A UV-curable organosilicon-modified bis-spirocyclic phosphate acrylate and its preparation method and application

Abstract

The present invention provides a UV-curable organosilicon-modified bis-spirocyclic phosphate acrylate and a preparation method and application thereof. The preparation method comprises the following steps: using mercaptopropyl polysiloxane and bis-spirocyclic phosphate acrylate as main raw materials, using photoinitiator 1173 as initiator, adding the initiator to the main raw materials and mixing them evenly, and obtaining the desired product after UV curing for 20-120s. The UV-curable material prepared by the present invention has a very good flame retardant effect, with an LOI of 26.5-35.5%, a flame retardant grade of V-1-V-0, a pencil hardness of 4-9H, an initial thermal decomposition temperature of 280.2-305.5°C, and a water absorption rate of 0.5-3.8%. It can be used as flame-retardant three-proof paint for electronic components, flame-retardant industrial paint, flame-retardant tent cloth coating, etc.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a UV-curable organosilicon-modified bis-spirocyclic phosphate acrylate and a preparation method and application thereof. Background Art

[0002] Organic polymer materials have the advantages of good chemical stability, high mechanical strength and easy molding, and have been widely used in people's lives. However, they have the disadvantage of being easy to burn, which can easily cause fires and endanger people's lives and property. Therefore, it is urgent to modify organic polymer materials to be flame retardant and expand their application fields.

[0003] Spiro-type flame retardants have good compatibility with polymer materials and can maintain their excellent flame retardancy under high temperature or harsh environment. They are widely used in flame retardant modification of organic polymer materials. In addition, spiro-type flame retardants have a unique chemical structure, which enables them to quickly form a stable carbon layer when heated, thereby effectively isolating oxygen and heat, slowing down the burning speed of organic polymer materials, and preventing the further spread of flames, thereby improving the flame retardant properties of the materials. Spiro-type flame retardants usually contain multiple elements such as phosphorus and nitrogen, and multiple elements can synergistically enhance the flame retardant effect. Compared with traditional flame retardants, spiro-type flame retardants also have low toxicity.

[0004] Ultraviolet (UV) curing is a new energy-saving and environmentally friendly technology with the advantages of fast curing and environmental friendliness. It has been widely used in important fields such as coatings, inks and electronic packaging. Summary of the invention

[0005] The purpose of the present invention is to provide a UV-curing organosilicon-modified bis-spirocyclic phosphate acrylate and a preparation method thereof in view of the shortcoming that the existing UV-curing acrylate is easy to burn.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A method for preparing UV-curable organosilicon-modified bis-spirocyclic phosphate acrylate comprises the following steps:

[0008] The main raw materials are mercaptopropyl polysiloxane and bis-spirocyclic phosphate acrylate, and the initiator is photoinitiator 1173. The initiator is added to the main raw materials and mixed evenly. The desired product is obtained after UV curing for 20-120 seconds.

[0009] Among the main raw materials, mercaptopropyl polysiloxane and bispirocyclic phosphate acrylate are mixed in a molar ratio of mercaptopropyl group to acrylate group of 1:1 to 1:4;

[0010] The dosage of photoinitiator 1173 is 1-9% of the total mass of the main raw materials.

[0011] As a specific implementation manner, the raw materials of the mercaptopropyl polysiloxane include component A and component B, component A is a mercaptopropyl-containing alkoxysilane, using one or two of mercaptopropyl methyldimethoxysilane and 3-propylmethyldiethoxysilane; component B is a dimethylalkoxysilane, using one or two of dimethyldimethoxysilane and dimethyldiethoxysilane.

[0012] As a specific implementation method, the preparation process of the mercaptopropyl polysiloxane is as follows: component A and component B are put into a reactor, 40-200% of the total mass of component A and component B is added toluene, and the mixture is evenly mixed under mechanical stirring, and then the mixture is added dropwise to a mixture of deionized water and 36.5% concentrated hydrochloric acid, and the co-hydrolysis-condensation reaction is carried out at 50°C for 3 hours, and the mixture is washed with water until neutral, and the solvent and small molecules are removed under reduced pressure to obtain the mercaptopropyl polysiloxane, wherein the molar number of deionized water added is equal to the sum of the molar numbers of alkoxy groups of component A and component B, and the mass of 36.5% concentrated hydrochloric acid is 0.5-8% of the total mass of component A and component B.

[0013] As a specific embodiment, the molar amount of component A is 5-50% of the total molar amount of component A and component B.

[0014] As a specific implementation method, the preparation process of the bispirocyclic phosphate acrylate is as follows:

[0015] Step 1, pentaerythritol and phosphorus oxychloride are added to a three-necked flask in a molar ratio of 1:2, and the temperature is raised to 100°C for reaction for 12 hours under stirring. The tail gas is absorbed by a saturated NaOH solution. After the reaction is completed, it is cooled to room temperature and filtered with a Buchner funnel to obtain a white solid, which is then washed with anhydrous dichloromethane and dried in a vacuum oven at 60°C to constant weight to obtain a white solid powder SPDPC. The specific reaction formula is as follows:

[0016] ;

[0017] Step 2, dissolve SPDPC in anhydrous acetonitrile of equal mass, and dropwise add 2 times molar amount of diethanolamine and 2 times molar amount of triethylamine in anhydrous acetonitrile solution, then react at 60°C for 2 h, then heat and reflux for 12 h, cool and filter, and remove acetonitrile from the filtrate under reduced pressure to obtain a liquid tetrahydroxy SPDPC derivative. The specific reaction formula is as follows:

[0018] ;

[0019] Step 3, dissolving the tetrahydroxy SPDPC derivative in anhydrous acetonitrile of equal mass, adding dropwise 4 times molar amount of acryloyl chloride and 4 times molar amount of triethylamine in anhydrous acetonitrile solution, reacting at 60°C for 2 h, cooling and filtering, removing acetonitrile from the filtrate under reduced pressure, and obtaining a light yellow bispirocyclic phosphate acrylate liquid product, the specific reaction formula is as follows:

[0020] .

[0021] The second object of the present invention is to provide a UV-curable organosilicon-modified bis-spirocyclic phosphate acrylate prepared by the above-mentioned preparation method of UV-curable organosilicon-modified bis-spirocyclic phosphate acrylate.

[0022] The third object of the present invention is to provide the use of the UV-curable organosilicon-modified bis-spirocyclic phosphate acrylate in flame-retardant three-proof paint for electronic components, flame-retardant industrial paint, and flame-retardant tent cloth coating.

[0023] Beneficial effects of the present invention:

[0024] 1) The UV curing material prepared by the technical solution of the present invention has a very good flame retardant effect, with an LOI of 26.5~35.5% and a flame retardant grade of V-1~V-0;

[0025] 2) The UV curing material prepared by the technical solution of the present invention has a pencil hardness of 4~9H, an initial thermal decomposition temperature of 280.2~305.5℃, and a water absorption rate of 0.5~3.8%, and can be used as flame retardant three-proof paint for electronic components, flame retardant industrial paint, flame retardant tent cloth coating, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is a tetrahydroxy SPDPC derivative obtained in the preparation process of dispirocyclic phosphate acrylate. 1 H NMR spectrum;

[0027] Figure 2 This is the FT-IR spectrum of the tetrahydroxy SPDPC derivative obtained during the preparation of the dispirocyclic phosphate acrylate. DETAILED DESCRIPTION

[0028] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0029] The present invention provides a method for preparing a UV-curable organosilicon-modified bispirocyclic phosphate acrylate, comprising the following steps:

[0030] The main raw materials are mercaptopropyl polysiloxane and bis-spirocyclic phosphate acrylate, and the initiator is photoinitiator 1173. The initiator is added to the main raw materials and mixed evenly. The desired product is obtained after UV curing for 20-120 seconds.

[0031] Among the main raw materials, mercaptopropyl polysiloxane and bispirocyclic phosphate acrylate are mixed in a molar ratio of mercaptopropyl group to acrylate group of 1:1 to 1:4;

[0032] The dosage of photoinitiator 1173 is 1-9% of the total mass of the main raw materials.

[0033] The raw materials of the mercaptopropyl polysiloxane include component A and component B. Component A is an alkoxysilane containing mercaptopropyl, and one or two of mercaptopropyl methyldimethoxysilane and 3-propylmethyldiethoxysilane are used; component B is a dimethylalkoxysilane, and one or two of dimethyldimethoxysilane and dimethyldiethoxysilane are used.

[0034] The preparation process of mercaptopropyl polysiloxane is as follows: component A and component B are put into a reactor, 40-200% toluene of the total mass of component A and component B is added, and the mixture is evenly mixed under mechanical stirring, and then the mixed solution is added dropwise to a mixed solution of deionized water and 36.5% concentrated hydrochloric acid, and a co-hydrolysis-condensation reaction is carried out at 50° C. for 3 hours, and the mercaptopropyl polysiloxane is obtained after washing with water to neutrality and removing the solvent and small molecules under reduced pressure, wherein the added molar number of deionized water is equal to the total molar number of alkoxy groups of component A and component B, and the mass of 36.5% concentrated hydrochloric acid is 0.5-8% of the total mass of component A and component B.

[0035] The preparation process of the bispirocyclic phosphate acrylate is as follows:

[0036] Step 1, pentaerythritol and phosphorus oxychloride are added to a three-necked flask in a molar ratio of 1:2, and the temperature is raised to 100°C for reaction for 12 hours under stirring. The tail gas is absorbed by a saturated NaOH solution. After the reaction is completed, it is cooled to room temperature and filtered with a Buchner funnel to obtain a white solid, which is then washed with anhydrous dichloromethane and dried in a vacuum oven at 60°C to constant weight to obtain a white solid powder SPDPC. The specific reaction formula is as follows:

[0037] ;

[0038] Step 2, dissolve SPDPC in anhydrous acetonitrile of equal mass, and dropwise add 2 times molar amount of diethanolamine and 2 times molar amount of triethylamine in anhydrous acetonitrile solution, then react at 60°C for 2 h, then heat and reflux for 12 h, cool and filter, and remove acetonitrile from the filtrate under reduced pressure to obtain a liquid tetrahydroxy SPDPC derivative. The specific reaction formula is as follows:

[0039] ;

[0040] Step 3, dissolving the tetrahydroxy SPDPC derivative in anhydrous acetonitrile of equal mass, adding dropwise 4 times molar amount of acryloyl chloride and 4 times molar amount of triethylamine in anhydrous acetonitrile solution, reacting at 60°C for 2 h, cooling and filtering, removing acetonitrile from the filtrate under reduced pressure, and obtaining a light yellow bispirocyclic phosphate acrylate liquid product, the specific reaction formula is as follows:

[0041] .

[0042] The obtained liquid tetrahydroxy SPDPC derivative 1 H NMR spectra and FT-IR spectra are shown in Figure 1 , 2 shown. Example 1

[0043] This example provides a UV-curable silicone-modified bis-spirocyclic phosphate acrylate,

[0044] Step 1, preparation of mercaptopropyl polysiloxane: KH-970, KH-581, dimethyldimethoxysilane, dimethyldiethoxysilane and toluene were mixed evenly under mechanical stirring, then added dropwise to deionized water and 36.5% concentrated hydrochloric acid for 0.5 h, co-hydrolyzed and condensed at 50 ° C for 3 h, washed with water until neutral, and the solvent and small molecules were removed under reduced pressure at 120 ° C for 2 h to obtain mercaptopropyl polysiloxane. The specific reaction conditions and product numbers are shown in Table 1.

[0045] Table 1 Preparation ratio of mercaptopropyl polysiloxane

[0046]

[0047] In the above, the reaction temperature is 60°C, the reaction time is 3h, KH-970 is mercaptopropylmethyldimethoxysilane, KH-581 is 3-mercaptopropylmethyldiethoxysilane, the dosage unit of each substance in the table is g, the molecular weight of KH-970 is 180.34, the molecular weight of KH-581 is 208.39, the molecular weight of dimethyldimethoxysilane is 120.22, and the molecular weight of dimethyldiethoxysilane is 148.28.

[0048] Step 2, preparation of bis-spirocyclic phosphate acrylate:

[0049] 1) Add 136.15g of pentaerythritol and 306.66g of phosphorus oxychloride into a three-necked flask, heat to 100°C and react for 12h under stirring, absorb the tail gas with saturated NaOH solution, cool to room temperature after the reaction, filter with a Buchner funnel to obtain a white solid, wash with anhydrous dichloromethane and dry in a vacuum oven at 60°C to constant weight to obtain 136.62g of SPDPC as a white solid powder;

[0050] 2) SPDPC was dissolved in 136.62 g of anhydrous acetonitrile, and 96.725 g of diethanolamine and 400 ml of anhydrous acetonitrile solution containing 93.095 g of triethylamine were added dropwise, and then reacted at 60°C for 2 h, and then refluxed for 12 h. After cooling and filtering, the filtrate was decompressed to remove acetonitrile to obtain 369.13 g of liquid tetrahydroxy SPDPC derivative;

[0051] 3) The prepared tetrahydroxy SPDPC derivative was dissolved in 369.13 g of anhydrous acetonitrile, and 307.7 g of acryloyl chloride and 1500 ml of anhydrous acetonitrile solution containing 344.05 g of triethylamine were added dropwise, and the mixture was reacted at 60°C for 2 h. After cooling and filtering, the acetonitrile was removed from the filtrate under reduced pressure to obtain 398.52 g of a light yellow bispirocyclic phosphate acrylate liquid product.

[0052] Step 3: Mix the prepared mercaptopropyl polysiloxane No. 4 in Table 1 with the bis-spirocyclic phosphate acrylate in a certain proportion, add UV curing initiator photoinitiator 1173 for curing, and prepare a UV curing material, as shown in Table 2.

[0053] Table 2 Molar ratio of mercaptopropyl to acrylate

[0054]

[0055] The mercaptopropyl polysiloxane is number 4 in Table 1, the UV curing time is 60 s, and the amount of photoinitiator 1173 used is 5% of the total mass of mercaptopropyl polysiloxane and bisspirocyclic phosphate acrylate.

[0056] Pencil hardness: Determine according to GB / T 6739-2006 “Paints and varnishes - Determination of film hardness by pencil method”.

[0057] Water absorption rate: Cut the coating into squares of a certain shape, soak them in deionized water at room temperature for 24 hours, use filter paper to absorb the water on the surface of the coating, and calculate the water absorption rate of the coating according to the formula.

[0058] B = (m2-m1) ÷ m1 × 100%

[0059] Wherein B represents water absorption (%); m1 represents the mass of the coating before immersion; and m2 represents the mass of the coating after absorbing the liquid on the surface of the coating with filter paper after immersion.

[0060] LOI (Limiting Oxygen Index) Determination: According to ASTM-D2863 standard, use HC-3 oxygen index meter to measure the UV curing material (size 80×10×4mm 3 )'s limiting oxygen index.

[0061] The flame retardant rating is measured according to the UL94 vertical burning test method. Example 2

[0062] The mercaptopropyl polysiloxane in Table 1 and the bis-spirocyclic phosphate acrylate were mixed in a molar ratio of mercaptopropyl group to acrylate group of 1:3, and UV curing initiator 1173 was added for curing to prepare a UV curing material, as shown in Table 3.

[0063] Table 3 Effect of different mercaptopropyl polysiloxanes

[0064]

[0065] The molar ratio of mercaptopropyl to acrylate was 1:3, the UV curing time was 60 s, and the amount of initiator 1173 was 5% of the total mass of mercaptopropyl polysiloxane and bis-spirocyclic phosphate acrylate.

[0066] As can be seen from Table 3, the UV curing material prepared by using the mercaptopropyl polysiloxane of the main raw materials 3-mercaptopropylmethyldiethoxysilane and dimethyldiethoxysilane has the best pencil hardness, water absorption, initial thermal decomposition temperature, limiting oxygen index and flame retardant grade. Of course, the performance of the UV curing material prepared by using the mercaptopropyl polysiloxane of other components A and B is also better. Example 3

[0067] Take the mercaptopropyl polysiloxane No. 4 in Table 1 and mix it with the bis-spirocyclic phosphate acrylate in a molar ratio of mercaptopropyl to acrylate of 1:3, add different proportions of UV curing initiator 1173 for curing, and the UV curing time is 60 s to prepare a UV curing material, as shown in Table 4.

[0068] Table 4 Effect of different initiator dosages

[0069]

[0070] It can be seen from Table 4 that when the amount of photoinitiator is controlled at 1-9% of the total mass of mercaptopropyl polysiloxane and bisspirocyclic phosphate acrylate, the performance of the UV-curable material is better, especially when it accounts for 4-9%. At the same time, it can be seen that when the amount of initiator reaches 9%, its initial thermal decomposition temperature and limiting oxygen index begin to decline. Example 4

[0071] Take the mercaptopropyl polysiloxane No. 4 in Table 1 and mix it with the bis-spirocyclic phosphate acrylate in a molar ratio of mercaptopropyl group to acrylate group of 1:3, add UV curing initiator 1173 for curing, and prepare a UV curing material, as shown in Table 5.

[0072] Table 5 Effect of different curing time

[0073]

[0074] The amount of photoinitiator 1173 used is 5% of the total mass of mercaptopropyl polysiloxane and bis-spirocyclic phosphate acrylate.

[0075] It can be seen from Table 5 that when the curing time is 20-120s, the performance of the UV curing material is better. When the curing time exceeds 60s, the pencil hardness remains unchanged and the limiting oxygen index begins to decline.

[0076] The above is a detailed description of an embodiment of the present invention, but the content is only a preferred embodiment of the present invention and cannot be considered to limit the scope of implementation of the present invention. All equivalent changes and improvements made within the scope of the present invention should still fall within the scope of the patent coverage of the present invention.

Claims

1. A method for preparing UV-curable organosilicon-modified bis-spirocyclic phosphate acrylate, characterized in that: The following steps are involved: The main raw materials are mercaptopropyl polysiloxane and bis-spirocyclic phosphate acrylate, and the initiator is photoinitiator 1173. The initiator is added to the main raw materials and mixed evenly. The desired product is obtained after UV curing for 20-120 seconds. Among the main raw materials, mercaptopropyl polysiloxane and bispirocyclic phosphate acrylate are mixed in a molar ratio of mercaptopropyl group to acrylate group of 1:1 to 1:4; The dosage of photoinitiator 1173 is 1-9% of the total mass of the main raw materials. The structural formula of the bispirocyclic phosphate acrylate is as follows: ， The raw materials of the mercaptopropyl polysiloxane include component A and component B, wherein component A is an alkoxysilane containing mercaptopropyl, and one or two of mercaptopropyl methyl dimethoxy silane and 3-mercaptopropyl methyl diethoxy silane are used; component B is a dimethyl alkoxy silane, and one or two of dimethyl dimethoxy silane and dimethyl diethoxy silane are used. The preparation process of the mercaptopropyl polysiloxane is as follows: component A and component B are put into a reactor, 40-200% of the total mass of toluene of component A and component B are added, and the mixture is evenly mixed under mechanical stirring, and then the mixed solution is added dropwise to a mixed solution of deionized water and 36.5% concentrated hydrochloric acid, and a co-hydrolysis-condensation reaction is carried out at 50° C. for 3 hours, and the mercaptopropyl polysiloxane is obtained after washing with water to neutrality and removing the solvent and small molecules under reduced pressure, wherein the added molar number of deionized water is equal to the sum of the molar numbers of alkoxy groups of component A and component B, and the mass of 36.5% concentrated hydrochloric acid is 0.5-8% of the total mass of component A and component B.

2. The method for preparing a UV-curable organosilicon-modified bis-spirocyclic phosphate acrylate according to claim 1, characterized in that: The molar amount of component A is 5-50% of the total molar amount of component A and component B.

3. The method for preparing a UV-curable organosilicon-modified bis-spirocyclic phosphate acrylate according to claim 1, characterized in that: The preparation process of the bispirocyclic phosphate acrylate is as follows: Step 1, pentaerythritol and phosphorus oxychloride are added to a three-necked flask in a molar ratio of 1:2, and the temperature is raised to 100°C for reaction for 12 hours under stirring. The tail gas is absorbed by a saturated NaOH solution. After the reaction is completed, it is cooled to room temperature and filtered with a Buchner funnel to obtain a white solid, which is then washed with anhydrous dichloromethane and dried in a vacuum oven at 60°C to constant weight to obtain a white solid powder SPDPC. The specific reaction formula is as follows: ； Step 2, dissolve SPDPC in anhydrous acetonitrile of equal mass, and dropwise add 2 times molar amount of diethanolamine and 2 times molar amount of triethylamine in anhydrous acetonitrile solution, then react at 60°C for 2 h, then heat and reflux for 12 h, cool and filter, and remove acetonitrile from the filtrate under reduced pressure to obtain a liquid tetrahydroxy SPDPC derivative. The specific reaction formula is as follows: ； Step 3, dissolving the tetrahydroxy SPDPC derivative in anhydrous acetonitrile of equal mass, adding dropwise 4 times molar amount of acryloyl chloride and 4 times molar amount of triethylamine in anhydrous acetonitrile solution, reacting at 60°C for 2 h, cooling and filtering, removing acetonitrile from the filtrate under reduced pressure, and obtaining a light yellow bispirocyclic phosphate acrylate liquid product, the specific reaction formula is as follows: 。 4. A UV-curable organosilicon-modified bis-spirocyclic phosphate acrylate prepared by the method for preparing UV-curable organosilicon-modified bis-spirocyclic phosphate acrylate according to any one of claims 1 to 3.

5. Use of the UV-curable organosilicon-modified bis-spirocyclic phosphate acrylate according to claim 4 in flame-retardant three-proof paint for electronic components, flame-retardant industrial paint, and flame-retardant tent cloth coating.

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