WO2023078419A1 - Polyurethane acrylate, photocurable material, preparation method and use - Google Patents

Abstract

The present application discloses a polyurethane acrylate, a photocuring material, a preparation method and a use, and a method for fabricating an oral medical device. A polyether/polyester polyol soft segment having a special structure is introduced into the polyurethane acrylate, so that the polyurethane acrylate has the characteristics of low haze, high transmittance and high toughness. By combining bio-based polyurethane acrylate, high-strength aliphatic urethane acrylate, a monofunctional free radical acrylate monomer and a bifunctional free radical acrylate monomer, after curing, the photocurable material has a very suitable crosslinking density, good mechanical strength, good dimensional stability, excellent aging resistance, low haze, and high transmittance.

Description

Polyurethane acrylate, photocurable material, preparation method and application

Cross References to Related Applications

This application claims the priority of the Chinese patent application with application number 202111308532.8 and titled "Low Haze High Toughness Urethane Acrylate, Light Curing Material and Its Preparation and Application" submitted to the China Patent Office on November 05, 2021. The entire contents of which are incorporated by reference in this application.

technical field

The present application relates to the field of polymer technology, in particular to a polyurethane acrylate and a preparation method thereof, a photocurable material and a preparation method thereof, the application of the photocurable material in making oral medical devices, and a method for manufacturing oral medical devices.

Background technique

3D printing technology is usually also called additive manufacturing or incremental manufacturing. It is based on the data of three-dimensional mathematical models. It mainly uses continuous layer printing and superimposes layers to form a three-dimensional entity. As a highly customized industry, dentistry has a close relationship with 3D printing in its transition to digital. In the field of stomatology, 3D printing technology is being applied and researched more and more widely, including prosthodontics, dental implantology, orthodontics, and oral medicine, and also includes the production of dental implant guides, cranial jaws, etc. Fabrication of facial and orthopedic implants, as well as copings and frameworks for implants and dental restorations, among others.

With the continuous development of stomatology, the application of 3D printing in dentistry has become more in-depth. The research on dental 3D printing materials has become the research focus of many researchers. In recent years, great breakthroughs have been made. The field of stomatology. However, the current transparent products of 3D printed dental materials, including occlusal splints, surgical guides, retainers, orthodontic appliances, and directly printed invisible braces, still have high haze, low transmittance, and poor biocompatibility. A series of problems such as risk, poor toughness, and poor dimensional stability have caused the penetration rate to be far from enough.

Contents of the invention

This application aims to solve at least one of the technical problems existing in the prior art. For this reason, the application proposes a kind of urethane acrylate and its preparation method, light-cured material and its preparation method, the application of light-cured material in making oral medical device, the manufacturing method of oral medical device, can reduce the object made such as Haze of dental medical devices, improve transmittance and toughness.

In order to achieve the above object, according to one aspect of the present application, a kind of polyurethane acrylate is provided, this polyurethane acrylate contains the structural unit of polyether/polyester polyol, and polyether/polyester polyol has following formula I, formula II , at least one structural formula in formula III:

Wherein, n is an integer of 1-1000.

According to another aspect of the present application, a kind of preparation method of aforementioned polyurethane acrylate is provided, and this preparation method comprises the following steps: make polyether/polyester polyol and acrylate-2-hydroxyethyl ester, neopentyl glycol, methyl Hydroxyethyl acrylate and isocyanate are bulk polymerized to obtain polyurethane acrylate; polyether/polyester polyol has at least one structural formula in the following formula I, formula II, and formula III:

Wherein, n is an integer of 1-1000.

According to still another aspect of the present application, a photocurable material is provided, the photocurable material includes the above-mentioned urethane acrylate.

According to still another aspect of the present application, a method for preparing a photocurable material is provided, the photocurable material includes urethane acrylate, and the preparation method includes the above-mentioned method for preparing urethane acrylate.

According to yet another aspect of the present application, an application of the aforementioned light-curing material in making oral medical devices is provided.

According to yet another aspect of the present application, a method for manufacturing an oral medical device is provided. The manufacturing method includes the following steps: using the above-mentioned photo-curable material as a raw material, and performing photo-curing after molding to obtain an oral medical device.

The urethane acrylate of the present application contains random and complex polyether/polyester polyol soft segments. The sequence structure of the polyether/polyester polyol soft segments is disordered and has excellent flexibility. Polyether/polyester Due to the influence of the side methyl group, the subpolyoxypropylene group in the polyol soft segment has poor molecular regularity and is not easy to crystallize, so the overall crystallinity is greatly reduced. It can greatly improve the light transmittance and toughness of molded objects, and can reduce haze.

Description of drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following will briefly introduce the accompanying drawings used in the embodiments. It should be understood that the following drawings only show some embodiments of the present application, so It should be regarded as a limitation on the scope, and those skilled in the art can also obtain other related drawings based on these drawings without creative work.

Figure 1 is a photo of the matching test of the finished product/guide ring.

Detailed ways

The technical solution of the present application will be further described below in conjunction with specific examples. The raw materials used in the following examples, unless otherwise specified, can be obtained from conventional commercial channels; the processes used, unless otherwise specified, are conventional processes in the art.

The present application provides a polyurethane acrylate. In some embodiments, the polyurethane acrylate contains polyether/polyester polyol structural units. Wherein, polyether/polyester polyol has at least one structural formula in following formula I, formula II, formula III:

Wherein, n is an integer of 1-1000, for example, may be an integer of 10-1000.

It should be noted that the above-mentioned urethane acrylate contains random and complex polyether/polyester polyol soft segments in formula I, formula II, and formula III, and the sequence of the polyether/polyester polyol soft segments The structure is disordered and the flexibility is excellent; in addition, due to the influence of the side methyl group, the sub-polyoxypropylene group in the soft segment of polyether/polyester polyol has poor molecular regularity and is not easy to crystallize, so the overall crystallization is greatly reduced degree, which greatly improves the light transmittance, reduces the haze, and has high toughness.

In some embodiments, urethane acrylate contains a chain segment shown in the following formula IV:

Among them, R0 is

R ₁ , R ₁ ' are independently selected from

R _1a and R _1b are independently selected from H or C _1-3 alkyl; R ₂ is a structural unit of polyether/polyester polyol. It should be pointed out that the "independently selected from" mentioned in this application means that the selection of the options of the main body does not interfere with each other, for example, R _1a and R _1b are independently selected from H or C _1-3 alkyl, representing R _1a is selected from H or C _1-3 alkyl, R _1b is selected from H or C _1-3 alkyl.

In some embodiments, R ₁ and R ₁ ' are independently selected from

In some embodiments, both R ₁ and R ₁ ' are selected from

R ₂ is a structural unit of polyether/polyester polyol shown in formula I.

In some embodiments, both R ₁ and R ₁ ' are selected from

R ₂ is a structural unit of polyether/polyester polyol represented by formula II.

In some embodiments, both R ₁ and R ₁ ' are selected from

R ₂ is a structural unit of polyether/polyester polyol represented by formula III.

In some embodiments, the ASTM haze of the urethane acrylate is less than 10%, the transmittance is greater than 85%, and the notched impact strength of the urethane acrylate is greater than 60 J/M. Of course, in other embodiments, the properties of urethane acrylate can also satisfy one or both of them.

In some embodiments, polyether/polyester polyols are obtained by random copolymerization of fatty dibasic acids, aromatic dibasic acids, polyoxypropylene diols, and polyols.

It should be noted that the above-mentioned raw materials can form a relatively random polyether/polyester polyol soft segment with a main chain through random copolymerization. The introduction of aromatic dibasic acid in the process effectively destroys the sequence structure of polyether/polyester polyol, and the polyoxypropylene glycol soft segment formed by polyoxypropylene glycol (PPG) has molecular regularity due to the influence of side methyl groups. It is poor and not easy to crystallize, so the overall crystallinity is greatly reduced, thereby greatly improving the light transmittance and reducing the haze.

In some embodiments, the fatty dibasic acid includes adipic acid.

In some embodiments, the aromatic dibasic acid includes at least one of terephthalic acid and phthalic acid.

In some embodiments, the polyoxypropylene diol has a molecular weight of 300-600, specifically 300-500.

In some embodiments, the polyol includes diethylene glycol.

In some embodiments, the ratio of the total moles m1 of polyoxypropylene diol and polyol to the total moles m2 of fatty dibasic acids and aromatic dibasic acids m1:m2=1-2:1, such as 1.5- 1.8:1, specifically 1.52-1.71:1, such as 1.52:1, 1.55:1, 1.60:1, 1.65:1, 1.71:1, etc.

In some embodiments, the molar ratio of fatty dibasic acid to aromatic dibasic acid is 1:1-3, specifically 1:3, 1:2, 1:1, etc.

In some embodiments, the aromatic dibasic acid is a combination of terephthalic acid and phthalic acid, and the molar ratio of fatty dibasic acid, terephthalic acid and phthalic acid is 1:0.5-1.5:0.5-1.5 , specifically such as 1:1:1, 1:0.5:0.5, 1:1.5:1.5, 1:1.2:1.3, 1:0.8:0.6, etc.

In some embodiments, the molar ratio of polyoxypropylene diol to polyol is 1:0.5-1.5, specifically 1:1, 1:0.5, 1:1.5, 1:0.8, 1:1.3, etc.

In some embodiments, the preparation method of polyether/polyester polyol comprises the steps:

Mix aliphatic dibasic acid, aromatic dibasic acid, polyoxypropylene diol and polyol, and carry out random copolyesterification reaction to obtain random copolyesterification product; make random copolyesterification product in vacuum, React under acid catalyzed conditions until the acid value is less than 1 mgKOH/g to obtain polyether/polyester polyol.

In some embodiments, the temperature of the random copolyesterification reaction is 90-160°C, such as 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, etc., and the time is 2 -4h, such as 2h, 3h, 4h, etc.

In some embodiments, the reaction temperature of the random copolyesterification product under vacuum and acid-catalyzed conditions is 180-230°C, such as 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, etc., The reaction time is 1-4h, such as 1h, 2h, 3h, 4h, etc., and the vacuum degree is 0.08-0.09MPa.

In some embodiments, urethane acrylate is prepared from polyether/polyester polyol and 2-hydroxyethyl acrylate (HEA), neopentyl glycol (NPG), hydroxyethyl methacrylate (HEMA), isocyanate via bulk aggregated.

Polyether/polyester polyols are polymerized with HEA, NPG, HEMA, and isocyanate in bulk, and aliphatic polyurethane acrylic acid with high transmittance, low haze, and high toughness can be synthesized by controlling the reaction temperature, molar ratio, catalyst and other process conditions. ester. Moreover, by introducing NPG into the molecular chain, the crystallinity of the urethane acrylate can be lowered.

In some embodiments, the molar ratio of the total -OH of polyether/polyester polyol and neopentyl glycol to the -NCO in isocyanate is 1:0.5-2, for example 1:1.5-2, specifically 1:1.5 , 1:2, 1:1.7, etc.

In some embodiments, the molar ratio of polyether/polyester polyol to neopentyl glycol is 1:0.5-1.5, such as 1:1.5, 1:1.2, 1:1, 1:0.5, 1:1, etc.

In some embodiments, the total -OH of the polyether/polyester polyol, 2-hydroxyethyl acrylate, neopentyl glycol, and hydroxyethyl methacrylate is equal to the number of moles of -NCO in the isocyanate.

In some embodiments, the isocyanate has an asymmetric structure, including isophorone diisocyanate (IPDI). Due to the asymmetric molecular structure of the IPDI used, it is not easy to form crystals, so that the oligomer has a high low permeability, extremely low haze, and excellent elasticity and toughness. In actual operation, according to the application of urethane acrylate, IPDI with appropriate safety level can be selected. For example, when urethane acrylate is used to make oral equipment, IPDI is selected from FDA-certified food-grade IPDI curing agents that can be used in food contact applications.

The second aspect of the present application is to provide the preparation method of polyurethane acrylate, comprising the steps of: making polyether/polyester polyol and acrylate-2-hydroxyethyl ester, neopentyl glycol, hydroxyethyl methacrylate and isocyanate Bulk polymerization to obtain polyurethane acrylate with low haze and high toughness.

More specifically, the preparation method of polyurethane acrylate may include the following steps: mixing polyether/polyester polyol with neopentyl glycol and isocyanate, and reacting at least the system without -OH residues to obtain the first reactant; The product is mixed with 2-hydroxyethyl acrylate and hydroxyethyl methacrylate, and reacted until there is no -NCO residue in the system, and a polyurethane acrylate with low haze and high toughness is obtained.

It should be noted that the characteristics and proportions of each reaction raw material are similar to those in the aforementioned embodiments, and relevant details can be found in the aforementioned embodiments, and will not be repeated here.

In some embodiments, the reaction temperature of polyether/polyester polyol, neopentyl glycol and isocyanate is 30-70°C, such as 30°C, 40°C, 50°C, 60°C, 70°C, etc. In actual operation, the isocyanate is added dropwise to the mixture of polyether/polyester polyol and neopentyl glycol, and then the reaction is carried out to control the dropping speed. The dropping time is 1-2h, such as 1h, 1.2h, 1.4, 1.6h, 1.8h, 2h, etc.

In some embodiments, the reaction temperature after the first reactant is mixed with 2-hydroxyethyl acrylate and hydroxyethyl methacrylate is 50-90°C, such as 50°C, 60°C, 70°C, 80°C, 90°C ℃ and so on. In actual operation, 2-hydroxyethyl enoate and hydroxyethyl methacrylate are added dropwise to the first reactant, and the dropwise addition is controlled within 10-20 minutes. During the reaction process, the infrared spectrum of the system was measured at regular intervals (for example, 1 h). When the stretching vibration peak of -NCO at 2236 cm ^-1 disappeared, it indicated that the -NCO reaction was complete, and a polyurethane acrylate with low haze and high toughness was obtained.

The third aspect of the present application is to provide a photocurable material, and the raw material for preparing the photocurable material includes the above-mentioned urethane acrylate.

In some embodiments, the raw materials for preparing the photocurable material further include acrylate monomers. Acrylate monomers can be cross-linked and cured under light conditions.

In some embodiments, the acrylate monomers include monofunctional free radical acrylate monomers and difunctional free radical acrylate monomers.

In some embodiments, monofunctional free radical acrylate monomers include 4-acryloylmorpholine (ACMO), hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl acrylate (HEA), isobornyl acrylate (IBOA); the difunctional free radical acrylate monomer includes tricyclodecane dimethanol diacrylate (DCPDA).

In some embodiments, the mass ratio of the monofunctional free radical acrylate monomer to the difunctional free radical acrylate monomer is 1:0.5-2, such as 1:0.5, 1:1, 1:1.5, 1:2, etc. .

In some embodiments, the raw materials for the preparation of photocurable materials also include bio-based urethane acrylate, and the bio-based urethane acrylate has the following structural formula:

Among them, _R3 is

x and y are each independently selected from an integer of 1-100.

It should be noted that bio-based urethane acrylate contains polylactic acid (polylactide) diol and polyoxypropylene glycol (PPG) chain segments, which endow bio-based urethane acrylate with higher hardness and wear resistance, and at the same time have higher Excellent hydrolytic stability and excellent medical safety.

In some embodiments, the bio-based urethane acrylate is polymerized from at least the following raw materials: polylactide diol, polyoxypropylene diol, aliphatic polyisocyanate, and hydroxyethyl methacrylate (HEMA).

In some embodiments, the aliphatic polyisocyanate includes pentamethylene diisocyanate (PDI). Pentamethylene diisocyanate (PDI) is generally made of pentamethylenediamine (PDA). The production process can adopt a new gas phase method technology. Compared with the traditional process, this technology greatly reduces energy consumption and solvent usage. PDA uses biotechnology (specifically, fermentation process) to produce PDA finished products through biomass. Therefore, only two steps are needed to synthesize PDI, and 70% of the carbon content in pentamethylene diisocyanate (PDI) is derived from bio-based renewable resources, so it has a high biomass content and its performance is also very good.

In some embodiments, the polylactide diol has a molecular weight of 1000-2000, such as 1000, 1100, 1300, 1500, 1600, 1800, 2000, etc.

In some embodiments, the polyoxypropylene diol has a molecular weight of 300-500, such as 300, 350, 400, 450, 500, etc.

In some embodiments, the molar ratio of polylactide diol to polyoxypropylene diol is 1:0.5-2, such as 1:0.5, 1:1.5, 1:1.7, 1:2, 1:1, etc.

In some embodiments, the molar ratio of the total -OH of polylactide diol and polyoxypropylene diol to the -NCO of aliphatic polyisocyanate is 1:1-2, such as 1:1, 1:1.5, 1:1 2 etc.

In some embodiments, the total -OH of polylactide diol, polyoxypropylene diol, and hydroxyethyl methacrylate is equal to the number of moles of -NCO of aliphatic polyisocyanate.

In some embodiments, the preparation method of bio-based urethane acrylate is: polylactide diol, polyoxypropylene diol, aliphatic polyisocyanate, and hydroxyethyl methacrylate are polymerized to obtain bio-based urethane acrylate .

More specifically, the preparation method of bio-based urethane acrylate may include the following steps: polymerize polylactide diol, polyoxypropylene diol and aliphatic polyisocyanate until no -OH remains in the system; add methacrylic acid Hydroxyethyl ester, react until there is no -NCO residue in the system, to obtain bio-based polyurethane acrylate.

In some embodiments, the reaction temperature of the polylactide diol, polyoxypropylene diol and aliphatic polyisocyanate is 30-70°C, such as 30°C, 40°C, 50°C, 60°C, 70°C, etc. In actual operation, the aliphatic polyisocyanate is added dropwise to the mixture of polylactide diol and polyoxypropylene diol, and the dropping speed is controlled, and the dropping time is 1-2h, such as 1h, 1.2h, 1.4h, 1.6 h, 1.8h, 2h, etc.

In some embodiments, the reaction temperature of adding hydroxyethyl methacrylate is 50-90°C, such as 50°C, 60°C, 70°C, 80°C, 90°C, etc. In actual operation, the hydroxyethyl methacrylate is added dropwise to the reaction system, and the dropwise addition is controlled within 10-20 minutes. During the reaction process, the infrared spectrum of the system was measured at regular intervals (for example, 1 h). When the stretching vibration peak of -NCO at 2236 cm ^-1 disappeared, it indicated that the -NCO reaction was complete, and the bio-based urethane acrylate was obtained.

In some embodiments, the raw materials for preparing the photocurable material also include high-strength aliphatic urethane acrylate, and high-strength aliphatic urethane acrylate refers to an aliphatic urethane acrylate with a bending strength of not less than 90 MPa after complete curing, such as sand Doma's CN983NS, Changxing's 6164, 6145-100, etc.

In some embodiments, the raw materials for preparing the photocurable material further include a photoinitiator. Photoinitiators include Omnirad 819 [bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide], Omnirad DETX (2,4-diethylthioxanthone), Omnirad ITX (2- Isopropylthioxanthone), Omnirad TPO (2,4,6-trimethylbenzoyl-diphenylphosphine oxide).

In some embodiments, in parts by mass, the photocurable material includes 10-30 parts of urethane acrylate (that is, the aforementioned low-haze and high-toughness urethane acrylate), 10-30 parts of bio-based urethane acrylate, 10-30 parts 1 part of high-strength aliphatic urethane acrylate, 3-10 parts of monofunctional free radical acrylate monomer, 3-10 parts of bifunctional free radical acrylate monomer, and 1-10 parts of photoinitiator.

In some embodiments, in parts by mass, the photocurable material includes 25-30 parts of urethane acrylate (ie, the aforementioned low-haze and high-toughness urethane acrylate), 20-25 parts of bio-based urethane acrylate, 20-25 parts 1 part of high-strength aliphatic urethane acrylate, 5-10 parts of monofunctional free radical acrylate monomer, 5-10 parts of difunctional free radical acrylate monomer, and 1-5 parts of photoinitiator.

The fourth aspect of the present application is to provide a method for preparing a photocurable material, which includes the following steps: mixing all preparation raw materials to obtain a photocurable material. That is, low haze and high toughness urethane acrylate, bio-based urethane acrylate, high-strength aliphatic urethane acrylate, monofunctional free radical acrylate monomer, difunctional free radical acrylate monomer and photoinitiator are mixed, namely A photocurable material is obtained.

In some embodiments, it is necessary to prepare the above-mentioned various raw materials first, and then mix the prepared raw materials. Among them, the preparation methods of low-haze and high-toughness urethane acrylate and bio-based urethane acrylate are similar to those in the above-mentioned embodiments. For related details, please refer to the above-mentioned embodiments, and will not be repeated here.

The fifth aspect of the present application is to provide the application of photocurable materials in making oral medical devices. Dental medical devices include tooth models, occlusal splints, surgical guides, retainers, orthodontic appliances, braces, etc.

The present application also provides a method for manufacturing an oral medical device, which includes the following steps: taking a photocurable material as a raw material, and performing photocuring in a molding process to obtain a dental medical device.

In some embodiments, the method of shaping includes 3D printing. The temperature during the 3D printing process is 30-40°C, such as 35-38°C, and the humidity is 35%-55%, such as 35%, 40%, 45%, 50%, 55%, etc. Since the light-curing material contains more macromolecular resins and less small molecular substances, a special printing process is required during the 3D printing process. By controlling the conditions of 3D printing, the effect of reducing the viscosity of the printing material can be achieved, the printing accuracy can be improved, the layer pattern of the workpiece can be reduced, the detail resolution can be improved, and the overall stability of the printed workpiece can be improved.

In actual operation, the 3D printing process can adopt the following specific operations: During the printing process, the DLP printer turns on the internal dehumidifier, the DLP printer turns on the internal hot air circulation of the 37°C hot air fan, and the DLP printer uses the tray heating auxiliary function.

In some embodiments, the wavelength of the light source used in the photocuring process is 385-405nm, such as 385nm, 390nm, 395nm, 400nm, 405nm, etc.; after photocuring, the step of secondary curing can also be included, and the method of secondary curing treatment is Coat glycerin on the surface of the photocured sample, or soak the photocured sample in glycerin. The stability in the secondary curing process is improved through secondary curing, ensuring the stability of the overall performance during the entire printing process, thus guaranteeing the long-term follow-up use in the patient's oral cavity. Of course, in the secondary curing, glycerin may not be applied, but directly immersed in water and other media for curing, which is not limited here.

This application introduces a special structure polyether/polyester polyol soft segment into polyurethane acrylate, so that polyurethane acrylate has the characteristics of low haze, high transmittance and high toughness, combined with bio-based polyurethane acrylate, high strength Aliphatic urethane acrylate, monofunctional free radical acrylate monomer, and bifunctional free radical acrylate monomer work together to make the photocurable material have a very suitable crosslinking density after curing, good mechanical strength, good dimensional stability, Excellent aging resistance, low haze and high transmittance.

A light-curing material, the components included are shown in Table 1 and Table 2 below:

The raw material composition of table 1 photocurable material (unit: mass part)

The raw material composition of table 2 photocurable material (unit: mass part)

Each raw material in table 1 and table 2 is:

(1) Low haze and high toughness polyurethane acrylate

The ASTM haze of low-haze and high-toughness urethane acrylate is less than 10, and the transmittance is greater than 85. The specific synthesis method is:

(1) Determine the reaction conditions: molar ratio n (alcohol): n (acid) is 1.71, and the mass fraction of acid catalyst is 0.2% (in terms of carboxylic acid mass), adipic acid, terephthalic acid and phthalic acid The molar ratio of polyoxypropylene diol and diethylene glycol is 1:1.

Add adipic acid, terephthalic acid, phthalic acid, polyoxypropylene glycol and diethylene glycol into the reactor, conduct random copolyesterification at 100°C for 4 hours, and then raise the temperature to 200°C within 1 hour ℃ and start vacuuming, and add an acid catalyst, react at 200 ℃ for 4 hours under a vacuum of 0.09MPa, then measure the acid value, stop the reaction when the acid value is less than 1.0mgKOH/g, and obtain a viscous and transparent main chain Relatively random polyether/polyester polyol soft segment structure.

(2) Control n(-OH):n(-NCO) to be 1:1.5, the molar ratio of the main chain relatively random polyether/polyester polyol and NPG is 1:1, and the main chain is relatively random Polyether/polyester polyol and NPG are added to the reactor, and then IPDI is added dropwise, where IPDI is selected from FDA-approved food-grade IPDI curing agents that can be used in food contact applications. Control the IPDI drop rate, the drop time is 2h, and the reaction temperature is controlled at 60°C. After the reaction is complete, there is no residual -OH in the system, and the remaining unreacted groups -NCO.

Then control the ratio of n(-OH):n(-NCO) to 1:1, add HEA and HEMA dropwise into the system for further reaction, control the reaction temperature at 60°C, complete the dropwise addition in 20 minutes, measure the infrared spectrum of the system every 1h , when the stretching vibration peak of -NCO at 2236cm ^-1 disappears, it indicates that the -NCO reaction is complete, and the product low haze and high toughness polyurethane acrylate is obtained.

(2) Bio-based polyurethane acrylate

Bio-based urethane acrylate is obtained from polylactide diol with a molecular weight of 1000-2000 and polyoxypropylene diol (PPG) with a molecular weight of 400, HEMA, and PDI through bulk polymerization. The specific synthesis method is as follows:

(1) Control n(-OH):n(-NCO) to be 1:1.5, the molar ratio of polylactide diol and PPG to be 1:1, first add polylactide diol and PPG to the reactor, and then add PDI dropwise , control the dropping speed, the dropping time is 2h, and the reaction temperature is controlled at 50°C. After the reaction is complete, there is no remaining -OH in the system, and the remaining unreacted groups -NCO.

(2) Then control the ratio of n(-OH):n(-NCO) to 1:1, add HEMA dropwise into the system for further reaction, control the reaction temperature at 70°C, complete the dropwise addition in 20 minutes, measure the infrared of the system every 1h Spectrum, when the stretching vibration peak of -NCO at 2236cm ^-1 disappears, it shows that the reaction of -NCO is complete, and the product bio-based urethane acrylate is obtained.

(3) High-strength aliphatic urethane acrylate

The high-strength aliphatic urethane acrylate is a high-strength aliphatic urethane acrylate (CN983NS of Sartomer) with a flexural strength of not less than 90MPA after complete curing purchased from Sartomer.

A monofunctional acrylate is acryloylmorpholine (ACMO).

The difunctional acrylate is tricyclodecane dimethanol diacrylate (DCPDA).

Using the light-cured materials of the above-mentioned Example 1 and Comparative Examples 1-10 as raw materials, a DLP 3D printer was used to print a finished guide plate for implant surgery. During the printing process, the DLP printer turns on the internal dehumidifier (humidity is controlled at 35%-55%), the DLP printer turns on the internal hot air circulation of the 37°C hot air fan, and the DLP printer uses the heating auxiliary function of the tray to achieve the effect of reducing the viscosity of the printing material , improve the printing accuracy, reduce the layer pattern of the workpiece, improve the detail resolution, and improve the overall stability of the printed workpiece. Post-processing process: Post-curing adopts a curing box under the 385nm band light source, and performs post-processing secondary curing under medical glycerin to improve the stability of the secondary curing process and ensure the stability of the overall performance during the entire printing process. Thereby guaranteeing the follow-up use in the patient's oral cavity for a long time.

(1) Routine performance testing

Routine performance testing was carried out on the printed finished product, and at the same time a comparison was made with the commercially available finished product [Graphy competitor product, brand name Tera Harz TC-85, TC-85DAC (transparent)]. The results are shown in the table below.

Table 3 Performance gun test results

Table 4 performance test results

Among them, the test method for the dimensional stability of alcohol immersion and iodophor immersion is to soak the finished product in alcohol or iodophor for 30 minutes, and then detect the dimensional tolerance of the finished product.

The printed finished product was accelerated soaking in artificial saliva (ISO/TR10271, acidic) for 720 hours, and then its performance was tested, as shown in Tables 5 and 6 below.

Table 5 Performance test results of artificial saliva (ISO/TR10271, acidic) accelerated immersion for 720 hours

Table 6. Performance test results after accelerated immersion in artificial saliva (ISO/TR10271, acidic) for 720 hours

The printed finished product was soaked in artificial saliva (ISO/TR10271, neutral aseptic) for 720 hours at an accelerated rate, and then its performance was tested, as shown in Tables 7 and 8 below.

Table 7 Performance test results of artificial saliva (ISO/TR10271, neutral aseptic) accelerated immersion for 720 hours

Table 8 Performance test results of artificial saliva (ISO/TR10271, neutral aseptic) accelerated immersion for 720 hours

The printed finished product was placed at 37° C. and 80% humidity for 1440 hours, and then its performance was tested, as shown in Tables 9 and 10 below.

Table 9 Performance test results after 1440 hours at 37°C and 80% humidity

Table 10 Performance test results after 1440 hours at 37°C and 80% humidity

The test results show:

The 3D printed finished product of the light-cured material in Example 1 has good mechanical properties, low haze, high transmittance, good dimensional stability, excellent aging resistance, and the overall performance is significantly improved compared with the commercially available finished product. In comparison example 1, without the addition of difunctional acrylate, the crosslinking density is low, the reaction is slow, the overall curing is insufficient, the strength of mechanical properties is low, and the dimensional stability is poor. Comparative example 2 does not add monofunctional acrylate, the haze is high, the transmittance is low, and the toughness is poor; in comparative example 3, the amount of polyurethane acrylate with low haze and high toughness is increased, the overall reaction is slow, the strength is low, and the size Stability and aging resistance are poor; comparative example 4 reduces the amount of low-haze and high-toughness polyurethane acrylate, the haze increases, and the transmittance is low; comparative example 5 increases the amount of bio-based polyurethane acrylate, the overall strength is high, The toughness decreased, the haze increased, and the transmittance decreased; in comparative example 6, the amount of bio-based polyurethane acrylate was reduced, the overall strength was low, the aging resistance was deteriorated, and the dimensional stability was deteriorated; comparative example 7 increased the high-strength aliphatic polyurethane The amount of acrylate increases, the strength increases, the toughness decreases, the haze increases, and the transmittance is low; in comparative example 8, the amount of high-strength aliphatic urethane acrylate is reduced, the mechanical properties decrease, and the dimensional stability deteriorates; comparative example 9 does not add Low haze and high toughness aliphatic urethane acrylate, the haze is greatly increased. The transmittance decreased significantly; Comparative Example 10: No bio-based polyurethane acrylate was added, the dimensional stability deteriorated, and the aging resistance deteriorated.

(2) Compatibility of finished product/guide ring

As shown in Figure 1, the finished guide plate of Example 1 was matched with the guide ring, and the results showed that the guide plate was in place well, fit well with the tooth model, without warping, swinging, and moderate tightness; observed from the observation window, the guide plate and The teeth fit tightly, the tightness is suitable, the collar is flush with the platform of the guide ring hole, and it fits well.

(3) Biocompatibility test

The biocompatibility test was carried out on the printed finished product of the light-curing material of Example 1, and the results are shown in the table below:

Table 11

According to the method recommended in YY/T 0127.9-2009 "Biological Evaluation of Dental Medical Devices Unit 2: Test Method Cytotoxicity Test: Agar Diffusion Method and Membrane Diffusion Method", the finished product after printing the light-cured material of Example 1 was tested. In vitro toxicity test, according to the maximum dose method of GB/T16886.10-2017 "Biological Evaluation of Medical Devices Part 10: Irritation and Skin Sensitization Test", the potential test of delayed hypersensitivity in guinea pigs was carried out, using GB/T16886. 10-2017 "Medical Device Biological Evaluation Part 10: Irritation and Skin Sensitization Test" recommended method for oral mucosal irritation test, the results are shown in Table 12:

Table 12

The test results show that the finished product printed with the photocurable material of Example 1 has good biocompatibility, low cytotoxicity, no sensitization, and no irritation.

(4) Other regulations and standard requirements

In addition, in accordance with relevant regulations and standard requirements, the photocurable material of Example 1 was tested for other standard requirements before and after photocuring (ie, before and after polymerization), and the results are shown in Table 13 below:

Table 13

The above results show that the performance of the photocurable material in Example 1 meets the requirements of various regulations and standards.

The above-mentioned embodiment is a preferred implementation mode of the application, but the implementation mode of the application is not limited by the above-mentioned embodiment, and any other changes, modifications, substitutions, combinations, Simplifications should be equivalent replacement methods, and all are included in the protection scope of the present application.

Claims (25)

1. A kind of polyurethane acrylate, it is characterized in that, described polyurethane acrylate contains the structural unit of polyether/polyester polyol, and described polyether/polyester polyol has at least one in following formula I, formula II, formula III A structural formula:

   

   Wherein, n is an integer of 1-1000.
2. The polyurethane acrylate according to claim 1, wherein the polyurethane acrylate contains a chain segment shown in the following formula IV:

   

   where R ₀ is

   

   R ₁ , R ₁ ' are independently selected from

   

   The R _1a and R _1b are independently selected from H or C _1-3 alkyl;

   R ₂ is a structural unit of the polyether/polyester polyol.
3. The polyurethane acrylate according to claim 2, wherein said R ₁ and R ₁ ' are independently selected from

   
4. According to the polyurethane acrylate according to any one of claims 1 to 3, it is characterized in that the polyurethane acrylate meets the requirements of ASTM haze less than 10%, transmittance greater than 85%, and notched impact strength greater than 60J/M. at least one.
5. A preparation method of polyurethane acrylate described in any one of claims 1 to 4, is characterized in that, described preparation method comprises the steps: make polyether/polyester polyol and acrylate-2-hydroxyethyl ester, new Pentylene glycol, hydroxyethyl methacrylate and isocyanate carry out bulk polymerization to obtain polyurethane acrylate;

   Wherein, the polyether/polyester polyol has at least one structural formula in the following formula I, formula II, and formula III:

   

   Wherein, n is an integer of 1-1000.
6. The preparation method according to claim 5, characterized in that the polyether/polyester polyol is obtained by random copolymerization of fatty dibasic acid, aromatic dibasic acid, polyoxypropylene diol and polyol.
7. preparation method according to claim 6, is characterized in that, the preparation method of described polyether/polyester polyol comprises:

   Mix aliphatic dibasic acid, aromatic dibasic acid, polyoxypropylene diol and polyol, and carry out random copolyesterification reaction to obtain random copolyesterification product;

   performing an acid-catalyzed treatment on the random copolyesterification product to obtain the polyether/polyester polyol;

   Wherein, the temperature of the random copolymerization is 90-160°C, and the time is 2-4h; the reaction temperature of the acid-catalyzed treatment is 180-230°C, the time is 1-4h, and the vacuum degree is 0.08-0.09MPa.
8. The preparation method according to claim 6 or 7, wherein the fatty dibasic acid includes adipic acid; the aromatic dibasic acid includes at least one of terephthalic acid and phthalic acid; The molecular weight of the polyoxypropylene diol is 300-600; the polyol is diethylene glycol.
9. preparation method according to claim 8, is characterized in that, the total molar number of described polyoxypropylene diol and described polyvalent alcohol is m1, and the total molar number of described fatty dibasic acid and described aromatic dibasic acid is m2, m1:m2=1-2:1;

   The molar ratio of the fatty dibasic acid to the aromatic dibasic acid is 1:1-3;

   The aromatic dibasic acid is a combination of the terephthalic acid and the phthalic acid, and the molar ratio of the fatty dibasic acid, the terephthalic acid and the phthalic acid is 1:0.5 -1.5: 0.5-1.5;

   The molar ratio of the polyoxypropylene diol to the polyol is 1:0.5-1.5.
10. According to the preparation method described in any one of claims 5 to 9, it is characterized in that comprising the steps of:

    Mixing the polyether/polyester polyol with the neopentyl glycol and the isocyanate and performing a first reaction, at least no -OH remains in the reaction system to obtain a first reactant;

    The first reactant is mixed with the 2-hydroxyethyl acrylate and the hydroxyethyl methacrylate to perform a second reaction until no -NCO remains in the system to obtain urethane acrylate.
11. The preparation method according to claim 10, wherein, in the first reaction process, the isocyanate is added dropwise to the mixture of the polyether/polyester polyol and the neopentyl glycol, The dropping time is 1-2h, and the temperature of the first reaction is 30-70°C;

    During the second reaction, the 2-hydroxyethyl acrylate and the hydroxyethyl methacrylate are added dropwise to the first reactant for 10-20 minutes; the second reaction The temperature is 50-90°C.
12. The preparation method according to claim 10, characterized in that, the molar ratio of the total -OH of the polyether/polyester polyol and the neopentyl glycol to the -NCO in the isocyanate is 1: 0.5- 2;

    The molar ratio of the polyether/polyester polyol to the neopentyl glycol is 1:0.5-1.5;

    The total -OH of the polyether/polyester polyol, the 2-hydroxyethyl acrylate, the neopentyl glycol and the hydroxyethyl methacrylate is equal to the number of moles of -NCO in the isocyanate.
13. A photocurable material, characterized in that the photocurable material comprises the polyurethane acrylate described in any one of claims 1-4.
14. The light-curing material according to claim 13, wherein the light-curing material further comprises an acrylate monomer;

    Wherein, the acrylate monomer includes a monofunctional free radical acrylate monomer and a difunctional free radical acrylate monomer; the mass of the monofunctional free radical acrylate monomer and the difunctional free radical acrylate monomer The ratio is 1:0.5-2.
15. The photocurable material according to claim 13 or 14, wherein the monofunctional radical acrylate monomer is selected from the group consisting of 4-acryloylmorpholine, hydroxyethyl methacrylate, and 2-hydroxyethyl acrylate , any one or more of isobornyl acrylate; the difunctional radical acrylate monomer is tricyclodecane dimethanol diacrylate.
16. The photocurable material according to any one of claims 13 to 15, wherein the photocurable material further comprises bio-based urethane acrylate, and the bio-based urethane acrylate has the following structural formula:

    

    Among them, _R3 is

    

    x and y are each independently selected from an integer of 1-100.
17. The light-curing material according to any one of claims 13 to 16, wherein the light-curing material also includes high-strength aliphatic urethane acrylate, and the high-strength aliphatic urethane acrylate is bent after complete curing. Aliphatic urethane acrylate with strength not lower than 90MPa.
18. The photocurable material according to any one of claims 13 to 17, wherein the photocurable material also includes a photoinitiator selected from bis(2,4,6-trimethyl Benzoyl)-phenylphosphine oxide, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide any one or more of them.
19. The light-curing material according to claim 13, wherein, in parts by mass, the light-curing material comprises 10-30 parts of polyurethane acrylate, 10-30 parts of bio-based polyurethane acrylate, 10-30 parts of high-strength Aliphatic urethane acrylate, 3-10 parts of monofunctional free radical acrylate monomer, 3-10 parts of difunctional free radical acrylate monomer, 1-10 parts of photoinitiator.
20. A method for preparing a photocurable material, characterized in that the photocurable material includes polyurethane acrylate, and the preparation method includes the method for preparing polyurethane acrylate according to any one of claims 5 to 12.
21. The preparation method according to claim 20, wherein the photocurable material also includes bio-based urethane acrylate, and the preparation method also includes:

    performing a third reaction on the polylactide diol, the polyoxypropylene diol and the aliphatic polyisocyanate until no -OH remains in the system to obtain a third reactant;

    Adding hydroxyethyl methacrylate to the third reactant to carry out the fourth reaction until no -NCO remains in the system to obtain the bio-based urethane acrylate.
22. The preparation method according to claim 21, characterized in that, the temperature of the third reaction is 30-70°C; the temperature of the fourth reaction is 50-90°C;

    The aliphatic polyisocyanate is pentamethylene diisocyanate; the molecular weight of the polylactide diol is 1000-2000; the molecular weight of the polyoxypropylene diol is 300-500;

    The molar ratio of the polylactide diol to the polyoxypropylene diol is 1:0.5-2; The molar ratio of the -NCO of the isocyanate is 1:1-2; the total -OH of the polylactide diol, the polyoxypropylene diol and the hydroxyethyl methacrylate and the - of the aliphatic polyisocyanate NCO moles are equal.
23. Application of the light-curing material described in any one of claims 13 to 19 in making oral medical devices.
24. A method for manufacturing an oral medical device, characterized in that the manufacturing method comprises the following steps: using the light-curing material described in any one of claims 13 to 19 as a raw material, forming it through photo-curing treatment to obtain an oral medical device .
25. The manufacturing method of the oral medical device according to claim 24, wherein the forming method comprises 3D printing.

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