CN117903428A - Tocopherol block polyether and preparation method and application thereof - Google Patents
Tocopherol block polyether and preparation method and application thereof Download PDFInfo
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- CN117903428A CN117903428A CN202410315972.3A CN202410315972A CN117903428A CN 117903428 A CN117903428 A CN 117903428A CN 202410315972 A CN202410315972 A CN 202410315972A CN 117903428 A CN117903428 A CN 117903428A
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- tocopherol
- block polyether
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- catalyst
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- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229960001295 tocopherol Drugs 0.000 title claims abstract description 64
- 229930003799 tocopherol Natural products 0.000 title claims abstract description 64
- 235000010384 tocopherol Nutrition 0.000 title claims abstract description 64
- 239000011732 tocopherol Substances 0.000 title claims abstract description 64
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 title claims abstract description 64
- 229920000570 polyether Polymers 0.000 title claims abstract description 47
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000049 pigment Substances 0.000 claims abstract description 46
- 238000001816 cooling Methods 0.000 claims abstract description 43
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 27
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 229960000583 acetic acid Drugs 0.000 claims abstract description 10
- 230000018044 dehydration Effects 0.000 claims abstract description 10
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 10
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000003054 catalyst Substances 0.000 claims description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 239000012860 organic pigment Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 7
- 238000006467 substitution reaction Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 238000002715 modification method Methods 0.000 claims 1
- 238000009489 vacuum treatment Methods 0.000 abstract description 6
- 231100000344 non-irritating Toxicity 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000000976 ink Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 230000001276 controlling effect Effects 0.000 description 17
- 239000002270 dispersing agent Substances 0.000 description 17
- 238000010168 coupling process Methods 0.000 description 15
- 230000008878 coupling Effects 0.000 description 14
- 238000005859 coupling reaction Methods 0.000 description 14
- 235000011121 sodium hydroxide Nutrition 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 10
- 239000012954 diazonium Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000003916 acid precipitation Methods 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 235000010288 sodium nitrite Nutrition 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000203 mixture Substances 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
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 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
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 230000007059 acute toxicity Effects 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- AYOOGWWGECJQPI-NSHDSACASA-N n-[(1s)-1-(5-fluoropyrimidin-2-yl)ethyl]-3-(3-propan-2-yloxy-1h-pyrazol-5-yl)imidazo[4,5-b]pyridin-5-amine Chemical compound N1C(OC(C)C)=CC(N2C3=NC(N[C@@H](C)C=4N=CC(F)=CN=4)=CC=C3N=C2)=N1 AYOOGWWGECJQPI-NSHDSACASA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229960005489 paracetamol Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Polyethers (AREA)
Abstract
The invention discloses a tocopherol block polyether, a preparation method and application thereof, wherein tocopherol and inorganic strong base are added into a reaction kettle, negative pressure dehydration and temperature rise are carried out, propylene oxide is added after nitrogen replacement, and temperature control reaction is carried out; cooling, vacuum dehydration, adding inorganic strong base after cooling, heating, negative pressure dehydration, adding ethylene oxide after nitrogen replacement, temperature control reaction, cooling, vacuum treatment cooling, adding glacial acetic acid to adjust the pH to 6-8, stirring for half an hour, and cooling to obtain tocopherol block polyether; the tocopherol block polyether can completely replace alkylphenol ethoxylates, is nontoxic and nonirritating, and has good safety. The addition amount of the pigment is only 2-5%, so that the pigment dispersibility and the tinting strength and the vividness of the pigment can be improved.
Description
Technical Field
The invention relates to the technical field of organic pigment additives and fine chemical engineering, in particular to tocopherol block polyether, a preparation method and application thereof.
Background
The aqueous printing ink is an important environment-friendly product in the printing industry, has important significance for promoting the continuous and stable development of the field of the aqueous printing ink, wherein the organic pigment plays an important role in the development of the aqueous printing ink, but has the problems of poor aqueous dispersion and the like. For example, when the common azo pigment is applied to an aqueous system, the viscosity is higher, the storage stability is poorer, and the quality of a printed matter is unstable. The azo-based pigment may be subjected to a surface treatment to convert the hydrophobic surface of the pigment into a hydrophilic surface to improve dispersibility in an aqueous medium system.
In addition, alkylphenol ethoxylates (APEO) surfactant can be added in the process of pigment synthesis and post-treatment for surface modification, and the APEO surfactant has excellent emulsification, wetting and dispersion effects and can improve the application performance of the pigment in an aqueous system. APEO, however, contains alkyl chains bonded to the phenyl ring and chains of ethoxylated repeat units, and degradation to Alkylphenols (AP) in the environment ultimately results in the introduction of higher toxicity. APEO and its metabolite AP are therefore widely regarded as an environmental hormone, possessing a degree of bioaccumulation, carcinogenicity, acute toxicity, aquatic toxicity, etc., and have been gradually banned or restricted worldwide.
Therefore, the development of the environment-friendly water-based organic pigment surface modified dispersing agent has important significance for improving the application performance of the organic pigment in a water-based system.
Disclosure of Invention
The invention aims to solve the problem of poor environmental protection performance of a dispersing agent for surface modification of an aqueous organic pigment, and provides a tocopherol block polyether, a preparation method and application thereof, which can replace alkylphenol ethoxylates surfactant.
The invention aims to achieve the aim, and the aim is achieved by the following technical scheme:
a tocopherol block polyether has a structural formula shown in formula I:
The invention also comprises a preparation method of the tocopherol block polyether, which comprises the following steps:
Adding tocopherol and a first catalyst into a reaction kettle, heating to 80-85 ℃, carrying out negative pressure dehydration, heating to 100-105 ℃, carrying out nitrogen substitution for three times, starting to add propylene oxide, controlling the temperature to 130-145 ℃ and the pressure to be not more than 0.3MPa, and continuing to react for 50-70 minutes after the propylene oxide is fed; cooling to 100-110 ℃, vacuum dehydrating for 30-40 minutes, cooling to 80 ℃, adding a second catalyst, heating to 110-115 ℃, dehydrating for 30-40 minutes under negative pressure, replacing nitrogen for three times, starting to add ethylene oxide, controlling the temperature to be 110-125 ℃, continuing to react for 30-40 minutes after the ethylene oxide is fed, cooling to 90-100 ℃, vacuum treating for 30-40 minutes, cooling to below 80 ℃, adding glacial acetic acid to adjust the pH to 6-8, stirring for half an hour, cooling to 20-30 ℃, and obtaining the tocopherol block polyether;
the first catalyst and the second catalyst are inorganic strong base;
the mass ratio of the tocopherol to the first catalyst to the epoxypropane to the second catalyst to the epoxyethane is 100: 1.5-3: 260-410: 1.5-3: 610-820.
The reaction equation is as follows:
wherein m=20 to 30, n=60 to 80.
Preferably, the first catalyst and the second catalyst are sodium hydroxide or potassium hydroxide.
Preferably, the mass ratio of the tocopherol to the first catalyst to the propylene oxide to the second catalyst to the ethylene oxide is 100: 2-2.5: 300-350: 2-3: 650-700 parts.
Preferably, the reaction temperature after adding propylene oxide is 135-140 ℃.
Preferably, the reaction temperature after adding ethylene oxide is 115-120 ℃.
The invention also includes the use of tocopherol block polyethers for surface modification during the synthesis of organic pigments.
Preferably, the addition amount of the organic pigment is 2-5% of the mass of the pigment.
Compared with the prior art, the invention has the following advantages:
The tocopherol block polyether structure contains propoxy and ethoxy structures, and the molar ratio of propylene oxide to ethylene oxide is controlled to be about 20-30 in the preparation process: 60-80% to prepare the tocopherol block polyether, wherein the tocopherol block polyether with the structure has a strong adsorption effect on the surface of the pigment, so that the pigment has good dispersibility in an aqueous system.
The tocopherol block polyether can completely replace alkylphenol ethoxylates, is nontoxic and nonirritating, and has good safety. The addition amount of the pigment is only 2-5%, so that the pigment dispersibility and the tinting strength and the vividness of the pigment can be improved.
Detailed Description
The invention aims to provide a tocopherol block polyether, a preparation method and application thereof, and the invention is further described below with reference to specific examples.
Example 1a process for the preparation of a tocopherol block polyether comprising the steps of:
Adding 1kg of tocopherol and 15g of sodium hydroxide into a reaction kettle, heating to 80 ℃, carrying out negative pressure dehydration, heating to 100 ℃, carrying out nitrogen substitution for three times, then starting to add 2.6kg of propylene oxide, controlling the temperature to 130 ℃, controlling the pressure to be not more than 0.3MPa, and continuing to react for 70 minutes after the propylene oxide is fed; cooling to 100 ℃, dehydrating in vacuum for 30 minutes, cooling to 80 ℃, adding 15g of sodium hydroxide, heating to 110 ℃, dehydrating under negative pressure for 40 minutes, replacing with nitrogen for three times, then starting to add 6.1kg of ethylene oxide, controlling the temperature at 110 ℃, continuing to react for 40 minutes after the ethylene oxide is fed, cooling to 90 ℃, cooling to below 80 ℃ after vacuum treatment for 30 minutes, adding glacial acetic acid to adjust the pH to 6, stirring for half an hour, cooling to 20 ℃ and obtaining the tocopherol block polyether;
The mass ratio of the tocopherol to the first catalyst to the epoxypropane to the second catalyst to the epoxyethane is 100:1.5:260:1.5:610.
Example 2a process for the preparation of a tocopherol block polyether comprising the steps of:
Adding 1kg of tocopherol and 30g of potassium hydroxide into a reaction kettle, heating to 85 ℃, carrying out negative pressure dehydration, heating to 105 ℃, carrying out nitrogen substitution for three times, then starting to add 4.1kg of propylene oxide, controlling the temperature to 145 ℃, controlling the pressure to be not more than 0.3MPa, and continuing to react for 50 minutes after the propylene oxide is fed; cooling to 110 ℃, dehydrating in vacuum for 40 minutes, cooling to 80 ℃, adding 30g of potassium hydroxide, heating to 115 ℃, dehydrating under negative pressure for 40 minutes, replacing with nitrogen for three times, then starting to add 8.2kg of ethylene oxide, controlling the temperature to 125 ℃, continuing to react for 30 minutes after the ethylene oxide is added, cooling to 100 ℃, cooling to below 80 ℃ after vacuum treatment for 40 minutes, adding glacial acetic acid to adjust the pH to 8, stirring for half an hour, cooling to 20-30 ℃ and obtaining the tocopherol block polyether;
The mass ratio of the tocopherol to the first catalyst to the epoxypropane to the second catalyst to the epoxyethane is 100: 3: 410: 3: 820.
Example 3 a process for the preparation of a tocopherol block polyether comprising the steps of:
Adding 1kg of tocopherol and 20g of sodium hydroxide into a reaction kettle, heating to 82 ℃, carrying out negative pressure dehydration, heating to 102 ℃, carrying out nitrogen substitution for three times, starting to add 3kg of propylene oxide, controlling the temperature to 135 ℃ and the pressure to be not more than 0.3MPa, and continuing to react for 55 minutes after the propylene oxide is fed; cooling to 105 ℃, dehydrating in vacuum for 32 minutes, cooling to 80 ℃, adding 20g of potassium hydroxide, heating to 112 ℃, dehydrating in negative pressure for 32 minutes, replacing with nitrogen for three times, then starting to add 6.5kg of ethylene oxide, controlling the temperature to 115 ℃, continuing to react for 32 minutes after the ethylene oxide is added, cooling to 95 ℃, cooling to below 80 ℃ after the vacuum treatment is carried out for 32 minutes, adding glacial acetic acid, regulating the pH to 6.5, stirring for half an hour, cooling to 22 ℃ and obtaining the tocopherol block polyether;
The mass ratio of the tocopherol to the first catalyst to the epoxypropane to the second catalyst to the epoxyethane is 100:2:300:2:650.
Example 4 a process for preparing a tocopherol block polyether comprising the steps of:
Adding 1kg of tocopherol and 25g of potassium hydroxide into a reaction kettle, heating to 84 ℃, carrying out negative pressure dehydration, heating to 102 ℃, carrying out nitrogen substitution for three times, then starting to add 3.5kg of propylene oxide, controlling the temperature at 140 ℃ and the pressure not to exceed 0.3MPa, and continuing to react for 60 minutes after the propylene oxide is fed; cooling to 102 ℃, dehydrating in vacuum for 32 minutes, cooling to 80 ℃, adding 30g of sodium hydroxide, heating to 112 ℃, dehydrating in negative pressure for 32 minutes, replacing with nitrogen for three times, then starting to add 7kg of ethylene oxide, controlling the temperature to 120 ℃, continuing to react for 35 minutes after the ethylene oxide is fed, cooling to 98 ℃, cooling to below 80 ℃ after 38 minutes of vacuum treatment, adding glacial acetic acid, regulating the pH to 7.5, stirring for half an hour, cooling to 25 ℃, and obtaining the tocopherol block polyether;
the mass ratio of the tocopherol to the first catalyst to the epoxypropane to the second catalyst to the epoxyethane is 100:2.5:350: 3:700.
Example 5a process for preparing a tocopherol block polyether comprising the steps of:
Adding 1kg of tocopherol and 22g of potassium hydroxide into a reaction kettle, heating to 82 ℃, carrying out negative pressure dehydration, heating to 104 ℃, carrying out nitrogen substitution for three times, then starting to add 3.2kg of propylene oxide, controlling the temperature at 138 ℃ and the pressure not to exceed 0.3MPa, and continuing to react for 65 minutes after the propylene oxide is fed; cooling to 105 ℃, dehydrating in vacuum for 35 minutes, cooling to 80 ℃, adding 25g of potassium hydroxide, heating to 114 ℃, dehydrating in negative pressure for 35 minutes, replacing with nitrogen for three times, then starting to add 6.8kg of ethylene oxide, controlling the temperature to 118 ℃, continuing to react for 38 minutes after the ethylene oxide is added, cooling to 95 ℃, cooling to below 80 ℃ after 35 minutes of vacuum treatment, adding glacial acetic acid to adjust the pH to 7.0, stirring for half an hour, cooling to 28 ℃ and obtaining the tocopherol block polyether;
The mass ratio of the tocopherol to the first catalyst to the epoxypropane to the second catalyst to the epoxyethane is 100:2.2:320:2.5:680.
Use of the tocopherol block polyether obtained in example-6
The tocopherol block polyether or OP-10 obtained in example 1 was used in the preparation of pigment yellow 83 to modify pigment yellow 83, as follows:
preparation of pigment yellow 83
① Preparation of diazonium solution: adding 100ml of water into a 500ml beaker, adding 16g of hydrochloric acid and 10g of DCB, pulping for 30 minutes, and adding ice to cool to 0-3 ℃; rapidly adding 5.8g of sodium nitrite solution, stirring for 60 minutes, adding sulfamic acid to remove excessive sodium nitrite, adjusting the KI test paper to be bluish, adjusting V=300 ml, and T=0 ℃ to be coupled;
② Preparation of coupling liquid: 200ml of water and 3.75g of sodium hydroxide are added into a 500ml beaker, 22.5g of paracetamol AS-IRG is added, stirring, dissolving and clarifying are carried out, the temperature is adjusted to T=15 ℃, V=320 ml, and acid precipitation is carried out;
③ Preparation of acid precipitation liquid: 200ml of water, 6.5g of glacial acetic acid and 7.1g of anhydrous sodium acetate are added into a 3000ml beaker, stirred and dissolved, and T=18 ℃ and V=300 ml are adjusted;
④ Acid precipitation: adding the coupling solution into the acid precipitation solution within 30-40 minutes, wherein the endpoint T=20 ℃, the pH=5.6-6.0, stirring for 15 minutes, adding 1.6g of the water solution of the dispersing agent A, and stirring for 15 minutes for later use;
⑤ Coupling and post-treatment: dropping diazonium into a coupling component, controlling the pH value to be 4.5-5.0 by using NaOH solution in the coupling process at the temperature of T=16-20 ℃ for t=140-150 minutes, heating to 35 ℃ after coupling for 100 minutes, slowing down the coupling speed, measuring the excess condition of diazonium salt for a plurality of times, ensuring that the excess condition is not caused, and stirring for 30 minutes after coupling, wherein the pH value is 4.3-4.5 at the temperature of T=35-40 ℃ without excess diazonium salt; heating to T=95 ℃ or above, finishing color conversion, preserving heat for 30 minutes, cooling to 65 ℃ or below, suction filtering, rinsing to conductivity within 100, and drying at 90 ℃.
Example 6 when dispersant A is the tocopherol block polyether prepared in example 1 and comparative example 1 when dispersant A is OP-10.
Use of the tocopherol block polyether obtained in example 7
The tocopherol block polyether obtained in example 2 or peregal OS-15 was used in the preparation of pigment yellow 14 to modify pigment yellow 14, as follows:
Preparation of pigment yellow 14
① Preparation of diazonium solution: adding 150ml of water, 16.6g of hydrochloric acid and 10g of DCB into a 500ml beaker, pulping for 30 minutes, adding ice to cool to 0 ℃, adding 5.8g of sodium nitrite solution, and stirring for 60 minutes; adding sulfamic acid to remove excessive sodium nitrite, adjusting the KI test paper to be bluish, adjusting V=350 ml, and t=0deg.C to be coupled;
② Preparation of coupling liquid: 200ml of water is added into a 2L beaker, 13.4g of 30% caustic soda liquid, 15.6g of o-methyl diethyl ether are added, stirred and dissolved, 8.0g of acetic acid is added for acid precipitation, pH=5.6-6.0 after 15 minutes of acid precipitation is completed, and 0.52g of water solution of a dispersing agent B is added at 15 ℃ and stirred for 15 minutes;
③ Coupling and post-treatment: dripping diazonium solution into coupling solution within 80-90 min, and controlling pH=4.5-5.0 with alkali solution while controlling diazonium component not excessive; stirring for 30 minutes after coupling, heating to 80 ℃, adding 0.3g of aluminum sulfate solution, wherein the pH=5.0, continuously heating to 90 ℃, preserving heat for 30 minutes, cooling to below 65 ℃, carrying out suction filtration, and drying at 80 ℃.
Example 7 when dispersant B is the tocopherol block polyether prepared in example 1 and comparative example 2 when dispersant B is peregal OS-15.
Application of tocopherol block polyether obtained in examples 8-10
The tocopherol block polyether or OP-7 obtained in examples 3 to 5 was used for pigment red 57:1, pigment red 57:1, specifically as follows:
Pigment red 57:1 preparation of
① Preparation of diazonium solution: 150ml of water, 2.4g of sodium hydroxide and 11.22g of 4B acid are added into a 500ml beaker, dissolved and clear at room temperature, 4.4g of sodium nitrite is added into the solution, ice is added to cool to 0-3 ℃, 19.4g of hydrochloric acid is rapidly added, T=2deg.C and V=400 ml, and stirring is carried out for 30min for later use;
② Preparation of coupling liquid: 150ml of water, 6.0g of sodium hydroxide and 15.6g of 2,3 acid are added into a 2000ml beaker, the solution is dissolved and clear, a rosin solution (obtained by heating and dissolving 1.0g of rosin, 0.3g of sodium hydroxide and water) which is dissolved and clear is added, and the temperature of T=11 ℃ and the temperature of V=400 ml are adjusted;
③ Coupling: adding diazonium solution into coupling solution within 15min, wherein the reaction temperature is 11-14 ℃, the end point temperature is 13-14 ℃, and the end point pH is 6.5-7.0;
④ Post-treatment: adjusting the pH to 12 with 20% sodium hydroxide solution, t=14 ℃; stirring for 15min, adding 0.8g of dispersant C, pH=11.8 and T=18 ℃; after 30min, 23g of calcium chloride solution was added, the pH was tested=10.2, ph=11.8 was adjusted with 20% sodium hydroxide solution, t=19 ℃; after 15min, heating to 75 ℃, adding 10g of strontium chloride and 2.3g of magnesium chloride, continuously heating to 95 ℃, and preserving heat for half an hour; cooling to 75deg.C, adjusting pH with aluminum sulfate solution to=6.0-6.5, and stirring for 15min; washing with water and suction filtering; and drying at 85 ℃.
Examples 8 to 10 are in turn examples 8 to 10 when dispersant C is the tocopherol block polyether prepared in examples 3 to 5, and comparative example 3 when dispersant C is OP-7.
The pigments prepared in examples 6 to 10 and the pigments prepared in comparative examples 1 to 3 were prepared into aqueous inks to be tested. Composition of aqueous ink: 15 parts of pigment, 8.3 parts of acrylic resin, 1.2 parts of isopropanol, 13.5 parts of water and 60 parts of 2-3mm glass beads. The preparation method comprises the steps of dispersing the mixture for 60min by adopting an oscillation instrument to obtain the water-based printing ink, and then carrying out water-based printing ink: white pont paint = 1:19, and detecting the coloring power of the light color.
The water-based ink is coated on coated paper by a No. 6 silk stick in a scraping way, the diluted color is coated on coated paper by a No. 10 silk stick in a scraping way, after the ink layer is dried, the color and the coloring strength are tested by an X-Rite color meter, and the glossiness is tested by a JFL-BZ60 DEG glossiness meter. The aqueous ink prepared with the pigment of example 6 was normalized to the aqueous ink prepared with the pigment of comparative example 1, the aqueous ink prepared with the pigment of example 7 was normalized to the aqueous ink prepared with the pigment of comparative example 2, and the aqueous inks prepared with the pigments of examples 8-10 were normalized to the aqueous ink prepared with the pigment of comparative example 3. The water-based ink color measurement data are shown in table 1.
Table 1 color, tinctorial strength and gloss of aqueous inks prepared with pigments
As can be seen from the results in Table 1, example 6 was slightly darker than comparative example 1 (ΔL < 0), slightly stronger in red light (Δh < 0), improved in vividness (ΔC > 0), and improved in color power by 5.7%; example 7 was slightly darker than comparative example 2 (Δl < 0), slightly stronger red light (Δh < 0), significantly improved vividness (Δc > 0), and improved color power by 10.7%; examples 8 to 10 were slightly darker than comparative example 3 (Δl < 0), slightly stronger blue light (Δh < 0), improved vividness (Δc > 0), and improved color power by 6.0%, 7.2%, and 7.8%, respectively; the aqueous ink prepared by using the tocopherol block polyether as the dispersing agent has higher glossiness compared with the existing dispersing agent.
The viscosity of the aqueous ink was measured with a BrookFiedDV-III type viscometer (25 ℃), then sealed, placed in a 55 ℃ oven for 7 days, taken out, cooled to 25 ℃, and measured with a BrookFied DV-II type viscometer. The test results are shown in Table 2.
TABLE 2 initial viscosity and viscosity number after leaving of aqueous ink
As can be seen from the results of Table 2, the aqueous ink prepared by using the tocopherol block polyether as the dispersant modified pigment of the present invention can significantly reduce the viscosity of the aqueous ink compared with the existing dispersant, and has lower viscosity and better storage stability when applied to the aqueous ink after being placed.
The pigment dry powder particle sizes and wetting angles obtained in examples 6 to 10 were tested, wherein the pigment dry powder particle sizes were measured as follows: adding 0.1g of the obtained pigment into 1ml (concentration is 30%) of surfactant AEO-6 solution for full wetting, adding water to 25-30ml for ultrasonic dispersion for 5min, adding 800ml of water for ultrasonic dispersion for 2min, and analyzing and detecting by a Markov laser particle size analyzer to obtain a particle size distribution curve. The pigment dry powder wetting angle detection process is as follows: 0.5g of the powdery pigment was weighed, placed in a tabletting mold, and after tabletting for 30 seconds, it was placed in a EasyDrop type contact angle measuring apparatus manufactured by KRUSS, germany, and measured. The contact angle of the samples was tested at room temperature using water as the medium. The test results are shown in Table 3.
TABLE 3 contact angle and particle size of pigments
As can be seen from the results of Table 3, compared with the pigment prepared by the existing dispersing agent, the modified pigment prepared by using the tocopherol block polyether as the dispersing agent has the advantages of obviously reduced particle size, more concentrated particle size distribution, reduced pigment contact angle, improved hydrophilicity of the pigment and more excellent dispersion performance of the pigment in an aqueous medium.
Claims (8)
1. A tocopherol block polyether, characterized in that: the structural formula is shown as formula I:
。
2. A process for the preparation of a tocopherol block polyether according to claim 1, characterised in that: the method comprises the following steps:
Adding tocopherol and a first catalyst into a reaction kettle, heating to 80-85 ℃, carrying out negative pressure dehydration, heating to 100-105 ℃, carrying out nitrogen substitution for three times, starting to add propylene oxide, controlling the temperature to 130-145 ℃ and the pressure to be not more than 0.3MPa, and continuing to react for 50-70 minutes after the propylene oxide is fed;
Cooling to 100-110 ℃, vacuum dehydrating for 30-40 minutes, cooling to 80 ℃, adding a second catalyst, heating to 110-115 ℃, dehydrating for 30-40 minutes under negative pressure, replacing nitrogen for three times, starting to add ethylene oxide, controlling the temperature to be 110-125 ℃, continuing to react for 30-40 minutes after the ethylene oxide is fed, cooling to 90-100 ℃, vacuum treating for 30-40 minutes, cooling to below 80 ℃, adding glacial acetic acid to adjust the pH to 6-8, stirring for half an hour, cooling to 20-30 ℃, and obtaining the tocopherol block polyether;
the first catalyst and the second catalyst are inorganic strong base;
the mass ratio of the tocopherol to the first catalyst to the epoxypropane to the second catalyst to the epoxyethane is 100: 1.5-3: 260-410: 1.5-3: 610-820.
3. The process for preparing a tocopherol block polyether according to claim 2, characterized in that: the first catalyst and the second catalyst are sodium hydroxide or potassium hydroxide.
4. The process for preparing a tocopherol block polyether according to claim 2, characterized in that: the mass ratio of the tocopherol to the first catalyst to the epoxypropane to the second catalyst to the epoxyethane is 100: 2-2.5: 300-350: 2-3: 650-700 parts.
5. The process for preparing a tocopherol block polyether according to claim 2, characterized in that: the reaction temperature after adding propylene oxide is 135-140 ℃.
6. The process for preparing a tocopherol block polyether according to claim 2, characterized in that: the reaction temperature after adding ethylene oxide is 115-120 ℃.
7. Use of a tocopherol block polyether according to claim 1, characterised in that: the surface modification method is used for surface modification in the synthesis process of the organic pigment.
8. Use of a tocopherol block polyether according to claim 7, characterised in that: the addition amount of the organic pigment is 2-5% of the mass of the pigment.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7144919B1 (en) * | 2000-08-23 | 2006-12-05 | Youngdae Kim | Polyoxyethylene-polyoxypropylene vitamin E and process for preparation thereof |
| US20130149364A1 (en) * | 2010-07-28 | 2013-06-13 | Schwan-Stabilo Cosmetics Gmbh & Co. Kg | Water-based pigmented preparation |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7144919B1 (en) * | 2000-08-23 | 2006-12-05 | Youngdae Kim | Polyoxyethylene-polyoxypropylene vitamin E and process for preparation thereof |
| US20130149364A1 (en) * | 2010-07-28 | 2013-06-13 | Schwan-Stabilo Cosmetics Gmbh & Co. Kg | Water-based pigmented preparation |
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