CN110724436B - Epoxy grafted acrylate self-layering connecting paint and preparation method thereof - Google Patents
Epoxy grafted acrylate self-layering connecting paint and preparation method thereof Download PDFInfo
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- CN110724436B CN110724436B CN201911014546.1A CN201911014546A CN110724436B CN 110724436 B CN110724436 B CN 110724436B CN 201911014546 A CN201911014546 A CN 201911014546A CN 110724436 B CN110724436 B CN 110724436B
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention relates to the technical field of antifouling paint, and particularly relates to epoxy grafted acrylate self-layering connecting paint and a preparation method thereof, wherein the epoxy grafted acrylate self-layering connecting paint comprises the following raw materials in parts by mass: bisphenol A epoxy resin, acrylate resin, epoxy grafted acrylate resin, thixotropic agent, modifier, pigment, filler, solvent and curing agent. The epoxy grafted acrylate self-layering paint provided by the invention has excellent physical properties, can be used in combination with acrylate antifouling paint, obviously improves the connection performance, and can prolong the service life of a matched coating; and the connecting paint has low preparation cost, wide application range and higher economic benefit.
Description
Technical Field
The invention relates to the technical field of antifouling paint, in particular to epoxy grafted acrylate self-layering connecting paint and a preparation method thereof.
Background
In order to ensure that the part below the waterline of the hull is prevented from being corroded by seawater and attached by marine organisms, antirust paint and antifouling paint are coated on the hull. However, the antirust and antifouling paints are different in raw materials, coating time and the like, so that the antifouling paint cannot be directly coated on the antirust coating, and even if the antirust and antifouling paint can be coated, the adhesion performance also has defects.
Because the antifouling paint is generally acrylic acid or acrylic acid modified resin as a base material, the connecting paint is generally selected from resin with a structure similar to or similar to that of acrylic acid resin; other high strength resins such as epoxy and the like have been introduced in order to improve adhesion to the substrate.
Patent CN104513584A discloses a modified epoxy jointing paint and its manufacturing method, epoxy resin, epichlorohydrin resin, chlorinated rubber and acrylic resin are compounded, the mixture of cashew nut shell oil modified phenolic aldehyde amine curing agent and phenolic aldehyde amine curing agent is used as curing agent, the prepared jointing paint is used as rust-proof primer and antifouling paint or chlorinated rubber finish paint or intermediate paint of decorative finish paint, and good adhesion is ensured.
Patent CN103965742A discloses an epoxy connecting paint used for an antirust antifouling transition layer of a part below a ship waterline, epoxy, epichlorohydrin resin and vinyl chloride-vinyl acetate resin are compounded, amine or mercaptan is used as a curing agent, the prepared epoxy connecting paint can be used in a cross matching manner with antirust paints and antifouling paints of different types, the connecting strength of the antirust paints and the antifouling paints is improved, the epoxy connecting paint has universality and longer coating interval time, and the antirust antifouling construction requirements of the part below the ship waterline can be met.
The epoxy resin and the thermoplastic resin are only simply compounded, and the defects that the resin is easy to delaminate when the coating is stored, and the resin distribution mode is not clear after the coating is cured, so that the connection performance of the coating is reduced and the like exist.
Disclosure of Invention
In order to improve the storage stability between acrylate and epoxy resin, realize the directional distribution of resin after self-layering, improve the performance of a connecting coating and prolong the service life of the coating, the invention provides an epoxy grafted acrylate self-layering connecting paint which comprises a component A and a component B;
the component A comprises the following raw materials in parts by mass:
the component B comprises the following raw materials in parts by mass:
40-50 parts of curing agent
20-40 parts of a solvent.
On the basis of the scheme, the mass ratio of the component A to the component B is (6.1-7.2): 1.
in addition to the above scheme, the bisphenol a type epoxy resin is one of E12, E20, E44 and E51, and preferably E51 or E44 is used.
On the basis of the scheme, the structural formula of the epoxy grafted acrylate resin is as follows:
wherein R is a hydrocarbon group having 1 to 6 carbon atoms, preferably a straight-chain hydrocarbon group having 1 to 6 carbon atoms, and n is 1 to 5.
In addition to the above embodiments, the epoxy grafted acrylate resin (abbreviated as HB resin) is obtained by grafting an acrylate resin onto a side chain of a bisphenol a epoxy resin, and selecting a hydroxyl group that is likely to generate a radical as a grafting initiation point because other active groups on the epoxy side chain are small, and preferably by initiating polymerization of an acrylate monomer onto the hydroxyl group on the epoxy side chain by an azo initiator AIBN.
On the basis of the scheme, the acrylate resin comprises acrylate resin A and acrylate resin B, wherein the acrylate resin A contains an ethyl acrylate monomer, and the acrylate resin B contains a hydroxyethyl acrylate monomer.
On the basis of the scheme, further, the thixotropic agent is one or two of polyamide wax, hydrogenated castor oil and fumed silica.
On the basis of the scheme, the modifier is amino silicone or epoxy silicone and is used for improving the dispersibility between epoxy and filler.
On the basis of the scheme, the filler is one of mica dust, ferrotitanium powder, feldspar powder, mica powder and talcum powder.
On the basis of the scheme, the pigment is one or more of iron oxide red, high titanium yellow, high titanium ash and lemon yellow.
In addition to the above scheme, the solvent is a composition of two or more of aromatic hydrocarbons, esters, alcohols and ketones, and preferably a composition of two or more of xylene, butyl acetate, n-butanol and acetone.
On the basis of the scheme, the curing agent is one or two of cashew nut shell modified polyamide and poly fatty amine.
The invention provides a preparation method of an epoxy grafted acrylate self-layering connecting paint, which comprises the following preparation methods of a component A and a component B;
the preparation method of the component A comprises the following steps:
adding a solvent and a modifier into a reaction container, stirring and dispersing, wherein the stirring is preferably carried out at a rotating speed of 1000-3000 r/min, then adding a filler, a pigment and water, stirring and reacting, the stirring is preferably carried out at a rotating speed of 1000-3000 r/min, and the reacting time is preferably 30-60 minutes to obtain a uniform solution;
step two, adding bisphenol A epoxy resin into the uniform solution, stirring and dispersing, wherein the stirring is preferably carried out at a rotating speed of 1000-3000 r/min, and the stirring and dispersing time is preferably 30-60 min, so as to obtain a reaction product A;
adding epoxy grafted acrylate resin into the reaction product A, stirring and dispersing, wherein the stirring is preferably carried out at a rotating speed of 1000-3000 r/min, and the stirring and dispersing time is preferably 30-60 min, so as to obtain a reaction product B;
adding acrylic resin, a thixotropic agent and a solvent into the reaction product B, and stirring and dispersing, wherein the stirring is preferably carried out at a rotating speed of 1000-3000 r/min, and the stirring and dispersing time is preferably 30-90 min, so as to obtain a reaction product C;
step five, cooling, filtering and packaging the reaction product C to obtain a finished product;
the preparation method of the component B comprises the following steps:
step a, adding a solvent and a curing agent into a reaction vessel, stirring and dispersing, preferably stirring and dispersing at a rotating speed of 800-1200 r/min, wherein the stirring and dispersing time is preferably 10 min;
and step b, cooling, filtering and packaging the product obtained in the step a to obtain a finished product.
Compared with the prior art, the epoxy grafted acrylate self-layering connecting paint and the preparation method thereof provided by the invention have the following technical principles and beneficial effects:
1. the acrylate resin and the bisphenol A epoxy resin have large structural difference, large difference of solubility parameters and poor compatibility, and are easy to split phase in simple compounding, so that the defects of poor storage stability, reduced performance of a coating after curing and the like are caused; the invention selects a resin with the head end of epoxy and the tail end of acrylate as a transition resin, and acrylate monomers are grafted and polymerized on the epoxy side chain, so as to improve the compatibility between the acrylate and bisphenol A epoxy; meanwhile, the resin in directional distribution can be connected end to end when the coating is self-layered, and the mechanical property of the self-layered coating is ensured.
2. The filler is subjected to surface treatment, so that the filler is better dispersed and combined in the epoxy resin. Volume shrinkage can be generated in the epoxy resin curing process, and the bonding force to the anti-rust primer is easily reduced, so that the volume shrinkage can be improved by adding the filler, and the reduction of bonding points is reduced; meanwhile, the filler is distributed less in the acrylate, so that the acrylate on the surface of the self-separation layer is distributed more, the mechanical binding points are increased, and the interface binding force is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic diagram of a self-layering structure of epoxy grafted acrylate provided by the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention also provides the following examples and comparative examples:
table 1 table of the components of the examples
Table 2 comparative examples each component table
Comparative example 4
Adopting a connecting paint with the model number of 5BP provided by a commercial foreign company;
wherein, in the HB resin used in example 1, n ═ 1, R is ethyl; in the HB resin used in example 2, n is 2 and R is n-propyl; in the HB resin used in example 3, n ═ 4, R is n-pentyl; in the HB resin used in comparative example 2, n is 2, and R is an n-propyl group; in the HB resin used in comparative example 3, n is 4 and R is n-pentyl.
The epoxy grafted acrylate obtained by the preparation method provided by the invention has a good self-layering structure, as shown in figure 1,
is made of epoxy resin, and is characterized in that,
is an epoxy grafted acrylate resin, and is characterized in that,
is an acrylate resin;
the component a and the component b prepared in the above examples 1, 2 and 3 were mixed according to the ratio of 6.5:1, 7.2:1, 6.8:1 by direct mixing and stirring, whereas comparative examples 1, 2 and 3 are comparative example connecting paints obtained by direct mixing and stirring in a mass ratio of 6.1:1, 7.2:1 and 6.8:1, and the above examples and comparative examples are subjected to performance tests with the relevant test standards as shown in table 3 and the test results as shown in tables 4 and 5:
TABLE 3 epoxy grafted acrylate self-stratifying layer connect paint Primary specifications
Table 4 performance test data for the examples
TABLE 5 Performance test data for the comparative examples
From the above table, the invention provides an epoxy grafted acrylate self-layering connecting paint, which improves the compatibility of a resin system by using epoxy side chain grafted acrylate through a specific preparation method, and plays a role in transitional connection of acrylate and an epoxy system which can form self-layering; then, the pigment filler is modified to be more easily dispersed in the epoxy resin, so that the volume shrinkage rate during epoxy curing is reduced, and the reduction of interface bonding points is reduced; meanwhile, the fillers are distributed in the acrylate less, so that the acrylate on the surface of the self-separation layer is distributed more, the binding points are increased, the interface binding force is improved, the prepared epoxy grafted acrylate self-separation layer connecting paint has high drying speed, excellent adhesive force, flexibility, impact resistance and fresh water soaking resistance, and the service life of the matched coating of the underwater part of the ship is prolonged.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. An epoxy grafted acrylate self-layering connecting paint is characterized by comprising a component A and a component B;
the component A comprises the following raw materials in parts by mass:
14-18 parts of bisphenol A type epoxy resin;
14-16 parts of acrylate resin comprising acrylate resin A and acrylate resin B;
wherein the acrylate resin A contains an ethyl acrylate monomer, and the acrylate resin B contains a hydroxyethyl acrylate monomer;
6-8 parts of epoxy grafted acrylate resin;
0.4-0.8 part of thixotropic agent;
1.2-2 parts of a modifier;
10-15 parts of pigment;
28-32 parts of a filler;
15-20 parts of a solvent;
the epoxy grafted acrylate resin is grafted acrylate resin on a side chain of bisphenol A epoxy resin, and the structural formula of the epoxy grafted acrylate resin is as follows:
wherein R is a hydrocarbon group containing 1 to 6 carbon atoms, and n =1 to 5;
the component B comprises the following raw materials in parts by mass:
40-50 parts of a curing agent;
20-40 parts of a solvent.
2. The epoxy grafted acrylate self-stratifying paint of claim 1 wherein: the mass ratio of the component A to the component B is (6.1-7.2): 1.
3. the epoxy grafted acrylate self-stratifying paint of claim 1 wherein: the bisphenol A epoxy resin is one of E12, E20, E44 and E51.
4. The epoxy grafted acrylate self-stratifying paint of claim 1 wherein: the thixotropic agent is one or two of polyamide wax, hydrogenated castor oil and fumed silica.
5. The epoxy grafted acrylate self-stratifying paint of claim 1 wherein: the modifier is amino organosilicon or epoxy organosilicon.
6. The epoxy grafted acrylate self-stratifying paint of claim 1 wherein: the filler is one of micaceous iron ash, ferrotitanium powder, feldspar powder, mica powder and talcum powder.
7. A method of making the epoxy grafted acrylate self-stratifying layer connect lacquer according to any of claims 1-6, characterized by comprising the following method of making component a and component b;
the preparation method of the component A comprises the following steps:
step one, adding a solvent and a modifier into a reaction container, and stirring and dispersing; adding the filler and the pigment, stirring and reacting to obtain a uniform solution;
step two, adding bisphenol A epoxy resin into the uniform solution, and stirring and dispersing to obtain a reaction product A;
adding epoxy grafted acrylate resin into the reaction product A, and stirring and dispersing to obtain a reaction product B;
adding acrylate resin, a thixotropic agent and a solvent into the reaction product B, and stirring and dispersing to obtain a reaction product C;
step five, cooling, filtering and packaging the reaction product C to obtain a finished product;
the preparation method of the component B comprises the following steps:
step a, adding a solvent and a curing agent into a reaction container, and stirring and dispersing;
and step b, cooling, filtering and packaging the product obtained in the step a to obtain a finished product.
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| CN113308190B (en) * | 2021-06-11 | 2022-02-18 | 常熟理工学院 | High-adhesion gradient layered fouling release type marine antifouling paint |
| CN114854269A (en) * | 2022-04-15 | 2022-08-05 | 长安大学 | Self-layering waterproof bonding material for steel bridge deck and preparation method thereof |
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| CN102964516B (en) * | 2012-10-24 | 2015-06-24 | 中国船舶重工集团公司第七二五研究所 | Monocomponent epoxide-modified acrylic resin and application thereof |
| CN104046211A (en) * | 2013-04-25 | 2014-09-17 | 中国船舶重工集团公司第七二五研究所 | Epoxy modified acrylic resin gradient connection paint and preparation method thereof |
| CN104513584B (en) * | 2013-09-27 | 2017-03-15 | 中国石油天然气集团公司 | A kind of modified epoxy connection coating and manufacture method |
| CN104559682B (en) * | 2014-12-24 | 2017-07-25 | 江苏苏博特新材料股份有限公司 | A kind of water-based epoxy acrylic self demixing emulsion protected for concrete surface |
| CN108034329B (en) * | 2017-11-30 | 2020-08-28 | 中国船舶重工集团公司第七二五研究所 | Epoxy acrylic acid connecting paint for ships and preparation method thereof |
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