CN110511347A - A kind of side chain degradable polyurethane and its preparation method and application - Google Patents
A kind of side chain degradable polyurethane and its preparation method and application Download PDFInfo
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- CN110511347A CN110511347A CN201910871060.3A CN201910871060A CN110511347A CN 110511347 A CN110511347 A CN 110511347A CN 201910871060 A CN201910871060 A CN 201910871060A CN 110511347 A CN110511347 A CN 110511347A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D5/1662—Synthetic film-forming substance
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D5/1687—Use of special additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2230/00—Compositions for preparing biodegradable polymers
Abstract
The invention discloses a kind of side chain degradable polyurethanes and its preparation method and application, are related to marine anti-pollution field of material technology.A kind of side chain degradable polyurethane provided by the invention and its preparation method and application, pass through polyether Glycols and di-isocyanate reaction, form the segment that end group is isocyanates, again by itself and band carboxyl diol reaction, the carboxylic polyurethane of side chain is prepared by chain extender, side chain degradable polyurethane is prepared into finally by Kocide SD neutralization, to by degrade mode be mainly main chain degradation it is polyurethane-modified for degradation mode be mainly side-chain hydrolysis mode side chain degradable polyurethane, it is low in oceanographic equipment surface adhesive strength to solve marine antifouling coating, anti-fouling effect is poor, the low technical problem of antifouling persistence, reach and improves marine antifouling coating in oceanographic equipment surface adhesive strength, improve the technical effect of anti-fouling effect and effect comprehensive performance of antifouling phase.
Description
Technical field
The present invention relates to marine anti-pollution field of material technology, in particular to a kind of side chain degradable polyurethane and its preparation side
Method and application.
Background technique
With the development of world economy, the mankind increase marine resources development and marine economy development, but marine anti-pollution is asked
Topic always affects the development of marine economy.Ocean engineering and ship bring are endangered for marine pollutant, it is most effective at present
Mode be oceanographic equipment external coating marine antifouling coating.Wherein acrylic acid occupies predominantly from polishing marine antifouling coating
Position, the ester bond which mainly passes through acrylic resin side chain gradually hydrolyze in the seawater, and nonpolluting coating is made to have certain parent
It is aqueous, while under the lasting immersion of seawater and souring, coating surface self refresh promotes anti-fouling agent to stablize release, thus
Make marine fouling organism be difficult to adhere to, achievees the effect that marine anti-pollution.
Due to the special construction of acrylic resin, it is poor with the adhesive strength of corrosion-inhibiting coating to make it, therefore in nonpolluting coating
One layer of connection paint of spraying, significantly increases application cost before construction." hot sticky cold crisp " of acrylic resin at the same time, pole
The earth limits the application of acrylic acid from polishing antifouling coating.
Such issues that in order to solve, the prior art carry out marine anti-pollution material using degradable polyurethane substitution acrylic resin
The preparation of material.For example, Chinese patent CN107163224A discloses a kind of Biodegradable macromolecule ocean anti-fouling material, have
Preferable mechanical performance and certain anti-fouling effect；Chinese patent CN102731745A discloses a kind of degradation type polyurethane ocean
Anti-fouling material has preferable mechanical property and certain anti-fouling effect；Chinese patent CN109337565A is mainly prepared for double
Component degradable polyurethane nonpolluting coating does not need connection paint, can direct spraying in corrosion-inhibiting coating surface, and have certain anti-
Dirty effect.
In the implementation of the present invention, inventor find the relevant technologies the prior art has at least the following problems:
The marine antifouling coating being prepared using degradable polyurethane substitution acrylic resin, is formed on oceanographic equipment surface
Totality antifouling phase effect of marine anti-pollution coating can not show a candle to the effect of antifouling phase of acrylic acid nonpolluting coating.
Summary of the invention
For the above problem existing for the relevant technologies, the present invention provides a kind of side chain degradable polyurethane and its preparation sides
Method and application introduce carboxylic group by formula design and process optimization in polyurethane side chain, then by carboxylic group and hydrogen-oxygen
Change copper and organic acid neutralizes, form side chain hydrolyzable segment, the side chain degradable polyurethane being prepared has preferable mechanical
Performance, the marine antifouling coating and corrosion-inhibiting coating being prepared using the side chain degradable polyurethane have good attachment strong
Degree, while there is controllable degradation property, make anti-fouling agent controlled release, reaches excellent marine anti-pollution effect.Skill of the invention
Art scheme is as follows:
First aspect according to an embodiment of the present invention provides a kind of preparation method of side chain degradable polyurethane, the method
Include:
10 ~ 25 parts of polyether Glycols are dissolved in the first solvent and obtain reaction solution, the reaction solution is then warming up to 110 ~
120 °C, 1 ~ 2h of stewing process is kept the temperature after removing water using condensing reflux mode, first solvent includes dimethylbenzene, in toluene
It is at least one；
The reaction solution after stewing process will be kept the temperature and be cooled to 60 ~ 90 °C, then by 20 ~ 60 parts of diisocyanate and 0.1 ~
0.3 part of catalyst adds to the reaction solution, after keeping 60 ~ 90 °C of reaction temperature to react 2 ~ 4 h, by 5 ~ 15 parts of band carboxyls two
First alcohol adds to the reaction solution, continues 60 ~ 90 °C of holding of reaction temperature and reacts 2 ~ 4 h；
The second solvent and 1 ~ 10 part of chain extender are added respectively to the reaction solution, and 60 ~ 90 °C of reaction temperature is kept to carry out instead
Answer, during reaction in reaction solution described in the real time measure isocyanate group degree value, when determining the isocyanic acid
When the degree value of ester group is less than 0.01%, the reaction solution is cooled to 20 ~ 30 °C, Xiang Suoshu reaction solution is added 5
~ 20 parts of Kocide SDs and 5 ~ 20 parts of organic acids continue after the reaction solution to be warming up to 80 ~ 100 °C and reacts 5 ~ 7 h, will
The reaction solution is cooled to 40 ~ 60 °C and carries out revolving processing, and side chain degradable polyurethane, second solvent is prepared
Including at least one of N,N-dimethylformamide DMF, dimethyl sulfoxide DMSO.
In a preferred embodiment, the band carboxyl dihydric alcohol includes dimethylolpropionic acid, in dihydromethyl propionic acid
At least one.
In a preferred embodiment, the catalyst includes dibutyl tin dilaurate, lauric acid bismuth, isooctyl acid bismuth
At least one of.
In a preferred embodiment, the polyether Glycols include polytetrahydrofuran ether dihydric alcohol PTMG, polycyclic oxygen
At least one of propane dihydric alcohol PPG, polyethylene oxide glycol PEG.
In a preferred embodiment, the diisocyanate includes 1, hexamethylene-diisocyanate HDI, toluene diisocyanate
Acid esters TDI, isophorone diisocyanate IPDI, naphthalene -1,5- diisocyanate NDI, methyl diphenylene diisocyanate MDI
At least one of.
In a preferred embodiment, the chain extender be ethylenediamine, Putriscine, 1,5- pentanediamine, ethylene glycol,
1,4- butanediol, 1,6-HD, diglycol, 2- methyl-1, at least one of 3 propylene glycol.
The second aspect according to an embodiment of the present invention, provides a kind of side chain degradable polyurethane, and the side chain is degradable
Polyurethane is obtained by the preparation method of above-mentioned any side chain degradable polyurethane, the stretching of the side chain degradable polyurethane
11 ~ 14 MPa of intensity, elongation at break 100% ~ 250%.
In terms of third according to an embodiment of the present invention, the application of side chain degradable polyurethane as described above is provided, it is described
Side chain degradable polyurethane is applied to the preparation of marine antifouling coating, and the preparation method of the marine antifouling coating includes:
By 20 ~ 40 parts of side chain degradable polyurethanes, 25 ~ 46 parts of cuprous oxide, 1 ~ 5 part of copper pyrithione, 1 ~ 6 part of pyridine sulphur
Ketone zinc, 2 ~ 6 parts of chloro- 2- n-octyl -3- isothiazolinone of 4,5- bis-, 4 ~ 9 parts of auxiliary agents, 15 ~ 40 parts of solvents are uniformly mixed, and obtain sea
Foreign antifouling paint semi-finished product, the solvent are at least one of dimethyl sulfoxide DMSO or n,N-Dimethylformamide DMF；
The marine antifouling coating semi-finished product are placed in high speed disperser after 1 ~ 2 h of high speed dispersion and are filtered, marine anti-pollution is obtained
Coating, the revolving speed of the high speed disperser are 1500 ~ 2000 r/min.
Preferably, the auxiliary agent is at least one of pigment dispersing agent, defoaming agent, anti-settling agent, levelling agent.
4th aspect according to an embodiment of the present invention, provides a kind of marine antifouling coating, the marine antifouling coating by
The preparation method of above-mentioned any marine antifouling coating obtains, and the fineness of the marine antifouling coating is less than 100 μm.
Compared with prior art, side chain degradable polyurethane provided by the invention and its preparation method and application has following
Advantage:
A kind of side chain degradable polyurethane provided by the invention and its preparation method and application, passes through polyether Glycols and two isocyanides
Acid esters reaction forms the segment that end group is isocyanates, then by itself and band carboxyl diol reaction, is prepared into side by chain extender
The carboxylic polyurethane of chain is prepared into side chain degradable polyurethane finally by Kocide SD neutralization, thus the mode master that will degrade
It to be side chain degradable polyurethane that degradation mode is mainly side-chain hydrolysis mode for the polyurethane-modified of main chain degradation, to solve
Marine antifouling coating of having determined is low in oceanographic equipment surface adhesive strength, and anti-fouling effect is poor, and the low technical problem of antifouling persistence reaches
To marine antifouling coating is improved in oceanographic equipment surface adhesive strength, the technology of anti-fouling effect and effect comprehensive performance of antifouling phase is improved
Effect.
Detailed description of the invention
The drawings herein are incorporated into the specification and forms part of this specification, and shows and meets implementation of the invention
Example, and in specification together principle for explaining the present invention.
Fig. 1 is a kind of method flow of the preparation method of side chain degradable polyurethane shown according to an exemplary embodiment
Figure.
Fig. 2 is a kind of schematic diagram of the molecular formula of side chain degradable polyurethane shown according to an exemplary embodiment.
Fig. 3 is a kind of synthesis schematic diagram of side chain degradable polyurethane shown according to an exemplary embodiment.
Fig. 4 is a kind of method flow diagram of the preparation method of marine antifouling coating shown according to an exemplary embodiment.
Fig. 5 is the degradation rate of side chain degradable polyurethane in each marine antifouling coating of 1-3 of embodiment of the present invention offer
Line chart.
Fig. 6 is the copper ion rate of release line chart for each marine antifouling coating that 1-3 of the embodiment of the present invention is provided.
Specific embodiment
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for
For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings other
Attached drawing.
Fig. 1 is a kind of method flow of the preparation method of side chain degradable polyurethane shown according to an exemplary embodiment
Figure, as shown in Figure 1, the preparation method of the side chain degradable polyurethane includes:
Step 101: 10 ~ 25 parts of polyether Glycols being dissolved in the first solvent and obtain reaction solution, then by the reaction solution liter
Temperature keeps the temperature 1 ~ 2h of stewing process to 110 ~ 120 °C after removing water using condensing reflux mode.
First solvent includes at least one of dimethylbenzene, toluene.
In a preferred embodiment, the polyether Glycols include polytetrahydrofuran ether dihydric alcohol PTMG, polycyclic oxygen
At least one of propane dihydric alcohol PPG, polyethylene oxide glycol PEG.
Step 102: the reaction solution after heat preservation stewing process is cooled to 60 ~ 90 °C, it is then different by 20 ~ 60 part two
Cyanate and 0.1 ~ 0.3 part of catalyst add to the reaction solution, after keeping 60 ~ 90 °C of reaction temperature to react 2 ~ 4 h, by 5 ~
15 parts of band carboxyl dihydric alcohols add to the reaction solution, continue 60 ~ 90 °C of holding of reaction temperature and react 2 ~ 4 h.
In a preferred embodiment, the diisocyanate includes 1, hexamethylene-diisocyanate HDI, toluene diisocyanate
Acid esters TDI, isophorone diisocyanate IPDI, naphthalene -1,5- diisocyanate NDI, methyl diphenylene diisocyanate MDI
At least one of.
In a preferred embodiment, the band carboxyl dihydric alcohol includes dimethylolpropionic acid, in dihydromethyl propionic acid
At least one.
In a preferred embodiment, the catalyst includes dibutyl tin dilaurate, lauric acid bismuth, isooctyl acid bismuth
At least one of.
Step 103: Xiang Suoshu reaction solution adds the second solvent and 1 ~ 10 part of chain extender respectively, keeps 60 ~ 90 °C anti-
Answer temperature to be reacted, during reaction in reaction solution described in the real time measure isocyanate group degree value, work as measurement
When the degree value of the isocyanate group is less than 0.01% out, the reaction solution is cooled to 20 ~ 30 °C, Xiang Suoshu
5 ~ 20 parts of Kocide SDs and 5 ~ 20 parts of organic acids are added in reaction solution, continue for the reaction solution to be warming up to 80 ~ 100 °C simultaneously
After reacting 5 ~ 7 h, the reaction solution is cooled to 40 ~ 60 °C and carries out revolving processing, side chain degradable poly ammonia is prepared
Ester.
In a kind of possible embodiment, the molecular formula for the side chain degradable polyurethane being prepared is as shown in Figure 2.
Second solvent is intensive polar solvent, and in a kind of preferred embodiment, the organic acid includes acetic acid, butyric acid
At least one of, second solvent includes at least one of n,N-Dimethylformamide DMF, dimethyl sulfoxide DMSO.
In order to improve the reaction efficiency of each component in reaction solution, the reaction solution is added in 1 ~ 10 part of chain extender
Afterwards, the ratio of isocyanate group described in the reaction solution and amino or hydroxy is 1, i.e. [- NCO]/[- OH or-NH2]=
1。
It is detected, 11 ~ 14 MPa of tensile strength for the side chain degradable polyurethane being prepared, elongation at break 100% ~
250%。
Wherein, revolving processing is for removing the minor amount of water in reaction solution after each component reaction, in the final product of formation
Part and part small molecule.
In a preferred embodiment, the chain extender be ethylenediamine, Putriscine, 1,5- pentanediamine, ethylene glycol,
1,4- butanediol, 1,6-HD, diglycol, 2- methyl-1, at least one of 3 propylene glycol.
It should be noted that the special construction of existing polyurethane determines that its degradation mode is main chain degradation, therefore, it is difficult to
Side-chain hydrolysis self refresh ability with similar acrylic resin, cannot keep the controlled release of anti-fouling agent, cause polyurethane anti-
The effect of antifouling phase of dirty coating is shorter；It is drop that degradation mode is the polyurethane-modified of chain degradation by above-mentioned preparation process by the present invention
Solution mode is the side chain degradable polyurethane of side-chain hydrolysis mode, so that the marine antifouling coating being prepared effectively be made to keep
While with corrosion-inhibiting coating compared with strong adhesion energy, additionally it is possible to possess lasting anti-pollution, to obtain excellent combination property
Marine antifouling coating.
The preparation method of side chain degradable polyurethane provided by the invention for ease of description, shows one kind shown in Fig. 3
The synthesis schematic diagram of side chain degradable polyurethane.
Fig. 4 is a kind of method flow diagram of the preparation method of marine antifouling coating shown according to an exemplary embodiment,
The raw material of the marine antifouling coating includes side chain degradable polyurethane as described above.As shown in figure 4, the marine antifouling coating
Preparation method includes:
Step 401: by 20 ~ 40 parts of side chain degradable polyurethanes, 25 ~ 46 parts of cuprous oxide, 1 ~ 5 part of copper pyrithione, 1 ~ 6 part of pyrrole
Pyridine thioketones zinc, 2 ~ 6 parts of chloro- 2- n-octyl -3- isothiazolinone of 4,5- bis-, 4 ~ 9 parts of auxiliary agents, 15 ~ 40 parts of solvents are uniformly mixed, and are obtained
To marine antifouling coating semi-finished product.
The solvent is at least one of dimethyl sulfoxide DMSO or N,N-dimethylformamide DMF.
Preferably, the auxiliary agent is at least one of pigment dispersing agent, defoaming agent, anti-settling agent, levelling agent.
Step 402: the marine antifouling coating semi-finished product are placed in high speed disperser after 1 ~ 2 h of high speed dispersion and are filtered,
Marine antifouling coating is obtained, the revolving speed of the high speed disperser is 1500 ~ 2000 r/min.
Wherein, the fineness of the marine antifouling coating is less than 100 μm.
Brought by side chain degradable polyurethane provided in order to better illustrate the present invention and its preparation method and application
Beneficial effect shows following embodiments 1 ~ 3 and is illustrated:
Embodiment 1
(1) by 10 parts of PEG100It is dissolved in dimethylbenzene and obtains reaction solution, the reaction solution is then warming up to 110 °C, use is cold
Stewing process 1h is kept the temperature after solidifying reflux type water removal.
(2) reaction solution after heat preservation stewing process is cooled to 60 °C, then by 35 parts of TDI and 0.1 part of February
Dilaurylate adds to the reaction solution, and after keeping 60 °C of reaction temperature reaction 2h, 11 parts of dihydromethyl propionic acids are added
To the reaction solution, continue to keep 75 °C of reaction temperature to react 2 h.
(3) Xiang Suoshu reaction solution adds DMF and 1.2 part of ethylene glycol respectively, so that isocyanates in the reaction solution
The ratio of base and hydroxy is 1, keeps 75 °C of reaction temperature to be reacted, during reaction in reaction solution described in the real time measure
The degree value of isocyanate group, when determining the degree value of the isocyanate group less than 0.01%, by institute
It states reaction solution and is cooled to 20 °C, 7.8 parts of Kocide SDs and 5 parts of acetic acid are added in Xiang Suoshu reaction solution, continue the reaction
After solution is warming up to 80 °C and reacts 5 h, the reaction solution is cooled to 40 °C and carries out revolving processing, side is prepared
Chain degradable polyurethane.
(4) by 30 parts of side chain degradable polyurethanes, 35 parts of cuprous oxide, 5 parts of copper pyrithiones, 4 parts of zinc pyrithione, 2
The chloro- 2- n-octyl -3- isothiazolinone of part 4,5- bis-, 6 parts of auxiliary agents, 18 parts of DMF are uniformly mixed, obtain marine antifouling coating half at
Product.
(5) the marine antifouling coating semi-finished product are placed in high speed disperser after 2 h of high speed dispersion and are filtered, obtain ocean
Antifouling paint, the revolving speed of the high speed disperser are 1500 r/min.
Embodiment 2
(1) by 10 parts of PPG100It is dissolved in toluene and obtains reaction solution, the reaction solution is then warming up to 115 °C, using condensation
Stewing process 1.5h is kept the temperature after reflux type water removal.
(2) reaction solution after heat preservation stewing process is cooled to 80 °C, then by 34 portions of HDI and 0.2 portion of laurels
Sour bismuth adds to the reaction solution, after keeping 80 °C of reaction temperature reaction 3h, 8.8 parts of dimethylolpropionic acids is added to described anti-
Solution is answered, continues to keep 80 °C of reaction temperature to react 2 h.
(3) Xiang Suoshu reaction solution adds DMSO and 3.6 part of butanediol respectively, so that isocyanates in the reaction solution
The ratio of base and hydroxy is 1, keeps 80 °C of reaction temperature to be reacted, during reaction in reaction solution described in the real time measure
The degree value of isocyanate group, when determining the degree value of the isocyanate group less than 0.01%, by institute
It states reaction solution and is cooled to 25 °C, 5.9 parts of Kocide SDs and 5.3 parts of butyric acid are added in Xiang Suoshu reaction solution, and continuing will be described anti-
After answering solution to be warming up to 80 °C and react 6 h, the reaction solution is cooled to 40 °C and carries out revolving processing, is prepared
Side chain degradable polyurethane.
(4) by 30 parts of side chain degradable polyurethanes, 30 parts of cuprous oxide, 4 parts of copper pyrithiones, 4 parts of zinc pyrithione, 3
The chloro- 2- n-octyl -3- isothiazolinone of part 4,5- bis-, 7 parts of auxiliary agents, 22 parts of DMSO are uniformly mixed, and obtain marine antifouling coating half
Finished product.
(5) the marine antifouling coating semi-finished product are placed in high speed disperser after 1.5 h of high speed dispersion and are filtered, obtain sea
Foreign antifouling paint, the revolving speed of the high speed disperser are 1800 r/min.
Embodiment 3
(1) by 20 parts of PPG200It is dissolved in dimethylbenzene and obtains reaction solution, the reaction solution is then warming up to 120 °C, use is cold
Stewing process 2h is kept the temperature after solidifying reflux type water removal.
(2) reaction solution after heat preservation stewing process is cooled to 80 °C, it is then different pungent by 34 parts HDI and 0.2 part
Sour bismuth adds to the reaction solution, after keeping 80 °C of reaction temperature reaction 4h, 9.4 parts of dihydromethyl propionic acids is added to described anti-
Solution is answered, continues to keep 80 °C of reaction temperature to react 4 h.
(3) Xiang Suoshu reaction solution adds DMF and 2.7 part of butanediol respectively, so that isocyanates in the reaction solution
The ratio of base and hydroxy is 1, keeps 80 °C of reaction temperature to be reacted, during reaction in reaction solution described in the real time measure
The degree value of isocyanate group, when determining the degree value of the isocyanate group less than 0.01%, by institute
It states reaction solution and is cooled to 30 °C, 6.9 parts of Kocide SDs and 6.2 parts of butyric acid are added in Xiang Suoshu reaction solution, and continuing will be described anti-
After answering solution to be warming up to 100 °C and react 7 h, the reaction solution is cooled to 40 °C and carries out revolving processing, is prepared
Side chain degradable polyurethane.
(4) by 40 parts of side chain degradable polyurethanes, 25 parts of cuprous oxide, 5 parts of copper pyrithiones, 4 parts of zinc pyrithione, 1
The chloro- 2- n-octyl -3- isothiazolinone of part 4,5- bis-, 5 parts of auxiliary agents, 20 parts of DMF are uniformly mixed, obtain marine antifouling coating half at
Product.
(5) the marine antifouling coating semi-finished product are placed in high speed disperser after 2 h of high speed dispersion and are filtered, obtain ocean
Antifouling paint, the revolving speed of the high speed disperser are 2000 r/min.
Each marine antifouling coating that above-described embodiment 1-3 is prepared is tested for the property, each reality tested
The performance test reference data for applying the marine anti-pollution coating of example offer is as follows.
Wherein, the degradation rate folding of side chain degradable polyurethane in each marine antifouling coating that Fig. 5 provides for embodiment 1-3
Line chart, Fig. 6 is the copper ion rate of release line chart for each marine antifouling coating that embodiment 1-3 is provided, in Fig. 5, Fig. 6, A generation
The corresponding broken line of table embodiment 1, B represent the corresponding broken line of embodiment 2, and C represents the corresponding broken line of embodiment 3.
In addition, the performance data of side chain degradable polyurethane is compared such as one institute of table in each marine antifouling coating that 1-3 is provided
Show:
Table one
The performance data comparison for each marine antifouling coating that embodiment 1-3 is provided is as shown in Table 2:
Table two
The correlation of the side chain degradable polyurethane and marine anti-pollution coating that are provided by each embodiment shown in above-mentioned table one, table two
For test data it is found that the physical property for the side chain degradable polyurethane that the embodiment of the present invention is prepared is stronger, degradation rate can
Control, is highly suitable to be applied for marine anti-pollution field, the marine antifouling coating being prepared using it is formed on oceanographic equipment surface
After marine anti-pollution coating, higher with the adhesive strength of oceanographic equipment corrosion-resistant coating, environmental adaptability is outstanding, and anti-pollution is compared
Conventional marine nonpolluting coating is more longlasting.
In conclusion a kind of side chain degradable polyurethane provided by the invention and its preparation method and application, passes through polyethers
Dihydric alcohol and di-isocyanate reaction form the segment that end group is isocyanates, then by itself and band carboxyl diol reaction, pass through
Chain extender is prepared into the carboxylic polyurethane of side chain, is prepared into side chain degradable polyurethane finally by Kocide SD neutralization, from
It and is mainly that the polyurethane-modified of main chain degradation can drop for the side chain that degradation mode is mainly side-chain hydrolysis mode by degradation mode
Polyurethane is solved, marine antifouling coating is low in oceanographic equipment surface adhesive strength, and anti-fouling effect is poor, antifouling persistence to solve
Low technical problem reaches and improves marine antifouling coating in oceanographic equipment surface adhesive strength, improves anti-fouling effect and antifouling phase
Imitate the technical effect of comprehensive performance.
Although having used general explanation, specific embodiment and test above, the present invention is described in detail,
But on the basis of the present invention, it can be modified or be improved, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.
Those skilled in the art will readily occur to of the invention other after considering specification and practice invention here
Embodiment.The present invention is directed to cover any variations, uses, or adaptations of the invention, these modifications, purposes or
Adaptive change follow general principle of the invention and including the undocumented common knowledge in the art of the present invention or
Conventional techniques.It should be understood that the invention is not limited to the accurate knots for being described above and being shown in the accompanying drawings
Structure, and various modifications and changes may be made without departing from the scope thereof.
Claims (10)
1. a kind of preparation method of side chain degradable polyurethane, which is characterized in that the described method includes:
10 ~ 25 parts of polyether Glycols are dissolved in the first solvent and obtain reaction solution, the reaction solution is then warming up to 110 ~
120 °C, 1 ~ 2h of stewing process is kept the temperature after removing water using condensing reflux mode, first solvent includes dimethylbenzene, in toluene
It is at least one；
The reaction solution after stewing process will be kept the temperature and be cooled to 60 ~ 90 °C, then by 20 ~ 60 parts of diisocyanate and 0.1 ~
0.3 part of catalyst adds to the reaction solution, after keeping 60 ~ 90 °C of reaction temperature to react 2 ~ 4 h, by 5 ~ 15 parts of band carboxyls two
First alcohol adds to the reaction solution, continues 60 ~ 90 °C of holding of reaction temperature and reacts 2 ~ 4 h；
The second solvent and 1 ~ 10 part of chain extender are added respectively to the reaction solution, and 60 ~ 90 °C of reaction temperature is kept to carry out instead
Answer, during reaction in reaction solution described in the real time measure isocyanate group degree value, when determining the isocyanic acid
When the degree value of ester group is less than 0.01%, the reaction solution is cooled to 20 ~ 30 °C, Xiang Suoshu reaction solution is added 5
~ 20 parts of Kocide SDs and 5 ~ 20 parts of organic acids continue after the reaction solution to be warming up to 80 ~ 100 °C and reacts 5 ~ 7 h, will
The reaction solution is cooled to 40 ~ 60 °C and carries out revolving processing, and side chain degradable polyurethane, second solvent is prepared
Including at least one of N,N-dimethylformamide DMF, dimethyl sulfoxide DMSO.
2. the method according to claim 1, wherein the band carboxyl dihydric alcohol includes dimethylolpropionic acid, two
At least one of hydroxymethyl propionic acid.
3. the method according to claim 1, wherein the catalyst includes dibutyl tin dilaurate, laurel
At least one of sour bismuth, isooctyl acid bismuth.
4. the method according to claim 1, wherein the polyether Glycols include polytetrahydrofuran ether dihydric alcohol
At least one of PTMG, polypropylene oxide glycol PPG, polyethylene oxide glycol PEG.
5. the method according to claim 1, wherein the diisocyanate include 1, hexamethylene-diisocyanate
HDI, toluene di-isocyanate(TDI) TDI, isophorone diisocyanate IPDI, naphthalene -1,5- diisocyanate NDI, diphenyl methane
At least one of diisocyanate MDI.
6. the method according to claim 1, wherein the chain extender is ethylenediamine, Putriscine, 1,5- penta
Diamines, ethylene glycol, 1,4- butanediol, 1,6-HD, diglycol, 2- methyl-1, at least one of 3 propylene glycol.
7. a kind of side chain degradable polyurethane, which is characterized in that the side chain degradable polyurethane is by any institute of claim 1 ~ 6
The preparation method for stating side chain degradable polyurethane is prepared, 11 ~ 14 MPa of tensile strength of the side chain degradable polyurethane,
Elongation at break 100% ~ 250%.
8. a kind of application of side chain degradable polyurethane as claimed in claim 7, which is characterized in that the side chain degradable poly ammonia
Ester is applied to the preparation of marine antifouling coating, and the preparation method of the marine antifouling coating includes:
By 20 ~ 40 parts of side chain degradable polyurethanes, 25 ~ 46 parts of cuprous oxide, 1 ~ 5 part of copper pyrithione, 1 ~ 6 part of pyridine sulphur
Ketone zinc, 2 ~ 6 parts of chloro- 2- n-octyl -3- isothiazolinone of 4,5- bis-, 4 ~ 9 parts of auxiliary agents, 15 ~ 40 parts of solvents are uniformly mixed, and obtain sea
Foreign antifouling paint semi-finished product, the solvent are at least one of dimethyl sulfoxide DMSO or n,N-Dimethylformamide DMF；
The marine antifouling coating semi-finished product are placed in high speed disperser after 1 ~ 2 h of high speed dispersion and are filtered, marine anti-pollution is obtained
Coating, the revolving speed of the high speed disperser are 1500 ~ 2000 r/min.
9. according to the method described in claim 8, it is characterized in that, the auxiliary agent be pigment dispersing agent, defoaming agent, anti-settling agent,
At least one of levelling agent.
10. a kind of marine antifouling coating, which is characterized in that the marine antifouling coating is by any ocean of claim 8 ~ 9
The preparation method of antifouling paint is prepared, and the fineness of the marine antifouling coating is less than 100 μm.
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| CN111234162A (en) * | 2020-03-19 | 2020-06-05 | 嘉兴学院 | Side chain grafted glyphosate degradable polyurethane and preparation method and application thereof |
| CN113913100A (en) * | 2021-10-26 | 2022-01-11 | 哈尔滨工程大学 | Polypyrrole-graphene/polyurethane antifouling paint, and preparation method and application thereof |
| CN114456699A (en) * | 2022-03-01 | 2022-05-10 | 嘉兴学院 | Seawater alternation resistant marine antifouling paint and preparation method thereof |
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| CN114456699A (en) * | 2022-03-01 | 2022-05-10 | 嘉兴学院 | Seawater alternation resistant marine antifouling paint and preparation method thereof |
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