CN111234162A - Side chain grafted glyphosate degradable polyurethane and preparation method and application thereof - Google Patents
Side chain grafted glyphosate degradable polyurethane and preparation method and application thereof Download PDFInfo
- Publication number
- CN111234162A CN111234162A CN202010196036.7A CN202010196036A CN111234162A CN 111234162 A CN111234162 A CN 111234162A CN 202010196036 A CN202010196036 A CN 202010196036A CN 111234162 A CN111234162 A CN 111234162A
- Authority
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- China
- Prior art keywords
- glyphosate
- parts
- side chain
- reaction solution
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 75
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 75
- 239000005562 Glyphosate Substances 0.000 title claims abstract description 69
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 69
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 25
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 87
- 230000003373 anti-fouling effect Effects 0.000 claims description 50
- 150000002009 diols Chemical class 0.000 claims description 30
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000012295 chemical reaction liquid Substances 0.000 claims description 28
- 239000003973 paint Substances 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 11
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- 229920001451 polypropylene glycol Polymers 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 8
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 7
- PORQOHRXAJJKGK-UHFFFAOYSA-N 4,5-dichloro-2-n-octyl-3(2H)-isothiazolone Chemical compound CCCCCCCCN1SC(Cl)=C(Cl)C1=O PORQOHRXAJJKGK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004970 Chain extender Substances 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 125000005442 diisocyanate group Chemical group 0.000 claims description 7
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 6
- UQOQXWZPXFPRBR-UHFFFAOYSA-K bismuth dodecanoate Chemical compound [Bi+3].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O UQOQXWZPXFPRBR-UHFFFAOYSA-K 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229940043810 zinc pyrithione Drugs 0.000 claims description 6
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 claims description 6
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 5
- QHNCWVQDOPICKC-UHFFFAOYSA-N copper;1-hydroxypyridine-2-thione Chemical compound [Cu].ON1C=CC=CC1=S.ON1C=CC=CC1=S QHNCWVQDOPICKC-UHFFFAOYSA-N 0.000 claims description 5
- 229940112669 cuprous oxide Drugs 0.000 claims description 5
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 5
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 5
- 229940007718 zinc hydroxide Drugs 0.000 claims description 5
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 claims description 4
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 4
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 4
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 4
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 4
- 239000005750 Copper hydroxide Substances 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 4
- 101100022323 Drosophila melanogaster Marf gene Proteins 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 239000002519 antifouling agent Substances 0.000 abstract description 7
- 238000013461 design Methods 0.000 abstract description 4
- 231100000053 low toxicity Toxicity 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000005457 optimization Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000003472 neutralizing effect Effects 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 16
- 239000004925 Acrylic resin Substances 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
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- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
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Abstract
The invention discloses side chain grafted glyphosate degradable polyurethane and a preparation method and application thereof, and relates to the technical field of novel materials. The invention provides a preparation method of side chain grafted glyphosate degradable polyurethane, which comprises the steps of grafting high-efficiency broad-spectrum, low-toxicity and residue-free broad-spectrum anti-fouling agent glyphosate to a polyurethane molecular side chain by a chemical method through formula design and process optimization, introducing a carboxyl group into the polyurethane side chain, neutralizing the carboxyl group with hydroxide and glyphosate to form a side chain hydrolysable chain segment, and obtaining the side chain grafted glyphosate degradable polyurethane which has better mechanical property.
Description
Technical Field
The invention relates to the technical field of novel materials, and particularly relates to side chain grafted glyphosate degradable polyurethane and a preparation method and application thereof.
Background
The marine fouling problem always influences the development of marine resources and the development of marine economy, and at present, the most effective marine antifouling coating is to brush acrylic acid self-polishing marine antifouling paint on the surface of marine equipment so as to form an acrylic acid self-polishing marine antifouling coating on the surface of the marine equipment. The working principle of the acrylic acid self-polishing marine antifouling coating is as follows: the ester bond of the acrylic resin side chain is gradually hydrolyzed in seawater to form acrylic resin with carboxyl on the side chain, and when the acrylic resin is hydrolyzed to a certain degree, the acrylic resin can be dissolved in the seawater, so that the surface of the coating is self-updated, the antifouling agent is stably released, and the marine antifouling effect is achieved. However, since the acrylic resin has a special structure of hot adhesion and cold brittleness, the adhesion strength of the acrylic resin and the traditional epoxy resin anticorrosive coating is poor, so that the adhesion strength of the antifouling coating needs to be improved by the connecting paint, and the material cost and the construction cost are increased.
In order to solve the problems of acrylic acid antifouling coatings, degradable polyurethane is generally adopted to prepare marine antifouling paint in the prior art. For example, chinese patent CN102731745A discloses a degradable polyurethane antifouling material, which has a good antifouling effect; the two-component degradable polyurethane antifouling coating prepared by the Chinese patent CN109337565A can be directly sprayed on the surface of an anticorrosive coating without connecting paint, so that the antifouling coating has a better antifouling effect.
In the process of implementing the invention, the inventor finds that the related art has at least the following problems:
after the degradable polyurethane provided by the prior art is applied to the marine antifouling paint, the polyurethane used in the antifouling coating is in a main chain degradation mode, and the degradation rate is uncontrollable, so that the degradable polyurethane has no self-polishing performance, the antifouling period is short, and the marine ecological environment safety is greatly damaged.
Disclosure of Invention
Aiming at the problems in the related art, the invention provides side chain grafted glyphosate degradable polyurethane and a preparation method and application thereof, the side chain grafted glyphosate degradable polyurethane is prepared by grafting high-efficiency, broad-spectrum, low-toxicity and residue-free broad-spectrum antifouling agent glyphosate to a polyurethane molecular side chain through formula design and process optimization and utilizing a chemical method, and has better mechanical property. The technical scheme of the invention is as follows:
according to a first aspect of embodiments of the present invention, there is provided a method for preparing a side-chain grafted glyphosate degradable polyurethane, the method comprising:
(1) dissolving 10-50 parts of polyether glycol in a first solvent to obtain a first reaction solution, heating the first reaction solution to 110-125 ℃, performing water removal treatment in a condensation reflux manner, preserving heat for 1-2 hours, and then cooling the temperature of the first reaction solution from 110-125 ℃ to 60-90 ℃, wherein the first solvent comprises at least one of xylene and toluene;
(2) adding 20-60 parts of diisocyanate and 0.2-0.5 part of catalyst into the cooled first reaction liquid, reacting at the reaction temperature of 60-90 ℃ for 2-4 h, adding 5-20 parts of dihydric alcohol with carboxyl into the first reaction liquid, and continuing to react for 2-4 h to obtain a second reaction liquid;
(3) adding a second solvent into the second reaction solution, then cooling the temperature of the second reaction solution from 60-90 ℃ to 20-80 ℃, slowly dropwise adding 0.5-10 parts of a chain extender into the second reaction solution, then heating the temperature of the second reaction solution from 20-80 ℃ to 60-90 ℃, and continuously reacting at the reaction temperature of 60-90 ℃ until the percentage content of isocyanate groups NCO in the second reaction solution is lower than 0.01%, wherein the second solvent comprises at least one of dimethyl sulfoxide DMSO, N-dimethylformamide DMFN and N-dimethylformamide DMF;
(4) and (3) cooling the temperature of the second reaction solution from 60-90 ℃ to 20-30 ℃, then adding 5-20 parts of hydroxide and 5-25 parts of glyphosate, heating the temperature of the second reaction solution from 20-30 ℃ to 80-100 ℃, reacting for 4-8 hours, cooling the temperature of the second reaction solution from 80-100 ℃ to 40-60 ℃, and performing rotary evaporation treatment to prepare the side chain grafted glyphosate degradable polyurethane with the solid content of 20-40%.
In a preferred embodiment, the polyether diol comprises at least one of polycarbonate diol PCDL, polyethylene oxide diol PEG, polytetrahydrofuran ether diol PTMG and polypropylene oxide diol PPG, and the number average molecular weight of the polyether diol is 400-3000.
In a preferred embodiment, the diol having carboxyl groups comprises at least one of dimethylolbutyric acid and dimethylolpropionic acid.
In a preferred embodiment, the catalyst comprises at least one of bismuth isooctanoate, dibutyltin dilaurate, bismuth laurate.
In a preferred embodiment, the diisocyanate comprises at least one of toluene diisocyanate TDI, isophorone diisocyanate IPDI, diphenylmethane diisocyanate MDI, 1, 6-hexamethylene diisocyanate HDI, naphthalene-1, 5-diisocyanate NDI.
In a preferred embodiment, the hydroxide includes at least one of copper hydroxide and zinc hydroxide.
In a preferred embodiment, the chain extender comprises at least one of 1, 4-butanediol, 1, 6-hexanediol, diethylene glycol, 2-methyl-1, 3-propanediol, ethylene glycol, ethylenediamine, 1, 4-butanediamine, 1, 5-pentanediamine.
According to a second aspect of the embodiments of the present invention, there is provided a side chain grafted glyphosate degradable polyurethane, wherein the side chain grafted glyphosate degradable polyurethane is obtained by the method for preparing the side chain grafted glyphosate degradable polyurethane according to any claim 1 to 7, the side chain grafted glyphosate degradable polyurethane has an elongation at break of 100% to 250%, a tensile strength of 7 to 9 MPa, a water absorption rate of less than 2%, and a number average molecular weight of 3.93 × 104~4.72×104And the molecular weight distribution index is 1.65-1.79.
According to a third aspect of the embodiments of the present invention, there is provided a use of the side-chain grafted glyphosate degradable polyurethane as described above, in preparation of a marine antifouling paint, the preparation method of the marine antifouling paint comprising:
respectively putting 30-60 parts of side chain grafted glyphosate degradable polyurethane, 0-16 parts of 4, 5-dichloro-2-n-octyl-3-isothiazolinone DCOIT, 0-10 parts of cuprous oxide, 0-10 parts of zinc pyrithione, 0-10 parts of copper pyrithione, 3-7 parts of an auxiliary agent and 15-45 parts of a solvent into a reaction container, and uniformly mixing to obtain a mixed raw material, wherein the auxiliary agent comprises at least one of a defoaming agent, an anti-settling agent, a leveling agent and a pigment dispersing agent, and the solvent is at least one of DMSO and DMF;
and (3) placing the reaction vessel on a high-speed dispersion machine, dispersing at a high speed for 1-2 hours at a rotating speed of 1500-2000 r/min, and filtering the mixed raw materials in the reaction vessel to prepare the marine antifouling paint.
According to a fourth aspect of the embodiments of the present invention, there is provided a marine antifouling paint, which is prepared by the method for preparing a marine antifouling paint as described above, and has a fineness of less than 100 μm.
Compared with the prior art, the side chain grafted glyphosate degradable polyurethane and the preparation method and application thereof provided by the invention have the following advantages:
the invention provides a preparation method of side chain grafted glyphosate degradable polyurethane, which comprises the steps of grafting high-efficiency broad-spectrum, low-toxicity and residue-free broad-spectrum anti-fouling agent glyphosate to a polyurethane molecular side chain by a chemical method through formula design and process optimization, introducing a carboxyl group into the polyurethane side chain, neutralizing the carboxyl group with hydroxide and glyphosate to form a side chain hydrolysable chain segment, and obtaining the side chain grafted glyphosate degradable polyurethane which has better mechanical property.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
Figure 1 is a process flow diagram illustrating a method for preparing a side-chain grafted glyphosate degradable polyurethane according to one exemplary embodiment,
fig. 2 is a schematic diagram illustrating the synthesis of a side-chain grafted glyphosate degradable polyurethane according to an exemplary embodiment.
FIG. 3 is a method flow diagram illustrating a method of preparing a marine antifouling paint, according to an exemplary embodiment.
FIG. 4 is an infrared spectrum of the side-chain grafted glyphosate degradable polyurethane provided in examples 1-3.
FIG. 5 is a graph showing the variation of the degradation rate of the side-chain grafted glyphosate degradable polyurethane provided in examples 1-3.
FIG. 6 is a line graph of the DCOIT release rate for each of the polyurethane anti-fouling coatings provided in examples 1-3.
Detailed Description
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a process flow diagram illustrating a method for preparing an aqueous polyurethane according to an exemplary embodiment, as shown in fig. 1, the method for preparing an aqueous polyurethane includes:
step (1): dissolving 10-50 parts of polyether glycol in a first solvent to obtain a first reaction solution, heating the first reaction solution to 110-125 ℃, performing water removal treatment in a condensation reflux manner, preserving heat for 1-2 hours, and then cooling the temperature of the first reaction solution from 110-125 ℃ to 60-90 ℃.
The first solvent comprises at least one of xylene and toluene.
In a preferred embodiment, the polyether diol comprises at least one of polycarbonate diol PCDL, polyethylene oxide diol PEG, polytetrahydrofuran ether diol PTMG and polypropylene oxide diol PPG, and the number average molecular weight of the polyether diol is 400-3000.
For example, the polyether diol may be polycarbonate diol PCDL or polyethylene oxide diol PEG or polypropylene oxide diol PPG, or may be a combination of polycarbonate diol PCDL and polyethylene oxide diol PEG, or a combination of polytetrahydrofuran ether diol PTMG and polypropylene oxide diol PPG.
Step (2): adding 20-60 parts of diisocyanate and 0.2-0.5 part of catalyst into the cooled first reaction liquid, reacting at the reaction temperature of 60-90 ℃ for 2-4 h, adding 5-20 parts of dihydric alcohol with carboxyl into the first reaction liquid, and continuing to react for 2-4 h to obtain a second reaction liquid.
In a preferred embodiment, the diisocyanate comprises at least one of toluene diisocyanate TDI, isophorone diisocyanate IPDI, diphenylmethane diisocyanate MDI, 1, 6-hexamethylene diisocyanate HDI, naphthalene-1, 5-diisocyanate NDI.
For example, the diisocyanate may be toluene diisocyanate TDI or isophorone diisocyanate IPDI or diphenylmethane diisocyanate MDI, a combination of toluene diisocyanate TDI and isophorone diisocyanate IPDI, or a combination of 1, 6-hexamethylene diisocyanate HDI and naphthalene-1, 5-diisocyanate NDI.
In a preferred embodiment, the diol having carboxyl groups comprises at least one of dimethylolbutyric acid and dimethylolpropionic acid.
For example, the carboxyl group-containing diol may be dimethylolbutanoic acid or dimethylolpropionic acid, or may be a combination of dimethylolbutanoic acid and dimethylolpropionic acid.
In a preferred embodiment, the catalyst comprises at least one of bismuth isooctanoate, dibutyltin dilaurate, bismuth laurate.
For example, the catalyst may be bismuth isooctanoate or dibutyltin dilaurate or bismuth laurate, a combination of bismuth isooctanoate and dibutyltin dilaurate, or a combination of dibutyltin dilaurate and bismuth laurate
And (3): adding a second solvent into the second reaction solution, then cooling the temperature of the second reaction solution from 60-90 ℃ to 20-80 ℃, slowly dropwise adding 0.5-10 parts of chain extender into the second reaction solution, then heating the temperature of the second reaction solution from 20-80 ℃ to 60-90 ℃, and continuing to react at the reaction temperature of 60-90 ℃ until the percentage content of isocyanate groups NCO in the second reaction solution is lower than 0.01%.
The second solvent comprises at least one of dimethyl sulfoxide DMSO, N-dimethylformamide DMFN, N-dimethylformamide DMF.
In a preferred embodiment, the chain extender comprises at least one of 1, 4-butanediol, 1, 6-hexanediol, diethylene glycol, 2-methyl-1, 3-propanediol, ethylene glycol, ethylenediamine, 1, 4-butanediamine, 1, 5-pentanediamine.
For example, the chain extender can be 1, 4-butanediol or 1, 6-hexanediol or diethylene glycol, or can be a combination of 2-methyl-1, 3-propanediol and ethylene glycol, or a combination of 1, 4-butanediamine and 1, 5-pentanediamine, ethylene glycol.
And (4): and (3) cooling the temperature of the second reaction solution from 60-90 ℃ to 20-30 ℃, then adding 5-20 parts of hydroxide and 5-25 parts of glyphosate, heating the temperature of the second reaction solution from 20-30 ℃ to 80-100 ℃, reacting for 4-8 hours, cooling the temperature of the second reaction solution from 80-100 ℃ to 40-60 ℃, and performing rotary evaporation treatment to prepare the side chain grafted glyphosate degradable polyurethane with the solid content of 20-40%.
In a preferred embodiment, the hydroxide includes at least one of copper hydroxide and zinc hydroxide.
For convenience of explaining the preparation method of the side chain grafted glyphosate degradable polyurethane provided by the invention, a synthetic schematic diagram of the side chain grafted glyphosate degradable polyurethane shown in fig. 2 is shown.
Fig. 3 is a flow chart illustrating a method for preparing a marine antifouling paint according to an exemplary embodiment, wherein the raw material for preparing the marine antifouling paint comprises the side-chain grafted glyphosate degradable polyurethane as described above. As shown in fig. 3, the preparation method of the marine antifouling paint comprises the following steps:
and (5): respectively putting 30-60 parts of side chain grafted glyphosate degradable polyurethane, 0-16 parts of 4, 5-dichloro-2-n-octyl-3-isothiazolinone DCOIT, 0-10 parts of cuprous oxide, 0-10 parts of zinc pyrithione, 0-10 parts of copper pyrithione, 3-7 parts of auxiliary agent and 15-45 parts of solvent into a reaction container, and uniformly mixing to obtain a mixed raw material.
The auxiliary agent comprises at least one of an antifoaming agent, an anti-settling agent, a leveling agent and a pigment dispersing agent, and the solvent is at least one of DMSO and DMF.
And (6): and (3) placing the reaction vessel on a high-speed dispersion machine, dispersing at a high speed for 1-2 hours at a rotating speed of 1500-2000 r/min, and filtering the mixed raw materials in the reaction vessel to prepare the marine antifouling paint.
In order to better illustrate the beneficial effects brought by the side chain grafted glyphosate degradable polyurethane provided by the invention, the preparation method and the application thereof, the following examples 1 to 3 are shown for illustration:
example 1
Step (1): 50 parts of PCDL500Dissolving in dimethylbenzene to obtain a first reaction solution, heating the first reaction solution to 110-125 ℃, performing water removal treatment in a condensation reflux manner, preserving heat for 1-2 hours, and then cooling the temperature of the first reaction solution from 110-125 ℃ to 80 ℃.
Step (2): adding 44.4 parts of IPDI and 0.1-0.3 part of dibutyltin dilaurate into the cooled first reaction liquid, reacting at the reaction temperature of 80 ℃ for 2-4 h, adding 6.7 parts of dimethylolpropionic acid into the first reaction liquid, and continuing to react for 2-4 h to obtain a second reaction liquid.
And (3): adding DMF into the second reaction solution, then cooling the temperature of the second reaction solution from 80 ℃ to 20 ℃, slowly dropwise adding 3 parts of ethylenediamine into the second reaction solution, heating the temperature of the second reaction solution from 20 ℃ to 80 ℃, and continuing to react at the reaction temperature of 80 ℃ until the percentage content of NCO in isocyanate groups in the second reaction solution is lower than 0.01%.
And (4): and (2) cooling the temperature of the second reaction solution from 80 ℃ to 20-30 ℃, then adding 5.01 parts of zinc hydroxide and 8.45 parts of glyphosate, heating the temperature of the second reaction solution from 20-30 ℃ to 80-100 ℃, reacting for 4-8 hours, cooling the temperature of the second reaction solution from 80-100 ℃ to 40-60 ℃, and performing rotary evaporation treatment to prepare the side chain grafted glyphosate degradable polyurethane with the solid content of 20%.
And (5): respectively putting 60 parts of side chain grafted glyphosate degradable polyurethane, 14 parts of 4, 5-dichloro-2-n-octyl-3-isothiazolinone DCOIT, 9 parts of zinc pyrithione, 5 parts of auxiliary agent and 12 parts of DMF (dimethyl formamide) into a reaction vessel, and uniformly mixing to obtain a mixed raw material.
And (6): and (3) placing the reaction vessel on a high-speed dispersion machine, dispersing at a high speed for 1-2 hours at a rotating speed of 1500-2000 r/min, and filtering the mixed raw materials in the reaction vessel to prepare the marine antifouling paint.
Example 2
Step (1): 50 parts of PPG400Dissolving the first reaction solution in toluene to obtain a first reaction solution, heating the first reaction solution to 110-125 ℃, performing water removal treatment in a condensation reflux manner, preserving heat for 1-2 hours, and then cooling the temperature of the first reaction solution from 110-125 ℃ to 80 ℃.
Step (2): adding 34 parts of HDI and 0.1-0.3 part of bismuth laurate into the cooled first reaction liquid, reacting at the reaction temperature of 80 ℃ for 2-4 h, adding 8.8 parts of dimethylolbutyric acid into the first reaction liquid, and continuing to react for 2-4 h to obtain a second reaction liquid.
And (3): adding DMSO (dimethyl sulfoxide) into the second reaction liquid, then reducing the temperature of the second reaction liquid from 80 ℃ to 30 ℃, slowly dropwise adding 1.35 parts of butanediol into the second reaction liquid, raising the temperature of the second reaction liquid from 30 ℃ to 80 ℃, and continuing to react at the reaction temperature of 80 ℃ until the percentage content of the isocyanate group NCO% of the second reaction liquid is lower than 0.01%.
And (4): and (2) cooling the temperature of the second reaction solution from 80 ℃ to 20-30 ℃, then adding 5.8 parts of copper hydroxide and 10 parts of glyphosate, heating the temperature of the second reaction solution from 20-30 ℃ to 80-100 ℃, reacting for 4-8 hours, cooling the temperature of the second reaction solution from 80-100 ℃ to 40-60 ℃, and performing rotary evaporation treatment to prepare the side chain grafted glyphosate degradable polyurethane with the solid content of 30%.
And (5): respectively putting 50 parts of side chain grafted glyphosate degradable polyurethane, 9 parts of 4, 5-dichloro-2-n-octyl-3-isothiazolinone, 5 parts of cuprous oxide, 6 parts of zinc pyrithione, 6 parts of copper pyrithione, 5 parts of auxiliary agent and 19 parts of DMSO into a reaction container, and uniformly mixing to obtain a mixed raw material.
And (6): and (3) placing the reaction vessel on a high-speed dispersion machine, dispersing at a high speed for 1-2 hours at a rotating speed of 1500-2000 r/min, and filtering the mixed raw materials in the reaction vessel to prepare the marine antifouling paint.
Example 3
Step (1): 40 parts of PTMG400Dissolving in dimethylbenzene to obtain a first reaction solution, heating the first reaction solution to 110-125 ℃, performing water removal treatment in a condensation reflux manner, preserving heat for 1-2 hours, and then cooling the temperature of the first reaction solution from 110-125 ℃ to 60 ℃.
Step (2): adding 35 parts of TDI and 0.2 part of dibutyltin dilaurate into the cooled first reaction liquid, reacting at the reaction temperature of 60 ℃ for 2-4 h, adding 12 parts of dimethylolpropionic acid into the first reaction liquid, and continuing to react for 2-4 h to obtain a second reaction liquid.
And (3): adding DMF into the second reaction liquid, then reducing the temperature of the second reaction liquid from 80 ℃ to 40 ℃, slowly dropwise adding 0.65 part of ethylene glycol into the second reaction liquid, raising the temperature of the second reaction liquid from 40 ℃ to 75 ℃, and continuing to react at the reaction temperature of 75 ℃ until the percentage content of the isocyanate group NCO% of the second reaction liquid is lower than 0.01%.
And (4): and (2) cooling the temperature of the second reaction solution from 75 ℃ to 20-30 ℃, then adding 8.8 parts of zinc hydroxide and 15 parts of glyphosate, heating the temperature of the second reaction solution from 20-30 ℃ to 80-100 ℃, reacting for 4-8 hours, cooling the temperature of the second reaction solution from 80-100 ℃ to 40-60 ℃, and performing rotary evaporation treatment to prepare the side chain grafted glyphosate degradable polyurethane with the solid content of 40%.
And (5): respectively putting 40 parts of side chain grafted glyphosate degradable polyurethane, 4 parts of 4, 5-dichloro-2-n-octyl-3-isothiazolinone, 10 parts of cuprous oxide, 8 parts of zinc pyrithione, 10 parts of copper pyrithione, 7 parts of auxiliary agent and 21 parts of solvent into a reaction vessel, and uniformly mixing to obtain a mixed raw material.
And (6): and (3) placing the reaction vessel on a high-speed dispersion machine, dispersing at a high speed for 1-2 hours at a rotating speed of 1500-2000 r/min, and filtering the mixed raw materials in the reaction vessel to prepare the marine antifouling paint.
The performance tests of the side chain grafted glyphosate degradable polyurethane prepared in the above examples 1-3 and the marine antifouling paint are carried out, and the reference data of the performance tests are shown in the table I and the table II.
The performance data of the side-chain grafted glyphosate degradable polyurethane provided in examples 1-3 is shown in table one:
The test data related to the side chain grafted glyphosate degradable polyurethane provided by each embodiment shown in the table one show that the tensile strength of the side chain grafted glyphosate degradable polyurethane synthesized by the embodiment of the invention is more than 7.32 Mpa, and the elongation at break is more than 140%, obviously, the mechanical property of each side chain grafted glyphosate degradable polyurethane is stronger, and the application of the marine antifouling paint can be met.
The performance data for the polyurethane antifouling coatings provided in examples 1-3 are shown in table two:
watch two
According to the relevant test data of the polyurethane antifouling coatings provided by the embodiments shown in the table II, after the polyurethane degradable based on the side chain grafted glyphosate is applied to the marine antifouling coating, the adhesion strength of the polyurethane degradable based on the side chain grafted glyphosate and a conventional epoxy resin anticorrosive coating is 3-4 MPa, the degradation rate of the antifouling coating is about 2.83-3.67 mu m/month, the marine antifouling efficiency is 52-72 months, the mechanical property is good, and the alkali resistance, the acid resistance and other properties are good.
It should be noted that the infrared spectrum of the side chain grafted glyphosate degradable polyurethane provided in examples 1 to 3 is detected, and the obtained infrared spectrum of the side chain grafted glyphosate degradable polyurethane is shown in fig. 4. Wherein, 3350cm-1Are characteristic absorption peaks of-NH-, 2911 and 2851 cm-1is-CH2Characteristic absorption peak of 1731 cm-1Is a characteristic absorption peak of carbonyl group, 1531 cm-1Is a characteristic absorption peak of-CO-NH-, 1247 cm-1Is a characteristic absorption peak of-C-O-C-.
Further, the present invention also tests the degradation rate of the side chain grafted glyphosate degradable polyurethane provided in examples 1-3, and the line graph of the degradation rate change of each side chain grafted glyphosate degradable polyurethane with time is shown in fig. 5.
Furthermore, the present invention also performed DCOIT release rate tests on the polyurethane antifouling coatings provided in examples 1-3, and the DCOIT release rate line graph of each polyurethane antifouling coating is shown in FIG. 6.
In conclusion, the invention provides a preparation method of side chain grafted glyphosate degradable polyurethane, through formula design and process optimization, broad-spectrum anti-fouling agent glyphosate with high efficiency, broad spectrum, low toxicity and no residue is grafted to a polyurethane molecular side chain by a chemical method, carboxyl groups are introduced into the polyurethane side chain, then the carboxyl groups, hydroxide and glyphosate are neutralized, the side chain grafted glyphosate degradable polyurethane obtained by synthesis has better mechanical property, and after being applied to the preparation of the marine antifouling paint, can stably release the anti-fouling agent glyphosate in the marine anti-fouling paint, thereby reducing the using amount of the anti-fouling agent, improving the marine anti-fouling period of the marine anti-fouling coating, the marine antifouling coating has the technical effect of environmental protection on marine ecological environment while improving the marine antifouling period.
While the invention has been described in detail in the foregoing by way of general description, and specific embodiments and experiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. This invention is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It will be understood that the invention is not limited to the precise arrangements described above and shown in the drawings and that various modifications and changes may be made without departing from the scope thereof.
Claims (10)
1. A preparation method of side chain grafted glyphosate degradable polyurethane is characterized by comprising the following steps:
(1) dissolving 10-50 parts of polyether glycol in a first solvent to obtain a first reaction solution, heating the first reaction solution to 110-125 ℃, performing water removal treatment in a condensation reflux manner, preserving heat for 1-2 hours, and then cooling the temperature of the first reaction solution from 110-125 ℃ to 60-90 ℃, wherein the first solvent comprises at least one of xylene and toluene;
(2) adding 20-60 parts of diisocyanate and 0.2-0.5 part of catalyst into the cooled first reaction liquid, reacting at the reaction temperature of 60-90 ℃ for 2-4 h, adding 5-20 parts of dihydric alcohol with carboxyl into the first reaction liquid, and continuing to react for 2-4 h to obtain a second reaction liquid;
(3) adding a second solvent into the second reaction solution, then cooling the temperature of the second reaction solution from 60-90 ℃ to 20-80 ℃, slowly dropwise adding 0.5-10 parts of a chain extender into the second reaction solution, then heating the temperature of the second reaction solution from 20-80 ℃ to 60-90 ℃, and continuously reacting at the reaction temperature of 60-90 ℃ until the percentage content of isocyanate groups NCO in the second reaction solution is lower than 0.01%, wherein the second solvent comprises at least one of dimethyl sulfoxide DMSO, N-dimethylformamide DMFN and N-dimethylformamide DMF;
(4) and (3) cooling the temperature of the second reaction solution from 60-90 ℃ to 20-30 ℃, then adding 5-20 parts of hydroxide and 5-25 parts of glyphosate, heating the temperature of the second reaction solution from 20-30 ℃ to 80-100 ℃, reacting for 4-8 hours, cooling the temperature of the second reaction solution from 80-100 ℃ to 40-60 ℃, and performing rotary evaporation treatment to prepare the side chain grafted glyphosate degradable polyurethane with the solid content of 20-40%.
2. The method according to claim 1, wherein the polyether diol comprises at least one of polycarbonate diol PCDL, polyethylene oxide diol PEG, polytetrahydrofuran ether diol PTMG and polypropylene oxide diol PPG, and the number average molecular weight of the polyether diol is 400-3000.
3. The method of claim 1, wherein the carboxyl-bearing diol comprises at least one of dimethylolbutanoic acid and dimethylolpropanoic acid.
4. The method of claim 1, wherein the catalyst comprises at least one of bismuth isooctanoate, dibutyltin dilaurate, and bismuth laurate.
5. The method of claim 1, wherein the diisocyanate comprises at least one of toluene diisocyanate TDI, isophorone diisocyanate IPDI, diphenylmethane diisocyanate MDI, 1, 6-hexamethylene diisocyanate HDI, naphthalene-1, 5-diisocyanate NDI.
6. The method of claim 1, wherein the hydroxide comprises at least one of copper hydroxide and zinc hydroxide.
7. The method of claim 1, wherein the chain extender comprises at least one of 1, 4-butanediol, 1, 6-hexanediol, diethylene glycol, 2-methyl-1, 3-propanediol, ethylene glycol, ethylenediamine, 1, 4-butanediamine, 1, 5-pentanediamine.
8. The side chain grafted glyphosate degradable polyurethane is characterized by being prepared by the preparation method of the side chain grafted glyphosate degradable polyurethane as claimed in any claim 1 to 7, wherein the side chain grafted glyphosate degradable polyurethane has the elongation at break of 100 to 250 percent, the tensile strength of 7 to 9 MPa, the water absorption rate of less than 2 percent and the number average molecular weight of 3.93 x 104~4.72×104And the molecular weight distribution index is 1.65-1.79.
9. The use of the side-chain grafted glyphosate degradable polyurethane of claim 8 in the preparation of a marine antifouling paint by a method comprising:
respectively putting 30-60 parts of side chain grafted glyphosate degradable polyurethane, 0-16 parts of 4, 5-dichloro-2-n-octyl-3-isothiazolinone DCOIT, 0-10 parts of cuprous oxide, 0-10 parts of zinc pyrithione, 0-10 parts of copper pyrithione, 3-7 parts of an auxiliary agent and 15-45 parts of a solvent into a reaction container, and uniformly mixing to obtain a mixed raw material, wherein the auxiliary agent comprises at least one of a defoaming agent, an anti-settling agent, a leveling agent and a pigment dispersing agent, and the solvent is at least one of DMSO and DMF;
and (3) placing the reaction vessel on a high-speed dispersion machine, dispersing at a high speed for 1-2 hours at a rotating speed of 1500-2000 r/min, and filtering the mixed raw materials in the reaction vessel to prepare the marine antifouling paint.
10. A marine antifouling paint, which is prepared by the method for preparing the marine antifouling paint according to claim 9, and the fineness of the marine antifouling paint is less than 100 μm.
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