Polyurea composition, polyurea coating, preparation method of polyurea coating and workpiece shell

Abstract

The invention provides a polyurea composition, a polyurea coating, a preparation method of the polyurea coating and a workpiece shell. The polyurea composition comprises a component A and a component B. The component A comprises first fluorine-containing amino-terminated polysiloxane; the component B is prepared from isocyanate, second fluorine-containing amino-terminated polysiloxane and an amine compound. The polyurea coating prepared from the polyurea composition has good scratch resistance and wear resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of coatings, in particular to a polyurea composition, a polyurea coating and a preparation method thereof, and a workpiece shell. BACKGROUND

[0002] The statements herein are provided only to enhance understanding of the present application and are not necessarily intended to constitute prior art.

[0003] The coating on the surface of the workpiece mainly plays a protective role for the workpiece, but the workpiece will inevitably be subjected to scratches and collisions during use or transportation: for example, during the process of a ship docking at a wharf, the ship paint of the outer hull is often worn due to scratching the wharf or the rubber fender on the wharf, and seawater is easy to penetrate into the coating from the damaged coating, which accelerates the aging and peeling of the coating under the capillary action and the secretion of corrosive substances by microorganisms, and thus the ship hull is corroded; for another example, in the field of new energy vehicles, the battery is usually arranged below the vehicle chassis so that the heat of the battery monomer in the battery can be timely transferred to the outside of the battery, however, the working condition of the vehicle chassis is very harsh, such as high-speed impact of road stones, continuous erosion in rainy days, etc., and therefore a battery pack bottom guard plate is usually installed, and the battery pack bottom guard plate is required to have good scratch resistance and wear resistance. It can be seen that it is necessary to enhance the scratch resistance and wear resistance of the coating on the surface of the workpiece. SUMMARY

[0004] To achieve the above-mentioned purpose, the present application provides a polyurea composition, a polyurea coating and a preparation method thereof, and a workpiece shell, and the polyurea coating prepared by the polyurea composition has good scratch resistance and wear resistance.

[0005] In a first aspect, the present application provides a polyurea composition comprising a component A and a component B, wherein,

[0006] The component A comprises a first fluorine-containing amino-terminated polysiloxane;

[0007] The component B comprises an isocyanate, a second fluorine-containing amino-terminated polysiloxane and an amine compound.

[0008] The polyurea composition described above comprises the component A comprising the first fluorine-containing amino-terminated polysiloxane, and the component B comprising the isocyanate, the second fluorine-containing amino-terminated polysiloxane and the amine compound, and the polyurea coating prepared thereby can have good wear resistance and scratch resistance.

[0009] In some embodiments, the first fluorine-containing amino-terminated polysiloxane and the second fluorine-containing amino-terminated polysiloxane each independently has one or more of the following characteristics:

[0010] (1) the preparation monomer comprises a fluorine-containing cyclosiloxane monomer, or a combination of a cyclosiloxane monomer and a fluorine-containing cyclosiloxane monomer;

[0011] (2) the mass percentage of fluorine element is 20% to 40%.

[0012] In some embodiments, the first fluorine-containing terminal amino polysiloxane and the second fluorine-containing terminal amino polysiloxane each independently has one or more of the following characteristics:

[0013] (1) the fluorine-containing cyclosiloxane monomer includes one or more of trifluoropropylmethylcyclotrisiloxane and 2,4,6,8-tetramethyl-2,4,6,8-tetrakis(3,3,3-trifluoropropyl)cyclotetrasiloxane;

[0014] (2) the cyclosiloxane includes one or more of octamethylcyclotetrasiloxane, dodecamethylcyclohexasiloxane, decamethylcyclopentasiloxane, and hexamethylcyclotrisiloxane;

[0015] (3) in the combination of the cyclosiloxane monomer and the fluorine-containing cyclosiloxane monomer, the molar ratio of the cyclosiloxane monomer to the fluorine-containing cyclosiloxane monomer is 1:(1.5 to 4.5).

[0016] In some embodiments, the B component includes, in parts by weight:

[0017] isocyanate 55 to 75 parts,

[0018] second fluorine-containing terminal amino polysiloxane 20 to 35 parts, and

[0019] amine compound 5 to 10 parts.

[0020] In some embodiments, the amine compound includes one or more of a cycloalkyl group and a heterocyclic group.

[0021] In some embodiments, the amine compound includes one or more of 1,4-cyclohexanedimethylamine, terminal amino polytetrahydrofuran, isophorone diamine, N,N'-bisneopentylcyclohexanediamine, diaminodicyclohexylmethane, 1,3-cyclohexanedimethylamine, and 4,4-diaminodicyclohexylmethane.

[0022] In some embodiments, the isocyanate includes one or more of 4,4-diisocyanate dicyclohexylmethane, isophorone diisocyanate, 1,4-cyclohexaned diisocyanate, methylcyclohexane diisocyanate, and norbornane diisocyanate.

[0023] In some embodiments, the A component further includes a promoter, the promoter having one or more of the following characteristics:

[0024] (1) the first fluorine-containing terminal amino polysiloxane is 60 to 95 parts by weight, and the accelerator is 0.1 to 2 parts by weight;

[0025] (2) the accelerator comprises one or more of γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, and polyaminoalkyltrialkoxysilane.

[0026] In some embodiments, the A component further comprises a color filler, the first fluorine-containing terminal amino polysiloxane is 60 to 95 parts by weight, and the color filler is 1 to 20 parts by weight.

[0027] In some embodiments, the mass ratio of the A component to the B component is (1 to 10): 1.

[0028] In a second aspect of the present application, a method for preparing a polyurea coating is provided, comprising the following steps:

[0029] mixing the A component and the B component to perform a curing cross-linking reaction;

[0030] the A component comprises a first fluorine-containing terminal amino polysiloxane;

[0031] the B component comprises an isocyanate, a second fluorine-containing terminal amino polysiloxane, and an amine compound.

[0032] In some embodiments, the method for preparing the B component comprises:

[0033] under a protective gas atmosphere, adding the second fluorine-containing terminal amino polysiloxane and the amine compound into the isocyanate to perform a prepolymerization reaction.

[0034] In some embodiments, the method for preparing the first fluorine-containing terminal amino polysiloxane and the second fluorine-containing terminal amino polysiloxane comprises the following steps:

[0035] polymerizing a fluorine-containing cyclosiloxane monomer, or a combination of a cyclosiloxane monomer and a fluorine-containing cyclosiloxane monomer, in the presence of a basic catalyst;

[0036] adding an end-capping agent to perform an end-capping reaction.

[0037] In some embodiments, the method for preparing the polyurea coating has one or more of the following characteristics:

[0038] (1) the fluorine-containing cyclosiloxane monomer comprises one or more of trifluoropropylmethylcyclotrisiloxane and 2,4,6,8-tetramethyl-2,4,6,8-tetrakis(3,3,3-trifluoropropyl)cyclotetrasiloxane;

[0039] (2) The cyclosiloxanes include one or more of octamethylcyclotetrasiloxane, dodecylcyclohexasiloxane, decamethylcyclopentasiloxane and hexamethylcyclotrisiloxane;

[0040] (3) In the combination of the cyclosiloxane monomer and the fluorinated cyclosiloxane monomer, the molar ratio of the cyclosiloxane monomer to the fluorinated cyclosiloxane monomer is 1:(1.5 to 4.5);

[0041] (4) The conditions for polymerization reaction include: reaction at 80℃~90℃ for 5h~7h;

[0042] (5) The end-capping agent includes one or more of 1,3-bis(aminopropyl)tetramethyldisiloxane, N-2-aminoethyl-3-aminopropylmethyldimethoxysilane, N-aminoethyl-aminopropylmethyldimethoxysilane and 3-aminopropyldimethoxymethylsilane;

[0043] (6) The conditions for the end-capping reaction include: reacting at 60℃~100℃ for 30min~50min.

[0044] A third aspect of this application provides a polyurea coating, which is obtained by curing and crosslinking the polyurea composition described in the first aspect, or by the preparation method described in the second aspect.

[0045] A fourth aspect of this application provides a casing for a component, including a casing substrate and a protective coating adhered to the surface of the substrate, said protective coating including the polyurea coating described in the third aspect. Detailed Implementation

[0046] To facilitate understanding of this application, a more complete description is provided below, along with preferred embodiments. However, this application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of this application.

[0047] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0048] The "range" disclosed in this application can be defined in the form of a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of the specific range. Ranges defined in this way can include or exclude endpoints. Any endpoint can be included or excluded independently, and they can be combined arbitrarily; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60–120 and 80–110 are listed for a specific parameter, it is expected that ranges of 60–110 and 80–120 are also included. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are also listed, then the following ranges are all expected: 1–3, 1–4, 1–5, 2–3, 2–4, and 2–5. In this application, unless otherwise stated, the numerical range "a–b" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0" and "5" have been listed in this article; "0-5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is described as an integer ≥ 2, it is equivalent to listing integers such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc. For instance, when a parameter is described as an integer selected from "2-10", it is equivalent to listing the integers 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0049] In this application, the terms "multiple" or "various" are used unless otherwise specified, referring to a quantity greater than or equal to 2. For example, "one or more" means one or more types.

[0050] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0051] In this document, the term "embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment or implementation of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment mutually exclusive with other embodiments. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described herein can be combined with other embodiments. The term "implementation" as used herein has a similar understanding.

[0052] Those skilled in the art will understand that the order in which the steps are written in the methods of various embodiments or examples does not imply a strict execution order and does not constitute any limitation on the implementation process. The detailed execution order of each step should be determined by its function and possible internal logic. Unless otherwise specified, all steps of this application may be performed sequentially or randomly, preferably sequentially. For example, if the method includes steps (a) and (b), it means that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, if the method may also include step (c), it means that step (c) can be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0053] In this application, open-ended technical features or solutions described using terms such as "containing," "including," or "comprising" do not exclude additional members beyond those listed unless otherwise specified. They can be considered as providing both closed-ended features or solutions comprised of the listed members and open-ended features or solutions that include additional members beyond the listed members. For example, if A includes a1, a2, and a3, it may also include other members or exclude additional members unless otherwise specified. This can be considered as providing both the feature or solution that "A consists of a1, a2, and a3" and the feature or solution that "A includes not only a1, a2, and a3, but also other members."

[0054] In this application, unless otherwise specified, A (e.g., B) means that B is a non-limiting example of A, and it is understood that A is not limited to B.

[0055] In this application, "optionally," "optionally," and "optional" mean that something is optional, that is, it means that it is selected from either "with" or "without." If there are multiple "optional" entries in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "optional" entry shall be independent.

[0056] The term "cycloalkyl" refers to a non-aromatic hydrocarbon containing a ring of carbon atoms, which can be monocycloalkyl, spirocycloalkyl, or bridged cycloalkyl. Phrases containing this term, such as "C3-C9 cycloalkyl," refer to cycloalkyl compounds containing 3 to 9 carbon atoms, and each occurrence can independently be C3, C4, C5, C6, C7, C8, or C9 cycloalkyl. Suitable examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl. Additionally, "cycloalkyl" may contain one or more double bonds; representative examples of cycloalkyl compounds containing double bonds include cyclopentenyl, cyclohexenyl, cyclohexadienyl, and cyclobutadienyl.

[0057] The term "heterocyclic group" refers to a cycloalkyl group in which at least one carbon atom is replaced by a non-carbon atom, which can be an N atom, O atom, S atom, etc., and can be a saturated ring or a partially unsaturated ring. Phrases containing this term, such as "3- to 9-membered heterocyclic group," refer to heterocyclic groups containing 3 to 9 ring atoms, and each occurrence can independently be a 3-membered, 4-membered, 5-membered, 6-membered, 7-membered, 8-membered, or 9-membered heterocyclic group. Suitable examples include, but are not limited to: dihydropyridyl, tetrahydropyridyl (piperidinyl), tetrahydrothiophenyl, sulfur-oxidized tetrahydrothiophenyl, tetrahydrofuranyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, and dihydroindoleyl.

[0058] One embodiment of this application provides a polyurea composition comprising component A and component B, wherein...

[0059] Component A includes a first fluorinated amino-terminated polysiloxane;

[0060] Component B includes isocyanate, second fluorinated amino-terminated polysiloxane, and amine compounds.

[0061] The polyurea composition described above, comprising component A (a first fluorinated amino-terminated polysiloxane) and component B (an isocyanate, a second fluorinated amino-terminated polysiloxane, and an amine compound), produces a polyurea coating that exhibits good wear and scratch resistance. The possible principle behind this is as follows:

[0062] The polyurea coating obtained by the reaction of components A and B is dense, and there are hydrogen bonds between the polyurea segments in the polyurea coating, which can enhance the cohesive strength of the coating. At the same time, the -Si-O- bond length is relatively long and the internal rotation barrier is relatively small, which can give the coating good flexibility. The introduction of F element can increase the hardness of the coating and reduce the surface energy of the coating, making the coating surface smoother and reducing the coefficient of friction. In summary, the polyurea coating has good wear resistance and scratch resistance.

[0063] Furthermore, traditional marine paints used for ship hulls typically employ a waterline-based separation. Above the waterline, there are usually two coats of epoxy primer and one coat of polyurethane topcoat. Below the waterline, there are two coats of epoxy primer, one coat of epoxy bonding agent, and one coat of single-component acrylic antifouling paint. Each layer serves a different function: the primer generally acts as an anti-corrosion layer, the bonding agent typically serves as an anti-corrosion or bonding layer, the topcoat protects against direct sunlight and prevents aging and discoloration, and the antifouling paint prevents marine organisms from adhering to the hull. This multi-layered paint structure makes the coating process complex, time-consuming, and costly.

[0064] In addition, the coating on the bottom protective plate of the battery pack may face problems such as icing and mud splashing during transportation.

[0065] Furthermore, the polyurea coating provided in this application, while possessing excellent wear and scratch resistance, also exhibits good aging resistance, corrosion resistance, and antifouling properties. Based on these superior comprehensive properties, when applied to marine paints, it can replace multiple layers of traditional marine paint films with a single layer, achieving the same effect. This reduces the number of coating processes to one layer, decreasing process time and manufacturing costs. When applied to the bottom protective plate of a battery pack, it can prevent icing and mud / water accumulation. The possible principle is as follows:

[0066] (1) The polyurea coating obtained by reacting the isocyanate groups in the isocyanate-terminated prepolymer with the amino groups in the fluorine-terminated amino polysiloxane is dense, and the reaction rate of the two is greater than the reaction rate of the isocyanate groups with water, making it difficult for seawater to penetrate into the coating. The shielding effect of the dense coating can achieve good anti-corrosion function.

[0067] (2) Introducing fluorinated amino-terminated polysiloxane segments, the fluorinated side chains of which are not thermodynamically stable systems -CF- and -Si-O- tend to have a phase separation structure. -CF- can form a low surface energy layer on the coating surface, providing the coating with hydrophobic and oleophobic effects, thereby reducing the adsorption of marine organisms and achieving the purpose of antifouling.

[0068] (3) Introducing fluorine-containing amino-terminated polysiloxane segments makes the segments in the coating mainly -Si-O-, which have large bond energy and can play a good role in resisting ultraviolet aging and weathering.

[0069] Understandably, the first fluorinated amino-terminated polysiloxane and the second fluorinated amino-terminated polysiloxane may be of the same or different types.

[0070] In some embodiments, the monomers for preparing the first fluorinated amino-terminated polysiloxane and the second fluorinated amino-terminated polysiloxane each independently include a fluorinated cyclosiloxane monomer, or a combination of a cyclosiloxane monomer and a fluorinated cyclosiloxane monomer.

[0071] Further, the fluorinated cyclosiloxane monomer includes one or more of trifluoropropylmethylcyclotrisiloxane and 2,4,6,8-tetramethyl-2,4,6,8-tetra(3,3,3-trifluoropropyl)cyclotetrasiloxane;

[0072] Furthermore, the cyclosiloxane includes one or more of octamethylcyclotetrasiloxane, dodecylcyclohexasiloxane, decamethylcyclopentasiloxane, and hexamethylcyclotrisiloxane;

[0073] Further, in the combination of the cyclosiloxane monomer and the fluorinated cyclosiloxane monomer, the molar ratio of the cyclosiloxane monomer to the fluorinated cyclosiloxane monomer is 1:(1.5 to 4.5). Specifically, the molar ratio of the cyclosiloxane monomer to the fluorinated cyclosiloxane monomer includes, but is not limited to: 1:1.5, 1:1.6, 1:7, 1:8, 1:2, 1:2.5, 1:3, 1:3.5, 1:3.8, 1:4, 1:4.2, 1:4.5, or any range between the foregoing.

[0074] In some embodiments, the mass percentage of fluorine in the first and second fluorinated amino-terminated polysiloxanes is independently 20% to 40%. Specifically, the mass percentage of fluorine includes, but is not limited to: 20%, 22%, 24%, 26.7%, 28%, 30%, 31.8%, 33.7%, 35.3%, 37%, 40%, or any range between the foregoing.

[0075] In some embodiments, component B comprises, by weight:

[0076] 55 to 75 parts isocyanate

[0077] 20 to 35 parts of a second fluorinated amino-terminated polysiloxane, and

[0078] 5 to 10 parts of amine compounds.

[0079] Specifically, the isocyanate is included in parts by weight, but not limited to: 55 parts, 57 parts, 60 parts, 63 parts, 65 parts, 67 parts, 70 parts, 73 parts, 75 parts, or any combination thereof.

[0080] Specifically, the second fluorinated amino-terminated polysiloxane has weight parts including but not limited to: 20 parts, 23 parts, 25 parts, 27 parts, 30 parts, 33 parts, 65 parts or any two of the foregoing.

[0081] Specifically, the weight parts of the amine compound include, but are not limited to: 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, or any two of the foregoing.

[0082] In some embodiments, the amine compound comprises one or more of cycloalkyl and heterocyclic groups. Introducing cycloalkyl and heterocyclic groups into the amine compound allows them to form multiple hard-segment regions in the polyurea coating, further increasing the crosslinking density of the polyurea coating and thus improving its wear and scratch resistance. Without limitation, the cycloalkyl group may be C3-C9 cycloalkyl, and the heterocyclic group may be a 3- to 9-membered heterocyclic group.

[0083] In some embodiments, the amine compound includes one or more of 1,4-cyclohexanedimethylamine, amino-terminated polytetrahydrofuran, isofluranediamine, N,N'-bis(pentylcyclohexanediamine), diaminodicyclohexylmethane, 1,3-cyclohexanedimethylamine, and 4,4-diaminodicyclohexylmethane.

[0084] In some embodiments, the isocyanate includes one or more of 4,4-diisocyanate dicyclohexylmethane, isoflurone diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexane diisocyanate, and norbornene diisocyanate.

[0085] In some embodiments, component A further includes an accelerator. Adding an appropriate amount of accelerator to component A can improve the adhesion between the polyurea coating and the substrate.

[0086] Further, by weight, the first fluorinated amino-terminated polysiloxane is 60 to 95 parts, and the accelerator is 0.1 to 2 parts.

[0087] Specifically, in component A, the weight parts of the first fluorinated amino-terminated polysiloxane include, but are not limited to, 60 parts, 65 parts, 70 parts, 85 parts, 90 parts, 95 parts, or any two of the foregoing.

[0088] Specifically, in component A, the weight parts of the accelerator include, but are not limited to: 0.1 parts, 0.5 parts, 1, 1.5 parts, 2 parts, or any two of the foregoing.

[0089] Further, the promoter includes one or more of γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, and polyaminoalkyltrialkoxysilane.

[0090] In some embodiments, component A further includes pigments and fillers, wherein the first fluorinated amino-terminated polysiloxane is 60 to 95 parts by weight, and the pigments and fillers are 1 to 20 parts by weight. Specifically, the weight parts of the pigments and fillers in component A include, but are not limited to, 1 part, 5 parts, 10 parts, 15 parts, 20 parts, or any range between the foregoing.

[0091] Without limitation, the pigments and fillers include one or more of aluminum hydroxide, magnesium hydroxide, barium sulfate, calcium carbonate, talc, silica, glass microspheres, diatomaceous earth, kaolin, silica powder, titanium dioxide, carbon powder, phthalocyanine blue, alumina, aluminum nitride, boron nitride, beryllium oxide, magnesium oxide, and cerium oxide. It is understood that, depending on the different active groups in the pigments and fillers, they can also participate in the curing and crosslinking of the first fluorinated amino-terminated polysiloxane and isocyanate-terminated prepolymer, jointly forming a cured crosslinked product.

[0092] In addition, without limitation, the raw materials for preparing component A may also include 0 to 2 parts of additives. When the weight of the additive is 0 parts, it means that the additive is not included. Without limitation, the additives include one or more of the following: bactericides, fungicides, antibiotics, stabilizers, slip agents, defoamers, leveling agents, and wetting and dispersing agents.

[0093] In some embodiments, the raw materials for preparing component A include 0.1 to 2 parts of a wetting and dispersing agent. Without limitation, the wetting and dispersing agent may be, for example, a polyether-based wetting and dispersing agent. Specifically, the weight parts of pigments and fillers in the raw materials for preparing the wetting and dispersing agent include, but are not limited to: 0.1 parts, 0.5 parts, 1, 1.5 parts, 2 parts, or any range between the foregoing.

[0094] In some embodiments, the mass ratio of component A to component B is (1 to 10):1. Specifically, the mass ratio of component A to component B includes, but is not limited to: 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, or any range between the two aforementioned.

[0095] Other embodiments of this application provide a method for preparing a polyurea coating, comprising the following steps:

[0096] Mix component A and component B and carry out a curing and crosslinking reaction;

[0097] Component A includes a first fluorinated amino-terminated polysiloxane;

[0098] Component B includes isocyanate, second fluorinated amino-terminated polysiloxane, and amine compounds.

[0099] Understandably, the first fluorinated amino-terminated polysiloxane, isocyanate, second fluorinated amino-terminated polysiloxane, and amine compound are the same as described above and will not be repeated here.

[0100] In some embodiments, the preparation method of component B includes:

[0101] Under a protective gas atmosphere, the second fluorinated amino-terminated polysiloxane and the amine compound are added to the isocyanate to carry out a prepolymerization reaction. Further, the temperature is controlled to ≤40°C during the prepolymerization reaction. Without limitation, the prepolymer obtained by the prepolymerization reaction includes a prepolymer of isocyanate and fluorinated amino-terminated polysiloxane, or a prepolymer of isocyanate, fluorinated amino-terminated polysiloxane, and amine compound, or both of the aforementioned prepolymers.

[0102] In some embodiments, the preparation methods of the first fluorinated amino-terminated polysiloxane and the second fluorinated amino-terminated polysiloxane include the following steps:

[0103] Fluorinated cyclosiloxane monomers, or a combination of cyclosiloxane monomers and fluorinated cyclosiloxane monomers, are polymerized in the presence of an alkaline catalyst.

[0104] Add an end-capping agent to carry out the end-capping reaction.

[0105] In some embodiments, the polymerization reaction conditions include reacting at 80°C to 90°C for 5 to 7 hours.

[0106] In some embodiments, the capping agent comprises one or more of 1,3-bis(aminopropyl)tetramethyldisiloxane, N-2-aminoethyl-3-aminopropylmethyldimethoxysilane, N-aminoethyl-aminopropylmethyldimethoxysilane, and 3-aminopropyldimethoxymethylsilane.

[0107] In some embodiments, the capping reaction conditions include reacting at 60°C to 100°C for 30 to 50 minutes.

[0108] In addition, without limitation, the alkaline catalyst includes one or more of tetramethylammonium hydroxide silanolate, potassium hydroxide, and sodium hydroxide.

[0109] In addition, without limitation, after the end-capping reaction, post-processing steps are included, including catalyst decomposition reaction and low-boiling-point substance removal treatment. Further, the catalyst decomposition reaction includes heating the reaction system to 130°C to 160°C for decomposition reaction; the low-boiling-point substance removal treatment includes vacuuming the material after the decomposition reaction at a temperature of 150°C to 180°C.

[0110] In other embodiments of this application, a polyurea coating is also provided, which is obtained by curing and crosslinking the polyurea composition as described above, or by the preparation method described above.

[0111] Other embodiments of this application also provide a component housing, including a housing substrate and a protective coating adhered to the surface of the substrate, said protective coating comprising a polyurea coating as described above or a polyurea coating prepared by the method described above. Without limitation, the component housing includes a ship hull or a battery pack bottom cover. In some embodiments, the material of the housing substrate may be one or more of steel, aluminum, or composite materials thereof.

[0112] For experimental parameters not specified in the following specific embodiments, please refer to the guidelines given in this application document first, or refer to experimental manuals or other experimental methods known in the art, or refer to the experimental conditions recommended by the manufacturer.

[0113] The raw materials and reagents involved in the following specific embodiments can be obtained commercially or prepared by those skilled in the art using known methods.

[0114] Example 1

[0115] This embodiment describes a polyurea coating, and its preparation method is as follows:

[0116] (1) Prepare the ingredients of component A and component B according to the following weight proportions;

[0117] Component A:

[0118]

[0119] Component B:

[0120] 55 parts of 4,4-diisocyanate dicyclohexylmethane

[0121] 35 parts of fluorinated amino-terminated polysiloxane

[0122] 10 parts of 1,4-cyclohexanedimethylamine

[0123] The preparation method of the fluorinated amino-terminated polysiloxane is as follows:

[0124] 7956g of trifluoropropylmethylcyclotrisiloxane was stirred and mixed thoroughly. 59.67g of a basic catalyst, tetramethylammonium hydroxide silanolate, was added. The reaction vessel was heated to 80℃ and reacted for 6 hours. Then, 358g of 1,3-bis(aminopropyl)tetramethyldisiloxane was added for end-capping, and the reaction was allowed to proceed for 40 minutes. After the reaction was complete, the reaction vessel was heated to 140℃ to decompose the catalyst. Then, under negative pressure vacuum at 150℃, low-boiling-point substances were removed to obtain a fluorinated terminal amino polysiloxane with a fluorine content of 35.3 wt%.

[0125] (2) The preparation method of component A is as follows:

[0126] Mix all components thoroughly according to the ingredients to obtain component A;

[0127] (3) The preparation method of component B is as follows:

[0128] According to the ingredients, 55g of 4,4-diisocyanate dicyclohexylmethane was added to the reaction vessel. The vessel was protected with nitrogen gas, and the temperature was controlled not to exceed 40℃. Then, while stirring, 35g of fluorinated amino-terminated polysiloxane and 10g of 1,4-cyclohexanedimethylamine were added dropwise until the addition was complete, yielding component B, which contains at least one isocyanate prepolymer.

[0129] (4) During coating construction, component A and component B are mixed in a weight ratio of A:B = 4:1 and sprayed using a polyurea spraying equipment to obtain a polyurea coating.

[0130] Example 2

[0131] This embodiment describes a polyurea coating, prepared using the same method as in Example 1, with the main difference being the addition of 888g of octamethylcyclotetrasiloxane in the preparation of the fluorinated amino-terminated polysiloxane. The amounts of the alkaline catalyst and the end-capping agent are adjusted accordingly. Details are as follows:

[0132] 888g of octamethylcyclotetrasiloxane and 7956g of trifluoropropylmethylcyclotrisiloxane were mixed evenly, and 66.33g of tetramethylammonium hydroxide silanolate, an alkaline catalyst, was added. The reaction vessel was heated to 80℃ and reacted for 6 hours. Then, 398g of 1,3-bis(aminopropyl)tetramethyldisiloxane was added for end-capping, and the reaction was carried out for 40 minutes. After the reaction was completed, the reaction vessel was heated to 140℃ to decompose the catalyst, and then vacuumed under negative pressure at 150℃ to remove low-boiling substances, yielding a fluorinated terminal amino polysiloxane with a molar ratio (n / m) of 1:4 for octamethylcyclotetrasiloxane and a fluorine content of 31.8wt%.

[0133] Example 3

[0134] This embodiment describes a polyurea coating, prepared using the same method as in Example 1. The main difference lies in the addition of 3276g of trifluoropropylmethylcyclotrisiloxane to the preparation method of the fluorinated amino-terminated polysiloxane. The amounts of the alkaline catalyst and the end-capping agent are adjusted accordingly. Details are as follows:

[0135] 3276g of trifluoropropylmethylcyclotrisiloxane was stirred and mixed thoroughly. 24.57g of a basic catalyst, tetramethylammonium hydroxide silanolate, was added. The reaction vessel was heated to 80℃ and reacted for 6 hours. Then, 213g of 1,3-bis(aminopropyl)tetramethyldisiloxane was added for end-capping, and the reaction was allowed to proceed for 40 minutes. After the reaction was complete, the reaction vessel was heated to 140℃ to decompose the catalyst. Then, under negative pressure and vacuum at 150℃, low-boiling substances were removed to obtain a fluorinated terminal amino polysiloxane with a fluorine content of 33.7wt%.

[0136] Example 4

[0137] This embodiment describes a polyurea coating, prepared using the same method as in Example 1, with the main difference being that in the preparation method of the fluorinated amino-terminated polysiloxane, 888g of octamethylcyclotetrasiloxane and 3276g of trifluoropropylmethylcyclotrisiloxane are added, and the amounts of alkaline catalyst and end-capping agent are adjusted accordingly. Details are as follows:

[0138] 888g of octamethylcyclotetrasiloxane and 3276g of trifluoropropylmethylcyclotrisiloxane were stirred and mixed evenly. 31.23g of a basic catalyst, tetramethylammonium hydroxide silanolate, was added. The reaction vessel was heated to 80℃ and reacted for 6 hours. Then, 270.67g of 1,3-bis(aminopropyl)tetramethyldisiloxane was added for end-capping, and the reaction was allowed to proceed for 40 minutes. After the reaction was complete, the reaction vessel was heated to 140℃ to decompose the catalyst. Then, a vacuum was applied at 150℃ to remove low-boiling-point substances, yielding a fluorinated terminal amino polysiloxane. The molar ratio (n / m) of octamethylcyclotetrasiloxane to trifluoropropylmethylcyclotrisiloxane was 1:1.7, and the fluorine content was 26.7wt%.

[0139] Example 5

[0140] This embodiment is a polyurea coating, and its preparation method is the same as that in Example 1. The main difference is that the ingredients of component B are different, as detailed below:

[0141] 70 parts of 4,4-diisocyanate dicyclohexylmethane

[0142] 20 parts of fluorinated amino-terminated polysiloxane

[0143] 10 parts of 1,4-cyclohexanedimethylamine.

[0144] Example 6

[0145] This embodiment is a polyurea coating, and its preparation method is the same as that in Example 1. The main difference is that the ingredients of component B are different, as detailed below:

[0146] 60 parts of 4,4-diisocyanate dicyclohexylmethane

[0147] 35 parts of fluorinated amino-terminated polysiloxane

[0148] 5 parts of 1,4-cyclohexanedimethylamine.

[0149] Example 7

[0150] This embodiment is a polyurea coating, and its preparation method is the same as that in Example 1. The main difference is that the ingredients of component B are different, as detailed below:

[0151] 75 parts of 4,4-diisocyanate dicyclohexylmethane

[0152] 20 parts of fluorinated amino-terminated polysiloxane

[0153] 5 parts of 1,4-cyclohexanedimethylamine.

[0154] Example 8

[0155] This embodiment is a polyurea coating, and its preparation method is the same as that in Example 4. The main difference is that the ingredients of component B are different, as detailed below:

[0156] 70 parts of 4,4-diisocyanate dicyclohexylmethane

[0157] 20 parts of fluorinated amino-terminated polysiloxane

[0158] 10 parts of 1,4-cyclohexanedimethylamine.

[0159] Example 9

[0160] This embodiment is a polyurea coating, and its preparation method is the same as that in Example 4. The main difference is that the ingredients of component B are different, as detailed below:

[0161] 60 parts of 4,4-diisocyanate dicyclohexylmethane

[0162] 35 parts of fluorinated amino-terminated polysiloxane

[0163] 5 parts of 1,4-cyclohexanedimethylamine.

[0164] Example 10

[0165] This embodiment is a polyurea coating, and its preparation method is the same as that in Example 4. The main difference is that the ingredients of component B are different, as detailed below:

[0166] 75 parts of 4,4-diisocyanate dicyclohexylmethane

[0167] 20 parts of fluorinated amino-terminated polysiloxane

[0168] 5 parts of 1,4-cyclohexanedimethylamine.

[0169] Example 11

[0170] This embodiment is a polyurea coating, and its preparation method is the same as that in Example 1. The main difference is that in component B, isoflurone diamine is used in equal parts by weight to replace 1,4-cyclohexanedimethylamine.

[0171] Example 12

[0172] This embodiment is a polyurea coating, and its preparation method is the same as that in Example 1. The main difference is that in component B, 1,4-cyclohexanedimethylamine is replaced by an equal weight of amino-terminated polytetrahydrofuran.

[0173] Example 13

[0174] This embodiment is a polyurea coating, and its preparation method is the same as that in Example 1. The main difference is that in component B, isoflurone diisocyanate is used in equal parts by weight to replace 4,4-diisocyanate dicyclohexylmethane.

[0175] The main parameters of each embodiment are summarized in Table 1 below:

[0176] Table 1

[0177]

[0178] Comparative Example 1

[0179] This comparative example is a polyurea coating, prepared using the same method as in Example 1. The main difference is that in both component A and component B, an equal weight proportion of terminal amino polysiloxane is used to replace the fluorinated terminal amino polysiloxane. The specific preparation method of the terminal amino polysiloxane is as follows:

[0180] 7956g of octamethylcyclotetrasiloxane and 0g of trifluoropropylmethylcyclotrisiloxane were stirred and mixed evenly. 59.67g of tetramethylammonium hydroxide silanolate, an alkaline catalyst, was added. The reaction vessel was heated to 80℃ and reacted for 6 hours. Then, 358g of 1,3-bis(aminopropyl)tetramethyldisiloxane was added for end-capping, and the reaction was carried out for 40 minutes. After the reaction was completed, the reaction vessel was heated to 140℃ to decompose the catalyst. Then, a vacuum was applied at 150℃ to remove low-boiling-point substances, yielding an amino-terminated polysiloxane with a fluorine content of 0wt%.

[0181] Test example:

[0182] Test method:

[0183] (1) Using steel as the test substrate, the impact resistance, flexibility, adhesion, salt water resistance, salt spray resistance, artificial weathering resistance, and weather resistance were tested in accordance with the "GB-T 6745-2008 Ship Hull Paint" standard. Among them, the coating was applied directly to the test substrate during the test of impact resistance, flexibility, salt water resistance, salt spray resistance, artificial weathering resistance, and weather resistance. During the adhesion test, the surface of the test substrate was activated with a treatment agent before the coating was applied.

[0184] 1.1 Impact resistance

[0185] The test was conducted in accordance with GB / T 20624.1-2006. A spherical impact punch with a diameter of (20±0.3) mm was used, with a 1 kg hammer. Without a depth control ring, the hammer was dropped from a height of 500 mm. If no paint film peeling or cracking occurred within the deformation area of ​​the impact point, the impact point was considered passed. Two test plates were tested, with five impact points on each plate. If three or more impact points on one of the test plates showed no paint film peeling or cracking, the test item was rated as "passed".

[0186] 1.2 Flexibility

[0187] Perform the procedure according to GB / T 1731-1993. With both hands, place the test panel with the paint film facing upwards and press it firmly onto a shaft of the specified diameter. Using the strength of both thumbs, bend the test panel around the shaft within 2-3 seconds. After bending, the two thumbs should be symmetrical about the center line of the shaft. After bending, observe the paint film using a 4x magnifying glass (3.2). Check for any damage to the paint film, such as cracks, peeling, or other defects.

[0188] 1.3 Adhesion

[0189] The test shall be conducted in accordance with the provisions of GB / T 5210-2006. A tensile testing machine shall be used for the test.

[0190] 1.4 Salt water resistance

[0191] The test shall be conducted in accordance with GB / T 10834. The artificial seawater formulation is as follows: 24.53g sodium chloride, 11.11g sodium sulfate hexahydrate, 4.09g anhydrous sodium sulfate, 1.16g anhydrous calcium chloride, 0.7g potassium chloride, 0.2g sodium bicarbonate, and 0.1g potassium bromide, diluted with distilled water to a total volume of 1L. The test temperature is 27±6℃.

[0192] 1.5 Salt spray resistance

[0193] The test shall be conducted in accordance with GB / T 1771-2007. It shall be carried out in a salt spray chamber at a temperature of 35±2℃, using a sodium chloride aqueous solution with a concentration of (50±10) g / L.

[0194] 1.6 Resistant to artificial climate aging

[0195] The process shall be carried out in accordance with the provisions of GB / T14522-1993, with an irradiance of 0.68 W / m'. The xenon lamp aging shall be carried out in accordance with the provisions of Operation Procedure A in 9.3 of GB / T1865-1997, and the evaluation of the results shall be carried out in accordance with the provisions of GB / T1766-1995.

[0196] 1.7 Weather resistance

[0197] The procedures shall be carried out in accordance with GB / T 9276-1996. Exposure in natural climates shall be assessed in accordance with GB / T1766-1995.

[0198] (2) Abrasion resistance test: GB / T 1768, coating thickness 2mm, friction medium is CS17 rubber abrasive wheel, number of cycles is 3000.

[0199] (3) Using steel as the test substrate, the water droplet angle was measured in accordance with the "GB / T 30693-2014 Contact Angle Measurement" standard to test the static contact angle.

[0200] The test results are shown in Tables 2 and 3 below:

[0201] Table 2

[0202]

[0203] Table 3

[0204]

[0205] As can be seen, compared with Comparative Example 1, Examples 1-13 can effectively improve the wear resistance of the coating and significantly increase the water droplet angle, achieving better antifouling performance. At the same time, the coatings of Examples 1-13 also have good aging resistance and corrosion resistance, and can replace multiple layers of paint film in traditional marine paint with one layer, achieving the same effect as multiple layers of paint film.

[0206] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0207] The embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.

Claims

1. A polyurea composition, characterized in that, comprising a Group A component and a Group B component, wherein the Group A component comprises a first fluoro-terminated amino polysiloxane; the Group B component comprises an isocyanate, a second fluoro-terminated amino polysiloxane, and an amine compound.

2. The polyurea composition according to claim 1, characterized in that, the first fluoro-terminated amino polysiloxane and the second fluoro-terminated amino polysiloxane each independently have one or more of the following characteristics: (1) the monomers comprise a fluoro-cyclosiloxane monomer, or a combination of a cyclosiloxane monomer and a fluoro-cyclosiloxane monomer; (2) the mass percentage of fluorine element is 20% to 40%.

3. The polyurea composition according to claim 2, characterized in that, the first fluoro-terminated amino polysiloxane and the second fluoro-terminated amino polysiloxane each independently have one or more of the following characteristics: (1) the fluoro-cyclosiloxane monomer comprises one or more of trifluoropropylmethylcyclotrisiloxane and 2,4,6,8-tetramethyl-2,4,6,8-tetrakis(3,3,3-trifluoropropyl)cyclotetrasiloxane; (2) the cyclosiloxane comprises one or more of octamethylcyclotetrasiloxane, dodecamethylcyclohexasiloxane, decamethylcyclopentasiloxane, and hexamethylcyclotrisiloxane; (3) in the combination of the cyclosiloxane monomer and the fluoro-cyclosiloxane monomer, the molar ratio of the cyclosiloxane monomer to the fluoro-cyclosiloxane monomer is 1:(1.5 to 4.5).

4. The polyurea composition according to any one of claims 1 to 3, characterized in that the Group B component comprises, in parts by weight: an isocyanate 55 to 75 parts, a second fluoro-terminated amino polysiloxane 20 to 35 parts, and an amine compound 5 to 10 parts.

5. The polyurea composition according to any one of claims 1 to 4, characterized in that, The amine compound contains one or more of a cycloalkyl group and a heterocyclic group.

6. The polyurea composition according to claim 5, wherein The amine compound comprises one or more of 1,4-cyclohexanedimethylamine, an amino-terminated polytetrahydrofuran, isophorone diamine, N,N'-dialkylcyclohexanediamine, diaminodicyclohexylmethane, 1,3-cyclohexanedimethylamine, and 4,4-diaminodicyclohexylmethane.

7. The polyurea composition according to any one of claims 1 to 6, characterized in that, The isocyanate comprises one or more of 4,4-diisocyanate dicyclohexylmethane, isophorone diisocyanate, 1,4-cyclohexanedisocyanate, methylcyclohexanedisocyanate, and norbornane diisocyanate.

8. The polyurea composition according to any one of claims 1 to 7, characterized in that, The Group A component further comprises a promoter, which has one or more of the following characteristics: (1) the first fluoro-terminated amino polysiloxane is 60 to 95 parts by weight, and the promoter is 0.1 to 2 parts by weight; (2) the promoter comprises one or more of γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, and a polyaminoalkyltrialkoxysilane.

9. The polyurea composition according to any one of claims 1 to 8, characterized in that, The Group A component further comprises a pigment filler, and the first fluoro-terminated amino polysiloxane is 60 to 95 parts by weight, and the pigment filler is 1 to 20 parts by weight.

10. The polyurea composition according to any one of claims 1 to 9, characterized in that, The mass ratio of the Group A component to the Group B component is (1 to 10):

1.

11. A process for the production of a polyurea coating, characterized in that comprising the following steps: mixing the Group A component and the Group B component to perform a curing crosslinking reaction; the Group A component comprises a first fluoro-terminated amino polysiloxane; the Group B component comprises an isocyanate, a second fluoro-terminated amino polysiloxane, and an amine compound.

12. The method of claim 11, wherein the polyurea coating is prepared by the steps of: The preparation method of the Group B component comprises: The second fluorine-containing terminal amino polysiloxane and the amine compound are added to the isocyanate under a protective gas atmosphere to perform a prepolymerization reaction.

13. The method of producing a polyurea coating according to claim 11 or 12, characterized in that The first fluorine-containing terminal amino polysiloxane and the second fluorine-containing terminal amino polysiloxane are prepared by the following steps: A fluorine-containing cyclosiloxane monomer, or a combination of a cyclosiloxane monomer and a fluorine-containing cyclosiloxane monomer, is polymerized in the presence of a basic catalyst; An end-capping agent is added to perform an end-capping reaction.

14. The method of claim 13, wherein the polyurea coating is prepared by the steps of: One or more of the following characteristics: (1) The fluorine-containing cyclosiloxane monomer includes one or more of trifluoropropylmethylcyclotrisiloxane and 2,4,6,8-tetramethyl-2,4,6,8-tetrakis(3,3,3-trifluoropropyl)cyclotetrasiloxane; (2) The cyclosiloxane includes one or more of octamethylcyclotetrasiloxane, dodecamethylcyclohexasiloxane, decamethylcyclopentasiloxane, and hexamethylcyclotrisiloxane; (3) In the combination of the cyclosiloxane monomer and the fluorine-containing cyclosiloxane monomer, the molar ratio of the cyclosiloxane monomer to the fluorine-containing cyclosiloxane monomer is 1:(1.5-4.5); (4) The conditions of the polymerization reaction include 5-7 hours of reaction at 80-90°C; (5) The end-capping agent includes one or more of 1,3-bis(aminopropyl)tetramethyldisiloxane, N-2-aminoethyl-3-aminopropylmethyldimethoxysilane, N-aminoethyl-aminopropylmethyldimethoxysilane, and 3-aminopropyl dimethoxymethylsilane; (6) The conditions of the end-capping reaction include 30-50 minutes of reaction at 60-100°C.

15. A polyurea coating, characterized in that, The polyurea composition of any one of claims 1-10 is obtained by a curing cross-linking reaction, or is prepared by the preparation method of any one of claims 11-14.

16. An article housing, characterized by A protective paint including a shell base and a protective paint attached to the surface of the base, the protective paint including the polyurea coating of claim 15.

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