CN102746501A - Manufacturing method of dispersant and dispersant - Google Patents
Manufacturing method of dispersant and dispersant Download PDFInfo
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- CN102746501A CN102746501A CN2012102082454A CN201210208245A CN102746501A CN 102746501 A CN102746501 A CN 102746501A CN 2012102082454 A CN2012102082454 A CN 2012102082454A CN 201210208245 A CN201210208245 A CN 201210208245A CN 102746501 A CN102746501 A CN 102746501A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 title abstract description 12
- 239000004642 Polyimide Substances 0.000 claims abstract description 63
- 229920001721 polyimide Polymers 0.000 claims abstract description 63
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 4
- 239000006185 dispersion Substances 0.000 claims description 72
- 239000003795 chemical substances by application Substances 0.000 claims description 70
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 239000002904 solvent Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 32
- 239000000126 substance Substances 0.000 claims description 31
- -1 SULPHOSUCCINIC ACID ESTER Chemical class 0.000 claims description 24
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 22
- 150000008065 acid anhydrides Chemical class 0.000 claims description 19
- 238000004873 anchoring Methods 0.000 claims description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 12
- 239000005639 Lauric acid Substances 0.000 claims description 11
- KEJQTHYHDVZLMT-UHFFFAOYSA-N bis(2-methylpropyl)tin Chemical compound CC(C)C[Sn]CC(C)C KEJQTHYHDVZLMT-UHFFFAOYSA-N 0.000 claims description 11
- 150000002596 lactones Chemical class 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 8
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 8
- SXNBVULTHKFMNO-UHFFFAOYSA-N 2,2-dihydroxyoctadecanoic acid Chemical class CCCCCCCCCCCCCCCCC(O)(O)C(O)=O SXNBVULTHKFMNO-UHFFFAOYSA-N 0.000 claims description 5
- 241001101993 Tepa Species 0.000 claims description 5
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical class CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 4
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 7
- 229910019142 PO4 Inorganic materials 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 2
- 239000010452 phosphate Substances 0.000 abstract description 2
- 229920000578 graft copolymer Polymers 0.000 abstract 1
- 239000000049 pigment Substances 0.000 description 19
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 18
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 12
- 239000002002 slurry Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000000605 extraction Methods 0.000 description 7
- 239000005711 Benzoic acid Substances 0.000 description 6
- 235000010233 benzoic acid Nutrition 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000010534 mechanism of action Effects 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- MJJJJEUEZVGFLW-UHFFFAOYSA-N 2-dodecyl-2-sulfobutanedioic acid Chemical class CCCCCCCCCCCCC(S(O)(=O)=O)(C(O)=O)CC(O)=O MJJJJEUEZVGFLW-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Chemical group 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229920000570 polyether Chemical group 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- WBHHMMIMDMUBKC-QJWNTBNXSA-N ricinoleic acid Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(O)=O WBHHMMIMDMUBKC-QJWNTBNXSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
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- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention discloses a manufacturing method of a dispersant and a dispersant; the manufacturing method of the dispersant comprises the following steps: mixing hydroxycarboxylic acid and polyvinylamine, reacting to obtain polyimide with a hydroxyl, wherein the polyimide is used as a skeleton of the dispersant to be manufactured; performing solvatable chain grafting of the obtained polyimide; mixing and reacting the grafted polymer with phosphate or anhydride to obtain the finished product of the dispersant. With the above mode, the dispersant of the invention is suitable for different solution systems, and the wetability and adsorptivity of the dispersant are improved.
Description
Technical field
The present invention relates to the dispersion agent field, particularly relate to a kind of method of manufacture and dispersion agent of dispersion agent.
Background technology
Dispersion agent is a kind of interfacial agent that has oleophilicity and two kinds of opposite nature of wetting ability simultaneously at intramolecularly, but homogeneous disperses to be insoluble in the solid particulate of inorganic, the pigment dyestuff of liquid, prevents the sedimentation and the cohesion of solid particulate simultaneously.Present dispersion agent has: polyester chain phosphate dispersant and polyimide dispersion agent (polyester chain carboxylic acid and vinyl-amine reaction are synthetic) etc.
In the prior art, the method for manufacture of dispersion agent is varied, as: by polyester chain, polycaprolactone or hydroxycarboxylic acid and polyvinylamine reaction synthetic dispersing agent; With urethane is that stone grafting polyester, polyacrylic ester and polyether chain are solvent chain, are the polyurethanes dispersion agent of anchoring group reaction generation with a resistance amine.
Utilize above-mentioned dispersion agent all can form good dispersion-s, but also have defective simultaneously, as: the polyester chain SULPHOSUCCINIC ACID ESTER only is suitable for disperseing mineral-type pigment (white titanium pigment or lime carbonate etc.), when running into nonpolar pigment dyestuff, just can't disperse.The polyimide of polycaprolactone class chain is separated out at low temperatures easily, and because consistency is wide inadequately, causes applicable system to be restricted.The polyurethanes dispersion agent; Because residual chemical ion (as: NH or the NHCONH etc.) amino (as: acid catalyst in the baking vanish) easy and the acid catalysis class in reaction back reacts; Perhaps with two component polyurethane in solidifying agent reflection generate carbonic acid gas and water; Thereby dispersion effect reduces greatly, and this dispersion agent anchoring group comparatively small amt, and absorption property is lower.
Summary of the invention
The technical problem that the present invention mainly solves provides a kind of method of manufacture and dispersion agent of dispersion agent, can make dispersion agent be suitable for different solution systems, improves the wettability and the adsorptivity of dispersion agent simultaneously.
For solving the problems of the technologies described above, the invention provides a kind of method of manufacture of dispersion agent, comprising: hydroxycarboxylic acid is mixed with polyvinylamine, obtain the polyimide that has hydroxyl after the reaction, wherein, polyimide is as the skeleton of desire system dispersion agent; The polyimide that obtains is carried out the grafting of solvent chain; With the polymkeric substance after the grafting and SULPHOSUCCINIC ACID ESTER or acid anhydrides hybrid reaction, to process the finished product dispersion agent.
Wherein, hydroxycarboxylic acid is mixed with polyvinylamine, the step of obtaining the polyimide that has hydroxyl after the reaction comprises: 536～656 gram ricinolic acids, 130～160 gram triethylene tetramines and 18～22 gram Dibutyltin oxides are mixed, and the reaction back obtains polyimide; Or with 540～660 grams, ten dihydroxystearic acids, 170～206 gram TEPAs and 18～22 gram Mono-n-butyltins mixing, the reaction back obtains polyimide.
Wherein, solvent chain is solvent chain, caprolactone or the oxyethane with carboxyl.
Wherein, The step of the polyimide that obtains being carried out the grafting of solvent chain comprises: 126～154 gram polyimide, 270～330 are restrained oneself, and lactone, 270～330 restrains the hard ester acid of ten dihydroxyl and 18～22 grams, two LAURIC ACID 99 MIN diisobutyl tin mix, the polyimide that obtains is carried out the grafting of solvent chain; Or, add 270～330 restrain oneself lactone and 18～22 grams, two LAURIC ACID 99 MIN diisobutyl tin again, the polyimide that obtains is carried out the grafting of solvent chain earlier with 126～154 gram polyimide, 450～550 gram end carboxyl polymethylmethacrylate hybrid reactions.
Wherein, polyimide has two symmetric hydroxyls, and wherein, hydroxyl combines with the solvent chain with carboxyl, caprolactone or oxyethane.
Wherein, with the polymkeric substance after the grafting and SULPHOSUCCINIC ACID ESTER or acid anhydrides hybrid reaction, comprise with the step of processing dispersion agent: the hydroxylic moiety of polymkeric substance or secondary amine combine to generate dispersion agent with SULPHOSUCCINIC ACID ESTER or acid anhydrides.
Wherein, dispersion agent has end carboxyl or hydroxy functional group.
For solving the problems of the technologies described above, the present invention also provides a kind of dispersion agent, and dispersion agent comprises: polyimide, solvent chain and anchoring group, wherein, after anchoring group is polyimide grafting solvent chain, again with SULPHOSUCCINIC ACID ESTER or anhydride reaction and form.
Wherein, the solvent chain in the dispersion agent comprises one or more.
Wherein, the anchoring group in the dispersion agent comprises one or more.
The invention has the beneficial effects as follows: a kind of dispersion agent provided by the invention comprises polyimide, solvent chain and anchoring group.Its method of manufacture does; At first hydroxycarboxylic acid is mixed with polyvinylamine, obtain the polyimide that has hydroxyl after the reaction, then polyimide is carried out the grafting of solvent chain as the skeleton of desire system dispersion agent; With the polymkeric substance after the grafting and SULPHOSUCCINIC ACID ESTER or acid anhydrides hybrid reaction, process dispersion agent at last.Wherein, polymkeric substance after the grafting and SULPHOSUCCINIC ACID ESTER or acid anhydrides hybrid reaction are to generate anchoring group.By the way, the present invention can make dispersion agent be suitable for different solution systems, improves the wettability and the adsorptivity of dispersion agent simultaneously.
Description of drawings
Fig. 1 is the schematic flow sheet of method of manufacture one embodiment of dispersion agent of the present invention;
Fig. 2 is a dispersion agent mechanism of action synoptic diagram of the present invention.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is elaborated.
As shown in Figure 1, Fig. 1 is the schematic flow sheet of method of manufacture one embodiment of dispersion agent of the present invention, may further comprise the steps:
Step 101 is mixed hydroxycarboxylic acid with polyvinylamine, obtain the polyimide that has hydroxyl after the reaction, and wherein, polyimide is as the skeleton of desire system dispersion agent;
Polyimide is as the basic framework of dispersion agent, and its compound method is divided into following two kinds according to the raw material difference:
A., water trap is installed in the four-hole boiling flask; And feeding nitrogen; Add raw material 536～656 gram ricinolic acids, 130～160 gram triethylene tetramines and 18～22 gram Dibutyltin oxides according to ratio then; 162～198 ℃ were mixed after 7～9 hours, vacuumized 0.5～1.5 hour, can obtain polyimide a.
The present invention through the concrete operations that aforesaid method obtains polyimide a does; Water trap is installed in the four-hole boiling flask; And feeding nitrogen, add raw material 596 gram ricinolic acids, 145 gram triethylene tetramines and 20 gram Dibutyltin oxides according to ratio then, 180 ℃ were mixed after 8 hours; Vacuumized 1 hour, and can obtain polyimide a.
In other embodiments, the quality of ricinolic acid can be 536 grams or 656 grams; The quality of triethylene tetramine can be 130 grams or 160 grams; The quality of Dibutyltin oxide can be 18 grams or 22 grams; Mixing temperature also can be 162 ℃ or 198 ℃; Mixing time can be 7 or 9 hours; Pumpdown time can be 0.5 or 1.5 hour.In force, above-mentioned parameter can arbitrary combination.
B., water trap is installed in the four-hole boiling flask; And feeding nitrogen; Add raw material 540～660 grams ten dihydroxystearic acids, 170～206 gram TEPAs and 18～22 gram Mono-n-butyltins according to ratio then; 162～198 ℃ were mixed after 7～9 hours, vacuumized 0.5～1.5 hour, can obtain polyimide b.
The present invention through the concrete operations that aforesaid method obtains polyimide b does; Water trap is installed in the four-hole boiling flask; And feeding nitrogen, add raw material 600 grams ten dihydroxystearic acids, 188 gram TEPAs and 20 gram Mono-n-butyltins according to ratio then, 180 ℃ were mixed after 8 hours; Vacuumized 1 hour, and can obtain polyimide b.
In other embodiments, the quality of ten dihydroxystearic acids can be 540 grams or 660 grams; The quality of TEPA can be 170 grams or 206 grams; The quality of Mono-n-butyltin can be 18 grams or 22 grams; Mixing temperature also can be 162 ℃ or 198 ℃; Mixing time can be 7 or 9 hours; Pumpdown time can be 0.5 or 1.5 hour.In force, above-mentioned parameter can arbitrary combination.
Wherein, the polyimide of acquisition has two symmetric hydroxyls.
Step 102 is carried out the grafting of solvent chain to the polyimide that obtains;
Through the solvent chain different to the polyimide grafting, can make it adapt to different systems, as: the liquid for low polarity, Semi-polarity or water-based all has good compatibility.
Wherein, but the solvent chain of grafting comprise: solvent chain, caprolactone and oxyethane etc. with carboxyl.In the grafting process, two symmetrical hydroxyls of polyimide combine with the solvent chain with carboxyl, caprolactone or oxyethane respectively.
Be example with the caprolactone below, its grafting process be described:
A.126～154 gram polyimide a, 270～330 restrains oneself, and lactone, 270～330 restrains the hard ester acid of ten dihydroxyl and 18～22 grams, two LAURIC ACID 99 MIN diisobutyl tin mix; Preserved 5～7 hours for 90～110 ℃; Vacuum hydro-extraction is 1～3 hour then, i.e. grafting success, the polymkeric substance a1 after the acquisition grafting.
In the present embodiment, its concrete operations are that 140 gram polyimide a, 300 are restrained oneself, and lactone, 300 restrains the hard ester acid of ten dihydroxyl and 20 grams, two LAURIC ACID 99 MIN diisobutyl tin mix; Preserved 6 hours for 100 ℃; Vacuum hydro-extraction is 2 hours then, i.e. grafting success, the polymkeric substance a1 after the acquisition grafting.
In other embodiments, the quality of polyimide a can be 126 or 154 grams; The quality of caprolactone can be 270 or 330 grams; The quality of the hard ester acid of ten dihydroxyl can be 270 or 330 grams; The quality of two LAURIC ACID 99 MIN diisobutyl tin can be 18 or 22 grams; Storage temperature can be 90 or 110 ℃; Shelf time can be 5 or 7 hours; The vacuum hydro-extraction time is 1 or 3 hours.In concrete operations, above-mentioned parameter can arbitrary combination.
B.126～154 gram polyimide b, 270～330 restrains oneself, and lactone, 270～330 restrains the hard ester acid of ten dihydroxyl and 18～22 grams, two LAURIC ACID 99 MIN diisobutyl tin mix; Preserved 5～7 hours for 90～110 ℃; Vacuum hydro-extraction is 1～3 hour then, i.e. grafting success, the polymkeric substance b1 after the acquisition grafting.
In the present embodiment, its concrete operations are that 140 gram polyimide b, 300 are restrained oneself, and lactone, 300 restrains the hard ester acid of ten dihydroxyl and 20 grams, two LAURIC ACID 99 MIN diisobutyl tin mix; Preserved 6 hours for 100 ℃; Vacuum hydro-extraction is 2 hours then, i.e. grafting success, the polymkeric substance b1 after the acquisition grafting.
C. earlier 126～154 gram polyimide b, 450～550 gram end carboxyl polymethylmethacrylates are mixed, 90～110 ℃ were stirred vacuum hydro-extraction 1～3 hour 0.5～1.5 hour.And then add 270～330 restrain oneself lactone and 18～22 grams, two LAURIC ACID 99 MIN diisobutyl tin, and to preserve 7～9 hours for 180～200 ℃, i.e. grafting success obtains the polymkeric substance b2 after the grafting.
In the present embodiment, preferred 140 gram polyimide b, 500 gram end carboxyl polymethylmethacrylates mix, and 100 ℃ were stirred vacuum hydro-extraction 2 hours 1 hour.And then add 300 restrain oneself lactone and 20 grams, two LAURIC ACID 99 MIN diisobutyl tin, preserved 8 hours, and carried out grafting for 190 ℃.
Wherein, hold the acquisition mode of carboxyl polymethylmethacrylate to do, with Thiovanic acid and TEB 3K, 90 ℃ of reaction acquisitions in Diisopropyl azodicarboxylate (AIBN), its acid number is 18mgKOH/g.
Step 103 is with the polymkeric substance after the grafting and SULPHOSUCCINIC ACID ESTER or acid anhydrides hybrid reaction, to process the finished product dispersion agent.
With the concrete mode of the polymkeric substance after the grafting and SULPHOSUCCINIC ACID ESTER or acid anhydrides hybrid reaction do, the hydroxylic moiety or the secondary amine of polymkeric substance combined with SULPHOSUCCINIC ACID ESTER or acid anhydrides, to generate dispersion agent.Wherein, the dispersion agent of generation has end carboxyl or hydroxy functional group.
Can produce one or more anchoring group through above-mentioned reaction, reach stronger anchoring effect, make dispersion-s more stable.
Wherein, to hold carboxyl or hydroxyl and resistance position amine compound dispersion agent to have higher wetting and stable dispersiveness.
Its reactive mode has number of ways according to the difference of reactant, as follows:
A.45～55 gram tripropylene glycol monomethyl ether SULPHOSUCCINIC ACID ESTER and 360～440 restrains polymkeric substance a1, and 70～90 ℃ were reacted 1～3 hour, opened the solution of rare one-tenth 50% then with N-BUTYL ACETATE, and promptly product 1.
In the present embodiment specific operation process, preferred 50 gram tripropylene glycol monomethyl ether SULPHOSUCCINIC ACID ESTERs and 400 gram polymkeric substance a1,80 ℃ were reacted 2 hours, opened the solution of rare one-tenth 50% then with N-BUTYL ACETATE, and promptly product 1.
In other embodiments, the quality of tripropylene glycol monomethyl ether SULPHOSUCCINIC ACID ESTER can be 45 or 55 grams, and the quality of polymkeric substance a1 can be 360 or 440 grams, and temperature of reaction can be 70 or 90 ℃, and the reaction times can be 1 or 3 hour.As required can arbitrary combination to above-mentioned parameter.
B.315～385 inclined to one side benzoic acid three acid anhydrides of gram and 360～440 restrain polymkeric substance b1, and 70～90 ℃ were reacted 1～3 hour, opened the solution of rare one-tenth 50% then with N-BUTYL ACETATE, and promptly product 2.
In the present embodiment specific operation process, preferred 350 inclined to one side benzoic acid three acid anhydrides of gram and 400 gram polymkeric substance b1,80 ℃ were reacted 2 hours, opened the solution of rare one-tenth 50% then with N-BUTYL ACETATE, and promptly product 2.
In other embodiments, the quality of benzoic acid three acid anhydrides can be 315 or 385 grams partially, and the quality of polymkeric substance b1 can be 360 or 440 grams, and temperature of reaction can be 70 or 90 ℃, and the reaction times can be 1 or 3 hour.As required can arbitrary combination to above-mentioned parameter.
C.90～110 gram dodecyl SULPHOSUCCINIC ACID ESTER and 270～330 restrains polymkeric substance b2, and 70～90 ℃ were reacted 1～3 hour, opened the solution of rare one-tenth 50% then with N-BUTYL ACETATE, and promptly product 3.
In the present embodiment specific operation process, preferred 100 gram dodecyl SULPHOSUCCINIC ACID ESTERs and 300 gram polymkeric substance b2,80 ℃ were reacted 2 hours, opened the solution of rare one-tenth 50% then with N-BUTYL ACETATE, and promptly product 3.
In other embodiments, the quality of dodecyl SULPHOSUCCINIC ACID ESTER can be 90 or 110 grams, and the quality of polymkeric substance b2 can be 270 or 330 grams, and temperature of reaction can be 70 or 90 ℃, and the reaction times can be 1 or 3 hour.As required can arbitrary combination to above-mentioned parameter.
D.158～192 inclined to one side benzoic acid three acid anhydrides of gram and 270～330 restrain polymkeric substance b2, and 70～90 ℃ were reacted 1～3 hour, opened the solution of rare one-tenth 50% then with N-BUTYL ACETATE, and promptly product 4.
In the present embodiment specific operation process, preferred 175 inclined to one side benzoic acid three acid anhydrides of gram and 300 gram polymkeric substance b2,80 ℃ were reacted 2 hours, opened the solution of rare one-tenth 50% then with N-BUTYL ACETATE, and promptly product 4.
In other embodiments, the quality of benzoic acid three acid anhydrides can be 158 or 192 grams partially, and the quality of polymkeric substance b2 can be 270 or 330 grams, and temperature of reaction can be 70 or 90 ℃, and the reaction times can be 1 or 3 hour.As required can arbitrary combination to above-mentioned parameter.
For synthetic dispersion agent product of the present invention 1, product 2, product 3 and product 4, through with existing dispersion agent its meliority relatively is described, concrete contrast as follows:
At first utilize corresponding product on products obtained therefrom of the present invention and the market (50% contains polyurethanes property admittedly) preparation pigment slurry.For each part pigment slurry; The quality of product is 20 grams, also comprises the hydroxyl acrylic or the vibrin of 500 milliliters of Scattered Kettles, 100 gram grinding bead, 20 gram carbon black FW100 (DEGUSSA), 80 gram mixed solvents (YLENE/N-BUTYL ACETATE/1-Methoxy-2-propyl acetate (PMA)=1: 1: 1) and 80 grams.Table one is seen in concrete reaction.
Table one
Prepare coating according to pigment slurry then, the preparation process is seen table two.
Table two
The pigment slurry that above-mentioned each product and each product are corresponding and the performance comparison of coating are as shown in the table:
| Performance comparison | Pigment slurry 1 | Pigment slurry 2 | Pigment slurry 3 | Pigment slurry 4 | Pigment slurry 5 | Pigment slurry 6 |
| Mobile | 1 | 1 | 4 | 5 | 4 | 3 |
Table three
Annotate: 1～5 in order to explain mobile quality, and 5 is best, and 1 for the poorest.
| Performance comparison | Coating 1 | Coating 2 | Coating 3 | Coating 4 | Coating 5 | Coating 6 |
| Fineness (um) | 5 | 7.5 | 5 | 5 | 5 | 5 |
Table four
Table five
Annotate: 1～5 quality in order to explanation transparency, blackness, levelling, 5 is best, 1 for the poorest.
Table six
Through above-mentioned each property comparison, can find out that the dispersion agent of present embodiment compares with popular like product on the market, have impayable wettability and the effect that reduces viscosity.In depositing process, as: deposited one month for 60 ℃, in various degree anti-thick can appear in the like product on the market; Deposited one month for-5 ℃, the like product on the market is much all separated out phenomenon and is taken place, and dispersion agent of the present invention performance is slight.
Dispersion agent of the present invention is a symmetry polyimide skeleton, contains the high molecular weight dispersant of multiple anchoring group, and its application belongs to mixed type, i.e. nonionic and negatively charged ion or positively charged ion mating type.Cation constituent makes its pigment that is suitable for anionic surface, particularly carbon black and surface treated pigment; Anionic component is fit to the dispersing of pigments of cationic surface.Because special polyimide structures makes it be difficult for crystallization and separates out, the scope of application is wider in addition.Because dispersion agent of the present invention has many anchoring groups, making it not only have fabulous wettability has extraordinary adsorptivity again, reaches the effect of high speed dispersion and viscosity reduction, the very stable desorption that is difficult for of dispersion system simultaneously, and that has avoided that high temperature storage causes is slightly anti-.
Dispersion agent of the present invention is for the dispersion of high-carbon black pigment, and viscosity reduction is obvious in multiple system, and mill efficiency is high.Low-viscosity can be that the pigment of system reaches higher pigment ratio, grinding effect efficiently can be energy-conservation with enhance productivity.
Anti-thick phenomenon all can not appear in dispersion agent storage-stable of the present invention in cold and hot area, thereby guarantees the quality of product.
Fig. 2 is a dispersion agent mechanism of action synoptic diagram of the present invention, and as shown in the figure, dispersion agent comprises: polyimide (figure does not show), solvent chain 21 and anchoring group 22.
Wherein, after anchoring group 22 is polyimide grafting solvent chain 21, again with SULPHOSUCCINIC ACID ESTER or anhydride reaction and form.
In dispersion agent, solvent chain 21 comprises one or more.Anchoring group 22 also comprises one or more.
Be different from the situation of prior art, the present invention provides a kind of dispersion agent, comprises polyimide, solvent chain and anchoring group.Its method of manufacture does; At first hydroxycarboxylic acid is mixed with polyvinylamine, obtain the polyimide that has hydroxyl after the reaction, then polyimide is carried out the grafting of solvent chain as the skeleton of desire system dispersion agent; With the polymkeric substance after the grafting and SULPHOSUCCINIC ACID ESTER or acid anhydrides hybrid reaction, process dispersion agent at last.Wherein, polymkeric substance after the grafting and SULPHOSUCCINIC ACID ESTER or acid anhydrides hybrid reaction are to generate anchoring group.By the way, the present invention can make dispersion agent be suitable for different solution systems, improves the wettability and the adsorptivity of dispersion agent simultaneously.
The above is merely embodiments of the invention; Be not so limit claim of the present invention; Every equivalent structure or equivalent flow process conversion that utilizes specification sheets of the present invention and accompanying drawing content to be done; Or directly or indirectly be used in other relevant technical fields, all in like manner be included in the scope of patent protection of the present invention.
Claims (10)
1. the method for manufacture of a dispersion agent is characterized in that: comprising:
Hydroxycarboxylic acid is mixed with polyvinylamine, obtain the polyimide that has hydroxyl after the reaction, wherein, said polyimide is as the skeleton of desire system dispersion agent;
The said polyimide that obtains is carried out the grafting of solvent chain;
With the said polymkeric substance after the grafting and SULPHOSUCCINIC ACID ESTER or acid anhydrides hybrid reaction, to process the finished product dispersion agent.
2. method according to claim 1 is characterized in that:
Above-mentioned hydroxycarboxylic acid is mixed with polyvinylamine, the step of obtaining the polyimide that has hydroxyl after the reaction comprises:
536～656 gram ricinolic acids, 130～160 gram triethylene tetramines and 18～22 gram Dibutyltin oxides are mixed, and the reaction back obtains polyimide; Or
540～660 grams, ten dihydroxystearic acids, 170～206 gram TEPAs and 18～22 gram Mono-n-butyltins are mixed, and the reaction back obtains polyimide.
3. method according to claim 2 is characterized in that:
Said solvent chain is solvent chain, caprolactone or the oxyethane with carboxyl.
4. method according to claim 3 is characterized in that:
The above-mentioned step that the polyimide that obtains is carried out the grafting of solvent chain comprises:
Restrain oneself lactone, the hard ester acid of 270～330 gram ten dihydroxyl and 18～22 grams, two LAURIC ACID 99 MIN diisobutyl tin of 126～154 gram polyimide, 270～330 are mixed, the polyimide that obtains is carried out the grafting of solvent chain; Or
Earlier with 126～154 gram polyimide, 450～550 gram end carboxyl polymethylmethacrylate hybrid reactions, add 270～330 restrain oneself lactone and 18～22 grams, two LAURIC ACID 99 MIN diisobutyl tin again, the polyimide that obtains is carried out the grafting of solvent chain.
5. method according to claim 1 is characterized in that:
Said polyimide has two symmetric hydroxyls, and wherein, said hydroxyl combines with the solvent chain with carboxyl, caprolactone or oxyethane.
6. method according to claim 1 is characterized in that:
Above-mentioned with the polymkeric substance after the said grafting and SULPHOSUCCINIC ACID ESTER or acid anhydrides hybrid reaction, comprise with the step of processing the finished product dispersion agent: the hydroxylic moiety of said polymkeric substance or secondary amine combine to generate dispersion agent with SULPHOSUCCINIC ACID ESTER or acid anhydrides.
7. method according to claim 6 is characterized in that:
Said dispersion agent has end carboxyl or hydroxy functional group.
8. dispersion agent is characterized in that: comprising:
Polyimide, solvent chain and anchoring group, wherein, after said anchoring group is polyimide grafting solvent chain, again with SULPHOSUCCINIC ACID ESTER or anhydride reaction and form.
9. dispersion agent according to claim 8 is characterized in that:
Solvent chain in the said dispersion agent comprises one or more.
10. dispersion agent according to claim 8 is characterized in that:
Anchoring group in the said dispersion agent comprises one or more.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105001417A (en) * | 2015-07-15 | 2015-10-28 | 上海核心新材料科技有限公司 | Modified polyamide structural rheological agent as well as preparation method and application thereof |
| WO2018010615A1 (en) * | 2016-07-15 | 2018-01-18 | Deuchem (Shanghai) Chemical Co., Ltd. | Novel non-ionic polyamide rheology modifier for aqueous coating |
| CN108165993A (en) * | 2018-03-01 | 2018-06-15 | 合肥康之恒机械科技有限公司 | It is a kind of for metal polish of mining machinery and preparation method thereof |
| CN109628073A (en) * | 2018-12-06 | 2019-04-16 | 南京军盾化工科技有限公司 | Clay dispersion agent and preparation method thereof |
| CN111690134A (en) * | 2020-07-03 | 2020-09-22 | 江苏道赢科技有限公司 | Dispersing agent for improving flexibility of cathode sheet |
| CN113416511A (en) * | 2021-06-09 | 2021-09-21 | 广东工程职业技术学院 | Novel MS sealant for fabricated concrete and preparation method thereof |
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| CN1146371A (en) * | 1996-05-27 | 1997-04-02 | 华东理工大学 | Polyester type ultra-dispersant agent and preparation method thereof |
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| CN1146371A (en) * | 1996-05-27 | 1997-04-02 | 华东理工大学 | Polyester type ultra-dispersant agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105001417A (en) * | 2015-07-15 | 2015-10-28 | 上海核心新材料科技有限公司 | Modified polyamide structural rheological agent as well as preparation method and application thereof |
| CN105001417B (en) * | 2015-07-15 | 2017-09-29 | 上海核心新材料科技有限公司 | A kind of modified polyamide structure rheological agent and its preparation method and application |
| WO2018010615A1 (en) * | 2016-07-15 | 2018-01-18 | Deuchem (Shanghai) Chemical Co., Ltd. | Novel non-ionic polyamide rheology modifier for aqueous coating |
| CN108165993A (en) * | 2018-03-01 | 2018-06-15 | 合肥康之恒机械科技有限公司 | It is a kind of for metal polish of mining machinery and preparation method thereof |
| CN109628073A (en) * | 2018-12-06 | 2019-04-16 | 南京军盾化工科技有限公司 | Clay dispersion agent and preparation method thereof |
| CN111690134A (en) * | 2020-07-03 | 2020-09-22 | 江苏道赢科技有限公司 | Dispersing agent for improving flexibility of cathode sheet |
| CN113416511A (en) * | 2021-06-09 | 2021-09-21 | 广东工程职业技术学院 | Novel MS sealant for fabricated concrete and preparation method thereof |
| CN113416511B (en) * | 2021-06-09 | 2023-09-26 | 广东工程职业技术学院 | MS sealant for assembled concrete and preparation method thereof |
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