CN116285413A - Preparation method of amino modified polyester resin fluorescent pigment - Google Patents
Preparation method of amino modified polyester resin fluorescent pigment Download PDFInfo
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- CN116285413A CN116285413A CN202310262884.7A CN202310262884A CN116285413A CN 116285413 A CN116285413 A CN 116285413A CN 202310262884 A CN202310262884 A CN 202310262884A CN 116285413 A CN116285413 A CN 116285413A
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- Prior art keywords
- polyester resin
- acid
- modified polyester
- amino modified
- fluorescent pigment
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- 229920001225 polyester resin Polymers 0.000 title claims abstract description 51
- 239000004645 polyester resin Substances 0.000 title claims abstract description 51
- 239000000049 pigment Substances 0.000 title claims abstract description 40
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000007850 fluorescent dye Substances 0.000 claims abstract description 20
- 229920000728 polyester Polymers 0.000 claims abstract description 18
- -1 amino compound Chemical class 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000002253 acid Chemical class 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 40
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 18
- 238000004321 preservation Methods 0.000 claims description 18
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 claims description 7
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 235000010233 benzoic acid Nutrition 0.000 claims description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- 229940049964 oleate Drugs 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 150000007519 polyprotic acids Polymers 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 150000001298 alcohols Chemical class 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000012643 polycondensation polymerization Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 22
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 229920000877 Melamine resin Polymers 0.000 description 3
- 229920002396 Polyurea Polymers 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 238000010902 jet-milling Methods 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 2
- FXFIDVQMNRVEGQ-UHFFFAOYSA-N (7e)-3-(diethylamino)-7-imino-7h-chromeno[3',2':3,4]pyrido[1,2-a]benzimidazole-6-carbonitrile Chemical compound C1=CC=C2N(C(=N)C(C#N)=C3C4=CC5=CC=C(C=C5O3)N(CC)CC)C4=NC2=C1 FXFIDVQMNRVEGQ-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- JZGUXCXDBKBCDN-UHFFFAOYSA-N 21295-57-8 Chemical compound C12=C3C(=O)C4=CC=CC=C4C1=CC(=O)N(C)C2=CC=C3NC1CCCCC1 JZGUXCXDBKBCDN-UHFFFAOYSA-N 0.000 description 1
- DZNJMLVCIZGWSC-UHFFFAOYSA-N 3',6'-bis(diethylamino)spiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(N(CC)CC)C=C1OC1=CC(N(CC)CC)=CC=C21 DZNJMLVCIZGWSC-UHFFFAOYSA-N 0.000 description 1
- UTTFXJZCRVZYQF-UHFFFAOYSA-N 3-(diethylamino)-7-oxo-7h-(1)benzopyrano(3',2':3,4)pyrido(1,2-a)benzimidazole-6-carbonitrile Chemical compound C1=CC=C2N(C(=O)C(C#N)=C3C4=CC5=CC=C(C=C5O3)N(CC)CC)C4=NC2=C1 UTTFXJZCRVZYQF-UHFFFAOYSA-N 0.000 description 1
- SDUIURJVOCHJCO-UHFFFAOYSA-N 3-[5-(Aminosulfonyl)benzoxazol-2-yl]-7-(diethylamino)coumarin Chemical compound NS(=O)(=O)C1=CC=C2OC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 SDUIURJVOCHJCO-UHFFFAOYSA-N 0.000 description 1
- QPQKUYVSJWQSDY-UHFFFAOYSA-N 4-phenyldiazenylaniline Chemical compound C1=CC(N)=CC=C1N=NC1=CC=CC=C1 QPQKUYVSJWQSDY-UHFFFAOYSA-N 0.000 description 1
- KBZFDRWPMZESDI-UHFFFAOYSA-N 5-aminobenzene-1,3-dicarboxylic acid Chemical compound NC1=CC(C(O)=O)=CC(C(O)=O)=C1 KBZFDRWPMZESDI-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- QFVDKARCPMTZCS-UHFFFAOYSA-N methylrosaniline Chemical compound C1=CC(N(C)C)=CC=C1C(O)(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 QFVDKARCPMTZCS-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
-
- 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
- C09B67/0075—Preparations with cationic dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a preparation method of an amino modified polyester resin fluorescent pigment, and relates to the technical field of fluorescent pigments. The invention takes alcohol compounds and acid compounds as raw materials, adds a catalyst, obtains polyester oligomer through polycondensation reaction, and continuously polycondensates the polyester oligomer and amino compounds as raw materials to obtain amino modified polyester resin; and finally, uniformly mixing the fluorescent dye, the auxiliary agent and the amino modified polyester resin to obtain the fluorescent pigment. According to the preparation method, the amide bond with higher rigidity is introduced on the polyester chain through the condensation polymerization of the amino compound and the polyester oligomer, so that the softening point of a product is improved, and the problem that the existing polyester resin fluorescent dye is easy to agglomerate at normal temperature is solved.
Description
Technical Field
The invention relates to the technical field of fluorescent pigments, in particular to a preparation method of an amino modified polyester resin fluorescent pigment.
Background
Fluorescent pigment is a special organic pigment, which can emit fluorescence under the irradiation of sunlight or ultraviolet light, and the color of the product is very bright, and is widely used for coloring plastics, paint ink, candles and textiles. The fluorescent pigment consists of carrier resin, fluorescent dye and assistant, wherein the fluorescent dye gives fluorescent effect to the pigment, and the carrier resin determines the solvent resistance, migration resistance, heat resistance and other properties of the pigment. Fluorescent pigments which are common in the market at present are classified into polyesters, polyamides, polyureas, melamine, styrene-acrylic emulsions and the like according to carrier resins. The polyamide and polyurea fluorescent pigment has high production cost, the melamine fluorescent pigment contains free formaldehyde, is not friendly to the environment, and the styrene-acrylic emulsion fluorescent pigment can only be applied to aqueous systems and has certain limit on the application field. The polyester fluorescent pigment is mainly applied to the plastic field, the product has strong cost advantage, does not contain formaldehyde, and is fluorescent pigment with high cost performance.
However, polyester resins, although having strong cost advantages over polyamide resins and polyurea resins, suffer from some drawbacks in performance, particularly in: (1) The polarity of the polyester molecules is relatively low, the intermolecular force is small, the softening point of the polyester resin is low, and the product is easy to agglomerate when the air temperature is high; (2) The polyester resin has lower compatibility with the fluorescent dye with high polarity, so that the coloring power of the polyester fluorescent pigment is lower; (3) The polyester resin fluorescent pigment has weak high temperature resistance and can only resist the temperature below 240 ℃. For example, chinese patent No. CN111978527B discloses a high hardness powder coating with excellent fluorescent properties, a method for preparing the same and a polyester resin used therein, and the invention discloses a polyester resin prepared by polycondensation of melamine, basic para-sulfonamide, epichlorohydrin, neopentyl glycol diglycidyl ether, N-methyldiethanolamine, octadecanedioic acid, 5-amino isophthalic acid, isobutyric acid, and xylene as raw materials, each having a softening point of 200 ℃ or lower.
Disclosure of Invention
The invention aims to provide a preparation method of an amino modified polyester resin fluorescent pigment, which solves the following technical problems:
the existing polyester resin fluorescent pigment has low softening point, easy caking, poor coloring capability and poor temperature resistance.
The aim of the invention can be achieved by the following technical scheme:
the preparation method of the amino modified polyester resin fluorescent pigment comprises the following steps:
(1) Weighing the components according to a proportion, adding an alcohol compound, an acid compound and a catalyst into a reaction kettle, and carrying out heat preservation reaction under the stirring condition to obtain a polyester oligomer;
(2) Adding an amino compound into a reaction kettle, continuously heating, and carrying out heat preservation reaction to obtain amino modified polyester resin;
(3) Adding the fluorescent dye and the auxiliary agent into a reaction kettle, stirring, discharging, cooling, sequentially coarsely crushing and jet milling to obtain the amino modified polyester resin fluorescent pigment.
As a further aspect of the invention: the weight percentages of the components added are as follows: 10-45% of polyalcohol, 15-60% of polybasic acid, 0.5-2.5% of catalyst, 5-30% of polyamine, 1-5% of fluorescent dye and 0.5-5% of auxiliary agent.
As a further aspect of the invention: the alcohol compound is one or more of glycol, glycerol, trimethylolethane, pentaerythritol, benzyl alcohol, neopentyl glycol and diethylene glycol which are mixed according to any ratio.
As a further aspect of the invention: the acid compound is one or more of oxalic acid, adipic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, azelaic acid, benzenesulfonic acid and cyclohexanedicarboxylic acid which are mixed according to any ratio.
As a further aspect of the invention: the catalyst is one or more of monobutyl tin oxide, dibutyl tin dilaurate, stannous octoate, stannous oleate, phosphoric acid, phosphorous acid and sulfuric acid which are mixed according to any ratio.
As a further aspect of the invention: the amino compound is one or more of ethylenediamine, hexamethylenediamine, aniline, benzylamine, m-xylylenediamine, isophorone diamine and cyclohexylamine which are mixed according to any ratio.
As a further aspect of the invention: the fluorescent dye is one or more of solvent red 196, solvent red 197, solvent red 49, solvent red 149, alkaline red 1, alkaline red 1:1, alkaline violet 10, alkaline violet 11, alkaline violet 11:1, alkaline yellow 40, solvent violet 9, solvent yellow 172 and solvent yellow 145 in any ratio.
As a further aspect of the invention: the auxiliary agent is one or more of antioxidant, ultraviolet-infrared absorbent, dispersing agent and antistatic agent, which are mixed according to any ratio.
As a further aspect of the invention: the heat preservation reaction in the step (1) is specifically as follows: heating to 180-220 deg.c, and maintaining the temperature for 2-4 hr.
As a further aspect of the invention: the heat preservation reaction in the step (2) is specifically as follows: heating to 240-270 deg.c, and maintaining the temperature for reaction for 1-2 hr.
As a further aspect of the invention: the molecular weight of the amino modified polyester resin is 1500-6000.
As a further aspect of the invention: the particle size of the fluorescent pigment is 5-60um.
The invention has the beneficial effects that:
(1) The preparation method comprises the steps of taking alcohol compounds and acid compounds as raw materials, adding a catalyst, performing polycondensation reaction to obtain a polyester oligomer, and continuously performing polycondensation on the polyester oligomer and an amino compound as raw materials to obtain amino modified polyester resin; and finally, uniformly mixing the fluorescent dye, the auxiliary agent and the amino modified polyester resin to obtain the fluorescent pigment. According to the preparation method, the amide bond with higher rigidity is introduced on the polyester chain through the condensation polymerization of the amino compound and the polyester oligomer, so that the softening point of a product is improved, and the problem that the existing polyester resin fluorescent dye is easy to agglomerate at normal temperature is solved.
(2) The amino modified polyester resin prepared by the application contains a large amount of amide groups, and is matched with fluorescent dye molecules of basic dye containing primary amino groups, secondary amino groups, tertiary amino groups or amide groups, so that the compatibility is better, the fluorescence degree of the product is better, and the tinting strength is higher.
(3) The amino modified polyester resin prepared by the application contains a large number of amide bonds on a molecular chain, the energy of the amide bonds is larger than that of the ester bonds, the stability is higher, the temperature resistance is better, the polarity of the amide bonds is higher than that of the ester bonds, the compatibility with fluorescent dye is better, and the protection performance of the fluorescent dye is better, so that the high temperature resistance of the prepared fluorescent pigment is better, and the temperature resistance of the product can reach more than 250 ℃.
Detailed Description
The following description will clearly and fully describe the technical solutions of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A preparation method of amino modified polyester resin comprises the following steps:
(1) 42.6g of neopentyl glycol, 18.7g of trimethylolethane, 116.2g of isophthalic acid and 1.5g of monobutyl tin oxide are added into a reaction kettle, the temperature is raised to 210 ℃, the stirring speed is 90rpm, and the heat preservation reaction is carried out for 2.5 hours to obtain a polyester oligomer;
(2) 21.4g of isophorone diamine is added into a reaction kettle, the temperature is continuously raised to 250 ℃, and the reaction is carried out for 1.5 hours with heat preservation, thus obtaining the amino modified polyester resin.
Example 2
A preparation method of amino modified polyester resin comprises the following steps:
(1) 31.4g of ethylene glycol, 16.5g of pentaerythritol, 76.2g of isophthalic acid, 52.9g of terephthalic acid and 1.5g of monobutyl tin oxide are added into a reaction kettle, the temperature is raised to 210 ℃, the stirring speed is 90rpm, and the heat preservation reaction is carried out for 2.5 hours to obtain a polyester oligomer;
(2) 11.4g of m-xylylenediamine and 16.3g of cyclohexylamine are added into a reaction kettle, the temperature is continuously raised to 250 ℃, and the reaction is carried out for 1.5 hours with heat preservation, thus obtaining the amino modified polyester resin.
Example 3
A preparation method of amino modified polyester resin comprises the following steps:
(1) Adding 36.1g of diethylene glycol, 18.7g of trimethylolethane, 12.7g of benzoic acid, 86.4g of isophthalic acid and 4g of phosphoric acid into a reaction kettle, heating to 210 ℃, stirring at 90rpm, and reacting for 3 hours under heat preservation to obtain a polyester oligomer;
(2) 17.4g of hexamethylenediamine and 9.4g of m-xylylenediamine are added into a reaction kettle, the temperature is continuously raised to 260 ℃, and the reaction is carried out for 2 hours with heat preservation, thus obtaining the amino modified polyester resin.
Example 4
The preparation method of the amino modified polyester resin fluorescent pigment comprises the following steps:
adding 2.86g of fluorescent dye and 2.2g of auxiliary agent into a reaction kettle, stirring at a high speed of 500rpm, discharging, cooling to below 50 ℃, and sequentially coarsely crushing and jet milling to obtain the fluorescent pigment.
Example 5
In this example, compared with example 4, the amino-modified polyester resin prepared in example 1 used in example 4 was replaced with the amino-modified polyester resin prepared in example 2 in equal amounts, and the remaining components and steps were completely identical.
Example 6
In this example, compared with example 4, the amino-modified polyester resin prepared in example 1 used in example 4 was replaced with the amino-modified polyester resin prepared in example 2 in equal amounts, and the remaining components and steps were completely identical.
Comparative example 1
A method of preparing a carrier resin comprising the steps of:
(1) 51.8g of neopentyl glycol, 12.4g of trimethylolethane, 66.2g of isophthalic acid, 50.7g of terephthalic acid and 1.5g of monobutyl tin oxide are added into a reaction kettle, the temperature is raised to 210 ℃, the stirring speed is 90rpm, the heat preservation reaction is carried out for 2.5 hours, and the polyester oligomer is obtained through the polycondensation reaction;
(2) Continuously heating to 250 ℃, and carrying out heat preservation reaction for 3 hours to obtain the polyester resin.
Comparative example 2
A method of preparing a carrier resin comprising the steps of:
42.6g of neopentyl glycol, 18.7g of trimethylolethane, 116.2g of isophthalic acid and 1.5g of monobutyl tin oxide are added into a reaction kettle, the temperature is raised to 210 ℃, the stirring speed is 90rpm, the reaction is kept for 2.5h, the temperature is continuously raised to 250 ℃, and the reaction is kept for 3h, so that the carrier resin is obtained.
Comparative example 3
A method of preparing a carrier resin comprising the steps of:
31.4g of ethylene glycol, 16.5g of pentaerythritol, 76.2g of isophthalic acid, 52.9g of terephthalic acid and 1.5g of monobutyl tin oxide are added into a reaction kettle, the temperature is raised to 210 ℃, the stirring speed is 90rpm, the heat preservation reaction is carried out for 2.5h, the temperature is continuously raised to 250 ℃, and the heat preservation reaction is carried out for 3h, thus obtaining the carrier resin.
Comparative example 4
A method of preparing a carrier resin comprising the steps of:
36.1g of diethylene glycol, 18.7g of trimethylolethane, 12.7g of benzoic acid, 86.4g of isophthalic acid and 4g of phosphoric acid are added into a reaction kettle, the temperature is raised to 210 ℃, the stirring speed is 90rpm, the reaction is kept for 3 hours, the temperature is continuously raised to 250 ℃, and the reaction is kept for 3 hours, so that the carrier resin is obtained.
Comparative example 5
In this comparative example, compared with example 4, only the amine-modified polyester resin prepared in example 1 used in example 4 was replaced with the carrier resin prepared in comparative example 1 in equal amounts, and the remaining components and steps were completely identical.
Comparative example 6
This comparative example was compared with example 4, and the amine-modified polyester resin prepared in example 1 used in example 4 was replaced with the support resin prepared in comparative example 2 in equal amounts, and the remaining components and steps were completely identical.
Comparative example 7
This comparative example was compared with example 4, and the amine-modified polyester resin prepared in example 1 used in example 4 was replaced with the carrier resin prepared in comparative example 3 in equal amounts, and the remaining components and steps were completely identical.
Comparative example 8
This comparative example was compared with example 4, and the amine-modified polyester resin prepared in example 1 used in example 4 was replaced with the carrier resin prepared in comparative example 4 in equal amounts, and the remaining components and steps were completely identical.
Performance detection
The fluorescent dyes prepared in examples 1-3 and comparative examples 5-8 were tested according to the industry standard HG/T5188-2017 fluorescent pigment, and the test results are shown in Table 1;
table 1: performance test data for examples 4-6, comparative examples 5-8
| Softening point (. Degree. C.) | Intensity (%) | Fluorescence intensity | Heat resistance (c) | |
| Example 4 | 91.4 | 102.84 | Good (good) | 250 |
| Example 5 | 98.2 | 108.42 | Good (good) | 255 |
| Example 6 | 93.7 | 107.51 | Preferably, it is | 250 |
| Comparative example 5 | 81.6 | 105.67 | In general | 230 |
| Comparative example 6 | 67.2 | 94.1 | Poor quality | 210 |
| Comparative example 7 | 72.4 | 96.6 | Poor quality | 200 |
| Comparative example 8 | 68.9 | 95.2 | Poor quality | 210 |
As shown in Table 1, the fluorescent pigment prepared by the method has a higher softening point, and solves the problem that the existing polyester resin fluorescent dye is easy to agglomerate at normal temperature. And the fluorescent dye has better compatibility with fluorescent dye, the fluorescence degree of the product is better, the tinting strength is higher, and the temperature resistance can reach more than 250 ℃.
The foregoing describes the embodiments of the present invention in detail, but the description is only a preferred embodiment of the present invention and should not be construed as limiting the scope of the invention. All equivalent changes and modifications within the scope of the present invention are intended to be covered by the present invention.
Claims (8)
1. The preparation method of the amino modified polyester resin fluorescent pigment is characterized by comprising the following steps of:
s1: weighing the components according to a proportion, adding an alcohol compound, an acid compound and a catalyst into a reaction kettle, and carrying out heat preservation reaction under the stirring condition to obtain a polyester oligomer;
s2: adding an amino compound into a reaction kettle, continuously heating, and carrying out heat preservation reaction to obtain amino modified polyester resin;
s3: adding the fluorescent dye and the auxiliary agent into a reaction kettle, uniformly stirring, discharging, cooling and crushing to obtain the amino modified polyester resin fluorescent pigment.
2. The preparation method of the amino modified polyester resin fluorescent pigment according to claim 1, wherein the fluorescent pigment comprises the following components in percentage by weight: 10-45% of polyalcohol, 15-60% of polybasic acid, 0.5-2.5% of catalyst, 5-30% of polyamine, 1-5% of fluorescent dye and 0.5-5% of auxiliary agent.
3. The preparation method of the amino modified polyester resin fluorescent pigment according to claim 1, wherein the alcohol compound is one or more of ethylene glycol, glycerol, trimethylolethane, pentaerythritol, benzyl alcohol, neopentyl glycol and diethylene glycol mixed in any ratio.
4. The method for preparing an amino modified polyester resin fluorescent pigment according to claim 1, wherein the acid compound is one or more of oxalic acid, adipic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, azelaic acid, benzenesulfonic acid and cyclohexanedicarboxylic acid.
5. The preparation method of the amino modified polyester resin fluorescent pigment according to claim 1, wherein the catalyst is one or more of monobutyl tin oxide, dibutyl tin dilaurate, stannous octoate, stannous oleate, phosphoric acid, phosphorous acid and sulfuric acid, which are mixed in any ratio.
6. The method for preparing an amino modified polyester resin fluorescent pigment according to claim 1, wherein the amino compound is one or more of ethylenediamine, hexamethylenediamine, aniline, benzylamine, m-xylylenediamine, isophorone diamine and cyclohexylamine.
7. The preparation method of the amino modified polyester resin fluorescent pigment according to claim 1, wherein the specific steps of the heat preservation reaction in S1 are as follows: heating to 180-220 deg.c, and maintaining the temperature for 2-4 hr.
8. The preparation method of the amino modified polyester resin fluorescent pigment according to claim 1, wherein the specific steps of the heat preservation reaction in S2 are as follows: heating to 240-270 deg.c, and maintaining the temperature for reaction for 1-2 hr.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3939093A (en) * | 1973-12-06 | 1976-02-17 | Hoechst Aktiengesellschaft | Daylight fluorescent pigments |
| US4975220A (en) * | 1989-11-09 | 1990-12-04 | Nalco Chemical Company | Polyamide-polyester fluorescent pigments |
| US5236621A (en) * | 1989-09-19 | 1993-08-17 | Day-Glo Color Corp. | Fluorescent pigments |
| US6103006A (en) * | 1998-01-28 | 2000-08-15 | Day-Glo Color Corporation | Fluorescent polymeric pigments |
| CN105062014A (en) * | 2015-08-10 | 2015-11-18 | 黄山加佳荧光材料有限公司 | Daylight fluorescent pigment with dissoluble color concentrate and preparation method of daylight fluorescent pigment |
| CN105885039A (en) * | 2016-06-07 | 2016-08-24 | 黄山加佳荧光材料有限公司 | Preparation method of high-performance daylight type fluorescent pigment for powder coating |
-
2023
- 2023-03-17 CN CN202310262884.7A patent/CN116285413A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3939093A (en) * | 1973-12-06 | 1976-02-17 | Hoechst Aktiengesellschaft | Daylight fluorescent pigments |
| US5236621A (en) * | 1989-09-19 | 1993-08-17 | Day-Glo Color Corp. | Fluorescent pigments |
| US4975220A (en) * | 1989-11-09 | 1990-12-04 | Nalco Chemical Company | Polyamide-polyester fluorescent pigments |
| US6103006A (en) * | 1998-01-28 | 2000-08-15 | Day-Glo Color Corporation | Fluorescent polymeric pigments |
| CN105062014A (en) * | 2015-08-10 | 2015-11-18 | 黄山加佳荧光材料有限公司 | Daylight fluorescent pigment with dissoluble color concentrate and preparation method of daylight fluorescent pigment |
| CN105885039A (en) * | 2016-06-07 | 2016-08-24 | 黄山加佳荧光材料有限公司 | Preparation method of high-performance daylight type fluorescent pigment for powder coating |
Non-Patent Citations (1)
| Title |
|---|
| 潘煜怡, 马胜军, 富秀玲, 李敏, 杨立新: "无甲醛耐热荧光树脂颜料的研究进展", 涂料工业, no. 07, 1 July 2003 (2003-07-01), pages 39 - 41 * |
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