Polyurethane acrylate with spirothiopyran group as well as synthesis method and application thereof

Abstract

The invention provides polyurethane acrylate with spirothiopyran groups as well as a synthesis method and application thereof, and relates to the technical field of denture base materials. In the polyurethane acrylate with the spirothiopyran group, a C-S weak covalent bond of spirothiopyran is introduced into a main chain of the polyurethane acrylate, energy is dissipated by utilizing the characteristic that the spirothiopyran is easy to crack under the action of external force, and cross-linking among chains is realized through a free radical mediated click reaction, so that the mechanical strength is enhanced, and the mechanical property of the polyurethane acrylate is improved. Therefore, the composite material is suitable for the fields of denture bases, dental prostheses, biomedical implants and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of denture base materials, and in particular to a polyurethane acrylate with a spirothiopyran group, a synthesis method and application thereof. Background Art

[0002] Polyurethane (meth)acrylates are a class of polymer compounds widely used in photocurable materials, but their mechanical properties and durability are still limited under complex stress environments. Traditional materials lack self-repairing and self-reinforcement capabilities, limiting their application in high-end fields.

[0003] Chinese invention patent publication number CN118027350A discloses aliphatic polyester polyurethane acrylates, their preparation methods and applications, and 3D printing photocurable materials, their preparation methods and applications. The provided aliphatic polyester polyurethane acrylates do not contain a benzyl ring structure, and the -NOC and -OH groups form hydrogen bonds, significantly improving the rigidity of the aliphatic polyester polyurethane acrylates and preventing yellowing. The ester groups provide excellent toughness and deformation resistance, and are non-hygroscopic. The combined action of hydrogen bonds and ester groups creates a tough aliphatic polyester polyurethane acrylate with excellent fracture and deformation resistance. The large six-membered ring occupies a large space, reducing volume shrinkage after curing and providing excellent deformation resistance. While the aliphatic polyester polyurethane acrylates disclosed in this patent can be used in 3D printing photocurable materials, they do not address the material's poor self-healing and self-reinforcement properties.

[0004] The Chinese invention patent with patent publication number CN117720705A discloses a self-healing photocurable polyurethane acrylate and its preparation method. Photosensitive groups and dynamic bonds are introduced into polyester or ether terminated with isocyanate groups. After photocuring, polyurethane acrylate with self-healing properties and high mechanical properties is obtained. The polyurethane acrylate has dynamic cross-linking bonds, which can achieve self-healing properties after curing, and also has the characteristics of high transparency and flexibility. Although disulfide dynamic bonds are introduced into polyurethane acrylate in this patent to improve its self-healing properties, its initial fracture toughness is not high enough, which limits its application in high-end fields (such as denture materials). Summary of the Invention

[0005] In order to solve the above problems, the present invention provides a kind of polyurethane acrylate with spirothiopyran group.Under the action of external stress, the polymer network easily forms cracks and expands rapidly, eventually leading to material failure.The present invention introduces a self-reinforced material design strategy based on weak covalent bond and mechanochemical synergy, and introduces the CS weak covalent bond of spirothiopyran (spirothiopyran, STP) into the polyurethane acrylate main chain, utilizes its characteristic that homolysis easily occurs under external force to dissipate energy, and realizes interchain crosslinking by free radical-mediated click reaction, thereby enhancing mechanical strength, making it suitable for the fields such as denture base, oral prosthesis, biomedical implant.

[0006] The first aspect of the present invention provides a polyurethane acrylate with a spirothiopyran group, wherein the general structural formula of the polyurethane acrylate with a spirothiopyran group satisfies any one or more of the following formulas I to III:

[0007]

[0008] Wherein, in Formula I, R1, R2, R3, R4, R6, R7, R8, and R9 are independently selected hydrocarbon groups or hydrocarbon groups containing heteroatoms;

[0009] r5、r 10 is H or methyl;

[0010] X is NH or O;

[0011] STP is a spirothiopyran group;

[0012]

[0013] Wherein, in Formula II, Z1, Z2, Z3, Z4, Z6, Z7, and Z8 are independently selected hydrocarbon groups or hydrocarbon groups containing heteroatoms;

[0014] Z9 and Z5 are H or methyl;

[0015] X is NH or O;

[0016] STP is a spirothiopyran group;

[0017]

[0018] Wherein, in Formula III, R, R1, R2, R4, R5, R7, and R8 are independently selected hydrocarbon groups or hydrocarbon groups containing heteroatoms;

[0019] R3, R6, and R9 are H or methyl;

[0020] At least one of W1, W2 and W3 is a spirothiopyran group, and the other two can be independently selected hydrocarbon groups or hydrocarbon groups containing heteroatoms.

[0021] Optionally, the heteroatom in the heteroatom-containing hydrocarbon group may be one or more of an oxygen atom, a nitrogen atom, and a sulfur atom.

[0022] Optionally, the structure of the spirothiopyran group is as follows: Wherein, C1 and C2 are selected from C1-C4 alkyl groups.

[0023] Optionally, the structure of the spirothiopyran group is

[0024] One of them.

[0025] Optionally, r1, r3, r6, r8, Z2, Z3, Z4, Z6, Z7, R1, R4, and R7 are all selected from

[0026] One of them.

[0027] Optional, r2, r7, Z1 are all selected from One of them.

[0028] Optionally, r4, r9, Z4, Z8, R2, R5, and R8 are all selected from C2-C4 hydrocarbon groups.

[0029] Optional, r4, r9, Z4, Z8, R2, R5, R8 are all selected from

[0030] Optional, R is selected from Wherein, B1, B2, and B3 are selected from C1-C7 hydrocarbon groups.

[0031] Urethane acrylate is the foundation of the final material, which determines the physical and chemical properties of the final product. Urethane acrylate is prepared by the polymerization reaction of polyols and polyisocyanates to prepare polyurethane prepolymers, which are then polymerized with acrylate or methacrylate monomers with hydroxyl groups.

[0032] The polyurethane acrylate may include at least one polyisocyanate oligomer, that is, the polyurethane acrylate may include one polyisocyanate oligomer or multiple polyisocyanate oligomers at the same time. It is understood that the polyurethane prepolymer contains multiple isocyanates (-NCO). Specifically, the polyurethane prepolymer includes a polyisocyanate oligomer generated by the reaction of at least one polyisocyanate and at least one polyol. Wherein, the polyisocyanate includes a diisocyanate or a polyisocyanate, that is, the polyurethane prepolymer may include a polyurethane oligomer generated by the reaction of at least one diisocyanate or a polyisocyanate and at least one polyol.

[0033] The polyurethane prepolymer can be a polyisocyanate oligomer generated by the reaction of polyisocyanates and polyols. And in the above-mentioned reaction process, the type of polyisocyanate can also be multiple, such as hexamethylene diisocyanate trimer (HDI trimer), isophorone diisocyanate trimer (IPDI trimer). Diisocyanates are included in the polyisocyanates. Wherein, the type of diisocyanate can be multiple, such as diisocyanates include but not limited to isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), methylene bis (phenyl isocyanate) (MDI), toluene diisocyanate (TDI), naphthalene diisocyanate (NDI), methylene bis (cyclohexyl isocyanate) (HMDI). The type of polyol can also be multiple, such as polyol includes but not limited to polyether polyol and polyester polyol, such as polyol is polytetramethylene glycol (PTMG). Due to the large variety of diisocyanates, polyisocyanates, and polyols, there are also many types of polyurethane prepolymers produced by reacting diisocyanates or polyisocyanates with polyols. Therefore, the polyurethane prepolymer may include at least one polyisocyanate oligomer produced by reacting at least one diisocyanate or at least one polyisocyanate with at least one polyol. For example, the polyurethane prepolymer may also include a polyisocyanate oligomer produced by reacting one diisocyanate or one polyisocyanate with one polyol, and a polyisocyanate oligomer produced by reacting another diisocyanate or another polyisocyanate with another polyol, and so on.

[0034] Optionally, the acrylate or methacrylate monomer having a hydroxyl group is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate (HEMA for short), hydroxypropyl acrylate, hydroxypropyl methacrylate, and hydroxybutyl acrylate.

[0035] Optionally, the polyol is one or more of a polyether polyol, a polyester polyol, a polycarbonate polyol, an acrylate-modified polyol, or a bio-based polyol. Furthermore, the polyether polyol may be polyoxypropylene glycol (PPG), which is a linear chain formed by ring-opening polymerization of propylene oxide (PO) and terminated with a hydroxyl group. Alternatively, the polyether polyol may be polytetramethylene ether glycol (PTMEG), which is polymerized from tetrahydrofuran (THF) and contains regular ether bonds.

[0036] Alternatively, the polyester polyol may be polybutylene adipate (PBA), which is formed by polycondensation of adipic acid and butanediol. Alternatively, the polyester polyol may be polycaprolactone polyol (PCL), which is formed by ring-opening polymerization of ε-caprolactone and contains terminal hydroxyl groups.

[0037] Alternatively, the polycarbonate polyol may be a polycarbonate diol (PCDL), having aliphatic segments connected by carbonate bonds (such as hexamethylene carbonate).

[0038] Alternatively, the acrylate-modified polyol may be a hydroxyl-containing acrylate oligomer, with hydroxyl groups introduced into the acrylate segment (such as HEMA or HPA copolymer).

[0039] Optionally, the bio-based polyol can be a plant oil derivative polyol, and further, can be obtained by chemical modification (such as epoxidation or hydroxylation) of castor oil or soybean oil.

[0040] Alternatively, the catalyst required for the synthesis of polyurethane acrylate may be dioctyl dilaurate, stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptan, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin mercaptan, dioctyltin thiocarboxylate, lead 2-ethylhexanoate, tetraalkyl titanate such as tetrabutyl titanate, triethylamine, N,N-dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, N,N-dimethyl-p-toluidine, β ... -(Dimethylamino)propionitrile, N-methylpyrrolidone, N,N-dicyclohexylmethylamine, dimethylaminoethanol, dimethylaminoethoxyethanol, triethylenediamine, N,N,N'-trimethylaminoethylethanolamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyl-1,3-diamine, N,N,N',N'-tetramethyl-1,6-hexanedioldiamine, bis(N,N-dimethylaminoethyl)ether, N'-cyclohexyl -N,N-dimethylformamidine, N,N'-dimethylpiperazine, trimethylpiperazine, bis(aminopropyl)piperazine, N-(N,N'-dimethylaminoethyl)morpholine, bis(morpholinoethyl)ether, 1,2-dimethylimidazole, N-methylimidazole, 1,4-diamidine, diazabicyclo-[2.2.2]octane, 1,4-diazabicyclo[3.3.0]oct-4-ene, 1,8-diazabicyclo-[4.3.0]non-5-ene, 1,8-diazabicyclo-[2.2.2]octane, One or more of bicyclo-[5.4.0]-undec-7-ene and phenol salts, salts such as octanoate, N,N,N',N"-pentamethyldiethylenetriamine, N,N,N',N"-pentamethyldipropylenetriamine, tetramethylguanidine, N-cyclohexyl-N',N',N",N"-tetramethylguanidine, N-methyl-N'-(2-dimethylaminoethyl)piperazine, 1,3,5-tris(N,N-dimethyl-propyl)-hexahydro-1,3,5-triazine.

[0041] In an exemplary embodiment of the present invention, the method for preparing polyurethane acrylate with spirothiopyran groups comprises the following steps:

[0042] The method comprises mixing polyisocyanate and a derivative with a spirothiopyran group, adding a catalyst, reacting at a certain temperature, and then sequentially adding polyol, polyisocyanate, and acrylate or methacrylate monomers with a hydroxyl group to obtain the product through polymerization reaction.

[0043] In an exemplary embodiment of the present invention, the method for preparing polyurethane acrylate with spirothiopyran groups comprises the following steps:

[0044] The polyisocyanate and the acrylate or methacrylate monomer with hydroxyl group are mixed, a catalyst is added, and the mixture is reacted at a certain temperature. Then, a derivative with spirothiopyran group is added to continue the reaction to obtain a primary mixture, and then a polyurethane prepolymer is added to continue the reaction to obtain the polyurethane prepolymer.

[0045] In an exemplary embodiment of the present invention, the method for preparing polyurethane acrylate with spirothiopyran groups comprises the following steps:

[0046] The polyisocyanate and a derivative with a spirothiopyran group are mixed, a catalyst is added, and the mixture is reacted at a certain temperature. Then, the polyisocyanate and an acrylate or methacrylate monomer with a hydroxyl group are sequentially added and reacted to obtain the product.

[0047] In an exemplary embodiment of the present invention, a method for preparing a polyurethane acrylate with a spirothiopyran group includes the following steps: mixing a polyisocyanate and an acrylate or methacrylate monomer with a hydroxyl group, adding a catalyst, reacting at a certain temperature, and then sequentially adding 1,4-butanediol (BDO), polyisocyanate, a derivative with a spirothiopyran group, polyisocyanate, and an acrylate or methacrylate monomer with a hydroxyl group to react.

[0048] Optionally, the reaction temperature during the preparation process of the polyurethane acrylate with spirothiopyran group is 50°C-80°C.

[0049] In the present invention, the method for preparing polyurethane acrylates bearing spirothiopyran groups introduces the weak covalent bond of spirothiopyran (CS) into the polyurethane acrylate backbone, utilizing its propensity for homolytic cleavage under external forces to dissipate energy. Interchain crosslinking is achieved through free radical-mediated click reactions, thereby enhancing mechanical strength and making the polyurethane acrylate suitable for applications such as denture bases, oral prostheses, and biomedical implants. The method for preparing polyurethane acrylates bearing spirothiopyran groups is not limited thereto; those skilled in the art can introduce spirothiopyran groups based on the synthesis route of polyurethane acrylates.

[0050] Optionally, the derivative of the spirothiopyran group has the structural formula Wherein, A1 and A2 are selected from alcohol groups, and the alcohol group can be One of them.

[0051] Optionally, the derivative of the spirothiopyran group has the structural formula

[0052] A second aspect of the present invention provides a light-cured denture base material, the light-cured denture base material comprising:

[0053] 5-70 wt% of polyurethane acrylate with spirothiopyran groups;

[0054] 25-90 wt% of at least one monomeric acrylate;

[0055] 0.1-5 wt% of at least one photoinitiator;

[0056] and 0.05-2 wt% of at least one light stabilizer.

[0057] Alternatively, the photoinitiator may be 1-hydroxycyclohexylphenyl ketone (OMNIRAD 184), 2,2-dimethoxy-1,2-diphenylethyl-1-one (OMNIRAD 651), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (OMNIRAD 819), 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one (OMNIRAD 2959), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone (OMNIRAD 369), 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (OMNIRAD 379), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (OMNIRAD 907), oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone]ESACURE ONE (Lamberti SpA, Gallarate, Italy), 2-hydroxy-2-methyl-1-phenylpropan-1-one (DAROCUR 1173), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (OMNIRAD TPO) and 2,4,6-trimethylbenzoylphenylphosphinate (OMNIRAD TPO-L), benzyl dimethyl ketal, 2-methyl-2-hydroxypropiophenone, benzoin methyl ether, benzoin isopropyl ether, anisole methyl ether, aromatic sulfonyl chlorides or photoactive oximes, and combinations thereof.

[0058] The monomeric acrylate may be one or more of methyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, fluoroalkyl (meth)acrylate, and isobornyl (meth)acrylate.

[0059] The light stabilizer can be one or more of 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-hexyloxyphenol, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, and poly(2,2,6,6-tetramethyl-4-piperidinyl) succinate.

[0060] Optionally, the light-curing denture base material further comprises 0.1-3 wt % of a colorant. The type of the colorant is not particularly limited, and any suitable colorant (eg, dye, pigment, etc. or a combination thereof) can be used in the light-curing denture base material.

[0061] The above raw materials are mixed and subjected to light-curing 3D printing at room temperature (eg, 20-35° C.) to obtain a light-curing denture base material.

[0062] The third aspect of the present invention provides the use of polyurethane acrylate with spirothiopyran groups in denture base materials.

[0063] A fourth aspect of the present invention provides the use of polyurethane acrylates with spirothiopyran groups in oral restoration materials.

[0064] A fifth aspect of the present invention provides the use of polyurethane acrylate with spirothiopyran groups in 3D printing photocurable materials.

[0065] Compared with the prior art, the present invention achieves at least one of the following beneficial effects:

[0066] (1) The present invention provides a polyurethane acrylate with a spirothiopyran group, wherein the CS weak covalent bond of spirothiopyran is introduced into the main chain of the polyurethane acrylate, and the energy is dissipated by utilizing the property that spirothiopyran is easily subjected to homolytic cleavage under the action of external force, and interchain crosslinking is achieved through a free radical-mediated click reaction, thereby enhancing the mechanical strength and giving the material self-repair and self-reinforcement capabilities.

[0067] (2) The present invention provides a polyurethane acrylate with a spirothiopyranyl group, which can be used in the fields of 3D printing light-curing materials, denture base materials, oral prosthetic materials, biomedical implants, etc. By introducing the spirothiopyranyl group into the polyurethane acrylate, the 3D printing light-curing materials, denture base materials, oral prosthetic materials, and biomedical implants are endowed with self-repairing and self-reinforcement capabilities.

[0068] (3) The present invention provides a light-curing denture base material, which is endowed with self-repairing and self-reinforcement capabilities by adding polyurethane acrylate with spirothiopyran groups. BRIEF DESCRIPTION OF THE DRAWINGS

[0069] The drawings described herein are used to provide a further understanding of the present invention and constitute a part of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings:

[0070] Figure 1 An exemplary embodiment of the 1H-NMR spectrum of compound e of the present invention is shown;

[0071] Figure 2 An exemplary embodiment of a mass spectrum of compound e of the present invention is shown;

[0072] Figure 3 The compound g of the present invention is shown 1 An exemplary embodiment of a H-NMR spectrum;

[0073] Figure 4 An exemplary embodiment of a mass spectrum of compound g of the present invention is shown. DETAILED DESCRIPTION

[0074] In order to more clearly illustrate the overall concept of the present invention, a detailed description is given below in an exemplary manner in conjunction with the accompanying drawings.

[0075] In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention may also be implemented in other ways different from those described herein. Therefore, the scope of protection of the present invention is not limited to the specific embodiments disclosed below.

[0076] Example 1 Synthesis of STP derivatives

[0077] Refer to the following reaction scheme to prepare STP derivatives:

[0078]

[0079] Specifically, the preparation process of 3-methacryloyloxymethyl-5-nitrosalicylicylaldehyde (b) comprises the following steps:

[0080] 0.20 g (0.93 mmol) of 3-chloromethyl-5-nitrosalicylicaldehyde (a) was reacted with 0.29 g (1.5 mmol) of silver methacrylate in anhydrous toluene at 120° C. for 2 hours. The solution was filtered and evaporated to give yellow solid b in 96% yield.

[0081] The preparation process of 3-methacryloyloxymethyl-2-O-(N,N-dimethylthiocarbamoyl)-5-nitrosalicylicylaldehyde (c) comprises the following steps:

[0082] 137.6 mg (0.519 mmol) of compound b was reacted with 96.2 mg (0.779 mmol) of N,N-dimethylthiocarbamoyl chloride and 111.7 mg (1.05 mmol) of 1,4-diazabicyclo[2.2.2]octane (DABCO) in 3 mL of anhydrous N,N-dimethylformamide at room temperature for 2 hours. The product was filtered, evaporated, dissolved in ethyl acetate, washed with saturated sodium chloride, and dried over anhydrous magnesium sulfate. The solution was evaporated to dryness to afford a reddish-brown tarry product c in a 90% yield.

[0083] Preparation of 3-methacryloyloxymethyl-2-S-(N,N-dimethylthiocarbamoyl)-5-nitrosalicylicaldehyde (d)

[0084] 9.86 g (28.8 mmol) of compound c was dissolved in anhydrous toluene and refluxed for 2 hours. The solution was evaporated to give a brown tar. Purification by silica gel column chromatography (eluting with ethyl acetate / benzene, 1 / 9 ratio) gave light yellow crystals d in a yield of 55%.

[0085] Preparation of 3-methacryloyloxymethyl-5-nitrosalicylicylaldehyde (e)

[0086] Dissolve 486.5 mg (1.38 mmol) of compound d in 50 mL of methanol, add 0.7 M aqueous sodium hydroxide solution dropwise, and stir at 20°C for 10 minutes. Add 1 M aqueous hydrochloric acid solution, and extract the product with ether. Wash the extract with saturated aqueous sodium chloride solution and dry over anhydrous sodium sulfate. Evaporate the solution to dryness to obtain a light yellow powder e in an 81% yield.

[0087] Preparation of 1-(2-hydroxyethyl)-2,3,3-trimethyl-3H-indole bromide (f)

[0088] Dissolve 318.5 mg of 2,3,3-trimethylindoline and 250 mg of 2-bromoethanol in toluene. Heat the reaction mixture to 80°C under a nitrogen (N2) atmosphere. Stir for 2 hours, then evaporate the toluene to dryness to obtain 1-(2-hydroxyethyl)-2,3,3-trimethyl-3H-indole bromide (f) in a 99% yield.

[0089] The synthesis method of 9,9,9a-trimethyl-2,3,9,9a-tetrahydro-oxazolo[3,2-a]indole (g) is as follows:

[0090] 315mg (5.62mmol) of anhydrous potassium hydroxide was ground into a fine powder. 1.00g (3.51mmol) of product f was added. The mixture was continuously ground until a fine paste was formed and the color changed from purple to yellow. The paste was extracted with petroleum ether. The extract was dried over anhydrous sodium sulfate, filtered, concentrated, and then dried in a vacuum. The product was finally obtained as a yellow oil with a yield greater than 99%.

[0091] The preparation process of STP derivatives includes the following steps:

[0092] 355.7mg (2.06mmol) product g is dissolved in 10mL 2-butanone, then 610.0mg (2.17mmol) product e is added in solution, and 50mg potassium bicarbonate powder is added.Reaction mixture is heated 20 hours under 70 ℃ of dark protection.After evaporating solvent, the red waxy thing that obtains is purified by silica gel column chromatography (using benzene / hexane, 1 / 1 ratio elution).The yellow solid that obtains is recrystallized from benzene / hexane (1 / 1) mixture, obtains yellow cubic crystal STP derivative, and productive rate is 41%.

[0093] Among them, compound e 1 H-NMR spectrum (CDCl3, 500MHz) Figure 1 As shown. The mass spectrum of compound e is shown in Figure 2. Figure 2 As shown, compound g 1 H-NMR spectrum (CDCl3, 500MHz) Figure 3 As shown, the mass spectrum of compound g is referenced Figure 4 shown.

[0094] Example 2: Synthesis of polyurethane acrylate 1 (prepolymer 1) without STP group

[0095] Step 1: IPDI and BDO were mixed in a 2:1 molar ratio and added to a 500 mL three-necked flask equipped with an overhead stirrer, nitrogen atmosphere, and a thermometer. 200 μL of the catalyst, dibutyltin dilaurate (DBTL), was then added to the flask, stirred, and heated to 70°C. After 4 hours of reaction, IPDI-BDO-IPDI was obtained.

[0096] Step 2: Add 2 molar ratios of PTMG1000 to the above three-necked flask, stir at 70°C, and react for 4 hours to obtain PTMG-IPDI-BDO-IPDI-PTMG;

[0097] Step 3: Add 2 molar ratio of IPDI to the above three-necked flask, stir at 70°C, and react for 4 hours to obtain IPDI-PTMG-IPDI-BDO-IPDI-PTMG-IPDI;

[0098] Step 4: 100 ppm of hydroquinone and 2 molar ratio of HEMA were added to the above three-necked flask, and the mixture was stirred at 70°C. After reacting for 4 hours, HEMA-IPDI-PTMG-IPDI-BDO-IPDI-PTMG-IPDI-HEMA (prepolymer 1) was obtained. The following formula is the reaction scheme of prepolymer 1.

[0099]

[0100] Example 3 Synthesis of polyurethane acrylate with STP group (prepolymer 2)

[0101] Compared with the prepolymer 1 without STP group in Example 2, the prepolymer 2 uses the STP derivative prepared in Example 1 instead of 1,4-butanediol (BDO), and the other steps are similar to the preparation process of prepolymer 1.

[0102] Step 1: IPDI and STP are mixed in a molar ratio of 2:1, a catalyst is added, and the mixture is reacted at the reaction temperature to obtain IPDI-STP-IPDI;

[0103] Step 2: Add PTMG1000 at a 2 molar ratio under stirring, add a catalyst, and react at the reaction temperature to obtain PTMG-IPDI-STP-IPDI-PTMG;

[0104] Step 3: Add 2 molar ratios of IPDI and catalyst under stirring, and react at the reaction temperature to obtain IPDI-PTMG-IPDI-STP-IPDI-PTMG-IPDI;

[0105] Step 4: HEMA at a 2 molar ratio was added under stirring, and a catalyst was added, and the mixture was reacted at the reaction temperature to obtain HEMA-IPDI-PTMG-IPDI-STP-IPDI-PTMG-IPDI-HEMA (prepolymer 2). The synthesis route of prepolymer 2 is shown below.

[0106]

[0107] Test Example 1: A formulation was prepared using Prepolymer 1 of Example 2 and Prepolymer 2 of Example 3, and a light-curing 3D printing test was performed.

[0108] The photoinitiator TPO was dissolved in isobornyl methacrylate and polyethylene glycol (600) dimethacrylate (PEG (600) DMA), and then the prepolymer (1 or 2) was added to the solution and the color paste was added. The rotor mixer was stirred for 30 minutes at a speed of 2000 r / min to obtain the required 3D printing material. The test specimens were printed using a Rayshape E2 printer according to the size required in 8.6.4 of YY 0270.1-2011 "Dental Base Polymers Part 1: Denture Base Polymers". After cleaning with IPA, the specimens were heated at 80000 uW / cm 2 The cured specimens were cured for 45 minutes at a light intensity of 100 nm. The total work of fracture and maximum stress intensity factor of the cured specimens were tested using an Instron tensile testing machine according to the YY 0270.1-2011 standard.

[0109] The weight percentages of the components and the test results are shown in Table 1. It can be seen that the inclusion of polyurethane acrylate with STP groups in the formulation significantly increases the maximum stress intensity factor and the total work of fracture.

[0110] Table 1

[0111]

[0112]

[0113] Example 4: Synthesis of polyurethane acrylate 3 (prepolymer 3) without STP group

[0114] Step 1: IPDI and HEMA were mixed in a 1:1 molar ratio and added to a 500 mL three-necked flask equipped with an overhead stirrer, nitrogen atmosphere, and a thermometer. 200 μL of the catalyst, dibutyltin dilaurate (DBTL), was then added to the flask, stirred, and heated to 70°C for 4 hours to yield HEMA-IPDI.

[0115] Step 2: Add 1 molar ratio of BDO to the above three-necked flask, stir at 70°C, and react for 4 hours to obtain HEMA-IPDI-BDO;

[0116] Step 3: IPDI and PTMG1000 were mixed in a 2:1 molar ratio and added to a 500 mL three-necked flask equipped with an overhead stirrer, nitrogen atmosphere, and a thermometer. 200 μL of the catalyst, dibutyltin dilaurate (DBTL), was then added to the flask, stirred, and heated to 70°C. After 4 hours of reaction, IPDI-PTMG-IPDI was obtained.

[0117] Step 4: 100 ppm of hydroquinone and a 2 molar ratio of HEMA-IPDI-BDO were added to the above three-necked flask, and the mixture was stirred at 70°C. After reacting for 4 hours, HEMA-IPDI-BDO-IPDI-PTMG-IPDI-BDO-IPDI-HEMA (prepolymer 3) was obtained. The synthesis route of prepolymer 3 is shown below.

[0118]

[0119] Example 5: Synthesis of polyurethane acrylate 4 (prepolymer 4) with STP groups

[0120] Step 1: IPDI and HEMA were mixed in a 1:1 molar ratio in a 500 mL three-necked flask equipped with an overhead stirrer, nitrogen atmosphere, and a thermometer. 200 μL of the catalyst, dibutyltin dilaurate (DBTL), was then added to the flask and stirred. The mixture was heated to 70°C and allowed to react for 4 hours. The catalyst was then added and the mixture was allowed to react at the reaction temperature to produce HEMA-IPDI.

[0121] Step 2: Add 1 molar ratio of STP to the above three-necked flask, stir at 70°C, and react for 4 hours to obtain HEMA-IPDI-STP;

[0122] Step 3: IPDI and PTMG1000 were mixed in a 2:1 molar ratio and added to a 500 mL three-necked flask equipped with an overhead stirrer, nitrogen protection, and a thermometer. 200 μL of the catalyst dibutyltin dilaurate (DBTL) was then added to the flask and stirred. The mixture was heated to 70°C and allowed to react for 4 hours. The catalyst was then added and the mixture was allowed to react at the reaction temperature to produce IPDI-PTMG-IPDI.

[0123] Fourth step: 100 ppm of hydroquinone and 2 molar ratio of HEMA-IPDI-STP were added into the above three-neck flask, stirred at 70 °C, and HEMA-IPDI-STP-IPDI- STP-IPDI-HEMA (Prepolymer 4) was obtained after 4 hours of reaction. The synthesis route of Prepolymer 4 is shown below.

[0124]

[0125] Test Example 2: Formulations were prepared using Prepolymer 3 of Example 4 and Prepolymer 4 of Example 5, and light curing 3D printing tests were performed.

[0126] The photoinitiator TPO was dissolved in 2-phenoxyethyl methacrylate, tris(2- hydroxyethyl) isocyanurate triacrylate, and methyl methacrylate, and then the prepolymer (3 or 4) was added to the solution, and color paste was added. A rotor stirrer was used to stir for 30 min at 2000 r / min to obtain the required 3D printing material. A Rayshape E2 printer was used to print test bars according to the size required in 8.6.4 of YY0270.1-2011 “Dentistry Base Polymers Part 1: Denture Base Polymers”. After cleaning with IPA, the bars were cured for 45 minutes at a light intensity of 80000 uW / cm 2 . The total breaking work and maximum stress intensity factor of the cured bars were tested according to the YY0270.1-2011 standard using an Instron tensile tester.

[0127] The weight fractions of the components and the test results are shown in Table 2 below. It can be seen that the presence of the polyurethane acrylate with STP groups in the formulation can greatly improve the maximum stress intensity factor and the total breaking work.

[0128] Table 2

[0129] Components Comparative Example Example Prepolymer 3 obtained from Example 4 50 - Prepolymer 4 obtained from Example 5 - 50 2-phenoxyethyl methacrylate 15 15 tris(2-hydroxyethyl) isocyanurate triacrylate 15 15 methyl methacrylate 20 20 photoinitiator TPO 0.5 0.5 white paste 0.3 0.3 red paste 0.05 0.05 <![CDATA[最大应力强度因子 / MPa m 1 / 2 ]]> 1.8 3.7 <![CDATA[总断裂功 / J / m 2 ]]> 1280 3251

[0130] Example 6: Synthesis of polyfunctional polyurethane acrylate 5 with STP groups (Prepolymer 5)

[0131] First step: HDI and STP were mixed in a 1:3 molar ratio and added to a 500 mL three-neck flask with an overhead stirrer, nitrogen protection, and a thermometer. Then 500 μL of catalyst tetrabutyl titanate was added to the flask and stirred, and the temperature was raised to 70 °C. HDI-(STP)3was obtained after 4 hours of reaction.

[0132] Second step: 3 molar ratio of IPDI was added to the above three-neck flask, stirred at 70 °C, and HDI-(STP-IPDI)3was obtained after 4 hours of reaction.

[0133] Step 3: To the above three neck flask, 1 mole ratio of HDI was added and stirred at 70 °C for 4 hours to obtain HDI-BDO-TDI-HEMA.

[0134]

[0135] Example 7: Synthesis of polyfunctional asymmetric structure urethane acrylate 6 (Prepolymer 6)

[0136] Step 1 : TDI and HEMA were mixed in 1 : 1 mole ratio and added to a 500 mL three neck flask with overhead stirrer, nitrogen protection and thermometer. Then 200 μL of catalyst dibutyltin dilaurate (DBTL) was added to the flask and stirred, and warmed to 70 °C, TDI-HEMA was obtained after 4 hours of reaction;

[0137] Step 2: To the above three neck flask, 1 mole ratio of BDO was added and stirred at 70 °C for 4 hours to obtain BDO-TDI-HEMA.

[0138] Step 3: To the above three neck flask, 1 mole ratio of HDI was added and stirred at 70 °C for 4 hours to obtain HDI-BDO-TDI-HEMA.

[0139] Step 4: To the above three neck flask, 100 ppm of hydroquinone and 2 mole ratio of HEMA were added and stirred at 70 °C for 4 hours to obtain HDI-(BDO-TDI-HEMA)(HEMA)2 (Prepolymer 6), the synthesis route of Prepolymer 6 is shown below.

[0140]

[0141] Example 8: Synthesis of polyfunctional asymmetric structure urethane acrylate 7 (Prepolymer 7)

[0142] Step 1 : TDI and HEMA were mixed in 1 : 1 mole ratio and added to a 500 mL three neck flask with overhead stirrer, nitrogen protection and thermometer. Then 200 μL of catalyst dibutyltin dilaurate (DBTL) was added to the flask and stirred, and warmed to 70 °C, TDI-HEMA was obtained after 4 hours of reaction;

[0143] Step 2: To the above three neck flask, 1 mole ratio of BDO was added and stirred at 70 °C for 4 hours to obtain BDO-TDI-HEMA.

[0144] Step 3: Add 1 mole ratio of HDI into the above three-neck flask, stir at 70°C, after 4 hours of reaction, HDI-BDO-TDI-HEMA is obtained;

[0145] Step 4: Add 2 mole ratio of STP into the above three-neck flask, stir at 70°C, after 4 hours of reaction, HDI-(BDO-TDI-HEMA)(STP)2 is obtained;

[0146] Step 5: Add 2 mole ratio of IPDI into the above three-neck flask, stir at 70°C, after 4 hours of reaction, HDI-(BDO-TDI-HEMA)(STP-IPDI)2 is obtained;

[0147] Step 6: Add 100 ppm of hydroquinone and 2 mole ratio of HEMA into the above three-neck flask, stir at 70°C, after 4 hours of reaction, HDI-(BDO-TDI-HEMA)(STP-IPDI-HEMA)2 (Prepolymer 7) is obtained. The synthesis route of Prepolymer 7 is shown below.

[0148]

[0149]

[0150] Test Example 3: Formulations were prepared using Prepolymer 5 of Example 6, Prepolymer 6 of Example 7, Prepolymer 7 of Example 8, and light curing 3D printing tests were performed.

[0151] The photoinitiator OMNIRAD 184 was dissolved in 2-phenoxyethyl methacrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, methyl methacrylate, light stabilizer 2-hydroxy-4-n-octyloxybenzophenone, and then the prepolymer (5, 6 or 7) was added to the solution, and color paste was added. A rotor stirrer was used to stir for 30 min at a speed of 2000 r / min to obtain the required 3D printing material. A Rayshape E2 printer was used to print test bars according to the size required in 8.6.4 of YY 0270.1-2011 “Dentistry Base Polymers Part 1: Denture Base Polymers”. After cleaning with IPA, the bars were cured for 45 minutes at a light intensity of 80000 uW / cm 2 The total breaking work and maximum stress intensity factor of the cured bars were tested according to the YY 0270.1-2011 standard using an Instron tensile machine.

[0152] The weight fractions of the components and the test results are shown in Table 3 below. It can be seen that the presence of polyurethane acrylate with STP groups in the formulation can greatly improve the maximum stress intensity factor and total breaking work.

[0153] Table 3

[0154]

[0155] Example 9

[0156] Based on prepolymer 2, hexamethylene diisocyanate (HDI) was used instead of IPDI, and the other steps were similar to the preparation process of prepolymer 2 to obtain prepolymer 8.

[0157] Based on prepolymer 2, methylene bis(phenyl isocyanate) (MDI) was used instead of IPDI, and the other steps were similar to the preparation process of prepolymer 2 to obtain prepolymer 9.

[0158] Based on prepolymer 2, toluene diisocyanate (TDI) was used instead of IPDI, and the other steps were similar to the preparation process of prepolymer 2 to obtain prepolymer 10.

[0159] Based on prepolymer 2, naphthalene diisocyanate (NDI) was used instead of IPDI, and the other steps were similar to the preparation process of prepolymer 2 to obtain prepolymer 11.

[0160] Based on prepolymer 2, methylenebiscyclohexyl isocyanate (HMDI) was used instead of IPDI, and the other steps were similar to the preparation process of prepolymer 2 to obtain prepolymer 12.

[0161] On the basis of prepolymer 2, polybutylene adipate (PBA) was used to replace PTMG1000, and the other steps were similar to the preparation process of prepolymer 2 to obtain prepolymer 13.

[0162] Based on prepolymer 2, polycarbonate diol (PCDL) was used to replace PTMG1000, and the other steps were similar to the preparation process of prepolymer 2 to obtain prepolymer 14.

[0163] Based on prepolymer 2, hydroxyethyl acrylate was used instead of HEMA, and the other steps were similar to the preparation process of prepolymer 2 to obtain prepolymer 15.

[0164] Based on prepolymer 2, hydroxypropyl acrylate was used to replace HEMA, and the other steps were similar to the preparation process of prepolymer 2 to obtain prepolymer 16.

[0165] Based on prepolymer 2, hydroxypropyl methacrylate was used to replace HEMA, and the other steps were similar to the preparation process of prepolymer 2 to obtain prepolymer 17.

[0166] Based on prepolymer 2, hydroxybutyl acrylate was used instead of HEMA, and the other steps were similar to the preparation process of prepolymer 2 to obtain prepolymer 18.

[0167] Test Example 4: Prepolymers 8-18 were formulated and subjected to a light-curing 3D printing test based on Test Example 1. The results are shown in Table 4.

[0168] Table 4

[0169]

[0170]

[0171] With reference to Tables 1-4, it can be seen that the maximum stress intensity factor Kmax of the polyurethane acrylate with spirothiopyran groups in the present invention is not less than 2.5 MPa m when tested as a 3D light-cured printing material. 1 / 2 , total fracture work W is not less than 1200J / m 2 To a certain extent, it is proved that the introduction of spirothiopyran groups into polyurethane acrylate can endow the material with good self-healing and self-reinforcement capabilities.

[0172] The foregoing is merely an embodiment of the present invention and is not intended to limit the present invention. It will be apparent to those skilled in the art that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention are intended to be included within the scope of the claims of the present invention.

Claims

1. A polyurethane acrylate with a spirothiopyran group, characterized in that: The general structural formula of the polyurethane acrylate with spirothiopyran group satisfies any one or more of the following formulas I to III: Wherein, in Formula I, R1, R2, R3, R4, R6, R7, R8, and R9 are independently selected hydrocarbon groups or hydrocarbon groups containing heteroatoms; r5、r 10 is H or methyl; X is NH or O; STP is a spirothiopyran group; Wherein, in Formula II, Z1, Z2, Z3, Z4, Z6, Z7, and Z8 are independently selected hydrocarbon groups or hydrocarbon groups containing heteroatoms; Z9 and Z5 are H or methyl; X is NH or O; STP is a spirothiopyran group; Wherein, in Formula III, R, R1, R2, R4, R5, R7, and R8 are independently selected hydrocarbon groups or hydrocarbon groups containing heteroatoms; R3, R6, and R9 are H or methyl; At least one of W1, W2 and W3 is a spirothiopyran group, and the other two can be independently selected hydrocarbon groups or hydrocarbon groups containing heteroatoms.

2. The polyurethane acrylate with spirothiopyran groups according to claim 1, characterized in that The structure of the spirothiopyran group is as follows:

3. The polyurethane acrylate with spirothiopyran groups according to claim 1, characterized in that R1, R3, R6, R8, Z2, Z3, Z4, Z6, Z7, R1, R4, and R7 are all selected from One of them.

4. The polyurethane acrylate with spirothiopyran groups according to claim 1, characterized in that r2, r7, and Z1 are all selected from One of them.

5. The polyurethane acrylate with spirothiopyran groups according to claim 1, characterized in that R4, R9, Z4, Z8, R2, R5, and R8 are all selected from C2-C4 hydrocarbon groups.

6. The polyurethane acrylate with spirothiopyran groups according to claim 5, characterized in that r4, r9, Z4, Z8, R2, R5, and R8 are all selected from 7. A light-cured denture base material, characterized in that: The light-cured denture base material comprises: 5-70 wt% of polyurethane acrylate with spirothiopyran groups; 25-90 wt% of at least one monomeric acrylate; 0.1-5 wt% of at least one photoinitiator; and 0.05-2 wt% of at least one light stabilizer.

8. Application of polyurethane acrylate with spirothiopyran groups in denture base materials.

9. Application of polyurethane acrylate with spirothiopyran groups in oral restoration materials.

10. Application of polyurethane acrylate with spirothiopyran groups in 3D printing photocurable materials.

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