CN116120821B - Double-component anti-doodling material composition and preparation method and application thereof - Google Patents
Double-component anti-doodling material composition and preparation method and application thereof Download PDFInfo
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- CN116120821B CN116120821B CN202211500223.5A CN202211500223A CN116120821B CN 116120821 B CN116120821 B CN 116120821B CN 202211500223 A CN202211500223 A CN 202211500223A CN 116120821 B CN116120821 B CN 116120821B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/778—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur silicon
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
- C14C11/006—Surface finishing of leather using macromolecular compounds using polymeric products of isocyanates (or isothiocyanates) with compounds having active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2150/00—Compositions for coatings
Abstract
The invention relates to a two-component anti-graffiti material composition, a preparation method and application thereof, wherein the two-component anti-graffiti material composition comprises a component A and a component B; the component A comprises organosilicon modified polyaspartic acid ester, wherein the organosilicon modified polyaspartic acid ester takes a polysiloxane chain segment as a main chain and takes at least 3 aspartate groups as side chains; the component B comprises organosilicon modified isocyanate; the mass ratio of the organosilicon modified polyaspartate in the component A to the organosilicon modified isocyanate in the component B is (22-50): (20.9-40.4). The two-component anti-graffiti material composition provided by the invention can be used for obtaining an anti-graffiti coating, has excellent anti-graffiti performance, has proper safe operation time and curing time, can realize self-drying at normal temperature, can meet the requirements of operation time and production efficiency of an application site, and can be widely applied to leather, synthetic leather and other materials.
Description
Technical Field
The invention relates to the technical field of anti-graffiti materials, in particular to a two-component anti-graffiti material composition, a preparation method and application thereof.
Background
The anti-graffiti performance is one of the high-end requirements of high-end paints and leather top coats. In general, anti-graffiti coatings can be derived from two base materials: organic fluorine materials and organic silicon materials, the organic fluorine materials have lower surface energy than the organic silicon materials, and it is speculated in theory that the organic fluorine materials can better realize the anti-graffiti effect. But the cost of the organic fluorine material is high, which is not beneficial to the commercial large-scale popularization. Compared with organic fluorine materials, the cost of the organic silicon material base material is relatively low, the industrial chain is perfect, and the organic silicon material used as the base material of the anti-graffiti resin has wider prospect.
In the research and development practice of the organosilicon modified anti-graffiti material, the organosilicon material has low crystallinity, the linear organosilicon material with the hundred thousand molecular weight is still in a flowable liquid state, the intensity of the ultrahigh molecular weight silicon rubber prepared by a vulcanization process is also limited, the surface energy of the organosilicon material is lower, and the simple organosilicon resin is difficult to be adhered to the surfaces of other substrates. In order to overcome the defects, a great deal of research work is done, and finally, the urethane bonds and the allophanate bonds are strong polar bonds with strong crystallinity, and the characteristic can exactly overcome the defects of weak crystallinity and low surface energy of the organosilicon material. The allophanate bond is generated by the reaction of amino and isocyanate groups, has stronger polarity and strength than the urethane bond, and has the advantages of high curing speed and high efficiency, and the primary amino and the isocyanate groups can react without heating or catalyst at the moment of contact. However, this also presents another difficulty in that the reaction rate between the amino groups and the isocyanate groups is too fast to control and the pot life is short. In order to solve this problem, material scientists and engineers at home and abroad have also made a great deal of research work. For example, patent CN105992785a reports a method of generating a secondary amino group, which has greatly reduced activity under steric hindrance after reacting a maleate compound with a primary amino group, which can coexist with an isocyanate group for a long time at normal temperature, thereby facilitating construction of a high-performance polyurea coating, and introducing an aspartic acid ester segment into an organosilicon segment can not only prolong the construction pot life, but also improve the overall properties of the resulting coating.
Currently, there are many reports on silicone/polyurea materials in other fields of application.
CN112250868A discloses a polysiloxane-asparaguse resin, the preparation raw materials of which comprise siloxane monomer, end-capping agent, maleate; the preparation method of the polysiloxane-asparaguse resin comprises the following steps: s1, preparing end-capped polysiloxane: reacting a siloxane monomer with a blocking agent under the action of a catalyst to obtain blocked polysiloxane; s2, preparation of polysiloxane-asparagus resin: the blocked polysiloxane is mixed with maleate to react to obtain polysiloxane-asparaguse resin. However, the organosilicon/aspartate materials disclosed therein do not give good anti-graffiti properties when applied in anti-graffiti coatings. CN103270087a and CN113354792a have similar problems. These prior art techniques all improve the water repellency and strength of the coating by introducing siloxane groups in the side chains of the polyaspartate. However, when the organosilicon/aspartate material disclosed in the prior art is applied to the anti-graffiti coating, better anti-graffiti performance cannot be obtained, and in practice, we find that the gel time is still very short after the organosilicon/aspartate is mixed with the conventional isocyanate trimer curing agent in the market, generally not more than 60 minutes, and the safe operation time which is so short can not meet the requirements of the application site.
CN111363460a discloses an environment-friendly baking-free varnish for spraying, a preparation method and a cured material, which discloses a method for reducing the reaction speed between isocyanate and polyaspartate by adding silicon modified polyisocyanate into a curing agent component, but the disclosed construction pot life is still shorter, and the disclosed components cannot obtain better anti-graffiti effect when being applied to leather or synthetic leather substrates.
CN113861816a discloses an organosilicon modified PAE polyurea coating, which comprises a component a and a component B, wherein the preparation method of organosilicon modified polyaspartic acid ester in the component a comprises the following steps: reacting vinyl alcohol or vinyl epoxy compound with terminal hydrogen-containing silicone oil to obtain functionalized silicone oil; reacting the functionalized silicone oil with a dialkyl maleate or maleic anhydride to obtain a dimeric maleate; the maleic acid dimeric siloxane ester reacts with aliphatic primary diamine to obtain the product; the preparation method of the isocyanate silicone oil curing agent in the component B comprises the following steps: reacting a vinyl dihalide or polyhalogenated compound with hydrogen-containing silicone oil to obtain polyhalogenated silicone oil; reacting polyhalogenated silicone oil with phthalimide salt and then heating hydrazine to hydrolyze polyamino silicone oil; dropwise adding trichloromethyl chloroformate into polyamino silicone oil, and performing irradiation reaction by using an incandescent lamp. However, when the coating is applied to anti-graffiti coating, a coating with long construction period and excellent anti-graffiti performance cannot be obtained.
In summary, it is important to develop a two-component anti-graffiti material with longer construction pot life, better cure speed, and excellent anti-graffiti properties.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a two-component anti-graffiti material composition, a preparation method and application thereof, wherein the two-component anti-graffiti material composition is used for obtaining an anti-graffiti coating, has excellent anti-graffiti performance, has proper safe operation time and curing time, can realize self-drying at normal temperature, can meet the requirements of operation time and production efficiency of application sites, and can be widely applied to leather, synthetic leather and other materials.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a two-part anti-graffiti material composition comprising a part a and a part B;
the component A comprises organosilicon modified polyaspartic acid ester, wherein the organosilicon modified polyaspartic acid ester takes a polysiloxane chain segment as a main chain and takes at least 3 aspartate groups as side chains;
the component B comprises organosilicon modified isocyanate;
the mass ratio of the organosilicon modified polyaspartate in the component A to the organosilicon modified isocyanate in the component B is (22-48): (20.9-40), wherein 22-48 may be 25, 30, 35, 40, 45, etc., and 20.9-40 may be 30, 32, 34, 36, 38, etc.
In the prior art, the organosilicon/polyaspartate takes a polyaspartate chain segment as a main chain and takes a siloxane chain segment as a side chain. In the invention, the organic silicon modified polyaspartic ester with the structure is a comb-shaped structure taking a siloxane chain segment as a core and aspartic ester as a shell, after the structure is mixed with organic silicon modified isocyanate serving as a curing agent in the component B, the safe operation time can reach more than 8 hours, not only can realize curing and crosslinking at normal temperature, but also can obtain a coating film with more sufficient curing, larger crosslinking degree and denser coating film after curing, and the obtained coating film can effectively prevent stain from penetrating and realize excellent graffiti resistance.
In the invention, the double components refer to: the components A and B are packaged separately, and the components are mixed in a specific ratio before use to be cured.
In the invention, the anti-graffiti refers to that graffiti such as a marker pen, an oily pen and the like cannot be painted on the coating by water and oil repellency of the coating, and the graffiti on the coating is easy to remove and does not leave graffiti marks.
In the present invention, the reason why the silicone-modified polyaspartate of the structure is preferable is that: the number of groups of the secondary amino group and the number average molecular weight of the silicone-modified polyaspartate are major factors affecting the curing speed, the coating film properties, and the like. The larger the molecular weight of the organosilicon modified polyaspartic acid ester is, the more secondary amino groups are, the faster the curing speed is, the more compact the coating film is, and the anti-graffiti performance is better, but the organosilicon modified polyaspartic acid ester has too large molecular weight, the too large number of groups of secondary amino groups and too fast the curing speed can cause too short safe operation time, so that the requirements of application sites cannot be met, but the too low molecular weight of the organosilicon modified polyaspartic acid ester can cause the anti-graffiti performance of the coating film to be unsatisfactory.
Preferably, the structure of the organosilicon modified polyaspartic acid ester is shown as a formula I:
wherein m is an integer from 1 to 300, such as 2, 3, 5, 10, 50, 100, 150, 200, 250, etc.;
n is an integer from 3 to 300, such as 5, 10, 50, 100, 150, 200, 250, etc.;
r1 and R2 are each independently C1-C20 alkanyl, such as C2, C4, C6, C8, C10, C12, C14, C16, C18, etc.
In the present invention, the term "C1-C20" means the number of main chain carbon atoms. Preferably, R1 and R2 are the same.
Preferably, the number m+n is sufficient to provide the polysiloxane segment with a number average molecular weight of 300-100000g/mol (e.g., 1000g/mol, 5000g/mol, 10000g/mol, 20000g/mol, 40000g/mol, 60000g/mol, 80000g/mol, etc.).
Preferably, the silicone modified isocyanate has a functionality of 2.
In the present invention, the functionality of the silicone modified isocyanate is preferably 2 because: compared with the commercial isocyanate curing agent, the organosilicon modified isocyanate not only has more proper curing speed, but also can further improve the anti-graffiti performance and the adhesion performance.
Preferably, the NCO content in the silicone modified isocyanate is 1-6wt%, e.g., 2wt%, 3wt%, 4wt%, 5wt%, etc.
Preferably, the structure of the organosilicon modified isocyanate is shown as a formula II:
wherein j and k are each independently an integer of 1 to 100, such as 2, 3, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, etc., k is further preferably an integer of 3 to 100;
r3, R4 and R5 are each independently any of C1-C20 alkanyl (e.g., C2, C4, C6, C8, C10, C12, C14, C16, C18, etc.), C6-C30 arene (e.g., C8, C10, C16, C20, C24, C28, etc.).
Each of R6 and R7 is independently selected from any one of the following groups;
wherein is the site of attachment.
Preferably, the amount j+k is sufficient to provide the silicone segment with a number average molecular weight of 800 to 20000g/mol (e.g., 1000g/mol, 5000000g/mol, 1000g/mol, 15000g/mol, etc.).
In the invention, the larger the molecular weight of the organosilicon modified isocyanate is, the slower the curing speed is.
Preferably, the reaction raw materials of the organosilicon modified polyaspartic ester comprise: polyaminosilicone oil, maleate and optionally solvent a.
Preferably, the mass ratio between the polyaminosilicone oil and the maleate is (20-40): (2-10), wherein 20-40 may be 25, 30, 35, etc., and 2-10 may be 4, 6, 8, etc.
Preferably, the polyaminosilicone oil comprises a pendant polyamino terminated silicone oil.
Preferably, the reaction raw materials of the organosilicon modified isocyanate comprise: a hydroxy silicone oil, a polyisocyanate and optionally a solvent B.
Preferably, the mass ratio between the hydroxyl silicone oil and the polyisocyanate is (19-30): (1.9-10.4), wherein 19-30 may be 20, 22, 24, 26, 28, etc., and 1.9-10.4 may be 2, 4, 6, 8, 10, etc.
Preferably, the A component further comprises an auxiliary agent and a solvent C.
Preferably, the adjunct comprises any one or a combination of at least two of a catalyst, an antioxidant, a dispersant, or a powder, wherein typical but non-limiting combinations include: the catalyst and the antioxidant are combined, the dispersant and the powder are combined, and the catalyst, the antioxidant, the dispersant and the powder are combined.
Preferably, the mass ratio between the total amount of the solvent a, the solvent B and the solvent C and the silicone-modified aspartic ester is (15-40): (22-50), wherein 15-40 may be 20, 25, 30, 35, etc., and 22-50 may be 25, 30, 35, 40, 45, etc.
In the present invention, the solvent is not particularly limited, and exemplified by Propylene Glycol Methyl Ether Acetate (PGMEA), toluene, xylene, N-Dimethylformamide (DMF), N-Dimethylpropionamide (DMPA), N-dimethylacetamide, ethyl Acetate (EA), butyl Acetate (BA), and homologs, derivatives, isomers, and the like thereof, may be used alone, or two or more thereof may be mixed.
Preferably, the mass ratio between the catalyst and the silicone-modified aspartic ester is (0-0.6): (22-50), wherein 0-0.6 may be 0.1, 0.2, 0.3, 0.4, 0.5, etc., and 22-50 may be 25, 30, 35, 40, 45, etc.
In the present invention, the catalyst is not necessarily an auxiliary component added, and may not be used.
In the present invention, the catalyst includes, for example, dibutyltin dilaurate, stannous octoate, organobismuth-based catalysts, organozinc-based catalysts, triethylenediamine, iron octoate, zinc naphthenate, tetraisobutyl titanate, etc., and homologs, derivatives and isomers thereof, and the above-mentioned catalysts may be used alone or in combination of two or more.
The catalyst can be used for adjusting the curing speed of the mixed components A and B, and the catalyst can be not added for a mixed system with higher reaction speed so as not to cause too short construction time.
Preferably, the mass fraction of the antioxidant to the silicone-modified aspartate is (0.2-1.5): (22-50), wherein 0.2-1.5 may be 0.4, 0.6, 0.8, 1, 1.2, 1.4, etc., and 22-50 may be 25, 30, 35, 40, 45, etc.
In the present invention, the antioxidant includes antioxidant 1010, antioxidant 1135, antioxidant JPP100, or the like, and the above antioxidants may be used alone or in combination.
Preferably, the mass ratio between the dispersant and the silicone-modified aspartic ester is (0-1), based on 100 parts by total mass of the a component and the B component: (22-50), wherein 0-1 may be 0.2, 0.4, 0.6, 0.8, etc., and 22-50 may be 25, 30, 35, 40, 45, etc.
In the present invention, the dispersant is not particularly limited, and examples thereof include 771N and 771D manufactured by molecularpolymer limited, guangzhou s Ke Gao.
The above-mentioned dispersing agent can be used for stably dispersing the powder, and when the powder is not added, the dispersing agent may not be added.
Preferably, the mass ratio between the powder and the organosilicon modified aspartate is (0-20): (22-50), wherein 0-20 may be 2, 4, 6, 8, 10, 12, 14, 16, 18, etc., and 22-50 may be 25, 30, 35, 40, 45, etc.
In the present invention, a powder known in the art, such as fumed silica or the like, which can be used to adjust the glossiness of the resin, can be used. Carbon meter 520 of silicon carbon cat (guangzhou) technology limited may be used. In a second aspect, the present invention provides a method for preparing the two-part anti-graffiti material composition of the first aspect, the method comprising the steps of:
(1) Reacting polyamino silicone oil with a first reaction system of maleate at a first set temperature to obtain organosilicon modified polyaspartic acid ester, and forming the component A;
(2) And (3) reacting the second reaction system of the hydroxyl silicone oil and the polyisocyanate at a second set temperature to obtain the organosilicon modified isocyanate, thereby forming the component B.
Preferably, in step (1), the first set temperature is 60-70 ℃, e.g. 62 ℃, 64 ℃, 66 ℃, 68 ℃, etc.
Preferably, in step (1), the reaction time is 4-10 hours, such as 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, etc.
Preferably, the reaction is carried out until after a primary ammonia content of 0mol/100g of the reaction system.
Preferably, the mixing mode of the polyamino silicone oil and the maleate comprises the following steps: the maleate ester was added dropwise to the polyaminosilicone oil.
Preferably, the mass ratio of the polyamino silicone oil to the maleate is (20-40): (2-10), wherein 20-40 may be 22, 24, 26, 27, 28, 29, 30, 31, 32, 34, 36, 38, etc., and 2-10 may be 3, 4, 5, 6, 7, 8, 9, etc.
Preferably, the polyaminosilicone oil comprises a pendant polyamino terminated silicone oil.
In the present invention, the polyaminosilicone oil may be prepared by a known method, and commercially available products may be selected. Examples of commercially available products include Silok4360F10 (molecular weight 100000) which is a model number of Silok Ke Gao molecular Polymer, silok3232, silok3200 and the like, and the amino-terminated silicone oil of the above-mentioned model number may be used alone or two or more of the amino-terminated silicone oils of the above-mentioned model number may be mixed and used.
Preferably, the polyaminosilicone oil has a number average molecular weight of 400-100000g/mol, for example 500g/mol, 1000g/mol, 5000g/mol, 10000g/mol, 20000g/mol, 40000g/mol, 60000g/mol, 80000g/mol, etc.
Preferably, the structure of the polyaminosilicone oil is shown as a formula III:
wherein m is an integer from 1 to 300, such as 2, 3, 5, 10, 50, 100, 150, 200, 250, etc.;
n is an integer from 3 to 300, such as 5, 10, 50, 100, 150, 200, 250, etc.
Preferably, the maleate comprises any one or a combination of at least two of monomethyl maleate, dimethyl maleate, diethyl maleate, dibutyl maleate, dipropyl maleate, dioctyl maleate or methylpropyl maleate, wherein typical but non-limiting combinations include: a combination of monomethyl maleate and dimethyl maleate, a combination of diethyl maleate, dibutyl maleate and dipropyl maleate, a combination of dibutyl maleate, dipropyl maleate, dioctyl maleate and methylpropyl maleate, and the like.
In the present invention, the maleate may also include homologs, derivatives, isomers, etc. of the above compounds, and the maleate may be used alone or in combination.
Preferably, the preparation of the a-component further comprises mixing the silicone modified polyaspartate with other components.
Preferably, in step (2), the second set temperature is 80-90 ℃, e.g. 82 ℃, 84 ℃, 86 ℃, 88 ℃, etc.
Preferably, in step (2), the reaction time is 2-4 hours, such as 2.5 hours, 3 hours, 3.5 hours, etc.
Preferably, the mass ratio of the hydroxyl silicone oil to the polyisocyanate is (19-30): (1.9-10.4), wherein 19-30 may be 20, 22, 24, 26, 28, etc., and 1.9-10.4 may be 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.
Preferably, the hydroxy silicone oil comprises a single ended bishydroxy terminated silicone oil.
In the invention, the hydroxyl silicone oil is preferably single-end double-hydroxyl terminated silicone oil, because: the reaction activity is high, and the graffiti resistance of the coating can be further improved.
In the present invention, the hydroxyl silicone oil may be prepared according to a known method, and commercially available products may be selected. Examples of commercially available products include single-ended dihydroxy-terminated silicone oils of the types 8832F1, 8832F2, 8822F1, etc. of the Guangzhou s-lo Ke Gao molecular polymer company, and single-ended dihydroxy-terminated silicone oils of the types mentioned above may be used alone or two or more of the types mentioned above may be mixed and used.
Preferably, the hydroxyl silicone oil has a number average molecular weight of 800-20000g/mol, for example 1000g/mol, 2000g/mol, 4000g/mol, 5000g/mol, 10000g/mol, 15000g/mol, etc.
Preferably, the structural formula of the hydroxyl silicone oil is shown as formula IV:
wherein j, k, p are each independently integers from 0 to 100, such as 2, 3, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, etc.;
the j.gtoreq.1, e.g., 2, 3, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, etc.;
the k is 3 or more, for example, 3, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, etc.;
the p.gtoreq.0, for example 2, 3, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, etc.
Preferably, the polyisocyanate comprises a diisocyanate.
Preferably, the diisocyanate comprises one or more of Toluene Diisocyanate (TDI), m-xylylene isocyanate (XDI), 4' -dicyclohexylmethane diisocyanate (HMDI), diphenylmethane diisocyanate (MDI), hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), and homologs, derivatives and isomers thereof.
As a preferable technical scheme, the preparation method comprises the following steps:
(1) The mass ratio is (20-40): reacting the side polyamino terminated silicone oil of (2-10) with maleic acid ester at 60-70 ℃ for 4-10 hours to obtain organosilicon modified polyaspartic acid ester, and then mixing the organosilicon modified polyaspartic acid ester with other components to form the component A;
(2) The mass ratio is (19-30): (1.9-10.4) reacting single-end dihydroxy terminated silicone oil with polyisocyanate at 80-90 ℃ for 2-4h to obtain organosilicon modified isocyanate, and forming the component B.
In the invention, no catalyst is added in the reaction in the step (1) and the step (2), and the temperature is controlled to regulate the reaction.
In a third aspect, the present invention provides a coated product comprising a substrate and a coating layer formed from a coating comprising the two-part anti-graffiti material composition of the first aspect applied to the substrate.
Preferably, the substrate comprises any one of leather, leather material or synthetic leather.
Preferably, the preparation method of the coating comprises the following steps:
s1, uniformly mixing the component A and the component B to obtain a mixture;
s2, coating the obtained mixture on a substrate, and standing for 3-7 days (such as 4 days, 5 days, 6 days and the like) at normal temperature for curing, or drying and curing for 3-5 min (such as 3.5min, 4min, 4.5min and the like) at 90-140 ℃ (such as 100 ℃, 110 ℃ and 130 ℃), so as to obtain the coating.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides a double-component anti-graffiti material which consists of an A component with an organosilicon modified aspartic ester as a main component and a B component with an organosilicon modified isocyanate as a main component, wherein after the A component and the B component are mixed, the safe operation time can reach more than 8 hours, a coating film with more sufficient curing, higher crosslinking degree and denser coating film can be obtained after curing, and the obtained coating film can effectively prevent stain infiltration and realize excellent anti-graffiti performance.
(2) The double-component anti-graffiti material composition can be widely applied to leather, synthetic leather and other materials, and can provide excellent anti-graffiti performance.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
In the present invention, the raw material information related to each embodiment is as follows:
amino silicone oil: supplied by Guangzhou, inc. of Stlo Ke Gao molecular Polymer.
Hydroxyl-terminated silicone oil: supplied by Guangzhou, inc. of Stlo Ke Gao molecular Polymer.
Dispersing agent: supplied by Guangzhou, inc. of Stlo Ke Gao molecular Polymer.
Powder: carbon rice 520, offered by silicon carbon cat (guangzhou) technologies.
Catalyst: organotin T9: win creating chemistry; organic bismuth: biCAT 8108, leading chemistry; organozinc, bicat3228, led to chemistry.
1. Preparation of organosilicon-modified aspartate and organosilicon-modified isocyanate.
Synthesis example 1
(1) The silicone-modified aspartic ester was produced by the following method.
Adding 10g of toluene into 20g of polyamino silicone oil (model 4360F10, number average molecular weight of 100000 g/mol), slowly heating to 60 ℃, slowly and uniformly dropwise adding 2.06g of dimethyl maleate, controlling the dropwise adding time to be 1 hour, heating to 70 ℃, keeping the temperature for reaction for 6 hours, detecting that the primary ammonia content of the reaction system is approximately 0mol/100g by using water Yang Quanfa, ending the reaction, cooling to 40 ℃, and discharging to obtain the organosilicon modified aspartic ester F1.
(2) The silicone-modified isocyanate was produced by the following method.
20g of hydroxyl-terminated silicone oil (model 8822F1, molecular weight is 1200 g/mol), 7.4g of IPDI and 10g of toluene are uniformly mixed, heated to 80 ℃ for reaction for 4 hours, discharged, filled with nitrogen and sealed, thus obtaining the organosilicon modified isocyanate curing agent B1.
Synthesis example 2
(1) The silicone-modified aspartic ester was produced by the following method.
Adding 2g of toluene into 20g of polyamino silicone oil (model 3232, number average molecular weight of 20000 g/mol), slowly heating to 60 ℃, slowly and uniformly dropwise adding 3g of diethyl maleate, controlling the temperature to be raised to 60 ℃ after 3 hours of dropwise adding are completed, carrying out heat preservation reaction for 10 hours, detecting that the primary ammonia content of the reaction system is approximately 0mol/100g by using water Yang Quanfa, ending the reaction, cooling to 40 ℃ and discharging to obtain the organosilicon modified aspartic ester F2.
(2) The silicone-modified isocyanate was produced by the following method.
20g of hydroxy silicone oil (model 8822F2, number average molecular weight is 1800 g/mol), 5.82g of HMDI and 10g of xylene are uniformly mixed, heated to 90 ℃ for reaction for 2 hours, discharged, filled with nitrogen and sealed, and the organosilicon modified isocyanate curing agent B2 is obtained.
Synthesis example 3
(1) The silicone-modified aspartic ester was produced by the following method.
Adding 6g of toluene into 30g of polyamino silicone oil (model 3200, number average molecular weight is 10000 g/mol), slowly heating to 60 ℃, slowly dripping 6g of dibutyl maleate at a constant speed, controlling the dripping to be completed in 3 hours, heating to 60 ℃, preserving heat for reaction for 9 hours, detecting that the primary ammonia content of the reaction system is approximately 0mol/100g by using water Yang Quanfa, ending the reaction, cooling to 40 ℃ and discharging to obtain the organosilicon modified aspartic ester F3.
(3) The silicone-modified isocyanate was produced by the following method.
30g of hydroxy silicone oil (model 8832F1, number average molecular weight is 4200 g/mol), 2.4g of HDI and 10g of dimethylbenzene are uniformly mixed, heated to 90 ℃ for reaction for 2 hours, discharged, filled with nitrogen and sealed, and the organosilicon modified isocyanate curing agent B3 is obtained.
Synthesis example 4
(1) The silicone-modified aspartic ester was produced by the following method.
Adding 2g of toluene into 30g of polyamino silicone oil (model 3232, number average molecular weight of 20000 g/mol), slowly heating to 60 ℃, slowly and uniformly dropwise adding 6g of dipropyl maleate, controlling the temperature to be raised to 60 ℃ after 3 hours of dropwise adding, keeping the temperature for reaction for 7 hours, detecting that the primary ammonia content of the reaction system is approximately 0mol/100g by using water Yang Quanfa, ending the reaction, cooling to 40 ℃ and discharging to obtain the organosilicon modified aspartic ester F4.
(2) The silicone-modified isocyanate was produced by the following method.
26g of hydroxy silicone oil (model 8832F2, number average molecular weight is 4800 g/mol), 1.9g of TDI and 10g of xylene are uniformly mixed, heated to 90 ℃ for reaction for 2 hours, discharged, filled with nitrogen and sealed, and the organosilicon modified isocyanate curing agent B4 is obtained.
Synthesis example 5
(1) The silicone-modified aspartic ester was produced by the following method.
30g of polyamino silicone oil (model 4360F10, number average molecular weight is 100000 g/mol), 10g of polyamino silicone oil (model 3232, number average molecular weight is 20000 g/mol) and 2g of toluene are added into a reaction kettle, after slowly heating to 60 ℃, 8g of methyl propyl maleate is slowly and uniformly added dropwise, after the dropwise addition is completed in 2 hours, the temperature is raised to 70 ℃ for heat preservation reaction for 4 hours, after detecting that the primary ammonia content of the reaction system is close to 0mol/100g by using water Yang Quanfa, the reaction is finished, and the temperature is reduced to 40 ℃ for discharging, thus obtaining the organosilicon modified aspartic ester F5.
(2) The silicone-modified isocyanate was produced by the following method.
25g of hydroxy silicone oil (model 8822F1, number average molecular weight is 1200 g/mol), 10.4g of MDI and 10g of dimethylbenzene are uniformly mixed, heated to 90 ℃ for reaction for 2 hours, discharged, filled with nitrogen and sealed, and the organosilicon modified isocyanate curing agent B5 is obtained.
Synthesis example 6
(1) The silicone-modified aspartic ester was produced by the following method.
20g of polyamino silicone oil (model 4360F10, number average molecular weight is 10000 g/mol), 10g of polyamino silicone oil (model 3200, number average molecular weight is 10000 g/mol) and 2g of toluene are added into a reaction kettle, slowly heating to 60 ℃, slowly and uniformly dropwise adding 10g of dimethyl maleate, controlling the dropwise adding to be completed in 2 hours, heating to 70 ℃ for heat preservation reaction for 5 hours, detecting that the primary ammonia content of the reaction system is approximately 0mol/100g by using water Yang Quanfa, ending the reaction, cooling to 40 ℃ and discharging to obtain the organosilicon modified aspartate F6.
(2) The silicone-modified isocyanate was produced by the following method.
30g of hydroxy silicone oil (model 8832F4, number average molecular weight is 5200 g/mol), 6g of XDI and 10g of dimethylbenzene are uniformly mixed, heated to 90 ℃ for reaction for 2 hours, discharged, filled with nitrogen and sealed, and the organosilicon modified isocyanate curing agent B6 is obtained.
Synthesis example 7
(1) The silicone-modified aspartic ester was produced by the following method.
20g of polyamino silicone oil (model 4360F10, number average molecular weight is 100000 g/mol), 10g of polyamino silicone oil (model 3232, number average molecular weight is 20000 g/mol) and 2g of toluene are added into a reaction kettle, after slowly heating to 60 ℃, 8g of dibutyl maleate is slowly and uniformly added dropwise, after the dropwise addition is completed in 2 hours, the temperature is raised to 65 ℃ and the heat preservation reaction is carried out for 7 hours, after detecting that the primary ammonia content of the reaction system is approximately 0mol/100g by using water Yang Quanfa, the reaction is finished, and the temperature is reduced to 40 ℃ for discharging, thus obtaining the organosilicon modified aspartic ester F7.
(2) The silicone-modified isocyanate was produced by the following method.
30g of hydroxy silicone oil (model 8822F1, number average molecular weight is 1200 g/mol), 9.7g of H6XDI and 10g of xylene are uniformly mixed, heated to 90 ℃ for reaction for 2 hours, discharged, filled with nitrogen and sealed, and the organosilicon modified isocyanate curing agent B7 is obtained.
Synthesis example 8
The difference between this synthesis example and synthesis example 1 is that: polyaminosilicone oil having a molecular weight of 6000 was prepared to obtain F8 in the same manner as in Synthesis example 1.
Synthesis example 9
The difference between this synthesis example and synthesis example 1 is that the hydroxyl silicone oil used in this synthesis example was a double-ended monohydroxy silicone prepolymer (Silok 8812F 2), and F9 was produced in the same manner as in synthesis example 1.
Synthesis of comparative example 1
This synthesis comparative example an organosilicon modified aspartic acid ester F10 was synthesized in the same manner as in Synthesis example 1, except that the aminosilicone was changed to N- (2-aminoethyl) -3-aminopropyl trimethoxysilane (molecular weight: 222 g/mol).
Synthesis of comparative example 2
This synthetic comparative example was prepared by referring to the method of comparative example 3 of patent CN113861816a to obtain a double amino silicone oil, substituting the double amino group for the polyaminosilicone oil of example 1, and preparing the silicone aspartate F11 in the same manner as in example 1.
2. Two-component anti-graffiti material composition
The two-part anti-graffiti material compositions provided in examples 1-9 and comparative examples 1-2 are shown in table 1 in terms of the composition of the parts by weight, wherein the weight% is based on the total weight of the two-part anti-graffiti material composition:
TABLE 1
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The raw materials of the component A are mixed, ground and dispersed according to the components and the proportions shown in the table 1, namely, the two-component anti-graffiti material composition is formed by the raw materials and the component B.
The compositions of the examples and the comparative examples only differ in raw materials, are mixed by the same method, are coated on a substrate and cured into a film, and specifically comprise the following steps:
s1, uniformly mixing the component A and the component B to obtain a mixture;
s2, coating the obtained mixture on a substrate, and standing for 7 days at normal temperature for curing, or drying and curing for 5min at 120 ℃ to obtain the anti-graffiti coating.
Performance testing
The anti-graffiti material compositions described in examples 1-9 and comparative examples 1-2 were tested as follows:
(1) Gel time: and mixing the components in the anti-graffiti material composition to obtain a mixture, judging gel points through a wire drawing method, testing once every 1h, judging to be qualified if the gel time exceeds 8 hours, and judging to be unqualified if the gel time is less than 8 hours.
(2) Anti-graffiti performance: mixing the components in the anti-graffiti material composition to obtain a mixture, coating the mixture on light-colored leather by using a wire rod, and drying the mixture at 100 ℃ for 3min to obtain an anti-graffiti coating; respectively writing and marking on the surface of the obtained anti-graffiti coating by using an oil ball pen of Mitsubishi pencil Co and an oil marking pen of zebra brand, then wiping cleanly by using dry cotton cloth, repeatedly writing and wiping for 10 times to observe the residual condition of stains, and classifying the residual degree of marks on the surface of the anti-graffiti coating into 1-5 grades, wherein the 1 grade is no marks, and the anti-graffiti performance is optimal; grade 5 is the most visible mark remaining, and the worst anti-graffiti performance.
(3) Surface drying time: and mixing the components in the anti-graffiti material composition to obtain a mixture, coating the mixture on leather by using a wire rod, and after the mixture is placed for 3 days at normal temperature, lightly touching the surface of a coating film by using fingers, wherein the degree of sticking the coating film on the fingers from paint liquid is classified into 4 grades, 1 grade is completely non-sticking, and 4 grades are the degree of serious sticking.
(4) Curing time: the components in the anti-graffiti material composition are mixed to obtain a mixture, the mixture is coated on leather by a wire rod, after the mixture is dried for 5min at the temperature of 100 ℃, the coating film is pressed by fingers, and rubbed by fingers, if no fingerprint remains on the coating film when the coating film is pressed by fingers, and no scratch remains on the coating film when the coating film is rubbed by fingers, the mixture is judged to be qualified, and if the fingerprint remains on the coating film when the coating film is pressed by fingers, and/or obvious scratches appear when the coating film is rubbed by fingers.
(5) Adhesion force: mixing the components in the anti-graffiti material composition to obtain a mixture, coating the obtained mixture on leather, drying and curing for 5min at 110 ℃ to obtain an anti-graffiti coating, wiping the surface of the leather back and forth for 10 times by using dust-free cloth, wherein the surface is 1-5 grades according to the situation of surface falling or abrasion, the grade 1 is the best, and the surface is free from falling and abrasion; grade 5 was worst, with severe flaking and wear.
The test results are summarized in table 2.
TABLE 2
As can be seen from analysis of the data in Table 2, the anti-graffiti material composition provided by the invention has excellent anti-graffiti performance, and has proper safe operation time and curing time, so that self-drying at normal temperature can be realized, and the requirements of operation time and production efficiency of an application site can be met.
Analysis of comparative examples 1-3 and example 1 shows that comparative examples 1-3 do not perform as well as example 1, demonstrating that the silicone-modified aspartate of the present invention in combination with the silicone-modified isocyanate provides an anti-graffiti material composition that performs better.
The present invention is described in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e., it does not mean that the present invention must be practiced depending on the above detailed methods. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (32)
1. A two-part anti-graffiti material composition, comprising a part a and a part B;
the component A comprises organosilicon modified polyaspartic acid ester, wherein the organosilicon modified polyaspartic acid ester takes a polysiloxane chain segment as a main chain and takes at least 3 aspartate groups as side chains;
the component B comprises organosilicon modified isocyanate;
the mass ratio of the organosilicon modified polyaspartate in the component A to the organosilicon modified isocyanate in the component B is (22-50): (20.9-40.4).
2. The two-part anti-graffiti material composition of claim 1, wherein the silicone-modified polyaspartic ester has the structure of formula i:
i
Wherein m is an integer of 1 to 300;
n is an integer of 3 to 300;
r1 and R2 are each independently C1-C20 alkanyl.
3. The two-part anti-graffiti composition of claim 2, wherein m+n is sufficient in number to provide the polysiloxane segments with a number average molecular weight of 300-100000 g/mol.
4. The two-part anti-graffiti composition of claim 1, wherein the silicone-modified isocyanate has a functionality of 2.
5. The two-part anti-graffiti composition of claim 1, wherein the silicone-modified isocyanate has an NCO content of 1-6wt%.
6. The two-part anti-graffiti material composition of claim 1, wherein the silicone-modified isocyanate has the structure of formula ii:
II type
Wherein j and k are each independently integers from 1 to 100;
r3, R4 and R5 are each independently any one of C1-C20 alkyl and C6-C30 aryl;
each of R6 and R7 is independently selected from any one of the following groups;
、/>、 />、、/>、；
wherein is the site of attachment.
7. The two-part anti-graffiti material composition of claim 6, wherein j+k is sufficient in amount to provide the silicone segment with a number average molecular weight of 800-20000 g/mol.
8. The two-part anti-graffiti material composition of claim 1, wherein the silicone-modified polyaspartate comprises: polyaminosilicone oil, maleate and optionally solvent a;
the reaction raw materials of the organosilicon modified isocyanate comprise: hydroxyl silicone oil, polyisocyanate and optional solvent B;
the component A also comprises an auxiliary agent and a solvent C.
9. The two-part anti-graffiti composition of claim 8, wherein the mass ratio between the polyamino silicone oil and maleate is (20-40): (2-10).
10. The two-part anti-graffiti composition of claim 8, wherein the polyaminosilicone oil comprises a pendant polyamino terminated silicone oil.
11. The two-part anti-graffiti composition of claim 8, wherein the mass ratio between the hydroxy silicone oil and the polyisocyanate is (19-30): (1.9-10.4).
12. The two-part anti-graffiti material composition of claim 8, wherein the adjuvant comprises any one or a combination of at least two of a catalyst, an antioxidant, a dispersant, or a powder.
13. The two-part anti-graffiti material composition of claim 8, wherein the mass ratio between the total amount of solvent a, solvent B and solvent C and the silicone-modified aspartate is (15-40): (22-50).
14. The two-part anti-graffiti material composition of claim 12, wherein the mass ratio between the catalyst and the silicone-modified aspartate is (0-0.6): (22-50).
15. The two-part anti-graffiti material composition of claim 12, wherein the mass ratio between the antioxidant and the silicone-modified aspartate is (0.2-1.5): (22-50).
16. The two-part anti-graffiti material composition of claim 12, wherein the mass ratio between the dispersant and the silicone-modified aspartate is (0-1): (22-50).
17. The two-part anti-graffiti material composition of claim 12, wherein the mass ratio between the powder and the silicone-modified aspartate is (0-20): (22-50) parts.
18. A method of preparing a two-part anti-graffiti material composition according to any one of claims 1-17, comprising the steps of:
(1) Reacting polyamino silicone oil with a first reaction system of maleate at a first set temperature to obtain organosilicon modified polyaspartic acid ester, and forming the component A;
(2) And (3) reacting the second reaction system of the hydroxyl silicone oil and the polyisocyanate at a second set temperature to obtain the organosilicon modified isocyanate, thereby forming the component B.
19. The method of claim 18, wherein in step (1), the first set temperature is 60-70 ℃.
20. The method of claim 18, wherein in step (1), the reaction is performed for a period of time ranging from 4 to 10 h.
21. The preparation method according to claim 18, wherein the mass ratio of the polyamino silicone oil to the maleate is (20-40): (2-10).
22. The method of preparation of claim 18, wherein the polyaminosilicone oil comprises a pendant polyamino terminated silicone oil.
23. The preparation method according to claim 18, wherein the polyaminosilicone oil has a number average molecular weight of 400 to 100000g/mol.
24. The method of claim 18, wherein the preparation of component a further comprises mixing the silicone modified polyaspartate with other components.
25. The method of claim 18, wherein in step (2), the second set temperature is 80-90 ℃.
26. The method of claim 18, wherein in step (2), the reaction time is 2-4 h.
27. The preparation method according to claim 18, wherein the mass ratio of the hydroxy silicone oil to the polyisocyanate is (19-30): (1.9-10.4).
28. The method of preparation of claim 18, wherein the hydroxy silicone oil comprises a single ended bis hydroxy terminated silicone oil.
29. The preparation method according to claim 18, wherein the hydroxyl silicone oil has a number average molecular weight of 800-20000 g/mol.
30. Use of a two-part anti-graffiti material composition according to any of claims 1-17 in an anti-graffiti coating.
31. A coated product comprising a substrate and a coating layer formed by applying a coating comprising the two-part anti-graffiti composition of any of claims 1-17 to the substrate.
32. The coated product of claim 31, wherein the substrate comprises any one of leather, leather stock, or synthetic leather.
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