CN105001417B - A kind of modified polyamide structure rheological agent and its preparation method and application - Google Patents
A kind of modified polyamide structure rheological agent and its preparation method and application Download PDFInfo
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- CN105001417B CN105001417B CN201510412952.9A CN201510412952A CN105001417B CN 105001417 B CN105001417 B CN 105001417B CN 201510412952 A CN201510412952 A CN 201510412952A CN 105001417 B CN105001417 B CN 105001417B
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- 229920002647 polyamide Polymers 0.000 title claims abstract description 59
- 239000004952 Polyamide Substances 0.000 title claims abstract description 56
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- -1 alkyl carboxylic acid Chemical class 0.000 claims abstract description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 3
- 239000006185 dispersion Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 239000012046 mixed solvent Substances 0.000 claims description 16
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 150000002118 epoxides Chemical group 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 9
- SXNBVULTHKFMNO-UHFFFAOYSA-N 2,2-dihydroxyoctadecanoic acid Chemical class CCCCCCCCCCCCCCCCC(O)(O)C(O)=O SXNBVULTHKFMNO-UHFFFAOYSA-N 0.000 claims description 7
- 239000013530 defoamer Substances 0.000 claims description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229920000178 Acrylic resin Polymers 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 claims description 4
- 229940070765 laurate Drugs 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- 125000000118 dimethyl group Polymers [H]C([H])([H])* 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 125000002950 monocyclic group Chemical group 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 3
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000013638 trimer Substances 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 125000003700 epoxy group Chemical group 0.000 abstract 2
- 230000004913 activation Effects 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000013008 thixotropic agent Substances 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 210000004508 polar body Anatomy 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004432 silane-modified polyurethane Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to rheological agent technical field, more particularly to a kind of modified polyamide structure rheological agent and its preparation method and application.Its specific preparation method is：Step (α)：Carboxylic component A, the component B containing amino and catalyst are mixed so that generate polyamide after carboxyl and amino reaction；Wherein, component A is the mixture of hydroxycarboxylic acid or hydroxycarboxylic acid and alkyl carboxylic acid, and component B structural formula is：H‑(NH‑CH2‑CH2)n‑NH2, n=1 5；Step (β)：By the polyamide obtained by step (α) and the mixed with polymers with epoxide group or isocyanate groups, the active hydrogen on polyamide is reacted with epoxide group or isocyanate groups, be prepared into modified polyamide structure rheological agent.The modified polyamide structure rheological agent prepared using this preparation method, it is applied widely, applied to the thixotroping having had in coating, anti-settling and anti-sag effect.
Description
Technical field
The present invention relates to rheological agent technical field, more particularly to a kind of modified polyamide structure rheological agent and preparation method thereof
And application.
Background technology
Conventional rheological agent has aerosil, bentonite, polyamide, ethylene oxide and urea modified polyurethane etc.,
But there is certain defect, aerosil and bentonite are thickened partially as, viscosity is too high under same anti-sag effect,
Anti-settling effect difference and the easily hard sedimentation of formation；Ethylene oxide class is suitable only for solvent-based system, is not suitable for water-based system；It is existing
Some polyamide rheological agent technologies can typically form good thixotroping system, but it is only used for middle polar system, and
Have to activate by strict technique and use, can not such as activate completely or activation excessively can all cause anti-thick problem,
And then make coating surface hydraulic performance decline, moreover, activation is required for very high temperature to cause the volatilization and production of solvent
The extension of time；Urea modified polyurethane need not activation, but be easy to particle issues occur to the polarity of system is very sensitive.
Because polyamide can form good thixotroping system, therefore there are many research, such as United States Patent (USP) in this field
No.761870 and United States Patent (USP) No.5723653 have studied polyamide-based situation about being mixed with ethylene oxide；Japan Patent
JP2002146336 have studied polyamide-based activation in a solvent；European patent No.06292039.2 have studied polyamide-based
Activation problem in PPG and DIUP；DE10039837.5 have studied the synthesis that urea is modified urethane class thixotropic agent；
A kind of method that DE102005049301.7 describes use sulfuric ester or phosphate modified acid amides, but it can not be all obtained each
There is the polyamide rheological agent of good compatibility in system such as low polarity, middle polarity and highly polar system.
CN102746501 patent of invention discloses a kind of dispersant and preparation method thereof, and its preparation method is included hydroxyl
Yl carboxylic acid is mixed with polyvinylamine, and the polyimides with hydroxyl is obtained after reaction, and solvation is carried out to the polyimides of acquisition
The grafting of chain, finally prepares dispersant with phosphate or acid anhydrides hybrid reaction again.But polyamide and epoxide group or isocyanide
Acid esters radical reaction, and be also rarely reported as the situation of rheological agent.
The content of the invention
In order to solve the above technical problems, first purpose of the present invention is to provide a kind of activation easily and with fabulous simultaneous
Modified polyamide structure rheological agent of capacitive and preparation method thereof, second object of the present invention is to provide this modified polyamide knot
Application process of the structure rheological agent in coating.
In order to realize first purpose, the technical solution adopted by the present invention is：
A kind of preparation method of modified polyamide structure rheological agent, including：
Step (α)：Carboxylic component A, the component B containing amino and catalyst are mixed so that carboxyl and amino reaction
After generate polyamide；Wherein, component A is the mixture of hydroxycarboxylic acid or hydroxycarboxylic acid and alkyl carboxylic acid, component B structural formula
For：H-(NH-CH2-CH2)n-NH2, n=1-5；
Step (β)：Polyamide obtained by step (α) is mixed with the polymer with epoxide group or isocyanate groups
Close, the active hydrogen in polyamide on secondary amine is reacted with epoxide group or isocyanate groups, be prepared into modified polyamide knot
Structure rheological agent, the active hydrogen is the hydrogen on nitrogen-atoms in polyamide molecule.
Wherein, the reaction temperature of reaction is 150-230 DEG C in the step (α), and the reaction time is 4-10 hours, after reaction
Also vacuumized at 180-230 DEG C 1 hour.
Wherein, the mol ratio of the component A and component B are 2：1；Catalyst accounts for component A and component B in the step (α)
The 1.4-1.7% of quality.
Wherein, the hydroxycarboxylic acid is castor oil acid or ten dihydroxystearic acids, and the alkyl carboxylic acid is laurate, institute
Structural formula is stated for H- (NH-CH2-CH2)n-NH2Material be diethylenetriamine, the catalyst be Dibutyltin oxide or list
Butyl tin oxide；
Wherein, the mixture of the hydroxycarboxylic acid and alkyl carboxylic acid is the mixing that ten dihydroxystearic acids are constituted with laurate
The ratio between amount of ten dihydroxystearic acids and bay acid substance is 1 in thing, the mixture：1.
Wherein, the ratio between amount of material of polymer is (0.8-2.5) in the component B and step (β)：1；The step
Reaction temperature in (β) is：80-85 DEG C, the reaction time is：2-4 hours.
Wherein, the polymer with epoxide group is the polyethyleneglycol diglycidylether that mean molecule quantity is 500
Or the monocyclic oxygen END CAPPED GROUP butyl polyacrylate in end that mean molecule quantity is 1000；The polymer with isocyanate groups
For：3- isocyanates methylenes -3,5,5- trimethylcyclohexylisocyanates.
Modified polyamide structure rheological agent prepared by a kind of preparation method by described modified polyamide structure rheological agent.
In order to realize second purpose, the modified polyamide rheological agent of preparation is applied in coating, specifically adopted by the present invention
Application technology scheme has 2 kinds, is respectively：
1st, application of a kind of modified polyamide structure rheological agent in coating, its concrete application method is：
(11) it is 1 according to mass ratio by dimethylbenzene, butyl acetate and propylene glycol methyl ether acetate (PMA):1:1 mixing is equal
It is even, mixed solvent a is made1；According to mass ratio it is 1 by butyl acetate and PMA:1 is well mixed, and obtains mixed solvent a2；
(12) by talcum powder, epoxide number is 0.48-0.52 equivalents/100g bisphenol A type epoxy resin, mixed solvent a1Press
It is 1.88 according to mass ratio:1.25:1 dispersion mixing is uniform, obtains mixture a；The epoxide number is 0.48-0.52 equivalents/100g
Bisphenol A type epoxy resin can be 128 resins.
(13) it is 30 according to mass ratio by mixture a and modified polyamide structure rheological agent：1 dispersion mixing is uniform, obtains
Dispersant a；
(14) by dispersant a, polyamide curing agent, mixed solvent a2, polyether-modified dimethyl silicone polymer levelling agent, fluorine
Modified organic silicon defoamer is 100 according to mass ratio：15：9：1：0.05 dispersion mixing is uniform.Wherein, described polyamide
Curing agent preferably domestic polyamide curing agent 115, the polyether-modified preferred core chemistry Lev of dimethyl silicone polymer levelling agent
F70, the preferred core chemistry FS of fluorine richness organic silicon defoamer.
2nd, application of another modified polyamide structure rheological agent in coating, its concrete application method is：
(21) it is 1 according to mass ratio by dimethylbenzene and butyl ester:1 dispersion mixing is uniform, and mixed solvent b is made1；By trimethylbenzene
(150#), dimethylbenzene and nylon acid dimethyl ester (DBE) are according to mass ratio 1:1:1 dispersion mixing is uniform, and mixed solvent b is made2；
(22) by titanium dioxide, barium sulfate, Hydroxylated acrylic resin, mixed solvent b1It is 1.43 according to mass ratio：1.43：
3.21：1 dispersion mixing is uniform, obtains mixture b；The preferred Hydroxylated acrylic resin 1184 (Nuplex) of acrylic resin；
(23) mixture b is 30 according to mass ratio with modified polyamide structure rheological agent：1 dispersion mixing is uniform, is divided
Powder b；
(24) by dispersant b, hexamethylene diisocyanate trimer curing agent, mixed solvent b2, polyether-modified poly- two
Methylsiloxane levelling agent, fluorine richness organic silicon defoamer are 100 according to mass ratio：5：19：1：0.05 dispersion mixing is uniformly
Can.Wherein, the preferred BAYER 3390 of the hexamethylene diisocyanate trimer curing agent, polyether-modified polydimethylsiloxanes
The preferred core chemistry Lev F70 of alkane levelling agent, the preferred core chemistry FS of fluorine richness organic silicon defoamer.
After technical scheme, relative to prior art, with advantages below：
(1) applicable system is broader.The present invention is linked by the segment of opposed polarity with polyamide, makes modified rheology
Agent has longer dissolving segment so that modified polyamide rheological agent is in for example low polarity of each system, middle polarity and highly polar body
In system, there is good compatibility.In low polar system such as SPUR glue, the UPR systems by solvent of styrene, PPG systems
It can be good at activation in water-repellent paint；In solvent-free system, the compatibility just having had without strict activating process, solution
Determined in solvent-free system, it is too thick using thixotropic agent, be not added with but can not be anti-settling the problem of；In senior property system, can directly it add
Enter modified polyamide rheological agent, simple scattered, the problem of solving easily anti-thick.
(2) present invention is based on the polyamide of special synthesis, by the reactive hydrogen and the solvent of opposed polarity on secondary amine
Change the epoxy on chain or NCO reactions obtain modified polyamide rheological agent, due to increasing on modified polyamide rheological agent strand
Nitrogen or oxygen in OH or ammonia ester bond, strand and the hydrogen formation spatial networks knot in itself or other hydrocarbons are added
The hydrogen bond of structure, improves the speed and quantity that hydrogen bond is formed in system, when the hydrogen bond of space net structure is destroyed by shearing force,
Viscosity reduction provides good application property, and hydrogen bond is re-formed after shearing force is removed, so that with good thixotroping, anti-settling and anti-
Sagging effect.Therefore the present invention relative to prior art products on the premise of same addition, with more preferable rheological characteristic.Together
When, also reduce requirement of some systems to activation temperature.
(3) because modified polyamide structure rheological agent can apply to solvent-free system, it is not necessary to add solvent, therefore this hair
Bright modified polyamide structure rheological agent is constant relative to prior art performance under conditions of system viscosity ensure that construction, more
It is economic and environment-friendly.
(4) product of the present invention is due to that can evade the problem of must activating, it will be apparent that improve production efficiency.
(5) product of the present invention has the stability under good storage stability, particularly high/low temperature so that hot and cold
Cold area is applicable.
Specific embodiment
Embodiment 1：
Step (α)：The synthesis of basic framework
Water knockout drum is installed in four-hole boiling flask, and is passed through nitrogen, 596 grams of castor oil acids are added, 105 grams of diethylenetriamines,
10 grams of Dibutyltin oxides, stirring after 180 DEG C are reacted 8 hours, is obtained in 670 grams after being vacuumized 1 hour at 180-230 DEG C
Mesosome M.
Step (β)：The grafting of solvent chain
By 330 grams of intermediate M, 100 grams of mean molecule quantities add four-hole boiling flask for 500 polyethyleneglycol diglycidylether
In, stirring is reacted 4 hours at 80 DEG C, obtains polymer 1.
Embodiment 2：
Step (α)：The synthesis of basic framework
Water knockout drum is installed in four-hole boiling flask, and is passed through nitrogen, 300 gram of ten dihydroxystearic acid, 200 grams of bays is added
Acid, 105 grams of diethylenetriamines, 10 grams of Mono-n-butyltins, stirring after 180 DEG C are reacted 8 hours, is vacuumized at 180-230 DEG C
575 grams of intermediate N are obtained after 1 hour.
Step (β)：The grafting of solvent chain
By 230 grams of intermediate N, 55 grams of 3- isocyanates methylenes -3,5,5- trimethylcyclohexylisocyanates
(IPDI) add in four-hole boiling flask, stirring, 80 DEG C of insulation reactions 2 hours obtain polymer 2.
Embodiment 3：
By 230 grams of intermediate N, it is the 1000 monocyclic oxygen end-blocking based polyacrylic acid fourth in end first to add 500 grams of mean molecule quantities
Ester (with mercaptoethanol and butyl acrylate, 90 DEG C of initiation reactions in the presence of azodiisobutyronitrile (AIBN), then epoxy seal
End), stirring, 80 DEG C of reactions obtain polymer 3 in 2 hours.
Preferred embodiment is these are only, is H- (NH-CH for structural formula2-CH2)n-NH2Component B, n take 1-5；
Reaction temperature is 150-230 DEG C in step (α), and the reaction time is 4-10 hours；Reaction temperature in step (β) is in 80-85
DEG C, the modified polyamide structure rheological agent of the present invention can be prepared.
Polymer 1-3 is prepared into coating, and its performance is detected.
1st, the preparation of dispersion
Formula one：By 450 grams of talcum powder, 128 300 grams of resins, mixed solvent (dimethylbenzene/butyl acetate/PMA mass ratioes
For 1:1:1) 240 grams are positioned in Scattered Kettle, 3000 revs/min, and sample jar is put in after disperseing 30 minutes.
Formula two：By 200 grams of titanium dioxide, 200 grams of barium sulfate, 450 grams of Hydroxylated acrylic resin 1184 (Nuplex), solvent
(dimethylbenzene/butyl ester mass ratio is 1:1) 140 grams, 3000 revs/min, sample jar is put in after disperseing 30 minutes.
Will 2 300 grams of one 300 grams of formula or formula and polymer 1 or 2 or 3 or the product of in the market (contrast product 1 and right
Than product 2) 10 grams of mixing are added in Scattered Kettle, 2000 revs/min, after disperseing 10 minutes, are put in sample jar, after standing 24 hours
To dispersion 1-8, specific formula and technique are：
The preparation formula and technique of the dispersion of table 1
2nd, the preparation of coating
Dispersion 1-8 is mixed with curing agent, solvent, levelling agent and defoamer respectively, coating 1-8 is prepared.It is specific to prepare
Formula and technique are shown in Table 2.
The preparation formula and technique of the coating of table 2
3rd, the measure of performance
The performance such as coating 1-8 gloss, levelability, fineness, viscosity, thixotroping, anti-settling is contrasted respectively, be the results are shown in Table
3-6。
Results of property after the paint spraying of table 3
The dope viscosity of table 4, thixotroping comparing result
The anti-settling comparing result of the coating of table 5
The coating sag resistance comparing result of table 6
| Sag resistance is contrasted | Coating 1 | Coating 2 | Coating 3 | Coating 4 | Coating 5 | Coating 6 | Coating 7 | Coating 8 |
| 500um/250um | 350 | 375 | 400 | 350+ | 100 | 125 | 125+ | 100 |
Note：Quality of the 1-5 to illustrate levelability：5 be best, and 1 is worst.
From table 3- tables 6 as can be seen that with the coating of polymer 1-3 preparations, in levelability, thixotropic index, anti-settling and anti-current
Performance in terms of extension effect is all better than the contrast product of in the market, illustrates that product prepared by the present invention has a wide range of applications field
With wide market prospects.Rational selection can be made according to actual needs when in use.
Only as described above, only the preferred embodiments of the invention, when the model of implementation of the invention can not be limited with this
Enclose, i.e., generally according to simple equivalent changes and modifications made by the content described in the claims in the present invention and description of the invention,
All it is still covered by the claims of the invention.Searched in addition, summary part and title are intended merely to auxiliary patent document
Seek and being used, not for limiting the interest field of the present invention.
Claims (6)
1. a kind of preparation method of modified polyamide structure rheological agent, it is characterised in that including：
Step (α)：Carboxylic component A, the component B containing amino and catalyst are mixed so that raw after carboxyl and amino reaction
Into polyamide；Wherein, component A is the mixture of hydroxycarboxylic acid or hydroxycarboxylic acid and alkyl carboxylic acid, and component B structural formula is：
H-(NH-CH2-CH2)n-NH2, n=1-5；
Step (β)：By the polyamide obtained by step (α) and the mixed with polymers with epoxide group or isocyanate groups,
The active hydrogen on polyamide is reacted with epoxide group or isocyanate groups, be prepared into modified polyamide structure rheological agent；
The reaction temperature of reaction is 150-230 DEG C in the step (α), and the reaction time is 4-10 hours；The component A and component
B mol ratio is 2：1；Catalyst accounts for the 1.4-1.7% of component A and component B mass in the step (α)；The hydroxycarboxylic acid
For castor oil acid or ten dihydroxystearic acids, the alkyl carboxylic acid is laurate, the catalyst be Dibutyltin oxide or
Person's Mono-n-butyltin；The mixture of the hydroxycarboxylic acid and alkyl carboxylic acid is ten dihydroxystearic acids and mixing that laurate is constituted
The ratio between amount of ten dihydroxystearic acids and bay acid substance is 1 in compound, the mixture：1；In the component B and step (β)
The ratio between amount of material of polymer is (0.8-2.5)：1；Reaction temperature in the step (β) is：80-85 DEG C, reaction time
For：2-4 hours；The polymer with epoxide group be the polyethyleneglycol diglycidylether that mean molecule quantity is 500 or
Person's mean molecule quantity is the 1000 monocyclic oxygen END CAPPED GROUP butyl polyacrylate in end；The polymer with isocyanate groups
For：3- isocyanates methylenes -3,5,5- trimethylcyclohexylisocyanates.
2. the preparation method of modified polyamide structure rheological agent as claimed in claim 1, it is characterised in that the step (α)
Also vacuumized after middle reaction at 180-230 DEG C 1 hour.
3. the preparation method of modified polyamide structure rheological agent as claimed in claim 1, it is characterised in that the active hydrogen is
The upper hydrogen of secondary amine in polyamide.
4. modification prepared by a kind of preparation method of modified polyamide structure rheological agent as described in any one of claims 1 to 3
Polyamide structure rheological agent.
5. application of the modified polyamide structure rheological agent as claimed in claim 4 in coating, it is characterised in that it specifically should
It is with method：
(11) it is 1 according to mass ratio by dimethylbenzene, butyl acetate and propylene glycol methyl ether acetate:1:1 is well mixed, and is made mixed
Bonding solvent a1；According to mass ratio it is 1 by butyl acetate and propylene glycol methyl ether acetate:1 is well mixed, and obtains mixed solvent a2；
(12) by talcum powder, epoxide number is 0.48-0.52 equivalents/100g bisphenol A type epoxy resin, mixed solvent a1According to matter
Amount is than being 1.88:1.25:1 dispersion mixing is uniform, obtains mixture a；
(13) it is 30 according to mass ratio by the modified polyamide structure rheological agent described in mixture a and claim 4：1 is scattered mixed
Close uniform, obtain dispersant a；
(14) by dispersant a, polyamide curing agent, mixed solvent a2, polyether-modified dimethyl silicone polymer levelling agent, fluorine richness
Organic silicon defoamer is 100 according to mass ratio：15：9：1：0.05 dispersion mixing is uniform.
6. application of the modified polyamide structure rheological agent as claimed in claim 4 in coating, it is characterised in that it specifically should
It is with method：
(21) it is 1 according to mass ratio by dimethylbenzene and butyl ester:1 dispersion mixing is uniform, and mixed solvent b is made1；By trimethylbenzene, diformazan
Benzene and nylon acid dimethyl ester are according to mass ratio 1:1:1 dispersion mixing is uniform, and mixed solvent b is made2；
(22) by titanium dioxide, barium sulfate, Hydroxylated acrylic resin, mixed solvent b1It is 1.43 according to mass ratio：1.43：3.21：1
Dispersion mixing is uniform, obtains mixture b；
(23) it is 30 according to mass ratio by the modified polyamide structure rheological agent described in mixture b and claim 4：1 is scattered mixed
Close uniform, obtain dispersant b；
(24) by dispersant b, hexamethylene diisocyanate trimer curing agent, mixed solvent b2, polyether-modified poly dimethyl silicon
Oxygen alkane levelling agent, fluorine richness organic silicon defoamer are 100 according to mass ratio：5：19：1：0.05 dispersion mixing is uniform.
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| CN107629538B (en) * | 2016-07-15 | 2022-01-14 | 德谦（上海）化学有限公司 | Novel nonionic polyamide rheology modifiers for aqueous coatings |
| EP3919546A4 (en) * | 2019-01-31 | 2022-10-12 | Kusumoto Chemicals, Ltd. | Viscosity regulator and curable composition |
| US10947473B2 (en) * | 2019-05-17 | 2021-03-16 | Vanderbilt Chemicals, Llc | Less corrosive organic compounds as lubricant additives |
| CN113248704B (en) * | 2021-05-14 | 2022-04-01 | 济宁南天农科化工有限公司 | Epoxy modified polyamide polyamine cylinder sticking agent 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 |
| CN115181416B (en) * | 2022-07-15 | 2023-12-22 | 华润化学材料科技股份有限公司 | Polyamide engineering plastic and preparation method and application thereof |
| CN117304732A (en) * | 2023-09-27 | 2023-12-29 | 江苏富琪森新材料有限公司 | Thixotropic agent and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1162242A1 (en) * | 2000-06-08 | 2001-12-12 | Elementis Specialties, Inc. | Rheological additives and paint and coating compositions containing such additives exhibiting improved intercoat adhesion |
| CN102597036A (en) * | 2009-09-08 | 2012-07-18 | 比克化学股份有限公司 | Polyureas as rheology control agents |
| CN102746501A (en) * | 2012-06-21 | 2012-10-24 | 广州市乾顺化工有限公司 | Manufacturing method of dispersant and dispersant |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1162242A1 (en) * | 2000-06-08 | 2001-12-12 | Elementis Specialties, Inc. | Rheological additives and paint and coating compositions containing such additives exhibiting improved intercoat adhesion |
| CN102597036A (en) * | 2009-09-08 | 2012-07-18 | 比克化学股份有限公司 | Polyureas as rheology control agents |
| CN102746501A (en) * | 2012-06-21 | 2012-10-24 | 广州市乾顺化工有限公司 | Manufacturing method of dispersant and dispersant |
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