照PUDA不含由式I所表示的羟基封端硅氧烷化合物。
表6.PU膜的水接触角以PUD A至PUD D来制备
| PUD A | PUD B | PUD C | PUD D | |
| 水接触角 | 87.7 | 95.5 | 104.5 | 100.8 |
(d)步骤3所制备的合成皮革制品的性能性质
上述步骤3)所制备的合成皮革制品的抗粘性根据标准GB/T 8948-2008进行表征。特别地，将合成皮革制品的两个90mm×60mm样品在1kg的压力下面对面粘贴在一起，并在85℃的烘箱中加热3小时。根据在室温下分离两个样品的过程中两个样品之间的粘性程度对抗粘性进行从1到5的分级：
等级1：完全不粘；
等级2：可以用少量力分离；
等级3：可以用一定的力分离并且不破坏表面；
等级4：可以用大的力分离并且表面出现不完全损坏；以及
等级5：无法分离。
根据标准GB/T 2726-2005，以No.-CS10的轮在1000g载荷下进行1000次循环，表征了上述步骤3)所制备的合成皮革制品的COF(摩擦系数)。当获得4级或更高颜色记分卡的结果时，合成皮革制品标记为“通过”。
表7.皮革制品的外观、抗粘性和COF。
图4示出了实例1至2和实例3至5所制备的合成皮革的照片，这些照片清楚地示出以羟基封端硅氧烷化合物所制备的合成皮革的优异抗粘性。
皮革外观：
视觉上检查皮革外观，并且“良好”意指光滑并且无气泡。
上述步骤3)所制备的合成皮革制品的湿色牢度根据GB/T20991进行表征。湿白狼布用于测试表面。当湿白狼布的表面呈暗色时，对数量进行计数。更多测试数量意味着更佳湿色牢度。
表8.皮革制品的外观、湿色牢度和COF。
表8的结果示出，实例3至4中所制备的合成皮革(其由具有高EO(约52％，基于重量)改性PUD的PEO-PDMS-PEO来制备)未示出相比于实例1的皮层的湿色牢度的任何改善；而实例2和实例5至6(其由不具有EO单元的羟基封端硅氧烷化合物(实例2和6)或具有低EO含量(约26％，基于重量)改性PUD的OH封端硅氧烷(实例5)来制备)，相比于实例1，可显著地改善皮层的湿色牢度。
Claims (17)
1.一种水性聚氨酯分散体，所述水性聚氨酯分散体包含分散在水中的聚氨酯颗粒，其中，所述水性聚氨酯分散体衍生自：
(A)包含一种或多种具有至少两个异氰酸酯基团的化合物的异氰酸酯组分；
(B)包含一种或多种具有至少两个异氰酸酯反应性基团的化合物的异氰酸酯反应性组分；
(C)由式I所表示的羟基封端硅氧烷化合物：
其中R1和R4的每一者独立地表示以选自由以下项组成的组的一个或两个取代基所任选取代的亚甲基：C1-C5烷基、C1-C5烷氧基、C6-C12芳基、C6-C12芳氧基和卤素；
R2和R3的每一者独立地表示以选自由以下项组成的组的一个或多个取代基所任选取代的C1-C6氧化烯基团：C1-C5烷基、C1-C5烷氧基、C6-C12芳基、C6-C12芳氧基和卤素；
R5、R6、R7、R8、R9和R10的每一者独立地表示以选自由以下项组成的组的一个或多个取代基所任选取代的C1-C5烷基：C1-C5烷基、C1-C5烷氧基、C6-C12芳基、C6-C12芳氧基和卤素；
其中a和e的每一者独立地为0至30的整数；b和d的每一者独立地为5至30的整数；并且c为3至100的整数；或
a和e的每一者独立地为1至30的整数；b和d的每一者独立地为0的整数；并且c为3至100的整数；
(D)催化剂；
(E)乳化剂；
(F)扩链剂；和
(G)水。
2.根据权利要求1所述的水性聚氨酯分散体，其中所述羟基封端硅氧烷化合物由式II表示：
其中a和e的每一者独立地为0至30的整数；b和d的每一者独立地为5至30的整数；并且c为3至100的整数；或
a和e的每一者独立地为1至30的整数；b和d的每一者独立地为0的整数；并且c为3至100的整数。
3.根据权利要求1所述的水性聚氨酯分散体，其中所述羟基封端硅氧烷化合物由式II表示：
其中a和e的每一者独立地为5至10的整数；b和d的每一者独立地为5至7的整数；并且c为20至40的整数。
4.根据权利要求1所述的水性聚氨酯分散体，其中所述羟基封端硅氧烷化合物由式II表示：
其中a和e的每一者独立地为0至30的整数；b和d的每一者独立地为5至30的整数；并且c为3至100的整数，并且其中所述羟基封端硅氧烷化合物的EO含量基于重量小于40％或小于30％。
5.根据权利要求1所述的水性聚氨酯分散体，其中具有至少两个异氰酸酯基团的所述一种或多种化合物选自由以下项组成的组：
a)包含至少两个异氰酸酯基团的C4-C12脂肪族聚异氰酸酯、包含至少两个异氰酸酯基团的C6-C15脂环族或芳香族聚异氰酸酯、包含至少两个异氰酸酯基团的C7-C15芳脂族聚异氰酸酯，以及它们的组合；和
b)通过使a)的一种或多种聚异氰酸酯与选自由以下项组成的组的一种或多种异氰酸酯反应性组分反应所制备的异氰酸酯预聚物：包含至少两个羟基基团的C2-C16脂肪族多元醇、包含至少两个羟基基团的C6-C15脂环族或芳香族多元醇、包含至少两个羟基基团的C7-C15芳脂族多元醇、分子量为500至5,000的聚酯多元醇、分子量为200至5,000的聚碳酸酯二醇、分子量为200至5,000的聚醚二醇、包含至少两个氨基基团的C2至C10聚胺、包含至少两个硫醇基团的C2至C10聚硫醇、包含至少一个羟基基团和至少一个氨基基团的C2-C10烷醇胺，以及它们的组合，条件是所述异氰酸酯预聚物包含至少两个自由异氰酸酯端基基团。
6.根据权利要求1所述的水性聚氨酯分散体，其中基于所述异氰酸酯反应性组分(B)和所述羟基封端硅氧烷化合物(C)的总摩尔含量，所述异氰酸酯组分(A)的含量为101摩尔％至300摩尔％(C)。
7.根据权利要求1所述的水性聚氨酯分散体，其中具有至少两个异氰酸酯反应性基团的所述一种或多种化合物选自由以下项组成的组：包含至少两个羟基基团的C2-C16脂肪族多元醇、包含至少两个羟基基团的C6-C15脂环族或芳香族多元醇、包含至少两个羟基基团的C7-C15芳脂族多元醇、分子量为500至5,000的聚酯多元醇、分子量为200至5,000的聚碳酸酯二醇、分子量为200至5,000的聚醚二醇、包含至少两个氨基基团的C2至C10聚胺、包含至少两个硫醇基团的C2至C10聚硫醇、包含至少一个羟基基团和至少一个氨基基团的C2-C10烷醇胺、具有至少两个羟基基团的植物油，以及它们的组合。
8.根据权利要求1所述的水性聚氨酯分散体，其中所述异氰酸酯反应性组分(B)的含量为50摩尔％至98摩尔％，基于所述异氰酸酯反应性组分(B)和所述羟基封端硅氧烷化合物(C)的总摩尔含量。
9.根据权利要求1所述的水性聚氨酯分散体，其中基于所述异氰酸酯反应性组分(B)和所述羟基封端硅氧烷化合物(C)的总摩尔含量，所述羟基封端硅氧烷化合物(C)的含量为2摩尔％至50摩尔％。
10.根据权利要求1所述的水性聚氨酯分散体，其中所述催化剂(D)选自由以下项组成的组：有机锡化合物、有机铋化合物、叔胺、吗啉衍生物、哌嗪衍生物，以及它们的组合；并且
其中基于所述异氰酸酯组分(A)、所述异氰酸酯反应性组分(B)和所述羟基封端硅氧烷化合物(C)的总重量，所述催化剂(D)的含量为1.0重量％或更少。
11.根据权利要求1所述的水性聚氨酯分散体，其中所述乳化剂(E)包含2至12个碳原子、至少一个离子亲水基团或潜在离子亲水基团，和至少两个异氰酸酯反应性基团，
其中所述离子亲水基团选自由以下项组成的组：磺酸基团、磺酸根、羧基基团、羧酸根、含磷酸基团、含磷酸盐基团、质子化叔胺基团和季铵基团，其中所述潜在离子亲水基团能够通过中和、水解或季铵化反应转化为所述离子亲水基团；
所述乳化剂中所含有的所述异氰酸酯反应性基团选自由以下项组成的组：羟基、胺基和巯基基团；和
其中所述乳化剂(E)的量为0.01重量％至10重量％，基于所述异氰酸酯组分(A)、所述异氰酸酯反应性组分(B)和所述羟基封端硅氧烷化合物(C)的总重量。
12.根据权利要求1所述的水性聚氨酯分散体，其中所述扩链剂(F)选自由以下项组成的组：包含至少两个胺基基团的C2-C16脂肪族多胺、包含至少两个胺基基团的C4-C15脂环族或芳香族多胺、包含至少两个胺基基团的C7-C15芳脂族多胺；并且
其中基于所述异氰酸酯组分(A)、所述异氰酸酯反应性组分(B)和所述羟基封端硅氧烷化合物(C)的总重量，所述扩链剂(F)的含量为1.0重量％至15重量％。
13.根据权利要求1所述的水性聚氨酯分散体，其中基于所述水性聚氨酯分散体的总重量，所述水性聚氨酯分散体具有5重量％至50重量％的固体含量；并且
所述聚氨酯颗粒具有的体积平均粒径为20nm至5μm。
14.一种用于制备根据权利要求1至13中任一项所述的水性聚氨酯分散体的方法，所述方法包括：
(i)在存在所述催化剂(D)的情况下使所述异氰酸酯组分(A)与所述异氰酸酯反应性组分(B)以及所述羟基封端硅氧烷化合物(C)反应以形成第一预聚合中间体；
(ii)使所述第一预聚合中间体与所述乳化剂(E)反应以形成第二预聚合中间体；
(iii)使所述第二预聚合中间体与所述扩链剂(F)反应以形成水性聚氨酯分散体。
15.根据权利要求1所述的方法，其中步骤(ii)所形成的所述第二预聚合中间体在与所述增链剂(F)反应之前以中和剂进行中和。
16.一种合成皮革制品，所述合成皮革制品从上到下包含：
衍生自根据权利要求1至13中任一项所述的水性聚氨酯分散体的聚氨酯皮膜；
衍生自2k PU复合组合物的基层；和
可选的背衬基材，其中，所述聚氨酯皮膜与所述基层直接接触，并且所述背衬基材在存在时与所述基层直接接触。
17.一种用于制备根据权利要求16所述的合成皮革制品的方法，所述方法包括：
a)提供根据权利要求1至13中任一项所述的水性聚氨酯分散体；
b)以所述水性聚氨酯分散体形成所述聚氨酯皮膜；
c)将所述2k PU复合组合物施加到所述聚氨酯皮膜的一侧上以形成所述基层；以及
d)可选地，将所述背衬基材施加到所述基层的与所述聚氨酯皮膜相反的一侧上。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2019/078233 WO2020186377A1 (en) | 2019-03-15 | 2019-03-15 | Waterborne polyurethane dispersion and method for preparing same |
| PCT/CN2020/084160 WO2020187336A1 (en) | 2019-03-15 | 2020-04-10 | Waterborne polyurethane dispersion and method for preparing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113825781A true CN113825781A (zh) | 2021-12-21 |
Family
ID=72518906
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201980094526.1A Pending CN113614134A (zh) | 2019-03-15 | 2019-03-15 | 水性聚氨酯分散体及其制备方法 |
| CN202080035429.8A Pending CN113825781A (zh) | 2019-03-15 | 2020-04-10 | 水性聚氨酯分散体及其制备方法 |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201980094526.1A Pending CN113614134A (zh) | 2019-03-15 | 2019-03-15 | 水性聚氨酯分散体及其制备方法 |
Country Status (6)
| Country | Link |
|---|---|
| US (2) | US20220177635A1 (zh) |
| EP (2) | EP3938413A4 (zh) |
| JP (2) | JP2022531827A (zh) |
| KR (2) | KR20210142130A (zh) |
| CN (2) | CN113614134A (zh) |
| WO (2) | WO2020186377A1 (zh) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109778550A (zh) * | 2017-11-15 | 2019-05-21 | 默克专利股份有限公司 | 生产合成皮革的方法 |
| US20220177635A1 (en) * | 2019-03-15 | 2022-06-09 | Yanli Feng | Waterborne polyurethane dispersion and method for preparing the same |
| WO2022151459A1 (en) * | 2021-01-18 | 2022-07-21 | Dow Global Technologies Llc | Internally emulsified polyurethane dispersion and method for preparing the same |
| CN113956424B (zh) * | 2021-11-26 | 2023-06-09 | 广州海豚新材料有限公司 | 具有抗涂鸦功能的阴离子水性聚氨酯的制备方法 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0571187A1 (en) * | 1992-05-20 | 1993-11-24 | Nippon Paint Co., Ltd. | Aqueous surface coating composition |
| WO1995021206A1 (en) * | 1994-02-04 | 1995-08-10 | Minnesota Mining And Manufacturing Company | Water-based polyurethane polymer, release coating, adhesive tape and process of preparation |
| CN103173179A (zh) * | 2013-03-07 | 2013-06-26 | 常州大学 | 一种层压复合织物用水性聚氨酯胶粘剂的制备方法 |
| CN105693989A (zh) * | 2016-04-14 | 2016-06-22 | 南通曙光染织有限公司 | 一种嵌段有机硅水性聚氨酯抗起毛起球剂的制备方法 |
| CN106519169A (zh) * | 2016-11-17 | 2017-03-22 | 上海佰奥聚新材料科技有限公司 | 水性有机硅聚氨酯分散体及其制备和应用 |
| CN109160994A (zh) * | 2018-08-02 | 2019-01-08 | 万华化学集团股份有限公司 | 一种用于干法涂层底胶水性聚氨酯分散体及其制备方法和用途 |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2742677B1 (fr) * | 1995-12-21 | 1998-01-16 | Oreal | Nanoparticules enrobees d'une phase lamellaire a base de tensioactif silicone et compositions les contenant |
| US6774183B1 (en) * | 2000-04-27 | 2004-08-10 | Bostik, Inc. | Copolyesters having improved retained adhesion |
| JP4098189B2 (ja) * | 2003-08-21 | 2008-06-11 | 大日精化工業株式会社 | 感熱記録材料 |
| CN100402574C (zh) * | 2006-05-23 | 2008-07-16 | 山东圣光化工集团有限公司 | 聚硅氧烷-聚醚共聚物改性水性聚氨酯的制造方法 |
| CN101735599B (zh) * | 2009-12-24 | 2011-12-07 | 华南理工大学 | 一种紫外光固化有机硅改性聚氨酯水分散体及其制备方法 |
| CN102206410B (zh) * | 2011-04-21 | 2013-07-17 | 常州大学 | 革用高固含水性聚氨酯的制备方法 |
| US8716396B2 (en) * | 2012-04-19 | 2014-05-06 | Arrowstar Llc | Nonfluorinated polyurethanes and methods of making and using thereof |
| EP2690117A1 (en) * | 2012-07-24 | 2014-01-29 | ALLNEX AUSTRIA GmbH | Aqueously Dispersible Polyurethane |
| CN102977315A (zh) * | 2012-11-13 | 2013-03-20 | 青岛文创科技有限公司 | 一种聚醚聚硅氧烷二元醇改性水性聚氨酯的制备方法 |
| CN106146785B (zh) * | 2016-07-29 | 2019-01-29 | 华南理工大学 | 皮革涂饰剂用有机硅改性羧酸/磺酸型水性聚氨酯及其方法 |
| CN108467472B (zh) * | 2018-04-01 | 2021-02-09 | 黎明化工研究设计院有限责任公司 | 一种无溶剂聚氨酯树脂及其在高剥离强度水性/无溶剂聚氨酯合成革中的应用 |
| US20220177635A1 (en) * | 2019-03-15 | 2022-06-09 | Yanli Feng | Waterborne polyurethane dispersion and method for preparing the same |
-
2019
- 2019-03-15 US US17/433,169 patent/US20220177635A1/en active Pending
- 2019-03-15 KR KR1020217032380A patent/KR20210142130A/ko not_active Application Discontinuation
- 2019-03-15 EP EP19920288.8A patent/EP3938413A4/en not_active Withdrawn
- 2019-03-15 CN CN201980094526.1A patent/CN113614134A/zh active Pending
- 2019-03-15 JP JP2021555467A patent/JP2022531827A/ja active Pending
- 2019-03-15 WO PCT/CN2019/078233 patent/WO2020186377A1/en active Application Filing
-
2020
- 2020-04-10 EP EP20773004.5A patent/EP3938417A4/en not_active Withdrawn
- 2020-04-10 WO PCT/CN2020/084160 patent/WO2020187336A1/en active Application Filing
- 2020-04-10 CN CN202080035429.8A patent/CN113825781A/zh active Pending
- 2020-04-10 US US17/435,726 patent/US20220153915A1/en active Pending
- 2020-04-10 KR KR1020217032570A patent/KR20220154006A/ko unknown
- 2020-04-10 JP JP2021555477A patent/JP2022524870A/ja active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0571187A1 (en) * | 1992-05-20 | 1993-11-24 | Nippon Paint Co., Ltd. | Aqueous surface coating composition |
| WO1995021206A1 (en) * | 1994-02-04 | 1995-08-10 | Minnesota Mining And Manufacturing Company | Water-based polyurethane polymer, release coating, adhesive tape and process of preparation |
| CN1139935A (zh) * | 1994-02-04 | 1997-01-08 | 美国3M公司 | 水性聚氨酯聚合物、剥离涂层、粘合带及制备方法 |
| CN103173179A (zh) * | 2013-03-07 | 2013-06-26 | 常州大学 | 一种层压复合织物用水性聚氨酯胶粘剂的制备方法 |
| CN105693989A (zh) * | 2016-04-14 | 2016-06-22 | 南通曙光染织有限公司 | 一种嵌段有机硅水性聚氨酯抗起毛起球剂的制备方法 |
| CN106519169A (zh) * | 2016-11-17 | 2017-03-22 | 上海佰奥聚新材料科技有限公司 | 水性有机硅聚氨酯分散体及其制备和应用 |
| CN109160994A (zh) * | 2018-08-02 | 2019-01-08 | 万华化学集团股份有限公司 | 一种用于干法涂层底胶水性聚氨酯分散体及其制备方法和用途 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2020186377A1 (en) | 2020-09-24 |
| JP2022524870A (ja) | 2022-05-10 |
| US20220153915A1 (en) | 2022-05-19 |
| KR20210142130A (ko) | 2021-11-24 |
| KR20220154006A (ko) | 2022-11-21 |
| EP3938413A1 (en) | 2022-01-19 |
| US20220177635A1 (en) | 2022-06-09 |
| CN113614134A (zh) | 2021-11-05 |
| EP3938417A1 (en) | 2022-01-19 |
| EP3938413A4 (en) | 2022-09-28 |
| WO2020187336A1 (en) | 2020-09-24 |
| JP2022531827A (ja) | 2022-07-12 |
| EP3938417A4 (en) | 2022-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113631616B (zh) | 水性聚氨酯分散体及其制备方法 | |
| WO2020187336A1 (en) | Waterborne polyurethane dispersion and method for preparing same | |
| JP2014534352A (ja) | 改善された屈曲耐久性を有する合成皮革 | |
| CN113079700B (zh) | 合成皮革制品及其制备方法 | |
| CN113039322B (zh) | 合成皮革制品及其制备方法 | |
| KR20230106678A (ko) | 엠보싱 가능한 비용매 pu 시트, 이를 포함하는 적층체 및 합성 피혁 | |
| KR100985513B1 (ko) | 엠보성형이 우수한 용액형 폴리우레탄 수지 조성물 및 그 제조방법 | |
| TW202229386A (zh) | 內乳化聚胺甲酸酯分散體及其製備方法 | |
| WO2023028726A1 (en) | Waterborne polyurethane dispersions for preparing polyurethane foam for synthetic leather and synthetic leather articles prepared with the same |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20211221 |