Composition of a bio-based modified light-cured flame-retardant floor coating and method for its preparation

Abstract

The present application relates to a kind of bio-based modified photocuring flame-retardant floor coatings and its preparation method.The base resin structure of the floor coatings contains high-functionality acrylate oligomer modified by plant soybean oil and modified by P and Si, has the characteristics of ultraviolet light curing, can greatly improve the hardness and flame-retardant performance of bio-based modified ultraviolet light curing coatings.When the ratio of P, N and Si elements is 1.5:0.8:0.6, the flame-retardant performance is the best;The method has high practicability and good feasibility, is a kind of excellent flame retardant for solving the ultraviolet light curing flame-retardant characteristics, and is green and environmentally friendly ultraviolet light curing coating.

Description

Technical Field

[0001] This invention belongs to the field of coating technology and relates to ultraviolet (UV) curable coatings. It is a bio-based modified photocurable flame-retardant floor coating and its preparation method. Background Technology

[0002] Ultraviolet (UV) curing is a type of radiation curing. Due to its "5E" characteristics (high efficiency, economy, energy saving, high adaptability, and environmental friendliness), it can significantly reduce curing energy consumption, has high energy utilization, and has advantages such as no pollution, fast curing speed, high coating quality, and suitability for continuous large-scale production. The raw materials required for its UV curing resins and monomers are mainly derived from non-renewable resources such as petroleum and coal.

[0003] Vegetable oils are a large class of natural organic compounds, characterized by abundant production (annual global production of 140 million tons), low price, distinctive structure, and biodegradability, making them a renewable resource. With the enormous challenges facing global resources, energy, and the environment, the traditional petroleum industry must address the problem of increasingly depleted resources, which will be a severe test. In recent years, several renewable bio-based resources, such as soybean oil and cashew nut shell extract, have been widely used and researched. Therefore, using bio-based raw materials to replace traditional petroleum raw materials, combined with ultraviolet light curing technology, is a "green" + "green" environmentally friendly solution.

[0004] As a rapidly developing "green" new technology, UV-curable coatings have become an important type of floor coating and are widely used. With the deepening research into UV-curable coatings, people have increasingly higher requirements for their performance and functions; UV-curable flame-retardant floor coatings are a typical example.

[0005] Improving the flame retardancy of UV-cured materials has become a key requirement in recent years, particularly in the furniture and building materials industries. The desire for flame retardant UV-cured coatings is strong. While cold-blending inorganic flame retardants in the composition is a common practice, excessive addition can negatively impact film-forming properties, while insufficient addition leads to inadequate flame retardancy and significantly affects coating clarity, failing to reveal the wood grain. In recent years, introducing flame-retardant elements through chemical modification has been a focus of research. Cheng Wei et al., in their paper "A UV-cured Flame-retardant Floor Coating and Its Preparation Method" (202111056489.0), mentioned synthesizing an acrylic oligomer containing Cl, P, and Si. This oligomer contains halogens and is not modified using renewable bio-based materials. In the event of a fire, it produces toxic HCl gas, hindering escape. Therefore, to improve the flame retardancy of floor coatings, it is crucial to synthesize an environmentally friendly bio-based coating that can participate in UV curing crosslinking, is halogen-free, and possesses flame-retardant properties.

[0006] Combining these two properties, we developed a high-functionality acrylic flame-retardant resin modified with soybean oil and containing P and Si modifications, and prepared a halogen-free bio-based modified photocurable flame-retardant floor coating. It has the characteristics of good flame retardant performance, high hardness and high clarity, which has important practical significance. Summary of the Invention

[0007] To overcome the shortcomings of the physicochemical properties of bio-based coatings, a photocurable high-functionality soybean oil flame-retardant resin was synthesized through chemical modification. This resin has the characteristics of high functionality, which gives it advantages such as fast curing speed, high hardness, and good wear resistance.

[0008] To overcome the technical problem of insufficient flame retardancy in existing floor coatings, the present invention aims to synthesize a bio-based modified flame retardant resin that is halogen-free and environmentally friendly. Combined with a hexafunctional polyurethane, a bio-based modified photocurable flame retardant floor coating is prepared by utilizing the synergistic flame retardant mechanism of P, N, and Si elements. This coating has a synergistic flame retardant effect and is cured by photocuring, which conforms to the trend of green, environmentally friendly, and energy-saving technologies.

[0009] The objective of this invention is achieved through the following technical solution: a bio-based modified photocurable flame-retardant floor coating, prepared by weight of the following components:

[0010]

[0011] The soybean oil-modified P and Si high-functionality acrylate resin is obtained by reacting epoxidized soybean oil, acrylic acid, phosphorus pentoxide, 3-glycidyl etheroxypropylmethyldiethoxysilane, triphenylphosphine catalyst, and p-hydroxyanisole polymerization inhibitor in ethyl acetate.

[0012] The soybean oil-modified P and Si high-functionality acrylate resin, by weight, comprises: 10-20 parts epoxidized soybean oil, 20-30 parts acrylic acid, 20-30 parts phosphorus pentoxide, 10-20 parts 3-glycidyl etheroxypropylmethyldiethoxysilane, 20-30 parts ethyl acetate, 0.2-0.4 parts triphenylphosphine catalyst, and 0.1-0.2 parts p-hydroxyanisole polymerization inhibitor.

[0013] The hexafunctional polyurethane acrylate is a synthetic product synthesized by reacting a hydroxyl-terminated polyester polyol with IPDI pre-branching and then capping it with PETA.

[0014] The active diluent is one or more of the following: tripropylene glycol diacrylate, trihydroxymethane triacrylate, 1,6-hexanediol diacrylate, and pentaerythritol triacrylate.

[0015] The photoinitiator is one or more of 2-hydroxy-2-methylphenylacetone, 1-hydroxycyclohexylphenyl ketone, and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

[0016] The wear-resistant powder is one or more of nano-silica and nano-alumina; the additive is one or more of TEGO920, BYK2008, BYK2013, and BYK025.

[0017] The method for preparing the bio-based modified photocurable flame-retardant floor coating first involves preparing the soybean oil-modified P and Si high-functionality acrylate resin according to the following method:

[0018] The reaction was carried out under nitrogen protection. First, epoxidized soybean oil, triphenylphosphine, p-hydroxyanisole, and ethyl acetate were added to the reaction flask, followed by the addition of acrylic acid. The reaction was carried out at 100°C for 8 hours, then cooled to 25°C. Phosphorus pentoxide was then slowly added, and the reaction was carried out at room temperature for 4 hours. 3-glycidyl etheroxypropylmethyldiethoxysilane was then added to the reaction flask and reacted at 100°C for 4-6 hours to obtain soybean oil-modified P and Si high-functionality acrylate resin. This resin was then formulated into a coating with other components.

[0019] Beneficial effects:

[0020] The bio-based modified photocurable flame-retardant floor coating prepared by this invention has the characteristics of good flame retardant performance, fast curing speed, high hardness, environmental protection, and energy saving. The flame retardant performance is best when the ratio of P, N, and Si elements is 1.5:0.8:0.6, and the coating amount reaches 350 g / m² when applied to wood flooring. 2 When tested according to GB8624-2012, the bio-based modified photocurable flame retardant floor coating composition achieved the highest flame retardant level B1b; the abrasion resistance was tested according to GB / T1768-2006, with an abrasion loss of 0.002g. Detailed Implementation

[0021] The formulations used in this invention are all commercially available conventional products, as long as they are qualified industrial products and not limited to those from manufacturers.

[0022] Throughout this application, the following terms have specific meanings:

[0023] Code or term Chinese name POA Soybean oil modified with P and Si high-functionality acrylate resin, homemade. PUA 6-functional polyurethane acrylate, obtained from Sartomer PETA Pentaerythritol triacrylate, obtained from Sartomer TMPTA Trimethylolpropane triacrylate, derived from Sartomer HDDA 1,6-Hexanediol diacrylate BKY333 Leveling agent, obtained from BYK TEGO920 Defoamer, obtained from Winsun. abrasion-resistant powder Alumina wear-resistant powder, obtained from Hangzhou Wanjing New Materials TPO 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide, obtained from Tianjin Jiuri Chemical Co., Ltd. 1173 2-Hydroxy-2-methyl-1-phenyl-1-propanone, obtained from Tianjin Jiuri Chemical Co., Ltd. IPDI Isophorone diisocyanate, derived from Bayer

[0024] A bio-based modified photocurable flame-retardant floor coating, characterized in that the bio-based modified photocurable flame-retardant floor coating is prepared from the following components by weight:

[0025]

[0026] The soybean oil-modified P and Si high-functionality acrylate resin is a reaction product of the following substances: epoxidized soybean oil, used in an amount of 10%-20% of the total reaction volume; acrylic acid, used in an amount of 20%-30% of the total reaction volume; phosphorus pentoxide, used in an amount of 20%-30% of the total reaction volume; 3-glycidyl etheroxypropylmethyldiethoxysilane, used in an amount of 10%-20% of the total reaction volume; the catalyst is triphenylphosphine, used in an amount of 0.2%-0.4% of the total reaction volume; and the polymerization inhibitor is p-hydroxyanisole, used in an amount of 0.1%-0.2% of the total reaction volume.

[0027] The soybean oil-modified P and Si high-functionality acrylate resin is synthesized as follows:

[0028] The reaction was carried out under nitrogen protection. First, epoxidized soybean oil, triphenylphosphine, p-hydroxyanisole, and ethyl acetate were added to the reaction flask. Then, acrylic acid was added to the reaction flask and reacted at 100°C for 8 hours, followed by cooling to 25°C. Then, phosphorus pentoxide was slowly added and reacted at room temperature for 4 hours. Finally, 3-glycidyl etheroxypropylmethyldiethoxysilane was added to the reaction flask and reacted at 100°C for 4-6 hours to obtain soybean oil-modified P and Si high-functionality acrylate resin.

[0029] The content of soybean oil modified with P and Si high-functionality acrylate resin is 50wt%-70wt%.

[0030] The hexafunctional polyurethane acrylate is a synthetic product synthesized by reacting a hydroxyl-terminated polyester polyol with IPDI and then capping it with PETA; the reactive diluent is one or more of tripropylene glycol diacrylate, trihydroxymethane triacrylate, 1,6-hexanediol diacrylate, and pentaerythritol triacrylate; the photoinitiator is one or more of 2-hydroxy-2-methylphenylacetone, 1-hydroxycyclohexylphenyl ketone, and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; the wear-resistant powder is one or more of nano-silica and nano-alumina; and the additives are one or more of TEGO920, BYK2008, BYK2013, and BYK025.

[0031] The flame retardant performance was best when the ratio of P, N, and Si elements was 1.5:0.8:0.6, with a coating coverage of 350 g / cm³ on wood. 2 According to GB8624-2012, its flame retardant performance level is B1b, which is the highest level of flame retardancy. Its abrasion resistance, according to GB / T 1768-2006, is 0.002g.

[0032] Example 1: Modified P and Si high-functionality acrylate resin POA using soybean oil

[0033] The synthesis of soybean oil-modified P and Si high-functionality acrylate resin was carried out according to the three sets of data listed in Table 2.

[0034] Table 2

[0035]

[0036]

[0037] Synthetic resin POA

[0038] The reaction was carried out under nitrogen protection. First, epoxidized soybean oil, triphenylphosphine, p-hydroxyanisole, and ethyl acetate were added to the reaction flask. Then, acrylic acid was added to the reaction flask and reacted at 100°C for 8 hours, followed by cooling to 25°C. Then, phosphorus pentoxide was slowly added and reacted at room temperature for 4 hours. Finally, 3-glycidyl etheroxypropylmethyldiethoxysilane was added to the reaction flask and reacted at 100°C for 4-6 hours to obtain soybean oil-modified P and Si high-functionality acrylate resin.

[0039] Example 2: Preparation of UV-cured flame-retardant floor coating

[0040] The coating is formulated according to the four sets of data in Table 3.

[0041] Table 3

[0042]

[0043] The above components were formulated into a coating, and relevant indicators were controlled: Fineness: <30µm; Curing speed: >400mJ / cm. 2 (Cure degree RAU 85%).

[0044] Example 3: Preparation of UV-cured flame-retardant floor coating

[0045] The coating is formulated according to the three sets of data in Table 4.

[0046] Table 4

[0047]

[0048] The above components were formulated into a coating, and relevant indicators were controlled: Fineness: <30µm; Curing speed: >400mJ / cm. 2 (Cure degree RAU 85%).

[0049] Example 4: Preparation of UV-curable flame-retardant floor coating

[0050] The coating is formulated according to the three sets of data in Table 5.

[0051] Table 5

[0052]

[0053]

[0054] The above components were formulated into a coating, and relevant indicators were controlled: Fineness: <30µm; Curing speed: >400mJ / cm. 2 (Cure degree RAU 85%).

[0055] Example 5: Test method for flame retardant performance:

[0056] 1. General conditions determined

[0057] Ambient temperature 20-25℃; relative humidity 40-60%; ambient air pressure 1.013*10 5 5% Pa; the laboratory cleanliness meets the requirements of GB50073-2001, and the dust content of Class 10,000 cleanliness is ≥0.5um≤350 particles / L.

[0058] 2. Preparation of coating samples

[0059] One hundred pieces of 120*900cm oak multi-layer solid wood flooring were first treated with 400-grit sandpaper, then the samples were thoroughly mixed and coated with a 35.0g / m² coating using a three-roll mill. 2 The coating is semi-cured using ultraviolet light, then the next step is applied, for a total of 10 coats. Finally, it is fully cured using three lamps. Markings are made on the painted floor using an oil-based marker, and the flame retardancy rating is determined according to the GB8624-2012 testing standard, based on the critical radiation flux. Table 6 shows the rating criteria.

[0060] Table 6

[0061]

[0062] Table 7 shows the flame retardant performance tests for the three groups of experiments above, 2, 3, and 4.

[0063] Table 7

[0064]

[0065]

[0066] The data above shows that the UV-curable coating with modified soybean oil and high-functionality P and Si acrylate resin, when applied to wood flooring, provides excellent protection against wood combustion and slows down the burning process. During combustion, the P and N elements form a stable carbon layer at high temperatures, isolating the wood from oxygen in the air, reducing the surface temperature of the wood, and releasing N2, which dilutes the oxygen in the air. The Si elements form a dense barrier layer at high temperatures, increasing the stability of the carbon layer. The flame-retardant effect is achieved through the synergistic effect of P, N, and Si. The flame-retardant performance continues to increase with the increase of the amount of P added. The presence of photocurable double bonds participates in the cross-linking reaction of the coating, and the wear resistance and adhesion increase with the addition of modified flame-retardant resin.

Claims

1. A bio-based modified light-cured flame-retardant flooring coating, characterized in that, By weight parts, prepared from the following components: Soybean oil modified P, Si containing high functionality acrylate resin 40~55 parts; 6 functional polyurethane acrylate 10~20 parts; Active diluent 5~20 parts; Photoinitiator 2~4 parts; Wear-resistant powder 1~3 parts; Auxiliary 1~3 parts; Among them, the soybean oil modified P, Si containing high functionality acrylate resin is composed of 10-20 parts of epoxy soybean oil, 20-30 parts of acrylic acid, 20-30 parts of phosphorus pentoxide, 10-20 parts of 3-glycidyl ether oxypropyl methyl diethoxysilane, 20-30 parts of ethyl acetate, 0.2-0.4 parts of catalyst triphenyl phosphorus, and 0.1-0.2 parts of polymerization inhibitor p-hydroxyanisole by weight parts; The preparation method of the bio-based modified photocuring flame-retardant floor coating is to prepare the soybean oil modified P, Si containing high functionality acrylate resin by the following method: The reaction is carried out under nitrogen protection. First, the epoxy soybean oil, triphenyl phosphorus, p-hydroxyanisole and ethyl acetate are added to the reaction bottle, then the acrylic acid is added to the reaction bottle for reaction, and after reaction at 100℃ for 8h, the temperature is lowered to 25℃; Then slowly add phosphorus pentoxide, react at room temperature for 4h, then add 3-glycidyl ether oxypropyl methyl diethoxysilane to the reaction bottle for reaction, react at 100℃ for 4-6h, to obtain the soybean oil modified P, Si containing high functionality acrylate resin; Then prepare the coating together with other components.

2. The bio-based modified light-cured fire-retardant flooring coating according to claim 1, characterized in that, The 6 functional polyurethane acrylate is a synthetic product containing hydroxyl-terminated polyester polyol and IPDI pre-grafting reaction, and then capped with PETA.

3. The bio-based modified light-cured fire-retardant flooring coating according to claim 1, wherein, The active diluent is one or more of tripropylene glycol diacrylate, 1,6-hexanediol diacrylate and pentaerythritol triacrylate.

4. The bio-based modified light-cured fire-retardant flooring coating according to claim 1, wherein, The photoinitiator is one or more of 2-hydroxy-2-methylpropyl phenone, 1-hydroxy cyclohexyl phenyl ketone and 2,4,6-trimethyl benzoyl-diphenyl phosphine oxide.

5. The bio-based modified light-cured fire-retardant flooring coating according to claim 1, wherein, The wear-resistant powder is one or more of nano silicon dioxide and nano aluminum oxide; The auxiliary is one or more of TEGO920, BYK2008, BYK2013 and BYK025.

6. A method of preparing a bio-based modified light-cured fire-retardant flooring coating according to any one of claims 1 to 5, characterized in that, The soybean oil modified P, Si containing high functionality acrylate resin is prepared by the following method: The reaction is carried out under nitrogen protection. First, the epoxy soybean oil, triphenyl phosphorus, p-hydroxyanisole and ethyl acetate are added to the reaction bottle, then the acrylic acid is added to the reaction bottle for reaction, and after reaction at 100℃ for 8h, the temperature is lowered to 25℃; Then slowly add phosphorus pentoxide, react at room temperature for 4h, then add 3-glycidyl ether oxypropyl methyl diethoxysilane to the reaction bottle for reaction, react at 100℃ for 4-6h, to obtain the soybean oil modified P, Si containing high functionality acrylate resin; Then prepare the coating together with other components.

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