CN109593451B - Bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating and preparation method and application thereof - Google Patents

Bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating and preparation method and application thereof Download PDF

Info

Publication number
CN109593451B
CN109593451B CN201811384640.1A CN201811384640A CN109593451B CN 109593451 B CN109593451 B CN 109593451B CN 201811384640 A CN201811384640 A CN 201811384640A CN 109593451 B CN109593451 B CN 109593451B
Authority
CN
China
Prior art keywords
bisphenol
cyclic carbonate
isocyanate polyurethane
polyurethane coating
hydrophobic
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.)
Active
Application number
CN201811384640.1A
Other languages
Chinese (zh)
Other versions
CN109593451A (en
Inventor
瞿金清
吴志军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CN201811384640.1A priority Critical patent/CN109593451B/en
Publication of CN109593451A publication Critical patent/CN109593451A/en
Application granted granted Critical
Publication of CN109593451B publication Critical patent/CN109593451B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
    • C08G71/04—Polyurethanes
    • 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
    • C09D5/08—Anti-corrosive paints

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a bisphenol AF-based hydrophobic oleophobicA non-isocyanate polyurethane coating and a preparation method and application thereof; the method takes bisphenol AF and perfluoro epoxy compound as raw materials in CO2Synthesizing bisphenol AF and perfluorocyclic carbonate under atmosphere, and further preparing a high-performance non-isocyanate polyurethane coating with different amine curing agents; wherein the preparation of the bisphenol AF-based cyclic carbonate: adding bisphenol AF epoxy cyclic oxide into a high-pressure reaction kettle, adding a bi-organic solvent and a catalyst, introducing carbon dioxide to maintain the pressure at 0.5-4.0Mpa, reacting, controlling the reaction temperature at 60-180 ℃, and reacting for 2-40 h; the coating of the non-isocyanate polyurethane prepared by the invention has very good hydrophobic, oleophobic and corrosion resistant properties, and also has high hardness, excellent impact resistance and chemical resistance, and is expected to become a multifunctional coating for replacing the traditional polyurethane.

Description

Bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating and preparation method and application thereof
Technical Field
The invention relates to non-isocyanate polyurethane, in particular to a bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating and a preparation method and application thereof.
Background
Polyurethane (PU) is one of the most important polymer materials, and because of its excellent properties, it is used to make plastics, foams, elastomers, leathers, adhesives, sealants, coatings, etc. and is applied to the fields of buildings, electronic products, airplanes, cruise ships, furniture, etc. In the traditional polyurethane preparation, diisocyanate is used as one of the starting materials, the diisocyanate is synthesized by a toxic phosgene method, the diisocyanate contains a toxic-NCO functional group, the diisocyanate cannot contain moisture when synthesizing PU, the storage, safety, transportation and cost increase are influenced due to the side reaction of water and-NCO, and the most important reason is that the traditional PU is toxic and has large pollution to the environment. Therefore, it is urgently needed to develop an isocyanate-free environment-friendly polyurethane to replace the traditional PU.
The non-isocyanate polyurethane coating (NIPU) does not contain toxic-NCO and consumes a large amount of greenhouse gas CO2The material is an environment-friendly material and has a very wide application prospect. Is expected to replace the application of the traditional PU in the fields of coatings, adhesives, foams, sealants and the like.
The Chinese patent application CN 102718964A discloses that non-isocyanate polyurethane is prepared by synthesizing corresponding binary cyclic carbonate by using polyether glycol diglycidyl ether as a raw material. However, the coating prepared by the application has no hydrophobic and oleophobic performance and no corrosion resistance. Therefore, there is a need to develop multifunctional non-isocyanate polyurethane coatings and to increase the range of applications of non-isocyanate polyurethanes.
Disclosure of Invention
The invention aims to provide a bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating with excellent physical properties, chemical resistance and thermal stability as well as good hydrophobic and oleophobic and corrosion resistance and a preparation method thereof.
The invention also aims to provide the application of the bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating in anticorrosion coating and industrial paint.
Firstly, synthesizing bisphenol AF cyclic carbonate and perfluorocyclic carbonate, and then curing the bisphenol AF cyclic carbonate and perfluorocyclic carbonate with different diamines to form a film; the invention uses double AF and perfluoro epoxy resin as raw materials, inserts carbon dioxide by a high pressure method to prepare double AF and perfluoro cyclic carbonate, and then cures with different amines to prepare a series of non-isocyanate polyurethane coatings.
The purpose of the invention is realized by the following technical scheme:
the preparation method of the bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating comprises the following steps:
1) preparation of bisphenol AF-based cyclic carbonate: adding a bisphenol AF-based epoxy compound into a high-pressure reaction kettle, adding an organic solvent accounting for 0-100% of the mass of the bisphenol AF-based epoxy compound, adding a catalyst, introducing carbon dioxide to maintain the pressure at 0.5-4.0Mpa, reacting at the reaction temperature of 60-180 ℃ for 2-40h to obtain the bisphenol AF-based epoxy carbonate; the dosage of the catalyst in the step is 0.5 to 5.0 percent of the mass of the bisphenol AF-based epoxy resin;
2) preparation of perfluorocyclic carbonate: adding a perfluorinated epoxy compound into a high-pressure reaction kettle, adding an organic solvent accounting for 0-100% of the mass of the bisphenol AF-based epoxy compound, adding a catalyst, introducing carbon dioxide to maintain the pressure at 0.5-4.0Mpa, reacting at the reaction temperature of 60-180 ℃ for 2-40h to obtain perfluorinated cyclic carbonate; the dosage of the catalyst in the step is 0.5 to 5.0 percent of the mass of the perfluorooctyl epoxy resin;
3) preparation of bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating (NIPU): uniformly stirring bisphenol AF-based cyclic carbonate and perfluorocyclic carbonate with a diamine or polyamine curing agent, an organic solvent and a defoaming agent at room temperature to obtain a bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating; spraying the bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating, baking and curing to form a film to obtain a bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating;
the catalyst in the steps 1) and 2) is one or a mixture of tetrabutylammonium bromide, lithium chloride, lithium bromide and tetrabutylammonium chloride.
The content of the perfluorocyclic carbonate in the coating is 0.1-10 wt%;
the molar ratio of the primary amine of the diamine or polyamine curing agent to the cyclic carbonate functional groups of the bisphenol AF-based cyclic carbonates and perfluorocyclic carbonates is NH2: carbonate 0.9-1.2: 1.
In order to further achieve the object of the present invention, preferably, the diamine curing agent is one or a mixture of two or more of ethylenediamine, butanediamine, hexanediamine, 1, 8-octanediamine, decanediamine, 1, 12-dodecanediamine, isophoronediamine, p-phenylenediamine, polyethyleneimine and polyether diamine; the polyamine curing agent is one or more than two of polyethyleneimine PEI, triethylene tetramine, tetraethylene pentamine and the like.
Preferably, the epoxy value of the bisphenol AF-based epoxy compound is one or more of 0.2, 0.44, 0.38 and 0.51.
Preferably, the defoaming agent is one or a mixture of more than two of BYK-R605, TEGO Airex 900 and TEGO Airex 962, and accounts for 0.5-1% of the mass of the raw materials.
Preferably, the organic solvent in the steps 1), 2) and 3) is one or a mixture of more than two of 1-ethyl-2-pyrrolidone (NEP), dimethyl sulfoxide (DMSO), Dimethylformamide (DMF), 1-methyl-2-pyrrolidone (NMP) and acetonitrile, and the total amount is 30-100% of the mass of the cyclic carbonate.
Preferably, the temperature for baking, curing and film forming in the step 3) is 60-150 ℃, and the time for baking, curing and film forming is 0.5-8 h.
A bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating is prepared by the preparation method.
The application of the bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating in the anticorrosive coating is characterized in that the static contact angle of the coating film to water is 85-115 degrees, the static contact angle to Dicrepresentative methane is 45-80 degrees, the static contact angle to hexadecane is 40-73 degrees, the hardness of the coating film is F-2H, the impact resistance is more than or equal to 50cm.kg, and the adhesive force is 0 grade; the flexibility is 1 grade, the coating film is not changed in more than 800 hours of 10wt% NaCl solution, and the 60-degree glossiness of the coating film is more than 90%.
The mechanism for synthesizing the bisphenol AF-based cyclic carbonate compound by the bisphenol AF epoxy resin is as follows:
Figure BDA0001872686770000031
the mechanism for synthesizing perfluorooctyl cyclic carbonate compounds from perfluorooctyl epoxy resin is as follows:
Figure BDA0001872686770000032
the basic principle of the invention is as follows: mechanism of reaction of bisphenol AF cyclic carbonates with amines: the first step is nucleophilic attack of the amine on the bisphenol AF cyclic carbonate to form a tetrahedral intermediate, and the second amine molecule attacks the tetrahedral intermediate formed in the first step again, losing one proton H+The oxygen anion in the third stage is rapidly reacted with H due to unstable breaking of carbon-oxygen bond and high electron cloud density of nitrogen atom+2Alcohol is formed and the final product is the carbamate with-OH NIPU. Cyclic carbonate and diamine generate non-isocyanate polyurethane coating under the condition of 60-150 ℃. The non-isocyanate coating film synthesized by the action of the synthesized bisphenol AF cyclic carbonate and various amines has excellent adhesion and very good coating filmCompared with the traditional non-isocyanate polyurethane, the hydrophobic and oleophobic polyurethane has better hydrophobic and oleophobic performances and corrosion resistance.
Compared with the prior art, the preparation method of the bisphenol AF-based non-isocyanate polyurethane coating has the following advantages:
(1) the bisphenol AF-based non-isocyanate polyurethane coating prepared by the invention has excellent physical properties, chemical resistance and thermal stability; the hardness of the obtained coating is F-2H, the impact resistance is more than or equal to 50cm.kg, and the adhesive force is 0 grade; the flexibility is 1 grade, the coating film is not changed in more than 800 hours of 10wt% NaCl solution, and the 60-degree glossiness of the coating film is more than 90%.
(2) According to the invention, different diamines and polyamines can be compounded according to the requirements of the coating performance to achieve the required performance;
(3) the bisphenol AF/perfluorocyclic carbonate prepared by the high-pressure method has high yield which is close to 100 percent.
(4) The bisphenol AF-based non-isocyanate polyurethane coating prepared by the method has good hydrophobic, oleophobic and corrosion resistant properties. The static contact angle of the coating film obtained by the invention to water is 85-115 degrees, the static contact angle to the Dicranostic methane is 45-80 degrees, and the static contact angle to hexadecane is 40-73 degrees.
Drawings
FIG. 1 is an infrared spectrum of perfluorooctyl epoxy resin (PFGE) and perfluorooctyl cyclic carbonate (PFGC) of example 1.
FIG. 2 is an infrared spectrum of bisphenol AF-based epoxy resin (E-AF), bisphenol AF-based cyclic carbonate (EC-AF) and NIPU-1 of example 1.
Detailed Description
For a better understanding of the present invention, the present invention will be further described with reference to the accompanying drawings and examples, but the embodiments of the present invention are not limited thereto.
The relevant test methods in the examples are as follows:
the coating performance is respectively tested according to GB/T9754-2007, GB/T6739-2006, GB/T1731-1993, GB/T20624.2-2006, GB/T9286-1998 and GB/T2893.1-2005, the coating is the gloss, pencil hardness, flexibility, impact resistance, adhesion and chemical resistance of the coating, the pencil is a high-grade drawing pencil produced by Shanghai China pencil factory, and all instruments are produced by Tianjin Ministry of Fine materials testing machine factory.
Example 1
Referring to table 1, a method for preparing a bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating comprises the following steps:
(1) preparation of bisphenol AF cyclic carbonate compound: adding bisphenol AF epoxy resin and tetrabutylammonium bromide (the addition amount is 0.5 percent of the mass of the epoxy resin) into a high-pressure reaction kettle, introducing carbon dioxide (the pressure is maintained at 1.0MPa) to react for 24 hours at 120 ℃, cooling and relieving pressure to obtain the bisphenol AF cyclic carbonate compound.
(2) Preparation of perfluorooctyl cyclic carbonate compound: adding perfluorooctyl epoxy resin and tetrabutylammonium bromide (the addition amount is 0.5 percent of the mass of the epoxy resin) into a high-pressure reaction kettle, introducing carbon dioxide (the pressure is maintained at 1.0MPa) to react for 24 hours at 120 ℃, cooling and relieving pressure to obtain the perfluorooctyl cyclic carbonate compound.
The perfluorooctyl epoxy resin, the perfluorooctyl cyclic carbonate, the bisphenol AF cyclic carbonate and the bisphenol AF cyclic epoxy resin prepared by the embodiment of the invention and the synthesized bisphenol AF-based non-isocyanate polyurethane thereof are characterized by the following methods: the structures of bisphenol AF-based epoxy resin, bisphenol AF-based cyclic carbonate, perfluorooctyl epoxy resin, perfluorooctyl cyclic carbonate and bisphenol AF-based non-isocyanate polyurethane NIPU are tested by a Spectrum 2000 Fourier infrared spectrometer, and the test results are shown in figure 1 and figure 2;
FIG. 1 is an infrared spectrum of perfluorooctyl epoxy resin (PFGE) and perfluorooctyl cyclic carbonate (PFGC) of example 1. As can be seen from the infrared spectrum 1, the epoxy characteristic peak of the epoxy resin in PFGE completely disappears, and a very obvious cyclic carbonate characteristic peak appears in PFGC, which indicates that the conversion rate of perfluorooctyl cyclic carbonate synthesized in this example is close to 100%; infrared Spectroscopy (PFGE: Perfluorooctyl epoxy resin, PFGC: Perfluorooctyl cyclocarbonate)
FIG. 2 is an infrared spectrum of bisphenol AF-based epoxy, bisphenol AF-based cyclic carbonate and NIPU-1 of example 1. The epoxy characteristic peak of the epoxy resin in E-AF in the infrared spectrum of FIG. 2 completely disappears, and a very distinct cyclic carbonate characteristic peak appears in EC-AF, which indicates that the conversion rate of the bisphenol AF-based cyclic carbonate synthesized in the present example is close to 100%; and the characteristic peak of the cyclic carbonate of the NIPU-1 completely disappears, and the characteristic peak of the carbamate appears, which indicates that the bisphenol AF cyclic carbonate and the diamine are completely cured to produce the bisphenol AF-based non-isocyanate polyurethane. Infrared spectrum (E-AF bisphenol AF epoxy resin, EC-AF bisphenol AF cyclic carbonate)
(3) Preparation of bisphenol AF-based non-isocyanate polyurethane coating (NIPU-1): according to the formula of table 1, the bisphenol AF cyclic carbonate, perfluorooctyl cyclic carbonate, dimethyl formamide (DMF), isophorone diamine curing agent and defoaming agent are uniformly stirred at room temperature, sprayed and cured for 6 hours at 120 ℃ to obtain the epoxy resin.
The formula is as follows:
TABLE 1
Figure BDA0001872686770000051
(4) Film coating Performance results were compared with that of Corsai Arcol Polyol 3553 polyester Polyol (curing agent is Duranate manufactured by Asahi Kasei Co., Ltd., Japan)TMHDI) and a Dow epoxy resin D.E.RTM331 coating film properties are shown in table 2 below.
From table 2, it can be seen that the bisphenol AF based non-isocyanate polyurethane coating of the present invention has better gloss than the two-component polyurethane coating; compared with the epoxy resin D.E.R, the inventionTM331 are better at gloss, impact strength and adhesion. The invention is superior to the adhesive force and the water resistance. The static contact angle of the invention to water, diiodomethane and n-hexadecane is far larger than that of epoxy resin D.E.RTM331, the invention has good hydrophobic and oleophobic effects, and the hardness and adhesion of the coating can reflect that the bisphenol AF-based non-isocyanate polyurethane coating prepared by the method has excellent physical properties; the water contact angle and the Didian methane and hexadecane contact angle are large, the hydrophobic and oleophobic properties are good, and the system is corrosion resistantThe bisphenol AF-based non-isocyanate polyurethane coating prepared by the method has excellent chemical resistance; meanwhile, as shown in Table 2, the bisphenol AF-based non-isocyanate polyurethane coating prepared by the method has good corrosion resistance.
TABLE 2
Figure BDA0001872686770000061
The invention reduces the production cost; and the invention uses CO2The raw materials consume greenhouse gases, and are green and environment-friendly.
According to specific performance requirements, short-chain amine or long-chain amine can be selected for compounding, and the hardness of a coating prepared from long-chain amine is softer than that of the short-chain amine.
The performance characteristics of the bisphenol AF-based non-isocyanate polyurethane coating layer in the embodiment enable the bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane to be used in the aspects of anticorrosive coatings and the like.
Example 2
Referring to table 3, a method for preparing a bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating includes the following steps:
(1) preparation of bisphenol AF cyclic carbonate compound: adding bisphenol AF epoxy resin and a catalyst lithium chloride (the addition amount is 1.0 percent of the mass of the epoxy resin) into a high-pressure reaction kettle, introducing carbon dioxide, maintaining the pressure at 1.5MPa, reacting for 24 hours at 130 ℃, cooling and relieving pressure to obtain the bisphenol AF cyclic carbonate.
(2) Preparation of perfluorooctyl cyclic carbonate compound: adding perfluorooctyl epoxy resin and a catalyst lithium chloride (the addition amount is 1.0 percent of the mass of the epoxy resin) into a high-pressure reaction kettle, introducing carbon dioxide (the pressure is maintained at 1.5MPa) to react for 24 hours at 120 ℃, cooling and relieving pressure to obtain the perfluorooctyl cyclic carbonate compound.
(3) Preparation of non-isocyanate polyurethane coating (NIPU-2): according to the formula of table 3, the perfluorooctyl cyclic carbonate, bisphenol AF cyclic carbonate, 1-ethyl-2-pyrrolidone (NEP) (the addition amount is 40% of the total mass of the coating), butanediamine curing agent and defoaming agent TEGO Airex 90 are sprayed after being stirred uniformly at room temperature, and the coating is cured at 130 ℃.
The formula is as follows:
TABLE 3
Figure BDA0001872686770000071
(3) The results of the film property comparison are shown in the following table 4:
TABLE 4
Figure BDA0001872686770000072
Example 3
Referring to table 5, a method for preparing a bisphenol AF based hydrophobic and oleophobic non-isocyanate polyurethane coating includes the following steps:
(1) preparation of bisphenol AF cyclic carbonate compound: adding bisphenol AF epoxy resin and a catalyst lithium bromide (the addition amount is 1.5 percent of the mass of the epoxy resin) into a high-pressure reaction kettle, introducing carbon dioxide, maintaining the pressure at 1.2MPa, reacting for 24 hours at 140 ℃, cooling and relieving pressure to obtain the bisphenol AF cyclic carbonate.
(2) Preparation of non-isocyanate polyurethane coating (NIPU-3): according to the formulation of table 5, the bisphenol AF cyclic carbonate, perfluorooctyl cyclic carbonate compound (perfluorooctyl cyclic carbonate compound obtained in step (2) of example 2), dimethyl sulfoxide (DMSO) (added in an amount of 55% of the total mass of the coating material), butanediamine curing agent and antifoaming agent TEGO Airex 962 were sprayed and cured at 130 ℃.
The formula is as follows:
TABLE 5
Figure BDA0001872686770000081
(3) The results of the film property comparison are shown in the following table 6:
TABLE 6
Figure BDA0001872686770000082
Figure BDA0001872686770000091
Example 4
Referring to table 7, a method for preparing a bisphenol AF based hydrophobic and oleophobic non-isocyanate polyurethane coating includes the following steps:
(1) preparation of bisphenol AF cyclic carbonate compound: adding bisphenol AF epoxy resin and tetrabutyl ammonium chloride (the addition amount is 2.0 percent of the mass of the epoxy resin) serving as a catalyst into a high-pressure reaction kettle, introducing carbon dioxide, maintaining the pressure at 2.0MPa, reacting for 36 hours at 120 ℃, cooling and relieving pressure to obtain the bisphenol AF cyclic carbonate.
(2) Preparation of perfluorooctyl cyclic carbonate compound: adding perfluorooctyl epoxy resin and tetrabutylammonium bromide (the addition amount is 2.0 percent of the mass of the epoxy resin)) into a high-pressure reaction kettle, introducing carbon dioxide (the pressure is maintained at 2.0MPa) to react for 24 hours at 120 ℃, cooling and relieving pressure to obtain the perfluorooctyl cyclic carbonate compound.
(3) Preparation of non-isocyanate polyurethane coating (NIPU-4): according to the formula of table 7, the perfluorooctyl cyclic carbonate, bisphenol AF cyclic carbonate, Dimethylformamide (DMF) (added in an amount of 55% of the total mass of the coating) and the decamethylene diamine curing agent and the antifoaming agent TEGO Airex 962 were uniformly stirred at room temperature, sprayed, and cured at 130 ℃.
The formula is as follows:
TABLE 7
Figure BDA0001872686770000092
(4) The results of the film property test are shown in the following table 8:
TABLE 8
Figure BDA0001872686770000093
Figure BDA0001872686770000101
Example 5
Referring to table 9, a method for preparing a bisphenol AF based hydrophobic oleophobic non-isocyanate polyurethane coating includes the following steps:
(1) preparation of bisphenol AF cyclic carbonate compound: adding bisphenol AF epoxy resin and tetrabutylammonium bromide (the addition amount is 1.5 percent of the mass of the epoxy resin) into a high-pressure reaction kettle, introducing carbon dioxide, maintaining the pressure at 3MPa, reacting at 120 ℃ for 18 hours, cooling and relieving pressure to obtain the bisphenol AF cyclic carbonate compound.
(2) Preparation of perfluorooctyl cyclic carbonate compound: adding perfluorooctyl epoxy resin and tetrabutylammonium bromide (the addition amount is 1.5 percent of the mass of the epoxy resin) into a high-pressure reaction kettle, introducing carbon dioxide (the pressure is maintained at 2.0MPa) to react for 24 hours at 120 ℃, cooling and relieving pressure to obtain the perfluorooctyl cyclic carbonate compound.
(3) Preparation of non-isocyanate polyurethane coating (NIPU-5): according to the formula of Table 9, perfluorooctyl cyclic carbonate, bisphenol AF cyclic carbonate, dimethyl formamide (DMF) (the addition amount is 50 percent of the total mass of the coating), a 1, 12-alkyl diamine curing agent and a defoaming agent TEGO Airex 962 are sprayed after being stirred uniformly at room temperature and cured at 110 ℃.
The formula is as follows:
TABLE 9
Figure BDA0001872686770000102
(4) The results of the film property test are shown in the following table 10:
watch 10
Figure BDA0001872686770000111
Example 6
Referring to table 11, a method for preparing a bisphenol AF based hydrophobic oleophobic non-isocyanate polyurethane coating includes the following steps:
(1) preparation of bisphenol AF cyclic carbonate compound: adding bisphenol AF epoxy resin and tetrabutylammonium bromide (the addition amount is 2.0 percent of the mass of the epoxy resin) into a high-pressure reaction kettle, introducing carbon dioxide, maintaining the pressure at 4MPa, reacting for 35 hours at 100 ℃, cooling and relieving pressure to obtain the bisphenol AF cyclic carbonate compound.
(2) Preparation of perfluorooctyl cyclic carbonate compound: adding perfluorooctyl epoxy resin and tetrabutylammonium bromide (the addition amount is 2.5 percent of the mass of the epoxy resin) into a high-pressure reaction kettle, introducing carbon dioxide (the pressure is maintained at 4.0MPa) to react for 35 hours at 120 ℃, cooling and relieving pressure to obtain the perfluorooctyl cyclic carbonate compound.
(3) Preparation of non-isocyanate polyurethane coating (NIPU-6): according to the formula of table 11, the perfluorooctyl cyclic carbonate, the bisphenol AF cyclic carbonate compound, acetonitrile (the addition amount is 50% of the total mass of the coating), the tetraethylenepentamine curing agent and the antifoaming agent TEGO Airex 962 are uniformly stirred at room temperature, sprayed and cured at 110 ℃.
The formula is as follows:
TABLE 11
Figure BDA0001872686770000112
Figure BDA0001872686770000121
(4) The film properties results are given in table 12 below:
TABLE 12
Figure BDA0001872686770000122
The above embodiments are merely representative implementations for illustrating the technical idea of the present invention, and the scope of the present invention should not be limited thereby, and any modifications made on the basis of the technical solution according to the technical idea of the present invention are within the scope of the present invention.

Claims (8)

1. The preparation method of the bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating is characterized by comprising the following steps:
1) preparation of bisphenol AF-based cyclic carbonate: adding bisphenol AF-based epoxy resin into a high-pressure reaction kettle, adding an organic solvent with the amount of 0-100% of that of the bisphenol AF-based epoxy resin, adding a catalyst, introducing carbon dioxide to maintain the pressure at 0.5-4.0Mpa, reacting at the temperature of 60-180 ℃ for 2-40h to obtain bisphenol AF-based cyclic carbonate; the dosage of the catalyst in the step is 0.5 to 5.0 percent of the mass of the bisphenol AF-based epoxy resin;
2) preparation of perfluorooctyl cyclic carbonate: adding perfluorooctyl epoxy resin into a high-pressure reaction kettle, adding an organic solvent accounting for 0-100% of the mass of the bisphenol AF epoxy compound, adding a catalyst, introducing carbon dioxide to maintain the pressure at 0.5-4.0Mpa, reacting for 2-40h at the reaction temperature of 60-180 ℃ to obtain perfluorooctyl cyclic carbonate; the dosage of the catalyst in the step is 0.5 to 5.0 percent of the mass of the perfluorooctyl epoxy resin;
3) preparation of bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating: uniformly stirring bisphenol AF-based cyclic carbonate and perfluorooctyl cyclic carbonate with diamine or polyamine curing agent, organic solvent and defoaming agent at room temperature to obtain bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating; spraying the bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating, baking and curing to form a film to obtain a bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating;
the catalyst in the steps 1) and 2) is one or a mixture of tetrabutylammonium bromide, lithium chloride, lithium bromide and tetrabutylammonium chloride;
the content of the perfluorooctyl cyclic carbonate in the coating is 1 to 10 weight percent;
the molar ratio of the primary amine of the diamine or polyamine curing agent to the cyclic carbonate functional groups of the bisphenol AF-based cyclic carbonate and the perfluorooctyl cyclic carbonate is NH2: carbonate =0.9-1.2: 1.
2. The method for preparing the hydrophobic and oleophobic non-isocyanate polyurethane coating of claim 1, wherein the diamine curing agent is one or a mixture of more than two of ethylenediamine, butanediamine, hexanediamine, 1, 8-octanediamine, decanediamine, 1, 12-dodecanediamine, isophorone diamine, p-phenylenediamine, polyethyleneimine and polyether diamine; the polyamine curing agent is one or more than two of polyethyleneimine PEI, triethylene tetramine and tetraethylene pentamine.
3. The method of claim 1, wherein the epoxy value of the bisphenol AF-based hydrophobic oleophobic non-isocyanate polyurethane coating is one or more of 0.2, 0.44, 0.38 and 0.51.
4. The preparation method of the bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating as claimed in claim 1, wherein the defoaming agent is one or a mixture of more than two of BYK-R605, TEGO Airex 900 and TEGO Airex 962, and accounts for 0.5-1% of the mass of the raw materials.
5. The method for preparing the hydrophobic and oleophobic non-isocyanate polyurethane coating based on the bisphenol AF group in claim 1, wherein the organic solvent in the steps 1), 2) and 3) is one or a mixture of more than two of 1-ethyl-2-pyrrolidone, dimethyl sulfoxide, dimethylformamide, 1-methyl-2-pyrrolidone and acetonitrile, and the total amount is 30-100% of the mass of the cyclic carbonate.
6. The preparation method of the bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating according to claim 1, wherein the baking and curing film forming temperature in the step 3) is 60-150 ℃, and the baking and curing film forming time is 0.5-8 h.
7. A hydrophobic and oleophobic non-isocyanate polyurethane coating based on bisphenol AF, characterized in that it has been obtained by the method of preparation according to any one of claims 1 to 6.
8. The use of bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating according to claim 7 in protection againstThe application of the anticorrosive paint is characterized in that the static contact angle of a coating film to water is 85-115oThe static contact angle to the classical methane is 45-80oThe static contact angle to hexadecane is 40-73oThe hardness of the coating film is F-2H, the impact resistance is more than or equal to 50cm.kg, and the adhesive force is 0 grade; the flexibility is 1 grade, the coating film is not changed in more than 800 hours of 10wt% NaCl solution, and the 60-degree glossiness of the coating film is more than 90%.
CN201811384640.1A 2018-11-20 2018-11-20 Bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating and preparation method and application thereof Active CN109593451B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811384640.1A CN109593451B (en) 2018-11-20 2018-11-20 Bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811384640.1A CN109593451B (en) 2018-11-20 2018-11-20 Bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN109593451A CN109593451A (en) 2019-04-09
CN109593451B true CN109593451B (en) 2020-07-28

Family

ID=65960184

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811384640.1A Active CN109593451B (en) 2018-11-20 2018-11-20 Bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN109593451B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113336949B (en) * 2021-06-21 2023-03-28 岭南师范学院 Amino organic silicon-based pentaerythritol cyclic carbonate and preparation method and application thereof
CN113881039B (en) * 2021-10-21 2022-11-15 北京化工大学 Preparation method of aromatic bicyclic carbonate and hybrid non-isocyanate polyurethane
CN115820090B (en) * 2022-11-14 2024-04-05 中国科学院山西煤炭化学研究所 Single-component hybrid non-isocyanate polyurethane coating and preparation method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110143138A1 (en) * 2009-12-10 2011-06-16 3M Properties Company Perfluoroelastomer bonding
CN108659689A (en) * 2018-04-12 2018-10-16 华南理工大学 A kind of sorb alcohol radical non-isocyanate polyurethane coating and preparation method thereof

Also Published As

Publication number Publication date
CN109593451A (en) 2019-04-09

Similar Documents

Publication Publication Date Title
CN109593451B (en) Bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating and preparation method and application thereof
Figovsky et al. Recent advances in the development of non-isocyanate polyurethanes based on cyclic carbonates
US9593258B2 (en) Modified glycidyl carbamate resins
Figovsky et al. Advances in the field of nonisocyanate polyurethanes based on cyclic carbonates
CN108659689A (en) A kind of sorb alcohol radical non-isocyanate polyurethane coating and preparation method thereof
CN100575380C (en) Polyurethane acrylate resin and epoxy coating with polyurethane acrylate resin
CN103013322B (en) Preparation method of epoxy non-isocyanate polyurethane heavy anti-corrosion coating
US9550748B2 (en) Cyclic carbonate monomers and polymers prepared therefrom
CA2767784C (en) Method of producing hybrid polyhydroxyurethane network on a base of carbonated-epoxidized unsaturated fatty acid triglycerides
CN112920068B (en) Synthesis method and application of polyaspartic acid ester
CN107189053B (en) Preparation method and application under a kind of polynary carbonic ester resin and its normal pressure
CN114437622A (en) Single-component solvent-free polyurethane coating and preparation method thereof
WO2016197305A1 (en) Coating composition
CN115109230A (en) Aqueous epoxy curing agent
CN113336949B (en) Amino organic silicon-based pentaerythritol cyclic carbonate and preparation method and application thereof
CN107916056B (en) Halogen-free flame retardant and flame-retardant polyurea elastomer coating
CN104987851B (en) One kind electrolysis door filling polyurethane cellular glue and preparation method thereof
CN108546262A (en) Aqueous syrups cyclic carbonate ester lotion and preparation method thereof and the application in water-based non-isocyanate polyurethane coating
CN107746458A (en) A kind of cold curing cyclic carbonate ester performed polymer and preparation method and application
CN114933846A (en) Non-isocyanate polyurethane coating and preparation method and application thereof
Figovsky et al. Advanced patented protective nanomaterials and coatings
EP3087117A1 (en) Epoxy resin composition
CN117069935A (en) Hydrophobic oleophobic non-isocyanate polyurethane and preparation method and application thereof
CN109824881B (en) Multi-cyclic carbonate resin and rapid preparation method and application thereof under normal pressure
CN115785783B (en) Weather-resistant floor paint and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant