CN113698788B - Macromolecular colorant for grease and preparation method thereof - Google Patents
Macromolecular colorant for grease and preparation method thereof Download PDFInfo
- Publication number
- CN113698788B CN113698788B CN202110919216.8A CN202110919216A CN113698788B CN 113698788 B CN113698788 B CN 113698788B CN 202110919216 A CN202110919216 A CN 202110919216A CN 113698788 B CN113698788 B CN 113698788B
- Authority
- CN
- China
- Prior art keywords
- macromolecular
- colorant
- grease
- hours
- preparing
- 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
- 239000003086 colorant Substances 0.000 title claims abstract description 64
- 239000004519 grease Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000000986 disperse dye Substances 0.000 claims description 38
- 239000003921 oil Substances 0.000 claims description 30
- 235000019198 oils Nutrition 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 150000001412 amines Chemical class 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 239000003925 fat Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 235000014593 oils and fats Nutrition 0.000 claims description 5
- 239000010775 animal oil Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 3
- 239000008158 vegetable oil Substances 0.000 claims description 3
- 229940008099 dimethicone Drugs 0.000 claims description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 239000000975 dye Substances 0.000 abstract description 19
- -1 tetradecyl primary amine Chemical class 0.000 description 20
- 229910052801 chlorine Inorganic materials 0.000 description 18
- 239000000460 chlorine Substances 0.000 description 17
- 150000003141 primary amines Chemical group 0.000 description 10
- 238000004040 coloring Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 229920000768 polyamine Polymers 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000985 reactive dye Substances 0.000 description 7
- 229920002545 silicone oil Polymers 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 239000012954 diazonium Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 235000013311 vegetables Nutrition 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- 229940035437 1,3-propanediol Drugs 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 1
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- ZAASRHQPRFFWCS-UHFFFAOYSA-P diazanium;oxygen(2-);uranium Chemical compound [NH4+].[NH4+].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[U].[U] ZAASRHQPRFFWCS-UHFFFAOYSA-P 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XWZDJOJCYUSIEY-UHFFFAOYSA-L disodium 5-[(4,6-dichloro-1,3,5-triazin-2-yl)amino]-4-hydroxy-3-phenyldiazenylnaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].Oc1c(N=Nc2ccccc2)c(cc2cc(cc(Nc3nc(Cl)nc(Cl)n3)c12)S([O-])(=O)=O)S([O-])(=O)=O XWZDJOJCYUSIEY-UHFFFAOYSA-L 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229940119170 jojoba wax Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000992 solvent dye Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010998 test method Methods 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
Classifications
-
- 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
- C09B43/00—Preparation of azo dyes from other azo compounds
- C09B43/40—Preparation of azo dyes from other azo compounds by substituting hetero atoms by radicals containing other hetero atoms
-
- 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
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
- C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
- C09B62/08—Azo dyes
- C09B62/085—Monoazo dyes
-
- 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
- C09B68/00—Organic pigments surface-modified by grafting, e.g. by establishing covalent or complex bonds, in order to improve the pigment properties, e.g. dispersibility or rheology
- C09B68/40—Organic pigments surface-modified by grafting, e.g. by establishing covalent or complex bonds, in order to improve the pigment properties, e.g. dispersibility or rheology characterised by the chemical nature of the attached groups
- C09B68/44—Non-ionic groups, e.g. halogen, OH or SH
- C09B68/446—Amines or polyamines, e.g. aminopropyl, 1,3,4,-triamino-pentyl or polyethylene imine
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a macromolecular colorant for grease and a preparation method thereof, belonging to the field of macromolecular dyes. The macromolecular colorant for grease has a structure shown in the following formula I: i is a kind ofWherein R is selected fromR 1 Selected from H, cl, NO 2 、CH 3 Or is absent; r is R 2 Selected from H, cl, NO 2 、CH 3 、CN;R 3 Selected from H, cl, NO 2 、CH 3 、CN;R 4 Selected from: or alternatively, the first and second heat exchangers may be,
Description
Technical Field
The invention belongs to the field of high molecular dyes, and particularly relates to a macromolecular colorant for grease and a preparation method thereof.
Background
Reactive dyes, disperse dyes, etc. are generally capable of providing desirable coloration to different materials, such as cotton, polyester, etc. However, these dyes have no coloring effect on insoluble substances. For example, reactive dyes and disperse dyes cannot color fuels, oils or waxes because they do not have any solubility in these media. The only solvent dyes that are currently available on the market to color these media, however, these dyes also have certain solubility problems and even do not color products such as silicone oils.
Various dyes exist in the prior art, but the solubility of the colorant obtained by modification is poor in grease due to poor oil solubility.
Disclosure of Invention
Based on the above-mentioned shortcomings in the art, the invention aims to provide a preparation method of a macromolecular colorant for grease, which is suitable for coloring natural grease, wax, silicone oil, synthetic grease and animal and vegetable grease, and has high solubility and complete color spectrum.
The technical scheme of the invention is as follows:
a macromolecular colorant for grease is characterized by having a structure represented by the following formula I:
wherein R is selected from
R 1 Selected from H, cl, NO 2 、CH 3 Or is absent; r is R 2 Selected from H, cl, NO 2 、CH 3 、CN;R 3 Selected from H, cl, NO 2 、CH 3 、CN;
R 4 Selected from:
the preparation method of the macromolecular colorant for grease is characterized by comprising the following steps: adding a solvent into the reactive disperse dye, uniformly mixing, and then adding fatty amine for heating;
the reactive disperse dye is selected from the following structures:
wherein R is 1 Selected from H, cl, NO 2 ,CH 3 ;R 2 Selected from H, cl, NO 2 ,CH 3 ,CN;R 3 =H,Cl,NO 2 ,CH 3 ,CN;R 4 Selected from H, cl, CH 3 Or is absent; r is R 5 Selected from H, cl, CH 3 Or a benzene ring attached to the position and its ortho position.
The reactive disperse dye has a structure shown in a formula III or a formula IV:
wherein R is 1 Selected from H, cl, NO 2 ,CH 3 ,R 2 Selected from H, cl, NO 2 ,CH 3 ,CN,R 3 Selected from H, cl, NO 2 ,CH 3 ,CN。
The solvent is selected from white oil, cyclopentadimethicone, vegetable oil, animal oil and dimethyl silicone oil;
the white oil is preferably No. 26 white oil;
the fatty amine is selected from primary amine, diamine or polyamine;
the primary amine is preferably coco primary amine, tetradecyl primary amine, or oleyl primary amine;
the diamine is preferably N-oil-1, 3-propylene diamine, N-coco-1, 3-propylene diamine;
the polyamine is selected from: polyethylene polyamine and polyethylene imine.
Before adding the solvent, an acid binding agent is added into the active disperse dye;
the acid binding agent is preferably sodium carbonate, potassium carbonate or potassium hydroxide.
The heating means that the temperature is firstly increased to 40-60 ℃, preferably 40 ℃, for 2-3 hours, preferably 3 hours, and then is increased to 80-100 ℃, preferably 90 ℃ for 2-3 hours; or heating to 80-100 deg.C under nitrogen protection, preferably 80 deg.C, and reacting for 3-6h, preferably 6h.
The mixing means stirring and mixing at 100-500 rpm, preferably 300 rpm.
Heating to 80-100 ℃ under the protection of nitrogen, reacting for 3-6h, and then introducing air to continue oxidizing for 1-3h.
After the temperature is raised to 80 ℃ under the protection of nitrogen for reaction for 6 hours, air is introduced for continuous oxidation for 3 hours.
The invention provides a macromolecular colorant for grease, which is prepared by the following steps:
step 1: preparation of reactive disperse dyes
Step 2: and (3) taking a three-neck flask, adding the reactive disperse dye and the acid binding agent in the step (1) into the flask, and then adding No. 26 white oil as a reaction solvent, wherein the stirring speed is controlled to be 300 r/min.
Step 3: adding fatty amine, raising the temperature to 40 ℃ for reaction for 2-3h, and controlling the stirring speed to 300 r/min.
Step 4: the reaction was continued for 2-3h at elevated temperature to 90 ℃. The stirring speed was controlled to 300 rpm.
Step 5: cooling to room temperature, and filtering to obtain macromolecular colorant for oil.
Further, the reactive disperse dye in the step 1 has the following structure:
wherein R is 1 =H,Cl,NO 2 ,CH 3 ;R 2 =H,Cl,NO 2 ,CH 3 ,CN;R 3 =H,Cl,NO 2 ,CH 3 ,CN;R 4 =H,Cl,CH 3 ;R 5 =H,Cl,CH 3
The R is 1 -R 5 Is of any combination of structures
Wherein R is 1 =H,Cl,NO 2 ,CH 3 Or is absent, R 2 =H,Cl,NO 2 ,CH 3 ,CN;R 3 =H,Cl,NO 2 ,CH 3 ,CN。
Further, the acid binding agent in the step 2 is one or more of sodium carbonate and potassium carbonate;
further, the fatty amine in the step 3 is an amine compound of saturated long-chain alkane, such as coco primary alkyl amine, tetradecyl primary amine, oleyl primary amine and the like; also included are di-and polyamine compounds such as N-oleyl-1, 3-propanediol diamine, N-coco-1, 3-propanediol diamine, and the like;
although the reactive disperse dye is a product which is developed but is not very commonly used, the reactive disperse dye with the structure shown in the formula II, the formula III or the formula IV is developed as an important precursor of the colorant for the macromolecular grease, and is a key factor for realizing high oil solubility and good coloring effect of the colorant for the macromolecular grease. The solubility of the reactive disperse dye used as a precursor raw material in grease is greatly broken through, and the reactive disperse dye contains reactive active groups and does not contain water-soluble groups, so that the reactive disperse dye is improved by using long-chain alkane, and can be used for coloring hydrocarbon and wax and coloring grease with poor solubility. And the macromolecular fatty amine grafting is carried out based on the reactive disperse dye with high solubility in the grease to obtain the macromolecular colorant with better oil solubility, so that the solubility of the dye in the grease is further improved, and the solubility of the colorant for macromolecular grease prepared based on the dye in the grease is further improved.
The invention further branches macromolecular fatty amine on the reactive disperse dye, and aims to further improve the final product: the macromolecular colorant is environment-friendly, safe and nontoxic, and the macromolecular colorant with large molecular weight is easier to wash when the skin or clothes are stained carelessly.
The beneficial effects of the invention include:
the macromolecular colorant for grease provided by the invention is suitable for coloring natural grease, wax, silicone oil, synthetic grease and animal and vegetable grease. The macromolecular colorant for grease prepared by the preparation method has simple production process, high solubility and complete chromatography.
The macromolecular colorant prepared by the preparation method provided by the invention can be well compatible with natural grease, wax, silicone oil, synthetic grease and animal and vegetable grease, and provides a good coloring effect.
The macromolecular colorant prepared by the preparation method is a liquid dye, and has good miscibility among various colors and simple color matching.
The macromolecular colorant of the invention, though the raw materials prepared by the macromolecular colorant are basically small molecules and have certain toxicity, the molecular weight of the final product (macromolecular colorant) obtained after the complete reaction of the preparation method of the invention is increased, the safety is improved, and unnecessary impurities and small molecules are removed through post-treatment, so that the content of toxic molecules and impurities is weak, and the final product of the macromolecular colorant of the invention is ensured to be safe and environment-friendly.
Detailed Description
The following describes the invention in more detail with reference to specific examples, but is not intended to limit the scope of the invention. Unless otherwise indicated, all the raw materials used in the experimental part of the present invention have the ordinary technical meanings conventionally understood by those skilled in the art, or are commercially available; the operations performed, the parameters employed, and the conditions have technical meanings commonly understood by those skilled in the art.
Reagent and consumable
Commercial dye reactive dye X-3B is a commercial product, and is commercially available, and the respective manufacturers and product models are as follows:
commercial dye reactive dye X-3B: the Zhejiang Yu is the product type of the reactive brilliant red X-3B of chemical industry Co.Ltd.
DYE1 and DYE2 are reactive disperse DYEs synthesized by the invention, and the structural formulas of the reactive disperse DYEs are respectively shown in the formula IV and the formula III.
Group 1 example, macromolecular colorant for fats and oils according to the present invention
The present set of examples provides a macromolecular colorant for grease. The macromolecular colorants for oils and fats of this example all have the structure shown in the following formula I:
wherein R is selected from
R 1 Selected from H, cl, NO 2 、CH 3 Or is absent; r is R 2 Selected from H, cl, NO 2 、CH 3 、CN;R 3 Selected from H, cl, NO 2 、CH 3 、CN;
R 4 Selected from:
the macromolecular colorant for grease shown in the formula I is obtained by further removing chlorine atoms at the 3 and 5 positions of a triazine ring on a core structure and grafting the chlorine atoms to macromolecular fatty amine on the basis of the core structure of the reactive disperse dye shown in the formulas IV-1 to IV-60 shown in the table 1 and the reactive disperse dye shown in the formulas III-1 to III-20 shown in the table 2.
Thus, in this particular group of embodiments, particular embodiments of the main structure of formula I can be referred to the structures of formulae IV-1 to IV-60 as set forth in Table 1 and the structures of formulae III-1 to III-20 as set forth in Table 2, the only difference being that the chlorine atom on the triazine ring is replaced by R 4 A group, and R 4 The group is selected from: n-coco-1, 3-propylenediamine
Cocoalkyl primary amines
Tetradecyl primary amine
Oil-based primary aminesAn isopolyamine group.
For economy, the formulae of the macromolecular colorants for oils and fats that graft the macromolecular fatty amine groups on the basis of the structures shown in formulae IV-1 to IV-60 and the structures shown in formulae III-1 to III-20 are not drawn one by one.
According to the description and teaching of the present invention, grafting macromolecular fatty amine groups (including but not limited to groups of N-coco-1, 3-propylenediamine, coco primary amine, tetradecyl primary amine, oleyl primary amine, etc.) and obtaining macromolecular colorants for oils and fats based on the structures represented by formulas IV-1 to IV-60 and the structures represented by formulas III-1 to III-20 according to the preparation method described in experimental examples 3 to 7 is definitely achieved and obtained by those skilled in the art. Any operation of grafting a macromolecular aliphatic amine group on the basis of the structures shown in the formulas IV-1 to IV-60 and the structures shown in the formulas III-1 to III-20, or any operation of grafting a compound with the structure shown in the formula I, or a compound with the structure shown in the formulas III-1 to III-20 on the 3 and 5 positions of the triazine ring by using macromolecular aliphatic amine except N-coco-1, 3-propanediol diamine, coco primary amine, tetradecyl primary amine and oleyl primary amine falls into the scope of the protection of the invention.
Group 2 example, method for producing macromolecular colorant for fats and oils according to the present invention
The embodiment of the group provides a preparation method of a macromolecular colorant for grease. All embodiments of this group share the following common features: the preparation method comprises the following steps: adding solvent into the reactive disperse dye, mixing uniformly, and then adding fatty amine to raise the temperature.
The solvent is generally oil-soluble, and because the reactive disperse dyes are solid in normal state, the solvent is used for better dissolving the dyes, so that the miscibility of the final product in the grease is improved. DYE1-DYE2 can be used as precursor materials for the colorants of the present invention, and they have in common that they have reactive groups such as halogen groups Cl, br, etc., which can undergo condensation reaction with amino groups as reactive groups.
The core principle of the preparation method for improving the oil solubility of the macromolecular colorant is that the active disperse dye is modified by adopting the fatty amine, and the fatty amine, such as coco primary alkyl amine, has the characteristic of grease dissolution, and is modified on the basis of finding a proper dye structure, so that the final product macromolecular colorant has excellent oil solubility.
In a preferred embodiment, the proportion of the active disperse dye, the solvent and the fatty amine is as follows: the positive effect of this ratio on the increase of the oil solubility is to increase the completeness of the reaction, preferably by 1:1-2:5-15:1-2, preferably by 1:10:1.
In some specific embodiments, the reactive disperse dye is selected from the following structures:
wherein R is 1 Selected from H, cl, NO 2 ,CH 3 Or is absent; r is R 2 Selected from H, cl, NO 2 ,CH 3 Or absent, CN; r is R 3 =H,Cl,NO 2 ,CH 3 CN or absent; r is R 4 Selected from H, cl, CH 3 Or is absent; r is R 5 Selected from H, cl, CH 3 Or a benzene ring attached to the position and its ortho position;
the compounds of formula II may further specifically include compounds of formula III or formula IV as follows:
wherein R is 1 =H,Cl,NO 2 ,CH 3 Or is absent, R 2 =H,Cl,NO 2 ,CH 3 Or is absent, CN, R 3 =H,Cl,NO 2 ,CH 3 CN or absent.
In specific embodiments, the solvent is selected from white oil, cyclopentadimethicone, vegetable oil, animal oil, dimethicone;
the white oil is preferably No. 26 white oil, because the white oil is cheap and has good dissolution effect;
in other embodiments, the fatty amine is selected from primary amines, diamines or polyamines;
the primary amine is preferably coco primary amine, tetradecyl primary amine, or oleyl primary amine;
the diamine is preferably N-oil-1, 3-propylene diamine, N-coco-1, 3-propylene diamine;
the polyamine is selected from: polyethylene polyamine and polyethylene imine.
In a further embodiment, an acid-binding agent is added to the reactive disperse dye before the solvent is added to the reactive disperse dye; the ratio of the addition amount of the acid binding agent to the amount of the active disperse dye is as follows: the mass ratio of 1-2:5-15 is preferably 1:10, and the dosage ratio plays the following positive roles in improving the grease solubility of the final product: improving the completeness of the reaction.
The acid binding agent is preferably sodium carbonate, potassium carbonate or potassium hydroxide, and the acid binding agent is added to improve the reaction rate and the acid reaction produced in the reaction.
In a preferred embodiment, the heating means that the temperature is raised to 40-60 ℃ preferably 40 ℃ for 2-3 hours preferably 3 hours, then raised to 80-90 ℃ preferably 90 ℃ for 2-3 hours, and the respective effects of 2 stages of heating are to react with chlorine on cyanuric chloride, wherein the second chlorine reaction temperature is about 40 ℃, and the third chlorine reaction temperature is about 90 ℃;
or alternatively, the first and second heat exchangers may be,
the reaction is carried out for 3 to 6 hours, preferably 6 hours, at 80 to 90 ℃ preferably 80 ℃ under the protection of nitrogen, and the step of directly heating to 80 ℃ serves to increase the reaction speed and the minimum temperature required by the reaction.
In other embodiments, the mixing means stirring the mixture at 100-500 rpm, preferably 300 rpm.
In a more preferred embodiment, after the reaction is carried out for 3 to 6 hours, preferably 6 hours, under the protection of nitrogen, the temperature is raised to 80 to 100 ℃, preferably 80 ℃, and then the oxidation is continued for 1 to 3 hours, preferably 3 hours, by introducing air.
Experimental example 1
Taking a three-port bottle, adding 14g of paranitroaniline, 30g of hydrochloric acid, 30g of water, pulping for 1h, cooling to 0 ℃, then adding 7.5g of sodium nitrite, preserving heat for 1h, and adding 2g of sulfamic acid to obtain diazonium liquor for later use; to another three-necked flask, 9g of aniline and 10g of water were added, and then the diazonium solution was slowly added dropwise to the flask over a period of 30 minutes, and the temperature was kept at 5 ℃. Coupling time was 5h. After the reaction is completed, 18g of cyanuric chloride is added, the temperature is controlled to be 5 ℃, the pH value is 3-4, and the condensation time is 3 hours. After the completion of the reaction, the pH was adjusted to neutral and then filtered and washed with water to give 25g of a yellow cake designated DYE1 having a chemical structure as described in the following formula IV-1.
In addition, DYE1 may also have chemical structures of the following formulas IV-2 through IV-60, which are prepared in a manner substantially identical to those described above, with only some differences in the parameters of the links, as set forth in Table 1 below:
TABLE 1 chemical structure of DYE1 and process for preparing the same
/>
/>
/>
/>
/>
/>
/>
/>
Experimental example 2
Adding 9g of aniline, 30g of hydrochloric acid and 30g of water into a three-port bottle, pulping for 1h, cooling to 0 ℃, then adding 7.5g of sodium nitrite, preserving heat for 1h, and adding 2g of sulfamic acid to obtain a diazonium solution for later use; 14g of 1-naphthylamine and 10g of water are added into another three-necked flask, and then the diazonium solution is slowly dripped into the flask, the dripping is completed in 30 minutes, and the temperature is kept at 5 ℃. Coupling time was 5h. After the reaction is completed, 18g of cyanuric chloride is added, the temperature is controlled to be 5 ℃, the pH value is 3-4, and the condensation time is 3 hours. After the reaction was completed, the pH was adjusted to neutral and then filtered and washed with water to obtain 30g of a red cake designated DYE2 having a chemical structure represented by the following formula III-1. In addition, DYE2 may also have chemical structures of the following formulas III-2 through III-20, which are prepared in a manner substantially identical to those described above, with only some differences in the parameters of the links, as described in Table 2 below:
TABLE 2 chemical structure of DYE2 and process for preparing the same
/>
/>
/>
Experimental example 3
10g of active disperse DYE DYE1 and 1g of sodium carbonate are added into a flask by taking a three-necked flask, and then 100g of No. 26 white oil is added, and the stirring speed is controlled to be 300 revolutions per minute. Adding primary cocoyl amine (NH) 2 C 12 H 25 ) 10g, firstly raising the temperature to 40 ℃ for reaction for 2 hours, and then raising the temperature to 90 ℃ for reaction for 3 hours. Cooling to room temperature, and filtering to obtain yellow filtrate, namely the macromolecular colorant 1#.
Experimental example 4
10g of active disperse DYE DYE2 and 1g of sodium carbonate are added into a flask by taking a three-necked flask, and then 100g of No. 26 white oil is added, and the stirring speed is controlled to be 300 revolutions per minute. Adding primary cocoyl amine (NH) 2 C 12 H 25 ) 10g, firstly raising the temperature to 40 ℃ for reaction for 2 hours, and then raising the temperature to 90 ℃ for reaction for 3 hours. Cooling to room temperature, and filtering to obtain red filtrate, namely the macromolecular colorant No. 2.
Experimental example 5
10g of disperse DYE DYE1 and 100g of No. 26 white oil are added into a flask by taking a three-necked flask, and the stirring speed is controlled to be 300 revolutions per minute. Adding tetradecyl primary amine (NH) 2 C 14 H 29 ) 10g, introducing nitrogen, raising the temperature to 80 ℃, reacting for 6 hours, introducing air after finishing, continuing to oxidize for 3 hours, cooling to room temperature, and filtering to obtain yellow filtrate, namely the macromolecular colorant No. 3.
Experimental example 6
10g of disperse DYE DYE2 and 100g of No. 26 white oil are added into a flask by taking a three-necked flask, and the stirring speed is controlled to be 300 revolutions per minute. Adding tetradecyl primary amine (NH) 2 C 14 H 29 ) 10g, introducing nitrogen, raising the temperature to 80 ℃, reacting for 6 hours, introducing air after the reaction is finished, continuing to oxidize for 3 hours, cooling to room temperature, and filtering to obtain red filtrate, namely the macromolecular colorant No. 4.
Experimental example 7
10g of active disperse DYE DYE1 and 1g of sodium carbonate are added into a flask by taking a three-necked flask, and then 100g of No. 26 white oil is added, and the stirring speed is controlled to be 300 revolutions per minute. Adding N-coco-1, 3-propylene diamine (NH) 2 C 21 H 42 N) 10g, the temperature is raised to 40 ℃ for 2 hours, and then the temperature is raised to 90 ℃ for 3 hours. Cooling to room temperature, and filtering to obtain yellow filtrate, namely the macromolecular colorant No. 5.
Comparative example 1
10g of reactive dye X-3B and 1g of sodium carbonate are added into a flask by taking a three-necked flask, then 20g of dipropylene glycol methyl ether is added, and the stirring speed is controlled to be 300 revolutions per minute. 10g of cocoyl primary amine is added, the temperature is raised to 40 ℃ for reaction for 2 hours, and then the temperature is raised to 90 ℃ for reaction for 3 hours. The resulting dye was cooled and designated 6#.
Experimental example 8 oil solubility experiment of the reactive disperse dye and macromolecular colorant of the present invention
DYE1-2 prepared in the above experimental examples 1-2, 1-5# macromolecular colorant prepared in the experimental examples 3-7, DYE 6# prepared in the comparative example 1, and active DYE X-3B of the existing product were respectively tested for their solubility in grease by the following specific test methods:
hydroxyl silicone oil, cyclopentadimethicone, jojoba oil, diesel oil, beeswax and lubricating oil are respectively used as different grease solvents;
the following samples were taken: reactive disperse DYE DYE1 (samples of 60 different products), DYE2 (samples of 20 different products), macromolecular colorant 1#, macromolecular colorant 2#, macromolecular colorant 3#, macromolecular colorant 4#, macromolecular colorant 5#, DYE 6#, reactive DYE X-3B, 10g of each sample is gradually and slowly added into 100g of each grease solvent in batches to form a group, and each group is repeated for 3 times. In each repetition, the adding method can be firstly and quantitatively added in a small amount, for example, 1-3g is added dropwise at a time, and the adding amount is increased under the condition of small amount of solubility. If the sample is very poorly soluble, the amount added can be further reduced, for example by adding only 1g or 0.5g or 0.1g at a time until the sample is completely dissolved in the fat. When the phenomena of insolubility, delamination, precipitation and the like occur once in the adding process, stopping adding, and counting the total amount of the sample which is added before. The amount of dissolved matter (unit: g) was obtained.
The test results are based on the average of 3 replicates in each group, and the statistical dissolution data are shown in table 3 below:
TABLE 3 comparison of the amounts of dissolved dyes and colorants in various oils prepared in the examples and comparative examples
/>
/>
/>
As can be seen from the results of the above examples, the untreated commercial dye reactive dye X-3B is insoluble in the grease and does not have any coloring effect, but the macromolecular colorant of the present invention has extremely high solubility in the grease and strong coloring power, and can color natural grease, wax, silicone oil, synthetic grease, animal and vegetable grease and the like on the market.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (11)
1. A macromolecular colorant for grease is characterized by having a structure represented by the following formula I:
i is a kind of;
Wherein R is selected fromOr->;
R 1 Selected from H, cl, NO 2 、CH 3 ;R 2 Selected from H, cl, NO 2 、CH 3 、CN;R 3 Selected from H, cl, NO 2 、CH 3 、CN;
R 4 Selected from:
、
、
。
2. the method for preparing a macromolecular colorant for grease according to claim 1, comprising: adding a solvent into the reactive disperse dye, uniformly mixing, and then adding fatty amine for heating;
the reactive disperse dye has a structure shown in a formula III or a formula IV:
formula III,
IV (IV)
Wherein R is 1 Selected from H, cl, NO 2 ,CH 3 ,R 2 Selected from H, cl, NO 2, CH 3 ,CN,R 3 Selected from H, cl, NO 2 ,CH 3 CN; the solvent is selected from white oil, cyclopentadimethicone, vegetable oil, animal oil, and dimethicone.
3. The method for producing a macromolecular colorant for fat according to claim 2, wherein the white oil is No. 26 white oil.
4. The method for preparing a macromolecular colorant for grease according to claim 2, wherein an acid-binding agent is added to the reactive disperse dye before the solvent is added.
5. The method for preparing a macromolecular colorant for oils and fats according to claim 4, wherein said acid-binding agent is selected from the group consisting of: sodium carbonate, potassium hydroxide.
6. The method for preparing a macromolecular colorant for grease according to claim 2, wherein the heating means is to heat up to 40-60 ℃ for 2-3 hours, and then heat up to 80-100 ℃ for 2-3 hours; or heating to 80-100 ℃ under the protection of nitrogen, and reacting for 3-6h.
7. The method for preparing a macromolecular colorant for grease according to claim 2, wherein the heating means is to heat up to 40 ℃ for 3 hours and then to 90 ℃ for 2-3 hours; or, heating to 80 ℃ under the protection of nitrogen, and reacting for 6h.
8. The method for preparing a macromolecular colorant for oils and fats according to claim 2, wherein the mixing means mixing by stirring at 100 to 500 rpm.
9. The method for preparing a macromolecular colorant for fat according to claim 8, wherein said mixing means mixing by stirring at 300 rpm.
10. The method for preparing a macromolecular colorant for oil and fat according to claim 6, wherein the macromolecular colorant is oxidized for 1-3 hours by introducing air after heating to 80-100 ℃ under the protection of nitrogen for 3-6 hours.
11. The method for preparing a macromolecular colorant for grease according to claim 10, wherein after the reaction is carried out for 6 hours under the protection of nitrogen and the temperature is raised to 80 ℃, air is introduced for continuous oxidation for 3 hours.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110919216.8A CN113698788B (en) | 2021-08-11 | 2021-08-11 | Macromolecular colorant for grease and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110919216.8A CN113698788B (en) | 2021-08-11 | 2021-08-11 | Macromolecular colorant for grease and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113698788A CN113698788A (en) | 2021-11-26 |
CN113698788B true CN113698788B (en) | 2023-10-20 |
Family
ID=78652243
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110919216.8A Active CN113698788B (en) | 2021-08-11 | 2021-08-11 | Macromolecular colorant for grease and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113698788B (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3459729A (en) * | 1963-01-15 | 1969-08-05 | Acna | Monoazo triazine containing dyestuffs |
-
2021
- 2021-08-11 CN CN202110919216.8A patent/CN113698788B/en active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3459729A (en) * | 1963-01-15 | 1969-08-05 | Acna | Monoazo triazine containing dyestuffs |
Non-Patent Citations (8)
Title |
---|
Effect of an isolating group derived from 2,4,6-trisubstituted 1,3,5-triazine on the light resistance of cationic dyes with isolated quaternary groups;Draganov, A. et al;Revistade Chimie (Bucharest, Romania);第27卷(第4期);283-285 * |
Effects of 1,3,5-triazinyl groups on the absorption spectra of aromatic amines;Kayama Ryuichi et al;Nippon Kagaku Kaishi(第3期);552-562 * |
Investigation of the activity of some unsaturated triazine dyes on their copolymerization with acrylonitrile;Konstantinova, T.;Angewandte Makromolekulare Chemie;第64卷(第1期);205-210 * |
Nonlinear optical chromophores with good transparency and high thermal stability;Liu Yangang et al;Dyes and Pigments;第45卷(第3期);189-193 * |
Preparation and properties of thermally stable copolyimides based on novel second-order nonlinear-optical chromophore containing diamines;Yu Sui et al;Journal of Applied Polymer Science;第76卷(第11期);1619-1626 * |
Reactive cationic dyes. I. New cationic dyes containing the s-triazine nucleus;Okazaki Mitsuo et al;Kogyo Kagaku Zasshi;第67卷(第1期);129-134 * |
Study on side-chain second-order nonlinear optical polyimides based on novel chromophore-containing diamines. I. Synthesis and characterization;Yu Sui et al;Journal of Polymer Science, Part A: Polymer Chemistry;第37卷(第23期);4330-4336 * |
Water-insoluble s-triazine dyes. I;Matsui, Koji et al;Yuki Gosei Kagaku Kyokaishi;第20卷(第4期);371-378 * |
Also Published As
Publication number | Publication date |
---|---|
CN113698788A (en) | 2021-11-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN113698788B (en) | Macromolecular colorant for grease and preparation method thereof | |
CN113652097B (en) | Reactive disperse dye and preparation method thereof | |
DE2727383A1 (en) | AZO DYES OF THE PYRIDONE SERIES | |
DE3301822A1 (en) | METHOD FOR PRODUCING DISAZO DYES | |
JPS6261617B2 (en) | ||
US4000965A (en) | Metal complex dyestuffs | |
JPS6399382A (en) | Dyeing of hydrophobic fiber using pyridone monoazo compound | |
TWI465523B (en) | Dark brown reactive dye | |
DE2801951A1 (en) | AZO DYES | |
US3685952A (en) | Coloration of polyester textile fibers with azo dyes | |
JPH01502918A (en) | phase change dye | |
DE3001266A1 (en) | ALPHA -HYDRAZONO- ALPHA -PHENYL- ACETONITRILES, PROCESS FOR THEIR PRODUCTION AND THEIR USE AS DISPERSION DYES FOR DYING ARTIFICIAL OR SYNTHETIC MATERIALS | |
DE2050900A1 (en) | Azo compounds that are poorly soluble in water, their production and use | |
DE2111734C3 (en) | Azo dyes and their uses | |
EP0342158B1 (en) | Water soluble phthalocyanine compounds, process for their preparation and their use | |
JPS6051505B2 (en) | Water-soluble monoazo dye | |
JP2556692B2 (en) | Method for dyeing hydrophobic fiber using pyridone monoazo compound | |
JP3580564B2 (en) | Cobalt-containing azo compound, its use and production method | |
JP2868143B2 (en) | Cobalt-containing azo dye composition and dyeing method using the same | |
JPS63199764A (en) | Pyridone monoazo compound and method of dyeing hydrophobic fiber by using the same | |
JP2556693B2 (en) | Method for dyeing or printing hydrophobic fiber using pyridone monoazo compound | |
DE1801328A1 (en) | New compounds and azo dyes and their use for dyeing hydrophobic fibers | |
CN116948426A (en) | Nostalgic dye composition and application thereof | |
JPH042625B2 (en) | ||
CN114525040A (en) | Red mordant dye and preparation method thereof |
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 |