CN117866158A - Hyper-dispersant, and preparation method and application thereof - Google Patents
Hyper-dispersant, and preparation method and application thereof Download PDFInfo
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- CN117866158A CN117866158A CN202410037085.4A CN202410037085A CN117866158A CN 117866158 A CN117866158 A CN 117866158A CN 202410037085 A CN202410037085 A CN 202410037085A CN 117866158 A CN117866158 A CN 117866158A
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- 239000002270 dispersing agent Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- -1 acrylic ester Chemical class 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000003999 initiator Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 5
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 5
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical group OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 5
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000002981 blocking agent Substances 0.000 claims description 3
- VPASWAQPISSKJP-UHFFFAOYSA-N ethyl prop-2-enoate;isocyanic acid Chemical group N=C=O.CCOC(=O)C=C VPASWAQPISSKJP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- WELLGRANCAVMDP-UHFFFAOYSA-N isocyanatoethane;prop-2-enoic acid Chemical compound CCN=C=O.OC(=O)C=C WELLGRANCAVMDP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 239000000986 disperse dye Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004873 anchoring Methods 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 3
- 238000005189 flocculation Methods 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000016615 flocculation Effects 0.000 abstract description 2
- 229920001002 functional polymer Polymers 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000000049 pigment Substances 0.000 abstract 2
- 239000002994 raw material Substances 0.000 abstract 1
- 238000004062 sedimentation Methods 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 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 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229940093499 ethyl acetate Drugs 0.000 description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the technical field of functional polymer material preparation, and particularly relates to a novel hyper-dispersant, a preparation method and application thereof. According to the invention, acrylic monomers are used as raw materials, and a hyperdispersant with long and complex branched chains is finally obtained through two polymerization reactions, and the branched chains of the dispersant are provided with a plurality of anchoring groups, so that a stronger adsorption effect can be generated on particles with low surface polarity. Meanwhile, the structure of the complex branched chain can generate stronger steric hindrance, so that agglomeration among particles can be effectively prevented. The acrylic ester comb dispersing agent provided by the invention can enable pigment to be stably dispersed in water, and pigment color paste prepared by using the acrylic ester comb dispersing agent has the advantages of strong stability, low viscosity and difficult generation of sedimentation and flocculation.
Description
Technical Field
The invention belongs to the technical field of functional polymer material preparation, and particularly relates to a hyper-dispersant, a preparation method and application thereof.
Background
The dispersing agent is widely applied to industries such as printing and dyeing, textile, papermaking and the like in industrial production, and the acrylic dispersing agent is used as a representative of the anionic dispersing agent, so that the environment-friendly property of the dispersing agent enables the dispersing agent to be widely applied to various fields. Since the hydrophilic groups of conventional dispersants are generally designed only for a certain affinity with water, the aim in many applications is to meet the requirements for capsule formation together with lipophilic groups, which are often placed in secondary positions for their adsorption fastness on the particle surface, hydrophilic groups are easily desorbed from the molecular structure, resulting in re-flocculation of the particles. The lipophilic group of the traditional dispersing agent is generally in a hydrocarbon chain structure, mainly comprises alkane chains, has better compatibility with nonpolar and low-grade organic solvents, can be fully stretched, but has very limited thickness because the chain length is too short, and cannot generate enough space to resist repulsive force so as to uniformly disperse particles.
Compared with the common dispersing agent which structurally consists of hydrophilic groups and lipophilic groups, the hyperdispersing agent is divided into anchoring groups and solvated chains in the molecular structure. Common anchoring groups are-OH, -NR 3 + 、-COOH、-COO - 、-SO 3 H、-PO4 2- And the functional groups anchor the dispersing agent on the surface of the particles through the actions of hydrogen bonds, covalent bonds, ionic bonds or Van der Waals force and the like, so that the dispersing performance of the dispersing agent is improved; common solvated chains are polyolefin, polyester, polyacrylate, polyether, and can be classified into three classes according to polarity size: (1) a lower polyolefin chain; (2) a moderately polar polyester or polyacrylate chain; (3) polyether chains of strong polarity. In the polarity-matched dispersion medium, the solvated chain has good compatibility with the dispersion medium, so that a relatively extended conformation is adopted in the dispersion medium, a protective layer with enough thickness is formed on the surface of the particles, the steric hindrance among the particles is increased, the particle agglomeration is effectively prevented, the steric stabilization effect is achieved, and the particles can be stably dispersed. In the hyperdispersant, the proportion of the groups is controlled to ensure the dispersing performance, and generally, the proportion of the anchoring groups is very small (5% -10%), and the solvated chain accounts for the main part (90% -95%). Meanwhile, the chain length of the hyperdispersant molecules is controlled, and if the chain length is too long, the chains are easy to fold.
For example, the Chinese patent application No. CN202010000394.6 discloses an aqueous dispersing agent, and the synthesized dispersing agent has good dispersibility and high stability. However, for particles with weak surface polarity, the number of anchor groups in the molecular structure of the hyperdispersant needs to be increased to ensure the adsorption capacity, but correspondingly, the number of solvated chains is reduced, so that the steric hindrance between particles is reduced, and flocculation occurs.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a hyperdispersant with complex branched chains and a preparation method thereof, wherein the hyperdispersant has large steric hindrance, so that particles can be effectively dispersed.
In order to achieve the above object, the present invention provides the following technical solutions:
a hyperdispersant, characterized by having a structure represented by the following formula:
the hyper-dispersant comprises a main chain and a branched chain structure, wherein the main chain structure comprises a structural unit 1, a structural unit 2 and a structural unit 3, and the branched chain structure comprises a structural unit 4;
wherein R is 1 Each independently represents H or methyl; r is R 2 、R 3 Each independently represents a H, C C10 aliphatic hydrocarbon group or a C6C 10 aromatic hydrocarbon group, and the structural unit 1 is different from the structural unit 2.
The ratio of o, m, n, p is 100 (100-350): 5-20): 50-100.
In the above structural formula, structural unit 1 refers to a repeating segment with subscript o; building block 2 refers to a repeat segment with subscript m; building block 3 refers to a repeat segment with subscript n; building block 4 refers to a repeat segment with subscript p; wherein the structure of the structural unit 3 comprises a structural unit 4.
Preferably, the relative molecular mass of the hyperdispersant is 8000-50000.
Preferably, R 2 Is one or more of a cyclic aliphatic hydrocarbon group and an aromatic hydrocarbon group. Preferably, R 2 Is cyclohexyl, phenyl, tolyl, phenyl,One or more of ethylphenyl groups.
Preferably, R 2 Is cyclohexyl or phenyl, and the ratio of the number of the repeating units of two groups is 1 (0.5-2); preferably, R 2 Is cyclohexyl or phenyl, and the ratio of the number of the repeating units of two groups is 1 (1-2).
Preferably, R 3 One or more aliphatic hydrocarbon groups of H, C1 to C10. Preferably, R 3 Is one or more of H, methyl, ethyl, butyl and isobornyl.
Preferably, R 3 The ratio of the number of the repeating units H to p is (0.4-0.8): 1; preferably, R 3 The ratio of the number of repeating units of H to p is (0.5-0.7): 1.
The invention also provides a preparation method of the hyper-dispersant, which comprises the following steps:
(1) Mixing a compound of the formula I-4 with a part of solvent to obtain a premix A; mixing an initiator, a chain terminator and a part of solvent to obtain a premix B; introducing nitrogen to empty air, heating, simultaneously dropwise adding the premix liquid A and the premix liquid B into the residual solvent for 3-6 hours, and preserving heat for 1-3 hours after the dropwise adding is finished. Finally adding a catalyst and a blocking agent, and reacting for 1-3 hours to obtain a compound shown in a formula I-3 after the reaction is finished;
(2) Mixing a compound of a formula I-1, a compound of a formula I-2 and a compound of a formula I-3 with a part of solvent to obtain a premix C; mixing an initiator with a part of solvent to obtain a premix D; introducing nitrogen to empty air, heating, simultaneously dropwise adding the premix C and the premix D into the residual solvent for 3-6 hours, and preserving heat for 1-3 hours after the dropwise adding is finished to obtain the hyper-dispersant.
Preferably, the chain terminator is one or more of mercaptoethanol, isopropanol, sodium bisulfite and sodium methallyl sulfonate. Preferably, the chain terminator is mercaptoethanol.
Preferably, the end-capping agent is one or more of hexamethylene diisocyanate, tert-butyl peroxy (2-ethylacetate), methyl ethyl ketone oxime and isocyanate ethyl acrylate. Preferably, the blocking agent is isocyanate ethyl acrylate.
Preferably, the initiator is one or more of persulfate initiator, azo initiator and peroxide initiator. Preferably, the initiator is azo initiator. Further preferred, the initiator is one or more of azobisisobutyronitrile, azodiisoheptonitrile, azobisisobutyronitrile, azobisisovaleronitrile, azobicyclohexylformamide, azobisisobutyronic acid methyl ester, azobicyanopentanoic acid, or azoiso Ding Qingji formamide.
Preferably, the solvent does not contain hydroxyl or amino groups. Preferably, the solvent is one or more of ethyl acetate, isopropyl acetate, propylene glycol methyl ether acetate, dichloroethane, toluene, xylene, tetrahydrofuran or cyclohexanone. Further preferably, the solvent is one or more of ethyl acetate and propylene glycol methyl ether acetate.
Preferably, the catalyst is dibutyl tin dilaurate.
Preferably, the reaction temperature is 50-80 ℃. More preferably, the reaction temperature is 60-70 degrees celsius.
Preferably, in the step (1), the weight ratio of the compound of the formula I-4, the solvent, the initiator, the catalyst, the chain transfer agent and the end capping agent is 100 (300-400): 0.5-3): 0.05-0.2): 0.25-1.5): 0.15-1.
Preferably, in the step (2), the weight ratio of the total weight of the compound of the formula I-1 to the compound of the formula I-2 to the compound of the formula I-3, the solvent and the initiator is 100 (300-400): 0.5-3.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, acrylic monomers are used as copolymers, and under the action of an initiator, the hyperdispersant with complex long-chain branches is synthesized through two polymerization reactions, compared with the common hyperdispersant, the anchoring groups on the branches increase adsorption sites, so that the adsorption capacity for particles is improved, and meanwhile, the complex space structure can generate larger steric hindrance, so that the particles can be effectively dispersed, aggregation is not easy to occur, and a stable dispersion state is maintained.
Detailed Description
The invention will be described below in connection with specific embodiments. The following examples are illustrative of the present invention and are not intended to limit the present invention. Other combinations and various modifications within the spirit of the invention may be made without departing from the spirit or scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
Example 1
(1) 30g of acrylic acid, 30g of ethyl acrylate and 40g of isobornyl acrylate are put into 200g of ethyl acetate and stirred uniformly to obtain a premix A. 0.5g of azobisisobutyronitrile and 0.25g of mercaptoethanol were added to 50g of ethyl acetate to obtain premix B. 100g of ethyl acetate was added to the reaction flask, nitrogen was introduced to empty the air, the temperature was raised to 60℃and simultaneously dropwise addition of premix A and premix B was started for 3 hours. After the completion of the dropwise addition, the temperature was kept for 2 hours. And finally adding 0.05g of dibutyltin dilaurate and 0.15g of ethyl isocyanate acrylate, reacting for two hours, and purifying after the reaction is finished to obtain the compound of the formula I-3.
(2) 30g of the compound of formula I-3, 30g of phenyl acrylate, 30g of cyclohexyl acrylate and 10g of isobornyl methacrylate are put into 200g of ethyl acetate and stirred uniformly to obtain a premix C. 0.5g of azobisisobutyronitrile was added to 50g of ethyl acetate to form titrant D. 100g of ethyl acetate was added to the reaction flask, nitrogen was introduced to empty the air, the temperature was raised to 60℃and simultaneously dropwise addition of premix C and premix D was started for 3 hours. After the dripping is finished, preserving heat for two hours, and purifying to obtain the hyper-dispersant 1.
Examples 2-23 and comparative examples 1-5 were prepared as described above, and the ingredients are shown below, in grams of data, with the total weight of initiator and solvent required for the overall reaction, and the amounts required to be added in each step were as per the ratio of example 1:
performance testing
Dispersion performance test: 1.0g of nano calcium carbonate was precisely weighed by an electronic balance and 0.05g of dispersant was added at 25 ℃. After stirring with an electromagnetic stirrer for 20 minutes, the mixture was left for 30 minutes. 12.5ml of the solution was placed in a 250ml volumetric flask, diluted to scale with distilled water, and the absorbance of the solution was measured at 550nm with a spectrophotometer. The greater the absorption rate, the more turbid the solution, the more powder suspended in the solution, and the better the dispersion.
The spectrophotometer used was model 721G manufactured by Shanghai electric analysis instruments, inc.
Viscosity performance test: adding 6g of nano calcium carbonate powder into 10g of water, uniformly stirring to obtain calcium carbonate powder slurry with the mass fraction of 60%, adding 0.2g of dispersing agent, stirring for 20 minutes by using an electromagnetic stirrer, standing for 30 minutes, and measuring the viscosity of each group and blank slurry. The lower the viscosity, the better the dispersing effect.
The viscosity of the obtained product is NDJ-79 manufactured by Shanghai Changji geological instruments Co.
The test results are shown in the following table:
| absorption at 550nm | Viscosity (Pa.S) | |
| Example 1 | 1.118 | 0.134 |
| Example 2 | 1.092 | 0.136 |
| Example 3 | 0.996 | 0.186 |
| Example 4 | 0.975 | 0.189 |
| Example 5 | 0.971 | 0.191 |
| Example 6 | 1.085 | 0.141 |
| Example 7 | 1.09 | 0.137 |
| Example 8 | 0.983 | 0.188 |
| Example 9 | 0.95 | 0.192 |
| Example 10 | 1.002 | 0.178 |
| Example 11 | 1.061 | 0.161 |
| Example 12 | 1.088 | 0.139 |
| Example 13 | 1.072 | 0.147 |
| Example 14 | 1.162 | 0.124 |
| Example 15 | 1.174 | 0.109 |
| Example 16 | 1.041 | 0.164 |
| Example 17 | 1.054 | 0.163 |
| Example 18 | 1.018 | 0.171 |
| Example 19 | 1.065 | 0.158 |
| Example 20 | 0.994 | 0.187 |
| Example 21 | 1.14 | 0.133 |
| Example 22 | 1.155 | 0.128 |
| Example 23 | 1.187 | 0.108 |
| Comparative example 1 | 0.624 | 0.434 |
| Comparative example 2 | 0.685 | 0.399 |
| Comparative example 3 | 0.732 | 0.315 |
| Comparative example 4 | 0.698 | 0.359 |
| Comparative example 5 | 0.583 | 0.495 |
| Blank examples | 0.073 | 1.588 |
As is clear from comparison of examples 1-23 and comparative example 5, the present invention uses acrylic monomers as copolymers, and synthesizes hyperdispersants with complex and long-chain branches through two polymerization reactions under the action of an initiator, so that a stable dispersion state can be maintained. As is clear from the comparison of examples 10 to 13, the control of the ratio of the number of cyclohexyl groups to the number of phenyl groups in the main chain within 1 (0.5 to 2) gives a better dispersion effect.
In addition, as can be seen from comparison of comparative examples 1 to 4 with example 1, the isobornyl groups in the structure of the present application have an important influence on the dispersing effect, and when isobornyl groups are replaced with other groups in the same mole, the dispersing effect is remarkably deteriorated; as is clear from the comparison of examples 1 and 14 to 15, the increase in the number of isobornyl groups on the main chain can also enhance the dispersing effect.
Furthermore, as can be seen from a comparison of examples 16-20, the control of R in the dispersant structure 3 When the ratio of the number of repeating units to p is (0.4-0.8): 1, the composition is excellent in both absorptivity and viscosity test data and good in dispersibility.
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement it, but not limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (10)
1. A hyperdispersant, characterized by having a structure represented by the following formula:
the hyper-dispersant comprises a main chain and a branched chain structure, wherein the main chain structure comprises a structural unit 1, a structural unit 2 and a structural unit 3, and the branched chain structure comprises a structural unit 4;
wherein R is 1 Each independently represents H or methyl; r is R 2 、R 3 Each independently represents a H, C-C10 aliphatic hydrocarbon group or a C6-C10 aromatic hydrocarbon group; the structural unit 1 is different from the structural unit 2;
the ratio of o, m, n, p is 100 (100-350): 5-20): 50-100.
2. A hyperdispersant according to claim 1, wherein the hyperdispersant has a relative molecular mass of 8000-50000.
3. A hyperdispersant as claimed in claim 1 or claim 2 wherein R 2 Is one or more of a cyclic aliphatic hydrocarbon group and an aromatic hydrocarbon group.
4. A hyperdispersant as claimed in claim 3 wherein R 2 Is cyclohexylOne or more of a group, phenyl, tolyl, and ethylphenyl group.
5. A hyperdispersant as claimed in claim 4 wherein R 2 Is cyclohexyl or phenyl, and the ratio of the number of the repeating units of the two groups is 1 (0.5-2).
6. A hyperdispersant as claimed in claim 1 or claim 2 wherein R 3 One or more aliphatic hydrocarbon groups of H, C to C10; preferably, R 3 Is one or more of H, methyl, ethyl, butyl and isobornyl.
7. The hyperdispersant of claim 6, wherein R 3 The ratio of the number of repeating units of H to p is (0.4-0.8): 1.
8. The method for preparing a hyperdispersant according to any one of claims 1 to 7, comprising the steps of:
(1) Mixing the compound of the formula I-4 with an initiator, a chain terminator and a solvent, reacting, adding a catalyst and a capping reagent, and obtaining the compound of the formula I-3 after the reaction is finished;
(2) Mixing a compound of a formula I-1, a compound of a formula I-2, a compound of a formula I-3, an initiator and a solvent, and reacting to prepare a hyperdispersant;
the chain terminator is mercaptoethanol, and the blocking agent is isocyanate ethyl acrylate.
9. The process for preparing hyperdispersant as claimed in claim 8, wherein in step (1), mercaptoethanol is used in an amount of 0.25 to 1.5% by weight and ethyl isocyanate acrylate is used in an amount of 0.15 to 1% by weight, based on the total weight of the compound of formula I-4 reacted.
10. Use of a hyperdispersant according to any one of claims 1 to 7 or obtainable by a process according to any one of claims 8 to 9 in the preparation of a liquid disperse dye.
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