Fluorocarbon-modified ethyoxylated bisphenol a diacrylate and preparation method therefor, and resin composition comprising same and use thereof

Abstract

Provided in the present disclosure are fluorocarbon-modified ethyoxylated bisphenol A diacrylate and a preparation method therefor, and a resin composition comprising same and the use thereof. In the present disclosure, modified ethyoxylated bisphenol A diacrylate containing a fluorocarbon chain segment is obtained by grafting an organic group containing at least three fluorine atoms to ethyoxylated bisphenol A diacrylate; and when used in a resin composition, the modified ethyoxylated bisphenol A diacrylate containing a fluorocarbon chain segment can reduce the viscosity of the resin composition and improve the efficiency of the permeation of a resin into a porous framework, thereby enabling the resin composition to have wide application prospects.

Description

Fluorocarbon-modified ethoxybisphenol A diacrylate, its preparation method, resin compositions containing it, and its applications.

[0001] Cross-reference of related applications

[0002] This disclosure claims priority to Chinese Patent Application No. 202410690166.4, filed on May 30, 2024, entitled "Fluorocarbon modified ethoxybisphenol A diacrylate and its preparation method and resin compositions comprising the same and applications", the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure relates to the field of resin-infiltrated ceramics technology, and more particularly to fluorocarbon-modified ethoxybisphenol A diacrylate, its preparation method, resin compositions comprising the same, and their applications. Background Technology

[0004] Since the 1980s, computer-aided design and computer-aided manufacturing (CAD / CAM) technologies have developed rapidly. These technologies are widely used in dental restoration, primarily in the manufacture of ceramic, polymer, and composite dental restorations. The rapid application of these technologies, along with digital scanning and other techniques, in dentistry has led to continuous upgrades and iterations of chairside dental systems. The concept of "immediate restoration" has taken root in the minds of both doctors and patients, and the ability for patients to have their teeth put back on the same day is no longer a distant dream.

[0005] Besides the necessary equipment, the consumable materials used in chairside systems play a crucial role in the speed of restoration. In addition to meeting the basic requirements of aesthetics, durability, and function, the fabrication of restorations must also achieve rapid tooth eruption to ensure faster patient placement and improve the overall treatment experience. While ceramic dental restorations require further sintering, glazing, and polishing after CAD design and CAM cutting to obtain the final restoration, polymer-based or composite materials do not require sintering or glazing; they only need polishing before placement, making them more suitable for chairside systems. Compared to polymer-based materials, composite materials possess superior mechanical properties and more closely resemble natural teeth, leading to their rapid development in dentistry.

[0006] In dentistry, composite materials mainly refer to resin-ceramic composites, encompassing two main types. One type is resin composites, where the matrix is ​​organic with inorganic filling particles dispersed within the organic structure primarily serving a reinforcing role. However, the aesthetic and wear-resistant properties of this type are inferior to another material known as "polymer-infiltrated ceramic network (PICN)" or "resin-infiltrated ceramic." Resin-infiltrated ceramic is obtained by preparing a porous ceramic framework, then infiltrating it with resin and curing it. This results in mechanical and aesthetic properties that more closely resemble those of natural teeth.

[0007] PICN materials mainly consist of two parts: a porous ceramic framework and a liquid organic resin. The framework is responsible for the main mechanical properties of the composite material. Therefore, in the material preparation, it is necessary to obtain a framework structure with a high ceramic content. This determines that the pore size inside the framework must be small (mostly below 1 μm). Under these conditions, the resin phase can only penetrate and fill the porous framework through capillary action. However, capillary action is mainly driven by intermolecular forces between the two phases. The penetration process is slow and time-consuming. For PICN product preparation, excessive time will inevitably lead to low production efficiency and greatly increase the production and manufacturing costs of the product.

[0008] The resin compositions used in existing resin-permeable ceramic samples are mostly difunctional acrylates such as bisphenol A dimethacrylate (Bis-GMA), urethane methacrylate (UDMA), and triethylene glycol dimethacrylate (TEGDMA). The problems are twofold: First, Bis-GMA, the main component for improving strength and hardness, contains hydroxyl groups, which easily form hydrogen bonds. These hydrogen bonds result in a high overall viscosity of the resin composition, increasing the resistance to resin penetration through the porous framework and reducing penetration efficiency. Second, the porous framework is modified with silane coupling agents, reducing its surface free energy. Since the surface tension of the resin is higher than that of the modified framework surface, the wettability of the resin to the framework deteriorates, further reducing resin penetration efficiency.

[0009] Therefore, it is necessary to develop new structures and products to improve the penetration efficiency of resins. Summary of the Invention

[0010] To address the aforementioned technical problems, this disclosure provides fluorocarbon-modified ethoxybisphenol A diacrylate, its preparation method, resin compositions containing the same, and their applications. By fluorocarbon modification of ethoxybisphenol A diacrylate, the efficiency of resin penetration into porous frameworks is improved, resulting in broad application prospects.

[0011] To achieve this objective, the present disclosure adopts the following technical solution:

[0012] In a first aspect, this disclosure provides a fluorocarbon-modified ethoxybisphenol A diacrylate, wherein the fluorocarbon-modified ethoxybisphenol A diacrylate includes a structure in which segment B is grafted onto segment A via carbon-carbon double bonds.

[0013] Wherein, chain segment A is as shown in equation (1), and chain segment B is as shown in equation (2).

[0014] In equation (1), the value of x ranges from 6 to 12;

[0015] Chain segment B is shown in equation (2):

[0016] In formula (2), R is an organic group containing at least 3 fluorine atoms.

[0017] In this disclosure, the range of values ​​for x can be, for example, 6, 7, 8, 9, 10, 11 or 12. The fluorine atom in R in equation (2) can be, for example, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18, etc.

[0018] This disclosure preferably uses the structure of formula (2) to graft ethoxybisphenol A diacrylate, wherein the ethoxybisphenol A diacrylate retains the benzene ring structure compared with bisphenol A dimethacrylate, giving the material higher hardness and strength. At the same time, the ethoxylated molecular chain segments give the monomer lower viscosity, resulting in a lower viscosity of the final modified ethoxybisphenol A diacrylate. Moreover, the polyfluorinated branched structure can significantly reduce the surface tension of the fluorocarbon modified ethoxybisphenol A diacrylate, which is beneficial to the wetting of the resin onto the skeleton. Based on the two points of stronger wettability and lower viscosity, the subsequent resin composition can better penetrate the porous skeleton, improving the penetration efficiency.

[0019] Preferably, R contains an ester group, and more preferably the ester group is connected to a carbon atom of the double bond shown in formula (2).

[0020] Preferably, R contains 5 to 10 fluorine atoms.

[0021] Preferably, the structural formula of R is shown in formula (3):

[0022] The fluorocarbon-modified ethoxybisphenol A diacrylate contains a grafted prepolymer of segment B and segment A, wherein the number of repeating units in a single prepolymer molecule is ≤3, for example, it can be 3, 2 or 1.

[0023] The present disclosure preferably has ≤3 repeating units in a single prepolymer molecule, which can further avoid the problem of increased viscosity of the entire system caused by an excessive number of repeating units in the prepolymer molecule, thereby better improving the penetration efficiency of the subsequent resin composition to the skeleton.

[0024] Preferably, the molecular weight of the fluorocarbon-modified ethoxybisphenol A diacrylate is 3000 to 7000, for example, it can be 3000, 3400, 3800, 4330, 4700, 5200, 5600, 6100, 6500 or 7000, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0025] Preferably, the viscosity of the fluorocarbon-modified ethoxybisphenol A diacrylate is 650–1026 mPa·s, for example, it can be 650 mPa·s, 670 mPa·s, 695 mPa·s, 710 mPa·s, 730 mPa·s, 760 mPa·s, 780 mPa·s, 800 mPa·s, 820 mPa·s, 850 mPa·s, 900 mPa·s, 950 mPa·s, 980 mPa·s, 1000 mPa·s, or 1026 mPa·s, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0026] In a second aspect, this disclosure provides a method for preparing the fluorocarbon-modified ethoxybisphenol A diacrylate described in the first aspect, wherein the raw materials for preparation include a first monomer, ethoxybisphenol A diacrylate, a chain transfer agent, an organic solvent, and a first initiator; wherein the first monomer is as shown in formula (2):

[0027] In formula (2), R is an organic group containing at least 3 fluorine atoms.

[0028] The second aspect of this disclosure provides a method for preparing fluorocarbon-modified ethoxybisphenol A diacrylate. First, ethoxybisphenol A diacrylate is selected for modification. Compared to bisphenol A dimethacrylate, it retains the benzene ring structure, resulting in higher hardness and strength. Simultaneously, the ethoxylated molecular chain segments give the monomer lower viscosity. Then, ethoxybisphenol A diacrylate is subjected to free radical polymerization with a structure containing at least three fluorine atoms (2). To avoid excessively high molecular weight and viscosity due to excessive polymerization, a chain transfer agent is added to control the polymer's molecular weight and reduce the viscosity of the finished product, thereby obtaining a low-viscosity prepolymer product: fluorocarbon-modified ethoxybisphenol A diacrylate. This fluorocarbon-modified ethoxybisphenol A diacrylate not only has low viscosity but also possesses a fluorine branched structure, exhibiting excellent surface wetting properties on the framework, making it well-suited for application in resin-infiltrated ceramics.

[0029] Preferably, the raw materials prepared are based on 200 parts of organic solvent and include, by mass fraction: 5-10 parts of the first monomer, 50-60 parts of ethoxybisphenol A diacrylate, 1-3 parts of chain transfer agent, and 0.05-0.1 parts of the first initiator.

[0030] The raw materials prepared in this preferred manner are prepared according to the above-mentioned mass fractions. Controlling the mass fraction of the first monomer within the above range not only allows the resin composition to have lower surface tension and better wettability with the skeleton, but also further ensures the strength properties of the cured resin composition. Furthermore, ensuring the content of ethoxybisphenol A diacrylate within the above range, based on the mass fraction of the first monomer, not only ensures a moderate content of rigid structural segments and high strength of the final cured resin, but also avoids the problem of reduced unsaturated double bonds at the prepolymer end groups due to insufficient ethoxybisphenol A diacrylate content, which would subsequently affect the crosslinking density of the final polymer and cause a decrease in resin strength. When the content of ethoxybisphenol A diacrylate is too high, there is a competitive reaction between ethoxybisphenol A diacrylate and the first monomer, resulting in a decrease in the fluorocarbon segment content of the prepolymer and a reduction in resin penetration efficiency. This disclosure preferably controls the content of the chain transfer agent within a specific range, which can ensure the degree of polymerization of the prepolymer, thereby better controlling the viscosity of the prepolymer and resin composition within a reasonable range. At the same time, it can also better avoid the problems of incomplete prepolymerization reaction, low molecular weight, and decreased strength of cured resin.

[0031] The first monomer comprises 5 to 10 parts, for example, 5 parts, 5.6 parts, 6.2 parts, 6.7 parts, 7.3 parts, 7.8 parts, 8.4 parts, 8.9 parts, 9.5 parts, or 10 parts, but is not limited to the listed values; other unlisted values ​​within this range are also applicable. The ethoxybisphenol A diacrylate comprises 50 to 60 parts, for example, 50 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, or 60 parts, but is not limited to the listed values; other unlisted values ​​within this range are also applicable. The chain transfer agent comprises 1 to 3 parts, for example, 1 part, 1.3 parts, 1.5 parts, 1.7 parts, 1.9 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts, or 3 parts, but is not limited to the listed values; other unlisted values ​​within this range are also applicable. The first initiator is 0.05 to 0.1 parts, for example, 0.05 parts, 0.06 parts, 0.07 parts, 0.08 parts, 0.09 parts or 0.1 parts, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0032] Preferably, the R of the first monomer contains an ester group, and more preferably the ester group is connected to a carbon atom of the double bond shown in formula (2).

[0033] Preferably, R contains 5 to 10 fluorine atoms, for example, 5, 6, 7, 8, 9 or 10.

[0034] In this disclosure, the first monomer must first contain at least three fluorine atoms, because fluorine atoms can reduce the surface tension of the resin. At least three fluorine atoms are required to ensure the final product meets the target surface tension requirements. Secondly, it needs to have C=C double bonds at the ends to facilitate grafting with ethoxybisphenol A diacrylate. Furthermore, it preferably contains ester groups. On the one hand, ester groups are generally carried along during the formation of the C=C double bonds at the ends; on the other hand, ester groups can improve the reactivity of the prepolymerization reaction and increase the content of the grafted structure.

[0035] Preferably, the first monomer comprises hexafluorobutyl methacrylate.

[0036] Preferably, the number of ethoxy groups in the ethoxybisphenol A diacrylate is 6 to 12, for example, 6, 7, 8, 9, 10, 11 or 12, etc., but not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0037] Preferably, the chain transfer agent is a thiol chain transfer agent, and the number of carbon atoms in the thiol chain transfer agent is preferably 4 to 15, for example, 4, 6, 7, 8, 9, 11, 12, 13, 14 or 15, but not limited to the listed values. Other unlisted values ​​within this range are also applicable, and it is further preferred that the number of carbon atoms is 12.

[0038] It is worth noting that this disclosure preferably uses thiol chain transfer agents, where the thiol groups can terminate the further reaction of monomers that have already polymerized, while also generating new free radicals. This ensures that other monomers can continue free radical polymerization. Under the action of the thiol chain transfer agent, the bifunctional monomers stop polymerization in time, while retaining the single-sided double bond, thus acting as a capping agent. Furthermore, the introduction of thiol chain transfer agents into fluorocarbon-modified ethoxybisphenol A diacrylate not only does not have a negative impact on the product, but also reduces the degree of polymerization of the prepolymer, allowing the prepolymer to retain its reactivity while also achieving the auxiliary advantage of low viscosity.

[0039] Furthermore, since the chain transfer agent disclosed herein relates to the issue of chain transfer efficiency, it is preferable to control the number of carbon atoms in the range of 4 to 15, which can better improve the chain transfer efficiency.

[0040] Preferably, the thiol chain transfer agent includes n-12-thiol.

[0041] Preferably, the organic solvent has a boiling point ≥70°C, such as 75°C, 80°C, 90°C, 100°C, 120°C, or 150°C.

[0042] This disclosure does not have any special requirements for the organic solvent, as long as it meets the above boiling point requirements and can dissolve the raw materials in this disclosure. For example, carbon tetrachloride, toluene, or butyl acetate can be used.

[0043] Preferably, the first initiator comprises benzoyl peroxide.

[0044] The preferred first initiator in this disclosure is benzoyl peroxide, which can better cooperate with the chain transfer agent and has the effect of synergistically controlling the molecular weight and viscosity of the product.

[0045] This disclosure does not specify any particular prepolymerization process for the fluorocarbon-modified ethoxybisphenol A diacrylate; any reaction process known to those skilled in the art can be used, such as the process described below.

[0046] Preferably, the preparation process includes: mixing the raw materials, carrying out a prepolymerization reaction, and preparing the fluorocarbon-modified ethoxybisphenol A diacrylate.

[0047] Preferably, the mixing includes: adding the first portion of organic solvent to the first portion of organic solvent with a first stirring and heating to the reaction temperature; adding ethoxybisphenol A diacrylate to the second portion of organic solvent with a second stirring; then adding the first monomer, chain transfer agent, and first initiator with a third stirring to obtain a mixed system; adding the mixed system to the first portion of organic solvent; and continuing with a fourth stirring to complete the prepolymerization reaction.

[0048] Preferably, after the prepolymerization reaction, the organic solvent is removed from the reacted material to obtain the fluorocarbon-modified ethoxybisphenol A diacrylate.

[0049] Thirdly, this disclosure provides a resin composition comprising the fluorocarbon-modified ethoxybisphenol A diacrylate described in the first aspect, or the fluorocarbon-modified ethoxybisphenol A diacrylate prepared by the method described in the second aspect; the resin composition further comprises a diol diacrylate and a second initiator.

[0050] The resin composition provided in the third aspect of this disclosure contains fluorocarbon-modified ethoxybisphenol A diacrylate. On the one hand, compared with bisphenol A dimethacrylate glycidyl acrylate, ethoxybisphenol A diacrylate retains the benzene ring structure, giving the material higher hardness and strength; on the other hand, the ethoxylated molecular chain segments give the monomers lower viscosity; and the fluorocarbon modification results in a polyfluorinated branched structure, which facilitates the wetting of the resin composition onto the framework, thereby improving the efficiency of resin penetration into the porous framework. The original time required for complete penetration was more than 5 days, but this disclosure can shorten it to less than 1 day.

[0051] Preferably, the diol diacrylate comprises any one or a combination of at least two of triethylene glycol dimethacrylate, triethylene glycol diethylacrylate, propylene glycol diethylacrylate, or 1,6-hexanediol dimethacrylate, wherein typical but non-limiting combinations are combinations of triethylene glycol dimethacrylate and triethylene glycol diethylacrylate, combinations of triethylene glycol dimethacrylate and propylene glycol diethylacrylate, and combinations of propylene glycol diethylacrylate and triethylene glycol diethylacrylate.

[0052] Preferably, the resin composition comprises, by mass fraction, 60-70 parts of fluorocarbon-modified ethoxybisphenol A diacrylate, 30-40 parts of diol diacrylate, and 0.3-0.7 parts of a second initiator.

[0053] The components are as follows: fluorocarbon-modified ethoxybisphenol A diacrylate: 60-70 parts, for example, 60, 62, 63, 64, 65, 66, 67, 68, 69, or 70 parts, but not limited to the listed values; other unlisted values ​​within this range also apply; diol diacrylate: 30-40 parts, for example, 30, 32, 33, 34, 35, 36, 37, 38, 39, or 40 parts, but not limited to the listed values; other unlisted values ​​within this range also apply; second initiator: 0.3-0.7 parts, for example, 0.3, 0.35, 0.39, 0.44, 0.48, 0.53, 0.57, 0.62, 0.66, or 0.7 parts, but not limited to the listed values; other unlisted values ​​within this range also apply.

[0054] This disclosure further optimizes the mass fractions of glycol diacrylate and fluorocarbon-modified ethoxybisphenol A diacrylate within the above-mentioned range. Essentially, this is to control the ratio of the two to be 30-40:60-70, thereby better ensuring the appropriate proportion of small molecule monomers, while better balancing the strength of the cured resin and the viscosity of the resin composition before curing.

[0055] Preferably, the second initiator comprises benzoyl peroxide.

[0056] Preferably, the viscosity of the resin composition is 300-500 mPa·s, for example, it can be 300 mPa·s, 320 mPa·s, 350 mPa·s, 360 mPa·s, 370 mPa·s, 380 mPa·s, 400 mPa·s, 420 mPa·s, 450 mPa·s, 480 mPa·s or 500 mPa·s, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0057] Preferably, the surface tension of the resin composition is <20mN / m, for example, it can be 19mN / m, 18mN / m, 17mN / m, 16mN / m, 15mN / m, 14mN / m, 13mN / m, 12mN / m or 10mN / m, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0058] This disclosure does not impose any special requirements on the preparation of the resin composition. Any preparation method known to those skilled in the art can be used, and adjustments can be made according to the actual situation, such as ultrasonic mixing or stirring mixing.

[0059] Fourthly, this disclosure provides the application of the resin composition described in the third aspect in resin-infiltrated ceramics.

[0060] The resin composition provided in the third aspect of this disclosure has low viscosity and low surface tension, which can better wet the skeleton and has high permeation efficiency in resin-permeable ceramics, showing broad application prospects.

[0061] Compared with the prior art, this disclosure has at least the following beneficial effects:

[0062] (1) The fluorocarbon modified ethoxybisphenol A diacrylate provided in this disclosure has a polyfluorinated branched structure, which can improve the interfacial wettability between the subsequent resin and the skeleton, thereby improving the penetration efficiency of the resin composition into the skeleton.

[0063] (2) The preparation method of fluorocarbon modified ethoxybisphenol A diacrylate provided in this disclosure controls the molecular weight of the prepolymer—fluorocarbon modified ethoxybisphenol A diacrylate by adding a chain transfer agent, which can better ensure that the number of repeating units and viscosity of the final fluorocarbon modified ethoxybisphenol A diacrylate are within a suitable range.

[0064] (3) The resin composition provided in this disclosure has low viscosity and a polyfluorinated branched structure on the surface. Its surface tension is lower than that of the skeleton interface after KH570 modification, which is beneficial to the wetting of the skeleton by the resin, thereby greatly improving the efficiency of resin penetration into the porous skeleton. The original complete penetration required more than 5 days, but this disclosure can shorten it to less than 1 day. Detailed Implementation

[0065] To facilitate understanding of this disclosure, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of this disclosure.

[0066] It should be understood that in the description of this disclosure, the terms "first," "second," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined with "first," "second," etc., may explicitly or implicitly include one or more of that feature. In the description of this disclosure, unless otherwise stated, "a plurality of" means two or more.

[0067] As a specific embodiment of this disclosure, a method for preparing fluorocarbon-modified ethoxybisphenol A diacrylate is provided, the method comprising:

[0068] In the first container equipped with an electric stirrer and a reflux condenser, add 100 parts of organic solvent, set the temperature of the constant temperature water bath to 65-75℃, and stir at 150-250 rad / min for 20-30 min.

[0069] Add the remaining 100 parts of carbon tetrachloride and 50-60 parts of ethoxybisphenol A diacrylate to the second container, stir at 300-500 rad / min for 20-40 min, then add 5-10 parts of the first monomer, 1-3 parts of chain transfer agent, and 0.05-0.1 parts of the first initiator and continue stirring for 15-30 min to obtain a mixed system. Then, add the mixed system to the first container containing organic solvent through a feed pump within 25-35 min, and stir at 250-300 rad / min for 0.8-1.5 h to complete the reaction.

[0070] The organic solvent was then removed by heating and evaporation using a rotary evaporator to obtain fluorocarbon-modified ethoxybisphenol A diacrylate.

[0071] As another specific embodiment of this disclosure, a method for preparing a resin composition is provided, the preparation method comprising:

[0072] Take 60-70 parts of fluorocarbon-modified ethoxybisphenol A diacrylate, add 30-40 parts of diol diacrylate and 0.3-0.7 parts of a second initiator, and stir at 450-550 rad / min for 25-35 min to obtain the resin composition.

[0073] However, the preparation of the fluorocarbon-modified ethoxybisphenol A diacrylate and resin composition in this disclosure is not limited to the above-described preparation method, and can be prepared by other feasible methods well known to those skilled in the art. For the convenience of experimentation, the following examples and comparative examples were conducted using the above method, as detailed below.

[0074] Example 1

[0075] This embodiment provides a method for preparing fluorocarbon-modified ethoxybisphenol A diacrylate, the preparation method comprising:

[0076] In a four-necked flask equipped with an electric stirrer and a reflux condenser, add 100 parts of carbon tetrachloride solvent, set the temperature of the constant temperature water bath to 70°C, and stir at 200 rad / min for 25 min.

[0077] Add the remaining 100 parts of carbon tetrachloride and 50 parts of decaethoxybisphenol A diacrylate to another flask, stir at 500 rad / min for 20 min, then add 5 parts of hexafluorobutyl methacrylate, 1 part of n-12-thiol and 0.05 parts of benzoyl peroxide and continue stirring for 20 min. Then, add the mixed solution to the 70°C flask containing carbon tetrachloride through a feed pump within 30 min, and stir at 280 rad / min for 1 h to complete the reaction.

[0078] The carbon tetrachloride was then removed by heating and evaporating the material at 70°C using a rotary evaporator to obtain fluorocarbon-modified decaethoxybisphenol A diacrylate.

[0079] The fluorocarbon-modified ethoxybisphenol A diacrylate prepared in this embodiment includes a structure in which segment B is grafted onto segment A via carbon-carbon double bonds.

[0080] Wherein, chain segment A is as shown in equation (1), and chain segment B is as shown in equation (2).

[0081] In equation (1), the value of x is 10;

[0082] Chain segment B is shown in equation (2):

[0083] The structural formula of R in equation (2) is shown in equation (3):

[0084] In this embodiment, the original viscosity of the mixture of 50 parts decaethoxybisphenol A diacrylate and 5 parts hexafluorobutyl methacrylate was 380 mPa·s. After the prepolymerization reaction, the viscosity of the mixture became 794 mPa·s, indicating that a polymerization reaction occurred and the viscosity increased.

[0085] Example 2

[0086] This embodiment provides a method for preparing fluorocarbon-modified ethoxybisphenol A diacrylate. In the preparation, except that the raw materials are based on 200 parts of organic solvent and include, by mass fraction: 10 parts of hexafluorobutyl methacrylate, 60 parts of decaethoxybisphenol A diacrylate, 3 parts of n-12-thiol and 0.1 parts of benzoyl peroxide, the rest are the same as in Example 1 and will not be repeated here.

[0087] Example 3

[0088] This embodiment provides a method for preparing fluorocarbon-modified ethoxybisphenol A diacrylate. In the preparation, except that the raw materials are based on 200 parts of organic solvent and include, by mass fraction: 7 parts of hexafluorobutyl methacrylate, 55 parts of decaethoxybisphenol A diacrylate, 2 parts of n-12-thiol and 0.08 parts of benzoyl peroxide, the rest are the same as in Example 1 and will not be repeated here.

[0089] Example 4

[0090] This embodiment provides a method for preparing fluorocarbon-modified ethoxybisphenol A diacrylate, the preparation method comprising:

[0091] In a four-necked flask equipped with an electric stirrer and a reflux condenser, add 100 parts of carbon tetrachloride solvent, set the temperature of the constant temperature water bath to 75°C, and stir at 250 rad / min for 30 min.

[0092] Add the remaining 100 parts of carbon tetrachloride and 52 parts of dodecaethoxybisphenol A diacrylate to another flask, stir at 450 rad / min for 18 min, then add 8 parts of octafluoroamyl methacrylate, 2.5 parts of n-butanethiol and 0.06 parts of benzoyl peroxide and continue stirring for 24 min. Then, add the mixed solution to a flask containing carbon tetrachloride at 75°C through a feed pump within 40 min, and stir at 300 rad / min for 1.5 h to complete the reaction.

[0093] The carbon tetrachloride was then removed by heating and evaporating the material at 75°C using a rotary evaporator to obtain fluorocarbon-modified decaethoxybisphenol A diacrylate.

[0094] Example 5

[0095] This embodiment provides a method for preparing fluorocarbon-modified ethoxybisphenol A diacrylate. The preparation method is the same as in Example 1 except that 3 parts of hexafluorobutyl methacrylate are added to the raw materials, and will not be repeated here.

[0096] Example 6

[0097] This embodiment provides a method for preparing fluorocarbon-modified ethoxybisphenol A diacrylate. The preparation method is the same as in Example 1 except that 20 parts of hexafluorobutyl methacrylate are added to the raw materials, and will not be repeated here.

[0098] Example 7

[0099] This embodiment provides a method for preparing fluorocarbon-modified ethoxybisphenol A diacrylate. The preparation method is the same as in Example 1 except that 0.5 parts of n-12-thiol are added to the raw materials, and will not be repeated here.

[0100] Example 8

[0101] This embodiment provides a method for preparing fluorocarbon-modified ethoxybisphenol A diacrylate. The preparation method is the same as in Example 1 except that 5 parts of n-12-thiol are added to the raw materials, and will not be repeated here.

[0102] Example 9

[0103] This embodiment provides a method for preparing fluorocarbon-modified ethoxybisphenol A diacrylate. The preparation method is the same as in Example 1, except that n-12-thiol in the raw materials is replaced with tert-butylthiol and other chain transfer agents. It will not be described again here.

[0104] Example 10

[0105] This embodiment provides a method for preparing fluorocarbon-modified ethoxybisphenol A diacrylate. The preparation method is the same as in Example 1, except that hexafluorobutyl methacrylate is replaced with tetrafluorobutyl methacrylate in the raw materials. It will not be described again here.

[0106] Comparative Example 1

[0107] This comparative example provides a method for preparing fluorocarbon-modified ethoxybisphenol A diacrylate. The preparation method is the same as in Example 1, except that decaethoxybisphenol A diacrylate is replaced with pentaethoxybisphenol A diacrylate, and will not be repeated here.

[0108] Comparative Example 2

[0109] This comparative example provides a method for preparing fluorocarbon-modified ethoxybisphenol A diacrylate. The preparation method is the same as in Example 1, except that decaethoxybisphenol A diacrylate is replaced with pentadecylethoxybisphenol A diacrylate, and will not be repeated here.

[0110] Comparative Example 3

[0111] This comparative example provides a method for preparing modified ethoxybisphenol A diacrylate, in which hexafluorobutyl methacrylate is not added, and the rest is the same as in Example 1, and will not be repeated here.

[0112] Comparative Example 4

[0113] This comparative example provides a method for preparing modified ethoxybisphenol A diacrylate, wherein hexafluorobutyl methacrylate is replaced with difluorobutyl methacrylate in the preparation method, and the rest is the same as in Example 1, and will not be repeated here.

[0114] Comparative Example 5

[0115] This comparative example provides a method for preparing modified ethoxybisphenol A diacrylate. Except for the absence of n-12-thiol, the preparation method is the same as in Example 1 and will not be repeated here.

[0116] Application Example 1

[0117] This application example provides a resin composition, the preparation method of which includes:

[0118] Take 70 parts of the fluorocarbon-modified ethoxybisphenol A diacrylate provided in Example 1, add 30 parts of triethylene glycol dimethacrylate and 0.3 parts of benzoyl peroxide, and stir at 500 rad / min for 30 min to obtain the resin composition.

[0119] Specifically, the resin composition comprises: 70 parts of fluorocarbon-modified ethoxybisphenol A diacrylate, 30 parts of triethylene glycol dimethacrylate, and 0.3 parts of benzoyl peroxide, as provided in Example 1.

[0120] Application Example 2

[0121] This application example provides a resin composition, the preparation method of which includes:

[0122] Take 60 parts of the fluorocarbon-modified ethoxybisphenol A diacrylate provided in Example 2, add 40 parts of triethylene glycol dimethacrylate and 0.7 parts of benzoyl peroxide, and stir at 500 rad / min for 30 min to obtain the resin composition.

[0123] Specifically, the resin composition comprises: 60 parts of fluorocarbon-modified ethoxybisphenol A diacrylate, 40 parts of triethylene glycol dimethacrylate, and 0.7 parts of benzoyl peroxide, as provided in Example 2.

[0124] Application Example 3

[0125] This application example provides a resin composition, the preparation method of which includes:

[0126] Take 65 parts of the fluorocarbon-modified ethoxybisphenol A diacrylate provided in Example 3, add 35 parts of triethylene glycol dimethacrylate and 0.5 parts of benzoyl peroxide, and stir at 500 rad / min for 30 min to obtain the resin composition.

[0127] Specifically, the resin composition comprises: 65 parts of fluorocarbon-modified ethoxybisphenol A diacrylate, 35 parts of triethylene glycol dimethacrylate, and 0.5 parts of benzoyl peroxide, as provided in Example 3.

[0128] Application Example 4

[0129] This application example provides a resin composition, the preparation method of which includes:

[0130] Take 66 parts of the fluorocarbon-modified ethoxybisphenol A diacrylate provided in Example 4, add 38 parts of triethylene glycol dimethacrylate and 0.2 parts of benzoyl peroxide, and stir at 450 rad / min for 25 min to obtain the resin composition.

[0131] Specifically, the resin composition comprises: 66 parts of fluorocarbon-modified ethoxybisphenol A diacrylate, 38 parts of triethylene glycol dimethacrylate, and 0.2 parts of benzoyl peroxide, as provided in Example 4.

[0132] Application Examples 5 to 10 and Comparative Examples 1 to 5 are identical to Application Example 1, except that they use the fluorocarbon-modified ethoxybisphenol A diacrylate prepared in Examples 5 to 10 and Comparative Examples 1 to 5, respectively.

[0133] Application Example 11

[0134] This application example provides a resin composition that is identical to Application Example 1 except that 25 parts of triethylene glycol dimethacrylate are added, and will not be described again here.

[0135] Application Example 12

[0136] This application example provides a resin composition that is identical to Application Example 1 except that 45 parts of triethylene glycol dimethacrylate are added, and will not be described again here.

[0137] Application Example 13

[0138] This application example provides a resin composition that is identical to that of Application Example 1, except that triethylene glycol dimethacrylate is replaced with ethyl methacrylate, and will not be described again here.

[0139] Application Comparative Example 6

[0140] This application comparative example provides a resin composition comprising: 60 parts of bisphenol A dimethacrylate glycidyl acrylate (Bis-GMA), 40 parts of triethylene glycol dimethacrylate (TEGDMA), and 0.3 parts of BPO. The mixing method is the same as in application example 1, and will not be repeated here.

[0141] Test method:

[0142] Viscosity: The viscosity of resin compositions with different proportions was tested at 25°C using a rotational viscometer. 20g of sample was taken.

[0143] Surface tension: When a capillary tube is inserted into a liquid, the liquid will rise along the capillary tube. After rising to a certain height, the liquid inside and outside the capillary tube will reach a state of equilibrium, and the liquid will stop rising. At this point, the upward pulling force exerted by the liquid surface on the liquid is equal to the downward force exerted by the liquid. Therefore, the surface tension is: γ = ρghr / (2cosθ).

[0144] In the formula: γ is the surface tension, r is the radius of the capillary, h is the height of the liquid level rise in the capillary, ρ is the density of the liquid being measured, g is the local gravitational acceleration, and θ is the contact angle between the liquid and the tube wall.

[0145] Infiltration time: Infiltration time is represented by T, and the unit is h or d. The modified ceramic skeleton is placed in a container, ensuring that the distance between them is greater than 1 cm. The prepared resin is then slowly added to the container along the container wall. When the resin completely submerges the skeleton, the addition of resin is stopped, and the container is placed in a vacuum drying oven and evacuated. Every 6 hours, the skeleton is taken out of the drying oven, and the skeleton is shone with a flashlight and observed from 6 sides. When the inside of the skeleton is uniformly transparent and without dark lines, the infiltration of the skeleton is complete.

[0146] The test was conducted according to the above method. Timing started from the first addition of resin and stopped when the skeleton was completely permeated. The time taken was recorded as T1, which is the time required for the resin to permeate completely.

[0147] Flexural strength: Samples were prepared according to GB30367 with dimensions of (16.0±0.2)*(4±0.2)*(1.2±0.2) mm. First, each surface of the sample was coarsely polished with 800-grit sandpaper and finely polished with 2000-grit sandpaper. Then, each surface was polished to a mirror finish with 3000-grit or 5000-grit sandpaper, and the sample was thoroughly cleaned. A universal tensile testing machine was used for testing, with a span of 12 mm and a descent speed of 1 mm / min.

[0148] This disclosure uses a Shimadzu tensile testing machine for testing, and the formula for calculating the flexural strength is as follows:

[0149] In the formula:

[0150] P—Break load (N);

[0151] L—Test span (mm);

[0152] ω — the width of the specimen, the dimension (mm) of the side perpendicular to the load direction;

[0153] b — The thickness of the specimen, the dimension (mm) of the side parallel to the load direction.

[0154] The test results of the above application examples and application comparison examples are shown in Table 1.

[0155] Table 1

[0156] The following points can be observed from Table 1:

[0157] (1) As can be seen from the comprehensive application examples 1 to 4, the resin composition provided in this disclosure has the advantages of low viscosity, low surface tension, long penetration time to the skeleton and high flexural strength after curing by adding fluorocarbon modified ethoxybisphenol A diacrylate. The viscosity of the resin composition is within 560 mPa·s, the surface tension is ≤32 mN / m, the penetration time of the resin composition to the skeleton is ≤48h, and the flexural strength after curing is ≥198 MPa. It has excellent performance and broad application prospects.

[0158] (2) Combining Application Examples 1 and 5-6, it can be seen that in Application Example 1, 5 parts of hexafluorobutyl methacrylate were used, compared with 3 parts and 20 parts of hexafluorobutyl methacrylate used in Application Examples 5-6, respectively. In Application Example 1, the viscosity of the resin composition was 320 mPa·s, the surface tension was 21 mN / m, and the flexural strength of the cured resin composition was 203 MPa. In Application Example 5, the viscosity of the resin composition was 420 mPa·s, and the surface tension was 41 mN / m, resulting in a penetration time of >4 days. In Application Example 6, the fluorocarbon segment content was too high, and the flexural strength of the cured resin composition was only 86 MPa. This shows that by using an appropriate amount of the first monomer, this disclosure can better ensure that the surface tension and viscosity of the resin composition are low, thereby further shortening the penetration time and making the flexural strength of the cured resin composition higher.

[0159] (3) Combining Application Examples 1 and 7-8, it can be seen that in Application Example 1, 1 part of n-12-thiol was used. Compared with Application Examples 7-8, 0.5 parts and 5 parts of n-12-thiol were used respectively. In Application Example 1, the viscosity of the resin composition was 320 mPa·s, the surface tension was 21 mN / m, and the flexural strength of the cured resin composition was 203 MPa. In Application Example 7, the viscosity of the resin composition was as high as 780 mPa·s, resulting in a penetration time of >5 days. In Application Example 8, the prepolymerization reaction was incomplete, the molecular weight was low, and the strength of the cured resin decreased to 153 MPa. This shows that by using an appropriate amount of chain transfer agent, this disclosure can better ensure that the surface tension and viscosity of the resin composition are low, thereby further shortening the penetration time and making the flexural strength of the cured resin composition higher.

[0160] (4) Combining Application Example 1 and Application Example 9, it can be seen that in Application Example 1, n-12-thiol is used as a chain transfer agent. Compared with the use of tert-butyritin in Application Example 9, the chain transfer constant of tert-butyritin in Application Example 9 is low, the degree of polymerization of the prepolymer is increased, the molecular weight of the prepolymer is increased, and the viscosity of the resin composition is increased to 648 mPa·s, and the penetration time is >4d. This shows that by preferentially using a specific chain transfer agent, this disclosure can better ensure the low viscosity of the resin composition, thereby further shortening the penetration time.

[0161] (5) Combining Application Example 1 and Application Example 10, it can be seen that hexafluorobutyl methacrylate is used as the first monomer in Application Example 1. Compared with tetrafluorobutyl methacrylate used in Application Example 10, the fluorine atom content of the first monomer in Application Example 10 is less. The surface tension of the final resin composition increases to 44 mN / m, resulting in a penetration time of >4 days. This shows that by preferably controlling the number of fluorine atoms in the first monomer within a specific range, this disclosure can better ensure that the surface tension of the resin composition is low, thereby further shortening the penetration time.

[0162] (6) As can be seen from the combined application examples 1 and 11-13, this disclosure can better ensure that the surface tension and viscosity of the resin composition are low by preferably using a specific diol diacrylate and controlling its content within a specific range, thereby further shortening the penetration time and making the flexural strength of the cured resin composition higher.

[0163] (7) Combining Application Example 1 and Comparative Examples 1-6, it can be seen that in Comparative Example 1, the number of ethoxy groups was only 5, which led to an increase in the viscosity of the resin composition and a prolonged penetration time; in Comparative Example 2, the number of ethoxy groups was as high as 15, resulting in an excessively high proportion of flexible segments and a decrease in the strength of the cured resin; in Comparative Example 3, no fluorocarbon modification was performed, which led to a significant increase in both surface tension and viscosity, and a penetration time > 8 days; in Comparative Example 4, the number of fluorine atoms was only 2, which led to a significant increase in both surface tension and viscosity, and a penetration time > 7 days, failing to achieve a good surface modification effect. In Comparative Example 5, the absence of a chain transfer agent resulted in a significant increase in prepolymer viscosity and a longer penetration time. In Comparative Example 6, the use of conventional bisphenol A dimethacrylate resulted in a resin composition with high viscosity and surface tension, and a penetration time > 5 days. This indicates that the present disclosure, by grafting organic groups containing at least three fluorine atoms onto ethoxybisphenol A diacrylate and using it as a resin composition, can reduce the viscosity and surface tension of the resin composition, thereby improving the efficiency of resin penetration into the porous framework and effectively ensuring the flexural strength of the cured resin.

[0164] This disclosure illustrates its detailed features through the above embodiments, but it is not limited to these detailed features, meaning that this disclosure does not necessarily rely on them for implementation. Those skilled in the art should understand that any improvements to this disclosure, equivalent substitutions for the selected technical features, additions of auxiliary technical features, and selection of specific methods all fall within the scope of protection and disclosure of this disclosure. Industrial applicability

[0165] This disclosure discloses a modified ethoxybisphenol A diacrylate containing fluorinated carbon segments obtained by grafting an organic group containing at least three fluorine atoms onto ethoxybisphenol A diacrylate. When used in resin compositions, this modified ethoxybisphenol A diacrylate containing fluorinated carbon segments can reduce the viscosity of the resin composition and improve the efficiency of resin penetration into porous frameworks, thus showing broad application prospects.

Claims

1. A fluorocarbon-modified ethoxylated bisphenol A diacrylate, characterized in that, The fluorocarbon-modified ethoxybisphenol A diacrylate includes a structure in which segment B is grafted onto segment A via carbon-carbon double bonds; Wherein, chain segment A is as shown in equation (1), and chain segment B is as shown in equation (2): In equation (1), the value of x ranges from 6 to 12; Chain segment B is shown in equation (2): In formula (2), R is an organic group containing at least 3 fluorine atoms.

2. The fluorocarbon-modified ethoxybisphenol A diacrylate according to claim 1, characterized in that, The R contains an ester group.

3. The fluorocarbon-modified ethoxybisphenol A diacrylate according to claim 2, characterized in that, Preferably, the ester group is connected to the carbon atom of the connecting double bond shown in formula (2).

4. The fluorocarbon-modified ethoxybisphenol A diacrylate according to claim 2 or 3, characterized in that, The R contains 5 to 10 fluorine atoms.

5. The fluorocarbon-modified ethoxybisphenol A diacrylate according to any one of claims 2 to 4, characterized in that, The structural formula of R is shown in equation (3): The fluorocarbon-modified ethoxybisphenol A diacrylate contains a grafted prepolymer of segment B and segment A, wherein the number of repeating units in a single prepolymer molecule is ≤3.

6. The fluorocarbon-modified ethoxybisphenol A diacrylate according to any one of claims 1 to 5, characterized in that, The molecular weight of the fluorocarbon-modified ethoxybisphenol A diacrylate is 3000-7000.

7. The fluorocarbon-modified ethoxybisphenol A diacrylate according to any one of claims 1 to 6, characterized in that, The viscosity of the fluorocarbon-modified ethoxybisphenol A diacrylate is 650–1026 mPa·s.

8. A method for preparing fluorocarbon-modified ethoxybisphenol A diacrylate according to any one of claims 1 to 7, characterized in that, The raw materials used in the preparation include a first monomer, ethoxybisphenol A diacrylate, a chain transfer agent, an organic solvent, and a first initiator; The first monomer is shown in equation (2): In formula (2), R is an organic group containing at least 3 fluorine atoms.

9. The preparation method according to claim 8, characterized in that, The raw materials prepared are based on 200 parts of organic solvent and include, by mass fraction: 5-10 parts of the first monomer, 50-60 parts of ethoxybisphenol A diacrylate, 1-3 parts of chain transfer agent, and 0.05-0.1 parts of the first initiator.

10. The preparation method according to claim 8 or 9, characterized in that, The R of the first monomer contains an ester group, preferably the ester group is attached to a carbon atom that forms a double bond as shown in formula (2); Preferably, R contains 5 to 10 fluorine atoms; Preferably, the first monomer comprises hexafluorobutyl methacrylate; Preferably, the number of ethoxy groups in the ethoxybisphenol A diacrylate is 6 to 12; Preferably, the chain transfer agent is a thiol chain transfer agent, and more preferably, the thiol chain transfer agent has 4 to 15 carbon atoms, and more preferably, it has 12 carbon atoms. Preferably, the thiol chain transfer agent includes n-12-thiol; Preferably, the organic solvent has a boiling point ≥70°C; Preferably, the first initiator comprises benzoyl peroxide.

11. The preparation method according to any one of claims 8 to 10, characterized in that, The preparation process includes: mixing the raw materials, carrying out a prepolymerization reaction, and preparing the fluorocarbon-modified ethoxybisphenol A diacrylate; Preferably, the mixing includes: first stirring and heating the organic solvent in the first part to the reaction temperature; adding ethoxybisphenol A diacrylate to the organic solvent in the second part, stirring for the second time, then adding the first monomer, chain transfer agent and first initiator and stirring for the third time to obtain a mixed system, and adding the mixed system to the organic solvent in the first part, and continuing to stir for the fourth time to complete the prepolymerization reaction; Preferably, after the prepolymerization reaction, the organic solvent is removed from the reacted material to obtain the fluorocarbon-modified ethoxybisphenol A diacrylate.

12. A resin composition, characterized in that, The resin composition includes the fluorocarbon-modified ethoxybisphenol A diacrylate as described in any one of claims 1 to 7, or the fluorocarbon-modified ethoxybisphenol A diacrylate prepared by the method described in any one of claims 8 to 11. The resin composition further includes diol diacrylate and a second initiator.

13. The resin composition according to claim 12, characterized in that, The diol diacrylate includes any one or a combination of at least two of triethylene glycol dimethacrylate, triethylene glycol diethyl acrylate, propylene glycol diethyl acrylate, or 1,6-hexanediol dimethacrylate. Preferably, the resin composition comprises, by mass fraction, 60-70 parts of fluorocarbon-modified ethoxybisphenol A diacrylate, 30-40 parts of diol diacrylate, and 0.3-0.7 parts of a second initiator; Preferably, the second initiator comprises benzoyl peroxide; Preferably, the viscosity of the resin composition is 300–500 mPa·s; Preferably, the surface tension of the resin composition is <20 mN / m.

14. The use of the resin composition of claim 12 or 13 in resin-infiltrated ceramics.

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