CN110684215B - 稠环芳香类色素和高分子材料的混合物、其制备方法及其下游产品 - Google Patents
稠环芳香类色素和高分子材料的混合物、其制备方法及其下游产品 Download PDFInfo
- Publication number
- CN110684215B CN110684215B CN201911047274.5A CN201911047274A CN110684215B CN 110684215 B CN110684215 B CN 110684215B CN 201911047274 A CN201911047274 A CN 201911047274A CN 110684215 B CN110684215 B CN 110684215B
- Authority
- CN
- China
- Prior art keywords
- ring aromatic
- pigment
- mixture
- fused
- polymer material
- 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.)
- Active
Links
- 239000000049 pigment Substances 0.000 title claims abstract description 84
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 53
- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 239000002861 polymer material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000000376 reactant Substances 0.000 claims abstract description 20
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims description 50
- 239000004595 color masterbatch Substances 0.000 claims description 42
- 239000003054 catalyst Substances 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 25
- 238000001125 extrusion Methods 0.000 claims description 20
- 150000001491 aromatic compounds Chemical class 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 14
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 12
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 12
- 125000001624 naphthyl group Chemical group 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- -1 mercapto, substituted mercapto, cyano, silyl Chemical group 0.000 claims description 11
- 238000004898 kneading Methods 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 150000008065 acid anhydrides Chemical group 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 150000003949 imides Chemical class 0.000 claims description 4
- 239000002841 Lewis acid Substances 0.000 claims description 3
- 239000002879 Lewis base Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 150000007517 lewis acids Chemical class 0.000 claims description 3
- 150000007527 lewis bases Chemical class 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 239000002516 radical scavenger Substances 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 2
- 125000003107 substituted aryl group Chemical group 0.000 claims 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 2
- 150000001299 aldehydes Chemical class 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 150000003014 phosphoric acid esters Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 25
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 8
- 239000004594 Masterbatch (MB) Substances 0.000 description 23
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 19
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 17
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 17
- 150000008064 anhydrides Chemical class 0.000 description 13
- 238000001228 spectrum Methods 0.000 description 13
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 12
- 239000004246 zinc acetate Substances 0.000 description 12
- 239000002699 waste material Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 239000000975 dye Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 8
- 239000004926 polymethyl methacrylate Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000003086 colorant Substances 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N NMP Substances CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- YFOOEYJGMMJJLS-UHFFFAOYSA-N 1,8-diaminonaphthalene Chemical compound C1=CC(N)=C2C(N)=CC=CC2=C1 YFOOEYJGMMJJLS-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004693 Polybenzimidazole Substances 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 2
- 239000001055 blue pigment Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 229920002480 polybenzimidazole Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000000984 vat dye Substances 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 229920001109 fluorescent polymer Polymers 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229940087654 iron carbonyl Drugs 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- FVDOBFPYBSDRKH-UHFFFAOYSA-N perylene-3,4,9,10-tetracarboxylic acid Chemical compound C=12C3=CC=C(C(O)=O)C2=C(C(O)=O)C=CC=1C1=CC=C(C(O)=O)C2=C1C3=CC=C2C(=O)O FVDOBFPYBSDRKH-UHFFFAOYSA-N 0.000 description 1
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920000058 polyacrylate Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000001062 red colorant Substances 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
- C09B67/0063—Preparation of organic pigments of organic pigments with only macromolecular substances
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
- C08K5/3447—Five-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3462—Six-membered rings
- C08K5/3465—Six-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/12—Perinones, i.e. naphthoylene-aryl-imidazoles
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0002—Grinding; Milling with solid grinding or milling assistants
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
-
- 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
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
-
- 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
-
- 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
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2433/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
-
- 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
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本申请涉及稠环芳香类色素和高分子材料的混合物、其制备方法及其下游产品。该方法可选用不同的热塑性高分子材料与用于生成稠环芳香类色素的反应物混合，通过调节各原料之间的反应摩尔比以及在整个反应体系中的用量，使反应物和高分子材料的混合物能够通过挤出或捏合，一步得到稠环芳香类色素和高分子材料的混合物，相较于色素，色素的原料反应物在高分子材料中有更好的分散性，因此经挤出或捏合，色素能够直接生成并均匀分散在高分子材料中，并且挤出或捏合过程中无需加入任何溶剂，邻二胺化合物也几乎完全被消耗，得到的混合物无需提纯，避免了传统色素合成过程中三废的产生，极大地简化了工艺流程，降低了能耗。
Description
技术领域
本发明涉及颜料技术领域，特别是涉及稠环芳香类色素和高分子材料的混合物、其制备方法及其下游产品。
背景技术
稠环芳香类还原染料(Vat Dyes)色泽鲜艳，各项坚牢度优良，尤其在耐晒、耐溶剂等方面性能优异。但由于稠环芳香类化合物在生产过程中分散性差，需使用高沸点、难去除的溶剂，以致产生大量废液，且由于染料分子的提纯也非常困难，以致该类染料反应收率低、价格高，加工的工艺也相对更复杂，大大限制了该类染料的应用和发展。
US20080139813使用钼酸铵、氧化钼、羰基钼、羰基钛、羰基铁等金属催化剂，在溶剂氮甲基吡咯烷酮(NMP)的存在下使苝-3,4,9,10-四羧酸、1,4,5,8-萘-四羧酸及其酸酐、酰亚胺与胺反应，得到苝二酐和苯二胺的反应产物，实施例中反应产率最高达96.7％，整个反应需在200℃左右进行，反应时间超过20小时，并且在反应过后产物需要用NMP和硫酸洗涤纯化才能得到最终产品，这过程势必会产生大量的含有NMP、硫酸和碱的废液。
US20070151478为苝二酐或萘二酐和芳香二胺的反应合成黑色颜料的方法，该发明使用高沸点溶剂如硝基苯、三氯苯、N,N-二甲基甲酰胺(DMF)等在150℃～250℃反应，并且用氯化锌、醋酸锌、乙酸、盐酸、哌嗪等作为催化剂。可见，该条件设计的反应溶剂大多毒性很大，反应后的废液也会对环境造成破坏。
WO2009074504使用四羧酸及衍生物、胺类化合物、添加剂、以及润湿剂作用下使用混合装置合成苝类染料或颜料，同样合成时间长，温度高，合成中需使用醇类溶剂，并且反应后粗产品需使用各类溶剂、酸和碱纯化，并没有降低合成该类色素时产生的废液量。
CN108329466使用原位聚合，将苝四酸二酐连接到尼龙6的高分子链中，得到含有苝染料的尼龙6材料，但该反应温度高，时间长，并且不排除使用如氯仿等有毒的有机溶剂。
EP0892018报道了将普通有机颜料分子和可聚合的物质混合并加热处理，冷却后得到颜料和高分子的复合材料。该方法采用的颜料分子有很大的局限性，颜料分子需要有可以进行反应的功能取代基。而且可聚合的物质大多在常温下是液体，造成该类材料的加工需使用加工性能更高的可液体进样的挤出机。而EP654711、EP542669以及EP456610则采用类似方法制备荧光颜料。由于这些颜料的制备方法不是真正合成颜料分子本身，并没有避免合成颜料分子时所产生的废液、废固以及废气等。同样J.APPL.POLYM.SCI.2015,DOI:10.1002/APP.42172也报道了可聚合的萘酰亚胺类荧光染料合成制备聚乙烯类的荧光高分子，但其中可聚合的萘酰亚胺也需要用传统方法合成，同样不能避免产生废液。
发明内容
基于此，有必要提供一种无需纯化、无三废产生的稠环芳香类色素和高分子材料的混合物的制备方法，具体方案如下：
一种稠环芳香类色素和高分子材料的混合物的制备方法，包括以下步骤：
将热塑性高分子材料和用于形成稠环芳香类色素的反应物混合，经捏合或挤出，得到稠环芳香类色素和高分子材料的混合物；所述用于形成稠环芳香类色素的反应物包括酸酐功能化的稠环芳香化合物衍生物、邻二胺化合物和催化剂，所述稠环芳香类色素和高分子材料的混合物中稠环芳香类色素的质量含量为0.1％～50％，所述邻二胺化合物与所述酸酐功能化的稠环芳香化合物衍生物中酸酐官能团的摩尔比为1:(1～1.1)，所述催化剂与所述酸酐功能化的稠环芳香化合物衍生物的摩尔比为(0.01～10):1。
在其中一个实施例中，所述酸酐功能化的稠环芳香化合物衍生物选自以下化合物中的至少一种：
其中，R1-R12分别独立地选自H、卤素、胺基、带有取代基的胺基、C1-C30烷基、C1-C20烷氧基、酚羟基、带有取代基的酚羟基、苯基、带有取代基的苯基、萘基、带有取代基的萘基、巯基、带有取代基的巯基、氰基、硅烷基、羧酸酯基、磺酸基、磺酸酯基、磷酸基及磷酸酯基中的一种；
R'选自H、C1-C30烷基、C1-C20烷氧基、苯基、带有取代基的苯基、萘基、带有取代基的萘基、硅烷基中的一种；
X1和X2分别独立地选自CH2、CHR”、CR”R”'、NR”、O、S、S＝O及SO2中的一种，R”和R”'分别独立地选自H、C1-C30烷基、C1-C20烷氧基、带有取代基的芳香基中的一种。
在其中一个实施例中，所述邻二胺化合物选自以下化合物中的至少一种：
其中，R1、R2、R3、R4分别独立地选自H、卤素、氰基、硝基、醛基、羧基、酸酐、酰胺、酰亚胺、酯基、烷基、烷氧基或巯基中的至少一种；
R'分别独立地选自H、C1-C30烷基、C1-C20烷氧基、带有取代基的芳香基中的一种；
X为含有S、N、O、CO、SO、SO2或C＝C基团的五元或六元环结构。
在其中一个实施例中，所述催化剂选自去水剂、路易斯酸、路易斯碱及金属氧化物中的至少一种。
在其中一个实施例中，所述挤出的温度沿物料前进的方向分别为进料段120℃～330℃、挤出段150℃～360℃、出样段180℃～380℃。
本申请还提供一种由上述任一项所述的制备方法制得的稠环芳香类色素和高分子材料的混合物。
此外，本申请还提供上述稠环芳香类色素和高分子材料的混合物的下游产品，如色母粒粗品、色母粒产品及高分子颜料，具体方案如下：
一种色母粒粗品，由上述稠环芳香类色素和高分子材料的混合物经冷却、干燥、切粒而得。
一种色母粒产品，由上述稠环芳香类色素和高分子材料的混合物的原料与添加剂混合，经挤出、冷却、干燥、切粒而得；或由上述色母粒粗品与添加剂混合，经挤出、冷却、干燥、切粒而得。
在其中一个实施例中，所述色母粒产品的粒径为200μm～0.5cm。
一种高分子颜料，由上述色母粒粗品或上述色母粒产品研磨而得。
在其中一个实施例中，所述高分子颜料的粒径为0.01μm～100μm。
上述稠环芳香类色素和高分子材料的混合物的制备方法，根据相溶性、加工温度和极性，可选用不同的热塑性高分子材料与用于形成稠环芳香类色素的反应物(酸酐功能化的稠环芳香化合物衍生物、邻二胺化合物和催化剂)混合，通过调节各原料之间的反应摩尔比以及在整个反应体系中的用量，使它们的混合物能够经挤出或捏合，一步得到稠环芳香类色素和高分子材料的混合物，相较于色素，色素的原料反应物在高分子材料中有更好的分散性，因此经挤出或捏合，色素能够直接生成并均匀分散在高分子材料中，并且挤出或捏合过程中无需加入任何溶剂，邻二胺化合物也几乎完全被消耗，得到的混合物无需分离纯化，避免了传统色素合成过程中三废的产生，极大地简化了工艺流程，不仅可以降低能耗，减少所需人工，也可以降低生产成本。
此外，上述稠环芳香类色素和高分子材料的混合物的制备方法，可以根据需要选择用于生成不同色素的反应物，结合产物可能的颜色，可以得到更多的颜色，并且相较于传统的将不同色素混合的方法，本申请得到的混合物颜色更均匀。
另外，由于色素的原料反应物在高分子材料中有更好的分散性，本申请的色素经挤出或捏合可直接生成并均匀分散于热塑性高分子材料中，相较于先生成色素，再将色素和热塑性高分子材料混合，本申请得到的混合物相容性更好。
附图说明
图1为实施例4制备的色母粒粗品与ABS混合的反射光谱图；
图2为实施例7制备的色母粒粗品与ABS混合的反射光谱图；
图3为实施例9制备的色母粒粗品与ABS混合的反射光谱图；
图4为实施例10制备的色母粒粗品与ABS混合的反射光谱图；
图5为实施例13制备的色母粒粗品与ABS混合的反射光谱图；
图6为实施例14制备的色母粒粗品与ABS混合的反射光谱图；
图7为实施例15制备的色母粒粗品与ABS混合的反射光谱图；
图8为实施例16制备的色母粒粗品与ABS混合的反射光谱图。
具体实施方式
为了便于理解本发明，下面将对本发明进行更全面的描述，并给出了本发明的较佳实施例。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。本文所使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。
一实施方式的稠环芳香类色素和高分子材料的混合物的制备方法，包括以下步骤：
将热塑性高分子材料和用于形成稠环芳香类色素的反应物混合，经捏合或挤出，得到稠环芳香类色素和高分子材料的混合物。
其中，用于形成稠环芳香类色素的反应物包括酸酐功能化的稠环芳香化合物衍生物、邻二胺化合物和催化剂。
需要说明的是，捏合或挤出过程中，酸酐功能化的稠环芳香化合物衍生物和邻二胺化合物能在催化剂作用下反应得到稠环芳香类色素。
进一步的，酸酐功能化的稠环芳香化合物衍生物选自以下化合物中的至少一种：
其中，R1-R12分别独立地选自H、卤素、胺基、带有取代基的胺基、C1-C30烷基、C1-C20烷氧基、酚羟基、带有取代基的酚羟基、苯基、带有取代基的苯基、萘基、带有取代基的萘基、巯基、带有取代基的巯基、氰基、硅烷基、羧酸酯基、磺酸基、磺酸酯基、磷酸基及磷酸酯基中的一种；
R'选自H、C1-C30烷基、C1-C20烷氧基、苯基、带有取代基的苯基、萘基、带有取代基的萘基、硅烷基中的一种；
X1和X2分别独立地选自CH2、CHR”、CR”R”'、NR”、O、S、S＝O及SO2中的一种，R”和R”'分别独立地选自H、C1-C30烷基、C1-C20烷氧基、带有取代基的芳香基中的一种。
进一步的，邻二胺化合物选自以下化合物中的至少一种：
其中，R1、R2、R3、R4分别独立地选自H、卤素、氰基、硝基、醛基、羧基、酸酐、酰胺、酰亚胺、酯基、烷基、烷氧基或巯基中的至少一种；
R'分别独立地选自H、C1-C30烷基、C1-C20烷氧基、带有取代基的芳香基中的一种；
X为含有S、N、O、CO、SO、SO2或C＝C基团的五元或六元环结构。
在本实施方式中，稠环芳香类色素和高分子材料的混合物中稠环芳香类色素选自以下化合物中的至少一种：
可以理解，本申请可生成的稠环芳香类色素不限于以上描述的几种，任何酸酐功能化的稠环芳香化合物衍生物与邻二胺化合物反应可得到的稠环芳香类色素均在本申请保护范围内，这里不再一一例举。
进一步的，稠环芳香类色素和高分子材料的混合物中稠环芳香类色素的质量含量为0.1％～50％。
可以理解，通过控制邻二胺化合物与酸酐功能化的稠环芳香化合物衍生物中酸酐功能团的摩尔比为1:(1～1.1)，催化剂与酸酐功能化的稠环芳香化合物衍生物的摩尔比为(0.1～10):1，使邻二胺化合物与酸酐功能化的稠环芳香化合物衍生物在催化剂的作用下基本完全反应，得到的混合物中邻二胺化合物的含量低于10ppm，降低了产品的毒性和致癌性。
进一步的，催化剂选自去水剂(如生石灰、活性氧化铝、氯化钙、硫酸钙、氯化锂、氯化钠、硫酸钠等)、路易斯酸、路易斯碱(如氯化锌、醋酸锌、氯化钛、烷基胺等)及金属氧化物(如氧化钛、氧化锌、氧化铝等)中的至少一种。
进一步的，热塑性高分子材料选自聚烯烃、聚芳香取代烯烃、聚丙烯酸酯、聚卤代烯烃、聚酰亚胺、聚酯、聚甲醛、聚乳酸、丙烯腈-丁二烯-苯乙烯共聚物(ABS树脂)，聚苯并咪唑(PBI)，聚醚醚酮(PEEK)，聚醚酰亚胺(PEI)，聚醚砜(PES)，聚苯醚(PPO)，聚苯硫醚(PPS)，聚偏二氟乙烯(PVDF)，聚碳酸酯(PC)，及聚酰胺(PA)中的至少一种。
进一步的，挤出在挤出机中进行。挤出机可以是单螺杆挤出机或双螺杆挤出机。
进一步的，挤出的温度沿物料前进的方向分别为：进料段120℃～330℃，挤出段150℃～360℃，出样段180℃～380℃。
可以理解，挤出反应的温度曲线与挤出机的总长度相适配，例如对于具有10节的双螺杆挤出机，挤出反应的温度曲线施加区域如下表所示：
对于具有10节的单螺杆挤出机，挤出反应的温度曲线施加区域如下表所示：
当然，上述温度曲线还可以施加于更多或更少节数的挤出机，通常取决于所选择的用于生成稠环芳香类色素的反应物及热塑性高分子材料。
上述稠环芳香类色素和高分子材料的混合物的制备方法，根据相容性、加工温度和极性，可选用不同的热塑性高分子材料与用于形成稠环芳香类色素的反应物(酸酐衍生物、邻二胺化合物和催化剂)混合，通过调节各原料之间的反应摩尔比以及在整个反应体系中的用量，使它们的混合物能够经挤出或捏合，一步得到稠环芳香类色素和高分子材料的混合物，相较于色素，色素的原料反应物在高分子材料中有更好的分散性，因此经挤出或捏合，色素能够直接生成并均匀分散在高分子材料中，并且挤出或捏合过程无需加入任何溶剂，邻二胺化合物也几乎完全被消耗，得到的混合物无需分离纯化，避免了传统色素合成过程中三废的产生，极大地简化了工艺流程，不仅可以降低能耗，减少所需人工，也可以降低生产成本。
可以理解，通过选择用于形成不同色素的反应物，结合产物可能的颜色，可在挤出或捏合过程中配制非三原色的色彩，如黑色，即可以通过使用可产生红色、黄色和蓝色色素的反应物加工得到；绿色，则可以通过使用可产生黄色和蓝色色素的反应物加工得到。相较于传统的将不同色素混合的方法，本申请得到的混合物颜色更均匀。
此外，由于色素的原料反应物在高分子材料中有更好的分散性，因此经挤出或捏合，本申请的色素可直接生成并均匀分散在热塑性高分子材料中，相较于先生成色素，再将色素和热塑性高分子材料混合的方法，本申请的混合物具有更好的相容性。
进一步的，将上述稠环芳香类色素和高分子材料的混合物经冷却、干燥、切粒，即可得到色母粒粗品。
进一步的，为了得到优质的色母粒产品，可以选择性地将传统色母粒所需的添加剂(如阻燃剂、荧光增白剂、紫外吸收剂、抗氧化剂、润滑剂、增塑剂、抗菌剂以及其他高分子所需填料)和上述色母粒粗品混合，经挤出、冷却、干燥、切粒，即可得到色母粒产品。或选择性地将上述添加剂和稠环芳香类色素和高分子材料的混合物的原料混合，经挤出、冷却、干燥、切粒，即可得到色母粒产品。
其中，色母粒产品的粒径为200μm～0.5cm。
将上述色母粒粗品或色母粒产品进一步研磨即可得到高品质的高分子颜料。
进一步的，高分子颜料的粒径为0.01μm～100μm。
以下为具体实施例。
为了更好的测试色母粒粗品的性能，取色母粒粗品，以1％的浓度和ABS混合后注塑得到不透明的薄片，测试其反射光谱图。
实施例1-6
实施例1～6均按以下方法制备：
将0.5kg的PMMA、(32g，119mmol)化合物(1-1)、(25g，231mmol)化合物(1-2)和催化剂混合，在单螺杆挤出机中挤出反应，冷却干燥切粒后得到含有化合物(1-3)的色母粒粗品。
实施例1～6基本相同，不同的是催化剂的种类和用量，具体如表1所示：
表1
图1为实施例4制备的色母粒粗品以1％的浓度混合ABS注塑得到1mm厚的塑料薄片的反射光谱图，由图1可知，其吸收主要在蓝到橙色光区域，与颜料橙43和颜料红194的混合物类似。
实施例7
将0.5kg的PMMA、(30g，152mmol)化合物(7-1)、(23.5g，148mmol)化合物(7-2)和(3.5g，19mmol)催化剂醋酸锌混合，在双螺杆挤出机中挤出反应，冷却干燥切粒后得到含有化合物(7-3)的色母粒粗品，该色母粒粗品呈黄红色。
请参阅图2，为实施例7制备的色母粒粗品以1％浓度混合ABS后的反射光谱图，由图2可知，该材料主要吸收在绿光区域。
实施例8
将0.5kg的PC、(28g，104mmol)化合物(8-1)、(32g，203mmol)化合物(8-2)和(4.7g，26mmol)催化剂醋酸锌混合，在单螺杆挤出机中挤出反应，冷却干燥切粒得到含有化合物(8-3)的色母粒粗品，该色母粒粗品呈深蓝色。
实施例9
将0.5kg的PET、(40g，75mmol)化合物(9-1)、(16g，148mmol)化合物(9-2)和(3.4g，19mmol)催化剂醋酸锌混合，在单螺杆挤出机中挤出反应，冷却干燥切粒得到含有化合物(9-3)的色母粒粗品，该色母粒粗品呈紫黑色。
请参阅图3，为实施例9制备的色母粒粗品以1％的浓度混合ABS后的反射光谱图，由图3可知，该材料主要吸收蓝色到红光。
实施例10
将0.5kg的PA、(36g，68mmol)化合物(10-1)、(21g，133mmol)化合物(10-2)和(3g,16mmol)催化剂醋酸锌混合，在双螺杆挤出机中挤出反应，冷却干燥切粒得到含有化合物(10-3)的色母粒粗品，该色母粒粗品呈蓝黑色。
请参阅图4，为实施例10制备的色母粒粗品以1％浓度混合ABS后的反射光谱图，由图4可知，该材料吸收可见光很强，但对红外光吸收很弱，可见该材料为非常好的“冷”黑色材料，即不吸收红外光的黑色材料。
实施例11
将1kg的PMMA、(10g，50mmol)化合物(11-1)、(5.4g，50mmol)化合物(11-2)和(3g，16mmol)催化剂醋酸锌混合，在单螺杆挤出机中挤出反应，冷却干燥切粒得到含有化合物(11-3)的色母粒粗品，该色母粒粗品呈粉色。
实施例12
将1kg的PMMA、(10g，50mmol)化合物(12-1)、(9.4g，50mmol)化合物(12-2)和(3.5g，19mmol)催化剂醋酸锌混合，在单螺杆挤出机中挤出反应，得到含有化合物(12-3)的色母粒粗品，该色母粒粗品呈灰红色。
实施例13
将0.5kg的PMMA、(12g，60mmol)化合物(13-1)、(16g，60mmol)化合物(13-2)、(28g，177mmol)化合物(13-3)和(3.3g，18mmol)催化剂醋酸锌混合，在双螺杆挤出机中挤出反应，得到含有化合物(13-4)和化合物(13-5)的色母粒粗品，该色母粒粗品呈蓝黑色。
请参阅图5，为实施例13制备的色母粒粗品以1％浓度混合ABS后的反射光谱图，由图5可知，该材料比实例10中的“冷”色效果更好，在红外区域吸收更弱，是非常好的减少太阳光产生热的蓝黑颜色产品。
实施例14
将0.5kg的PMMA、(20g，75mmol)化合物(14-1)、(11g，70mmol)化合物(14-2)、(8g，74mmol)化合物(14-3)和(1.7g，9mmol)催化剂醋酸锌混合，在双螺杆挤出机中挤出反应，得到含有化合物(14-4)、化合物(14-5)和化合物(14-6)的色母粒粗品，该色母粒粗品呈黑绿色。
请参阅图6，为实施例14制备的色母粒粗品以1％浓度混合ABS后的反射光谱图，由图6可知，该材料和实例10和13类似，但性能更好，吸收可见光非常强，但对红外光的吸收很弱。
实施例15
将0.5kg的PMMA、(38g，133mmol)化合物(15-1)、(20g，127mmol)化合物(15-2)、(6g，31mmol)化合物(15-3)作为阻止卤素和胺反应的抑制剂和(2.9g，16mmol)催化剂醋酸锌混合，在单螺杆挤出机中挤出反应，冷却干燥切粒得到含有化合物(15-4)的色母粒粗品，该色母粒粗品呈红色。
请参阅图7，为实施例15制备的色母粒粗品以1％浓度混合ABS后的反射光谱图，由图7可知，该材料只在蓝到橙光区域有吸收，是非常好的红色着色剂。
实施例16
将0.5kg的PMMA、(15g，52mmol)化合物(16-1)、(14g，52mmol)化合物(16-2)、(24g，152mmol)化合物(16-3)、(2.52g，13mmol)化合物(16-4)作为阻止卤素和胺反应的抑制剂和(2.8g，15mmol)催化剂醋酸锌混合，在双螺杆挤出机中挤出反应，冷却干燥切粒得到含有化合物(16-5)和化合物(16-6)的色母粒粗品，该色母粒粗品呈黑色。
图8为实施例16制备的色母粒粗品以1％浓度混合ABS树脂后的反射光谱图，由图8可知为很好的“冷”黑色产品。
为了测试挤出反应的效果，以邻苯二胺及1，8-二胺萘的0.01mg/mL溶液(溶剂由体积比为3:7的水和乙腈组成)为标样，取10mg左右的实例8，9，10的5mL溶液(溶剂由体积比为3:7的水和乙腈组成)，在测试范围内，实例8和10中未发现1，8-二胺萘，实例9中未发现邻苯二胺。说明该类方法可以得到转换率100％的安全色母粒粗品。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。
Claims (10)
1.一种稠环芳香类色素和高分子材料的混合物的制备方法，其特征在于，包括以下步骤：
将热塑性高分子材料和用于形成稠环芳香类色素的反应物混合，经捏合或挤出，得到稠环芳香类色素和高分子材料的混合物；所述用于形成稠环芳香类色素的反应物包括酸酐功能化的稠环芳香化合物衍生物、邻二胺化合物和催化剂，所述稠环芳香类色素和高分子材料的混合物中稠环芳香类色素的质量含量为0.1％～50％，所述邻二胺化合物与所述酸酐功能化的稠环芳香化合物衍生物中酸酐官能团的摩尔比为1:(1～1.1)，所述催化剂与所述酸酐功能化的稠环芳香化合物衍生物的摩尔比为(0.01～10):1；
所述酸酐功能化的稠环芳香化合物衍生物选自以下化合物中的至少一种：
其中，R1-R12分别独立地选自H、卤素、胺基、带有取代基的胺基、C1-C30烷基、C1-C20烷氧基、酚羟基、带有取代基的酚羟基、苯基、带有取代基的苯基、萘基、带有取代基的萘基、巯基、带有取代基的巯基、氰基、硅烷基、羧酸酯基、磺酸基、磺酸酯基、磷酸基及磷酸酯基中的一种；
R'选自H、C1-C30烷基、C1-C20烷氧基、苯基、带有取代基的苯基、萘基、带有取代基的萘基、硅烷基中的一种；
X1和X2分别独立地选自CH2、CHR”、CR”R”'、NR”、O、S、S＝O及SO2中的一种，R”和R”'分别独立地选自H、C1-C30烷基、C1-C20烷氧基、带有取代基的芳香基中的一种。
2.根据权利要求1所述的稠环芳香类色素和高分子材料的混合物的制备方法，其特征在于，所述邻二胺化合物选自以下化合物中的至少一种：
其中，R1、R2、R3、R4分别独立地选自H、卤素、氰基、硝基、醛基、羧基、酸酐、酰胺、酰亚胺、酯基、烷基、烷氧基或巯基中的至少一种；
R'分别独立地选自H、C1-C30烷基、C1-C20烷氧基、带有取代基的芳香基中的一种；
X为含有S、N、O、CO、SO、SO2或C＝C基团的五元或六元环结构。
3.根据权利要求1所述的稠环芳香类色素和高分子材料的混合物的制备方法，其特征在于，所述催化剂选自去水剂、路易斯酸、路易斯碱及金属氧化物中的至少一种。
4.根据权利要求1～3任一项所述的稠环芳香类色素和高分子材料的混合物的制备方法，其特征在于，所述挤出的温度沿物料前进的方向分别为进料段120℃～330℃、挤出段150℃～360℃、出样段180℃～380℃。
5.一种权利要求1～4任一项所述的制备方法制得的稠环芳香类色素和高分子材料的混合物。
6.一种色母粒粗品，其特征在于，由权利要求5所述的稠环芳香类色素和高分子材料的混合物经冷却、干燥、切粒而得。
7.一种色母粒产品，其特征在于，由权利要求5所述的稠环芳香类色素和高分子材料的混合物的原料与添加剂混合，经挤出、冷却、干燥、切粒而得；或由权利要求6所述的色母粒粗品与添加剂混合，经挤出、冷却、干燥、切粒而得。
8.根据权利要求7所述的色母粒产品，其特征在于，所述色母粒产品的粒径为200μm～0.5cm。
9.一种高分子颜料，其特征在于，由权利要求6所述的色母粒粗品或权利要求8所述的色母粒产品研磨而得。
10.根据权利要求9所述的高分子颜料，其特征在于，所述高分子颜料的粒径为0.01μm～100μm。
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911047274.5A CN110684215B (zh) | 2019-10-30 | 2019-10-30 | 稠环芳香类色素和高分子材料的混合物、其制备方法及其下游产品 |
| PCT/CN2019/115570 WO2021082032A1 (zh) | 2019-10-30 | 2019-11-05 | 稠环芳香类色素和高分子材料的混合物、其制备方法及其下游产品 |
| TW109136408A TWI730916B (zh) | 2019-10-30 | 2020-10-21 | 稠環芳香類色素和高分子材料的混合物、其製備方法、色母粒粗品、色母粒產品及高分子顏料 |
| US17/704,005 US20220213326A1 (en) | 2019-10-30 | 2022-03-25 | Mixture of fused-ring aromatic pigment and polymer material and its preparation method and downstream product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911047274.5A CN110684215B (zh) | 2019-10-30 | 2019-10-30 | 稠环芳香类色素和高分子材料的混合物、其制备方法及其下游产品 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110684215A CN110684215A (zh) | 2020-01-14 |
| CN110684215B true CN110684215B (zh) | 2021-03-02 |
Family
ID=69114880
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911047274.5A Active CN110684215B (zh) | 2019-10-30 | 2019-10-30 | 稠环芳香类色素和高分子材料的混合物、其制备方法及其下游产品 |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20220213326A1 (zh) |
| CN (1) | CN110684215B (zh) |
| TW (1) | TWI730916B (zh) |
| WO (1) | WO2021082032A1 (zh) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112226835B (zh) * | 2020-10-13 | 2021-09-10 | 广东永畅兴精密制造股份有限公司 | 一种有色合成纤维及其制备方法 |
| CN113583469B (zh) * | 2021-07-27 | 2022-12-20 | 东莞市彩材科技有限公司 | 一种高性能黑色色膏及其制备方法 |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19548453A1 (de) * | 1995-12-22 | 1997-06-26 | Bayer Ag | Verfahren zur Herstellung polycyclischer Verbindungen |
| US7169922B2 (en) * | 2000-08-04 | 2007-01-30 | Invitrogen Corporation | Derivatives of 1,2-dihydro-7-hydroxyquinolines containing fused rings |
| ATE495222T1 (de) * | 2004-02-11 | 2011-01-15 | Basf Se | Schwarze perylenpigmente |
| EP2235112B1 (de) * | 2007-12-10 | 2014-03-12 | Basf Se | Synthese von farbmitteln in mischapparaturen |
| EP2421920A2 (en) * | 2009-04-22 | 2012-02-29 | DyStar Colours Distribution GmbH | Dyes for polymer coloration, their preparation and their use |
| US9139571B2 (en) * | 2010-12-16 | 2015-09-22 | Transitions Optical, Inc. | Methods of making fused ring compounds |
| KR102310489B1 (ko) * | 2013-08-05 | 2021-10-12 | 바스프 에스이 | 시안화 나프탈렌벤즈이미다졸 화합물 |
| CN103740095A (zh) * | 2013-12-28 | 2014-04-23 | 宁波金富亮塑料科技有限公司 | 一种红色阻燃抗uv尼龙用色母粒 |
| CN107022066B (zh) * | 2016-08-17 | 2019-03-01 | 宁波龙欣精细化工有限公司 | 一种用于聚丙烯塑料染色的脂环族聚酯型高分子染料及其制备方法 |
| US20190047201A1 (en) * | 2017-08-10 | 2019-02-14 | Russell Neuman | A method of extruding a thermoplastic polymer of a desired color and an apparatus for performing the method |
-
2019
- 2019-10-30 CN CN201911047274.5A patent/CN110684215B/zh active Active
- 2019-11-05 WO PCT/CN2019/115570 patent/WO2021082032A1/zh active Application Filing
-
2020
- 2020-10-21 TW TW109136408A patent/TWI730916B/zh not_active IP Right Cessation
-
2022
- 2022-03-25 US US17/704,005 patent/US20220213326A1/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| US20220213326A1 (en) | 2022-07-07 |
| TW202116884A (zh) | 2021-05-01 |
| TWI730916B (zh) | 2021-06-11 |
| WO2021082032A1 (zh) | 2021-05-06 |
| CN110684215A (zh) | 2020-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1716208B2 (de) | Schwarze perylenpigmente | |
| CN110684215B (zh) | 稠环芳香类色素和高分子材料的混合物、其制备方法及其下游产品 | |
| JPS6359424B2 (zh) | ||
| EP3470472B1 (de) | Neue methinfarbstoffe | |
| CN102510882A (zh) | 用于使聚合物着色的无迁移着色共缩聚物 | |
| EP0277914A2 (de) | Feste Lösungen von Pyrrolo-[3,4-c]-pyrrolen mit Chinacridonen | |
| CN110790982B (zh) | 颜料黄138或其衍生物的高分子材料包裹物、其制备方法及其下游产品 | |
| CN1890326B (zh) | 热稳定的蒽吡啶酮组合物 | |
| JPS6158090B2 (zh) | ||
| CN114031765B (zh) | 一种含酰胺基团的聚合物及其制备方法和应用 | |
| JPS60161459A (ja) | アジン顔料、その製造方法及びその使用 | |
| JP3919248B2 (ja) | 黄色ジケトピロロピロール顔料 | |
| CN110746653B (zh) | 热塑性树脂包裹的颜料黄139或其衍生物、其制备方法及其下游产品 | |
| CA2148309A1 (en) | Pigment salts and their use for dyeing and pigmenting | |
| CN112226835B (zh) | 一种有色合成纤维及其制备方法 | |
| CN109096676A (zh) | 一种聚乙烯接枝转光流滴膜及其制备方法 | |
| CA1050018A (en) | Fluorescent benzanthronic dyes | |
| CN104672950A (zh) | 一种苯并咪唑酮固体溶液及制备方法 | |
| CN101392102B (zh) | 红色染料混合物 | |
| CN102964611A (zh) | 红色染料混合物 | |
| JPS5841293B2 (ja) | 熱可塑性樹脂の着色方法 | |
| JPH02187470A (ja) | 染料 | |
| JPS5910391B2 (ja) | 黄色有機化合物及び黄色有機化合物による高分子材料の着色方法 | |
| JPS595147B2 (ja) | イソインドリンユウドウタイガンリヨウノセイゾウホウ | |
| JPH03166266A (ja) | 新規なジアントラキノニル化合物 |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220113 Address after: 523000 Room 302, No.2, Sanxiang, nanzhashangnan Road, Humen Town, Dongguan City, Guangdong Province Patentee after: Guangdong QIANDU Technology Co.,Ltd. Address before: 523000, 1, University Road, Songshan science and Technology Industrial Park, Guangdong, Dongguan Patentee before: DONGGUAN University OF TECHNOLOGY |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220125 Address after: 523000 building 7, Ruiying international science and Technology Innovation Park, No. 9, University Road, Songshanhu Park, Dongguan City, Guangdong Province Patentee after: Dongguan Caicai Technology Co.,Ltd. Address before: 523000 Room 302, No.2, Sanxiang, nanzhashangnan Road, Humen Town, Dongguan City, Guangdong Province Patentee before: Guangdong QIANDU Technology Co.,Ltd. |