CN105001417A - Modified polyamide structural rheological agent as well as preparation method and application thereof - Google Patents
Modified polyamide structural rheological agent as well as preparation method and application thereof Download PDFInfo
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- CN105001417A CN105001417A CN201510412952.9A CN201510412952A CN105001417A CN 105001417 A CN105001417 A CN 105001417A CN 201510412952 A CN201510412952 A CN 201510412952A CN 105001417 A CN105001417 A CN 105001417A
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- modified polyamide
- rheological agent
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 76
- 229920002647 polyamide Polymers 0.000 title claims abstract description 48
- 239000004952 Polyamide Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 19
- -1 alkyl carboxylic acid Chemical class 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 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 4
- 229920000642 polymer Polymers 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- 239000011248 coating agent Substances 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 23
- 239000012046 mixed solvent Substances 0.000 claims description 17
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 16
- 150000001408 amides Chemical class 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 14
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 12
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- SXNBVULTHKFMNO-UHFFFAOYSA-N 2,2-dihydroxyoctadecanoic acid Chemical class CCCCCCCCCCCCCCCCC(O)(O)C(O)=O SXNBVULTHKFMNO-UHFFFAOYSA-N 0.000 claims description 7
- 150000002118 epoxides Chemical group 0.000 claims description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-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
- 239000002518 antifoaming agent Substances 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
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 6
- 229920001296 polysiloxane Polymers 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
- 239000004925 Acrylic resin Substances 0.000 claims description 5
- 229920000178 Acrylic resin Polymers 0.000 claims description 5
- 239000005639 Lauric acid Substances 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
- 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
- 239000002253 acid Substances 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 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical group 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
- 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
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 229920000058 polyacrylate Polymers 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
- 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
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 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
- 229920001778 nylon Polymers 0.000 claims description 2
- WBHHMMIMDMUBKC-QJWNTBNXSA-N ricinoleic acid Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(O)=O WBHHMMIMDMUBKC-QJWNTBNXSA-N 0.000 claims description 2
- 229960003656 ricinoleic acid Drugs 0.000 claims description 2
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 239000003973 paint Substances 0.000 abstract description 3
- 125000003700 epoxy group Chemical group 0.000 abstract 2
- 230000002265 prevention Effects 0.000 abstract 1
- 238000007665 sagging Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000004913 activation Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 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
- 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
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910002012 Aerosil® 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
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 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
- 150000002148 esters Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 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
- 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
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 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
- 125000002887 hydroxy group Chemical group [H]O* 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
- 239000000463 material Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 238000004321 preservation Methods 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
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004432 silane-modified polyurethane Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000008719 thickening Effects 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 invention relates to the technical field of rheological agents, particularly to a modified polyamide structural rheological agent, as well as a preparation method and the application thereof. The preparation method comprises the specific steps of: step (alpha), mixing a component A containing carboxyl, a component B containing amino, and a catalyst so that the carboxyl and the amino are in a reaction to generate polyamide; wherein the component A is hydroxyl carboxylic acid, or a mixture of the hydroxyl carboxylic acid and alkyl carboxylic acid; the structural formula of the component B is H-(NH-CH2-CH2)n-NH2, and n is equal to 1-5; and step (beta), mixing the polyamide obtained in the step (alpha) and a polymer with an epoxy group or an isocyanate group, so that active hydrogen on the polyamide reacts with the epoxy group or the isocyanate group, and the modified polyamide structural rheological agent is prepared. The modified polyamide structural rheological agent prepared by the preparation method is wide in application range, and has good effects of thixotropy, settlement prevention and sagging resistance when being applied to paint.
Description
Technical field
The present invention relates to rheological agent technical field, particularly a kind of modified polyamide structure rheological agent and its preparation method and application.
Background technology
Conventional rheological agent has aerosil, wilkinite, polymeric amide, ethylene oxide and urea modified polyurethane etc., but there is certain defect, as aerosil and the inclined thickening of wilkinite, under same anti-sag effect, viscosity is too high, anti-settling effect difference and easily form hard sedimentation; Ethylene oxide class is suitable only for solvent-based system, is not suitable for water-based system; Existing polymeric amide rheological agent technology generally can form good thixotroping system, but it can only be used for Semi-polarity system, and must could activate use by strict technique, anti-thick problem excessively all can be caused as do not activated completely or activate, and then make coating surface degradation, moreover, activation all needs very high temperature thus causes the volatilization of solvent and the prolongation of production time; Urea modified polyurethane need not activate, but to the polarity of system very responsive being easy to there is particle issues.
Because polymeric amide can form good thixotroping system, therefore there is many research in this field, as U.S. Patent No. 761870 and U.S. Patent No. 5723653 have studied polyamide-based situation about mixing with ethylene oxide; Japanese 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 of urea modification ammonia ester class thixotropic agent; DE102005049301.7 describes a kind of method of sulfuric ester or phosphate modified acid amides, but it all can not obtain in each system is as low polarity, Semi-polarity and high polar system, have well compatible polymeric amide rheological agent.
The patent of invention of CN102746501 discloses a kind of dispersion agent and preparation method thereof, its preparation method comprises and being mixed with polyvinylamine by hydroxycarboxylic acid, the polyimide with hydroxyl is obtained after reaction, the polyimide obtained is carried out to the grafting of solvent chain, finally prepare dispersion agent with phosphoric acid ester or acid anhydrides hybrid reaction again.But polymeric amide and epoxide group or isocyanate groups react, and also rarely have report as the situation of rheological agent.
Summary of the invention
In order to solve above technical problem, first object of the present invention is to provide a kind of activation easily and modified polyamide structure rheological agent with fabulous compatibility and preparation method thereof, and second object of the present invention is to provide the application method of this modified polyamide structure rheological agent in coating.
In order to realize first object, the technical solution used in the present invention is:
A preparation method for modified polyamide structure rheological agent, comprising:
Step (α): by carboxylic component A, containing amino B component and catalyst mix, generates polymeric amide after making carboxyl and amino reaction; Wherein, component A is the mixture of hydroxycarboxylic acid or hydroxycarboxylic acid and alkyl carboxylic acid, and the structural formula of B component is: H-(NH-CH
2-CH
2)
n-NH
2, n=1-5;
Step (β): by the polymeric amide of step (α) gained and the mixed with polymers with epoxide group or isocyanate groups, reactive hydrogen in polymeric amide on secondary amine and epoxide group or isocyanate groups are reacted, be prepared into modified polyamide structure rheological agent, described reactive hydrogen is the hydrogen in polyamide molecule on nitrogen-atoms.
Wherein, in described step (α), the temperature of reaction of reaction is 150-230 DEG C, and the reaction times is 4-10 hour, also vacuumizes 1 hour at 180-230 DEG C after reaction.
Wherein, the mol ratio of described component A and B component is 2:1; In described step (α), catalyzer accounts for the 1.4-1.7% of component A and B component quality.
Wherein, described hydroxycarboxylic acid is ricinolic acid or ten dihydroxystearic acids, and described alkyl carboxylic acid is lauric acid, and described structural formula is H-(NH-CH
2-CH
2)
n-NH
2material be diethylenetriamine, described catalyzer is Dibutyltin oxide or Mono-n-butyltin;
Wherein, the mixture of described hydroxycarboxylic acid and alkyl carboxylic acid is the mixture that ten dihydroxystearic acids and lauric acid form, and in described mixture, ten dihydroxystearic acids are 1:1 with the ratio of lauric acid amount of substance.
Wherein, the ratio of the amount of substance of described B component and the middle polymkeric substance of step (β) is (0.8-2.5): 1; Temperature of reaction in described step (β) is: 80-85 DEG C, and the reaction times is: 2-4 hour.
Wherein, the described polymkeric substance with epoxide group to be molecular-weight average be 500 polyethyleneglycol diglycidylether or molecular-weight average be 1000 end monocycle oxygen END CAPPED GROUP butyl polyacrylate; The described polymkeric substance with isocyanate groups is: 3-isocyanic ester methylene-3,5,5-trimethylcyclohexylisocyanate.
A kind of modified polyamide structure rheological agent prepared by the preparation method of described modified polyamide structure rheological agent.
In order to realize second object, the modified polyamide rheological agent of preparation is applied in coating by the present invention, and the concrete utilisation technology scheme adopted has 2 kinds, is respectively:
1, the application of modified polyamide structure rheological agent in coating, its embody rule method is:
(11) be that 1:1:1 mixes by dimethylbenzene, N-BUTYL ACETATE and propylene glycol methyl ether acetate (PMA) according to mass ratio, obtained mixed solvent a
1; Be that 1:1 mixes by N-BUTYL ACETATE and PMA according to mass ratio, obtain mixed solvent a
2;
(12) by talcum powder, oxirane value is the bisphenol A type epoxy resin of 0.48-0.52 equivalent/100g, mixed solvent a
1be that 1.88:1.25:1 dispersing and mixing is even according to mass ratio, obtain mixture a; Described oxirane value is the bisphenol A type epoxy resin of 0.48-0.52 equivalent/100g can be 128 resins.
(13) be that 30:1 dispersing and mixing is even by mixture a and modified polyamide structure rheological agent according to mass ratio, obtain dispersion agent a;
(14) by dispersion agent a, polyamide curing agent, mixed solvent a
2, polyether-modified polydimethylsiloxane flow agent, fluorine richness silicone antifoam agent according to mass ratio be 100:15:9:1:0.05 dispersing and mixing evenly.Wherein, the preferred domestic polyamide curing agent 115 of described polyamide curing agent, polyether-modified polydimethylsiloxane flow agent preferred core chemistry Lev F70, fluorine richness silicone antifoam agent preferred core chemistry FS.
2, the application of another kind of modified polyamide structure rheological agent in coating, its embody rule method is:
(21) be that 1:1 dispersing and mixing is even by dimethylbenzene and butyl ester according to mass ratio, obtained mixed solvent b
1; Trimethylbenzene (150#), dimethylbenzene and nylon acid dimethyl ester (DBE) is even according to mass ratio 1:1:1 dispersing and mixing, obtained mixed solvent b
2;
(22) by titanium dioxide, barium sulfate, Hydroxylated acrylic resin, mixed solvent b
1be that 1.43:1.43:3.21:1 dispersing and mixing is even according to mass ratio, obtain mixture b; The preferred Hydroxylated acrylic resin 1184 (Nuplex) of described acrylic resin;
(23) mixture b and modified polyamide structure rheological agent are that 30:1 dispersing and mixing is even according to mass ratio, obtain dispersion agent b;
(24) by dispersion agent b, hexamethylene diisocyanate trimer solidifying agent, mixed solvent b
2, polyether-modified polydimethylsiloxane flow agent, fluorine richness silicone antifoam agent according to mass ratio be 100:5:19:1:0.05 dispersing and mixing evenly.Wherein, the preferred BAYER 3390 of described hexamethylene diisocyanate trimer solidifying agent, polyether-modified polydimethylsiloxane flow agent preferred core chemistry Lev F70, fluorine richness silicone antifoam agent preferred core chemistry FS.
After adopting technical scheme of the present invention, relative to prior art, have the following advantages:
(1) applicable system is more wide.The present invention is linked with polymeric amide by the segment of opposed polarity, makes modified rheological agent have longer dissolving segment, makes modified polyamide rheological agent in each system as in low polarity, Semi-polarity and high polar system, has good compatibility.At low polar system as SPUR glue, take vinylbenzene as the UPR system of solvent, can be good at activation in the waterproof paint of PPG system; In solvent-free system, need not the compatibility that just had of strict activating process, solve in solvent-free system, use thixotropic agent too thick, do not add and cannot be anti-settling problem; In senior gonosome system, can directly add modified polyamide rheological agent, simply disperse, solve easily anti-thick problem.
(2) the present invention is based on the polymeric amide of special synthesis, the epoxy on the solvent chain of the active hydrogen on secondary amine and opposed polarity or NCO is relied on to be obtained by reacting modified polyamide rheological agent, due to modified polymeric amide rheological agent molecular chain adding OH or ammonia ester bond, the hydrogen bond of the hydrogen evolution space net structure in the nitrogen in molecular chain or oxygen and self or other hydrocarbon polymers, improve in system the speed and quantity that form hydrogen bond, when the hydrogen bond of space net structure is subject to shearing force destruction, viscosity reduces provides good application property, after shearing force is removed, hydrogen bond is formed again, thus the thixotroping had, anti-settling and anti-sag effect.Therefore the present invention relative to prior art products under the prerequisite of same addition, there is better rheological.Meanwhile, the requirement of some systems to activation temperature is also reduced.
(3) because modified polyamide structure rheological agent can be applied to solvent-free system, do not need to add solvent, therefore modified polyamide structure rheological agent of the present invention is constant relative to prior art performance can ensure the condition of constructing at system viscosity under, more economical environmental protection.
(4) product of the present invention is owing to can evade the problem that must activate, and significantly improves production efficiency.
(5) product of the present invention has the stability under good preservation stability, particularly high/low temperature, makes hot and cold area all applicable.
Specific embodiment
Embodiment 1:
Step (α): the synthesis of basic framework
In four-hole boiling flask, water trap is installed, and passes into nitrogen, add 596 grams of ricinolic acids, 105 grams of diethylenetriamines, 10 grams of Dibutyltin oxides, stir, after 8 hours, after vacuumizing 1 hour at 180-230 DEG C, obtain 670 grams of intermediate M 180 DEG C of reactions.
Step (β): the grafting of solvent chain
By 330 grams of intermediate M, 100 grams of molecular-weight average be 500 polyethyleneglycol diglycidylether add in four-hole boiling flask, stir, 80 DEG C of reactions 4 hours, obtain polymkeric substance 1.
Embodiment 2:
Step (α): the synthesis of basic framework
In four-hole boiling flask, water trap is installed, and passes into nitrogen, add 300 gram of ten dihydroxystearic acid, 200 grams of lauric acid, 105 grams of diethylenetriamines, 10 grams of Mono-n-butyltins, stir, after 8 hours, after vacuumizing 1 hour at 180-230 DEG C, obtain 575 grams of intermediate N 180 DEG C of reactions.
Step (β): the grafting of solvent chain
By 230 grams of intermediate N, 55 grams of 3-isocyanic ester methylenes-3,5,5-trimethylcyclohexylisocyanate (IPDI) add in four-hole boiling flask, stir, and 80 DEG C of insulation reaction 2 hours, obtain polymkeric substance 2.
Embodiment 3:
By 230 grams of intermediate N, first adding 500 grams of molecular-weight average is that the end monocycle oxygen END CAPPED GROUP butyl polyacrylate of 1000 is (with mercaptoethanol and butyl acrylate, 90 DEG C of initiation reactions under Diisopropyl azodicarboxylate (AIBN) exists, then epoxy-capped), stir, 80 DEG C of reactions obtain polymkeric substance 3 in 2 hours.
These are only preferred embodiment, is H-(NH-CH for structural formula
2-CH
2)
n-NH
2b component, n gets 1-5; In step (α), temperature of reaction is 150-230 DEG C, and the reaction times is 4-10 hour; Temperature of reaction in step (β) is at 80-85 DEG C, can prepare modified polyamide structure rheological agent of the present invention.
Polymkeric substance 1-3 is prepared into coating, and its performance is detected.
1, the preparation of dispersion
Formula one: by talcum powder 450 grams, 128 resins 300 grams, mixed solvent (dimethylbenzene/N-BUTYL ACETATE/PMA mass ratio is 1:1:1) 240 grams is positioned in Scattered Kettle, 3000 revs/min, disperses to be put in sample pot after 30 minutes.
Formula two: by titanium dioxide 200 grams, 200 grams, barium sulfate, Hydroxylated acrylic resin 1184 (Nuplex) 450 grams, solvent (dimethylbenzene/butyl ester mass ratio is 1:1) 140 grams, disperses to be put in sample pot after 30 minutes by 3000 revs/min.
Formula one 300 grams or formula 2 300 grams being mixed with the product (contrast product 1 and contrast product 2) 10 grams on polymkeric substance 1 or 2 or 3 or market adds in Scattered Kettle, 2000 revs/min, disperse after 10 minutes, be put in sample pot, leave standstill and obtain dispersion 1-8 after 24 hours, concrete composition and engineering is:
Table 1 dispersion prepare composition and engineering
2, the preparation of coating
Dispersion 1-8 is mixed with solidifying agent, solvent, flow agent and defoamer respectively, prepares coating 1-8.Concrete preparation formula and technique are in table 2.
Table 2 coating prepare composition and engineering
3, the mensuration of performance
Respectively the gloss of coating 1-8, levelling property, fineness, viscosity, thixotroping, the performance such as anti-settling are contrasted, the results are shown in Table 3-6.
Results of property after table 3 paint spraying
Table 4 dope viscosity, thixotroping comparing result
The anti-settling comparing result of table 5 coating
Table 6 coating sag resistance comparing result
| Sag resistance contrasts | 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: 1-5 is in order to illustrate the quality of levelling property: 5 for best, and 1 is the poorest.
As can be seen from table 3-table 6, with coating prepared by polymkeric substance 1-3, performance in levelling property, thixotropy index, anti-settling and anti-sag effect is all better than the contrast product on market, illustrates that product prepared by the present invention has a wide range of applications field and wide market outlook.Rational selection can be made according to actual needs in use.
Only as described above, be only the preferred embodiment of the present invention, when can not limit the scope of the invention process with this, namely generally according to equivalence change simple done by the content described in the claims in the present invention and description of the invention and modification, be all still covered by the claims of the invention.In addition, summary part and title are only used to the use of auxiliary patent document search, are not used for the interest field of restriction the present invention.
Claims (10)
1. a preparation method for modified polyamide structure rheological agent, is characterized in that, comprising:
Step (α): by carboxylic component A, containing amino B component and catalyst mix, generates polymeric amide after making carboxyl and amino reaction; Wherein, component A is the mixture of hydroxycarboxylic acid or hydroxycarboxylic acid and alkyl carboxylic acid, and the structural formula of B component is: H-(NH-CH
2-CH
2)
n-NH
2, n=1-5;
Step (β): by the polymeric amide of step (α) gained and the mixed with polymers with epoxide group or isocyanate groups, reactive hydrogen on polymeric amide and epoxide group or isocyanate groups are reacted, is prepared into modified polyamide structure rheological agent.
2. the preparation method of modified polyamide structure rheological agent as claimed in claim 1, it is characterized in that, in described step (α), the temperature of reaction of reaction is 150-230 DEG C, and the reaction times is 4-10 hour, also vacuumizes 1 hour at 180-230 DEG C after reaction.
3. the preparation method of modified polyamide structure rheological agent as claimed in claim 1, it is characterized in that, the mol ratio of described component A and B component is 2:1; In described step (α), catalyzer accounts for the 1.4-1.7% of component A and B component quality; Described reactive hydrogen is the upper hydrogen of secondary amine in polymeric amide.
4. the preparation method of modified polyamide structure rheological agent as claimed in claim 1, it is characterized in that, described hydroxycarboxylic acid is ricinolic acid or ten dihydroxystearic acids, and described alkyl carboxylic acid is lauric acid, and described catalyzer is Dibutyltin oxide or Mono-n-butyltin.
5. the preparation method of modified polyamide structure rheological agent as claimed in claim 4, it is characterized in that, the mixture of described hydroxycarboxylic acid and alkyl carboxylic acid is the mixture that ten dihydroxystearic acids and lauric acid form, and in described mixture, ten dihydroxystearic acids are 1:1 with the ratio of lauric acid amount of substance.
6. the preparation method of modified polyamide structure rheological agent as claimed in claim 5, is characterized in that, the ratio of the amount of substance of described B component and the middle polymkeric substance of step (β) is (0.8-2.5): 1; Temperature of reaction in described step (β) is: 80-85 DEG C, and the reaction times is: 2-4 hour.
7. the preparation method of modified polyamide structure rheological agent as claimed in claim 1, it is characterized in that, the described polymkeric substance with epoxide group to be molecular-weight average be 500 polyethyleneglycol diglycidylether or molecular-weight average be 1000 end monocycle oxygen END CAPPED GROUP butyl polyacrylate; The described polymkeric substance with isocyanate groups is: 3-isocyanic ester methylene-3,5,5-trimethylcyclohexylisocyanate.
8. the modified polyamide structure rheological agent prepared by the preparation method of the modified polyamide structure rheological agent described in any one of claim 1 to 7.
9. the application of modified polyamide structure rheological agent in coating as claimed in claim 8, it is characterized in that, its embody rule method is:
(11) be that 1:1:1 mixes by dimethylbenzene, N-BUTYL ACETATE and propylene glycol methyl ether acetate according to mass ratio, obtained mixed solvent a
1; Be that 1:1 mixes by N-BUTYL ACETATE and propylene glycol methyl ether acetate according to mass ratio, obtain mixed solvent a
2;
(12) by talcum powder, oxirane value is the bisphenol A type epoxy resin of 0.48-0.52 equivalent/100g, mixed solvent a
1be that 1.88:1.25:1 dispersing and mixing is even according to mass ratio, obtain mixture a;
(13) be that 30:1 dispersing and mixing is even by mixture a and modified polyamide structure rheological agent according to claim 8 according to mass ratio, obtain dispersion agent a;
(14) by dispersion agent a, polyamide curing agent, mixed solvent a
2, polyether-modified polydimethylsiloxane flow agent, fluorine richness silicone antifoam agent according to mass ratio be 100:15:9:1:0.05 dispersing and mixing evenly.
10. the application of modified polyamide structure rheological agent in coating as claimed in claim 8, it is characterized in that, its embody rule method is:
(21) be that 1:1 dispersing and mixing is even by dimethylbenzene and butyl ester according to mass ratio, obtained mixed solvent b
1; Trimethylbenzene, dimethylbenzene and nylon acid dimethyl ester is even according to mass ratio 1:1:1 dispersing and mixing, obtained mixed solvent b
2;
(22) by titanium dioxide, barium sulfate, Hydroxylated acrylic resin, mixed solvent b
1be that 1.43:1.43:3.21:1 dispersing and mixing is even according to mass ratio, obtain mixture b;
(23) be that 30:1 dispersing and mixing is even by mixture b and modified polyamide structure rheological agent according to claim 8 according to mass ratio, obtain dispersion agent b;
(24) by dispersion agent b, hexamethylene diisocyanate trimer solidifying agent, mixed solvent b
2, polyether-modified polydimethylsiloxane flow agent, fluorine richness silicone antifoam agent according to mass ratio be 100:5:19:1:0.05 dispersing and mixing evenly.
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| CN113195592B (en) * | 2019-01-31 | 2024-03-26 | 楠本化成株式会社 | Viscosity modifier and curable composition |
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| CN113248704A (en) * | 2021-05-14 | 2021-08-13 | 济宁南天农科化工有限公司 | Epoxy modified polyamide polyamine cylinder sticking agent and preparation method thereof |
| 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 |
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