A polyurethane acrylate with spirothiopyran group, and a synthesis method and application thereof

Abstract

The application provides a polyurethane acrylate with a spirothiopyran group and a synthesis method and application thereof, and relates to the technical field of denture base materials. In the polyurethane acrylate with the spirothiopyran group, the C-S weak covalent bond of spirothiopyran is introduced into the main chain of the polyurethane acrylate, the characteristics that the C-S weak covalent bond is easy to homolytic cleavage under external force are utilized to dissipate energy, and the chain is crosslinked through a free radical-mediated click reaction, so that the mechanical strength is enhanced, and the polyurethane acrylate is suitable for fields such as denture bases, oral prostheses, biomedical implants and the like.

Description

TECHNICAL FIELD

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

[0002] Polyurethane (meth) acrylate is a kind of polymer compound widely used in photocurable materials, but its mechanical properties and durability still have limitations in complex stress environment. Traditional materials lack self-repairing and self-reinforcing capabilities, limiting their application in high-end fields.

[0003] The Chinese invention patent with the patent publication number CN118027350A discloses an aliphatic polyester type polyurethane acrylate and its preparation method and application, a 3D printing photocurable material and its preparation method and application. The aliphatic polyester type polyurethane acrylate provided does not contain benzene ring benzyl structure, -NOC and -OH form hydrogen bond structure, which significantly improves the rigidity of the aliphatic polyester type polyurethane acrylate, avoids the yellowing phenomenon thereof; the ester group provides excellent toughness and anti-deformation ability, and has no water absorption; the hydrogen bond and the ester group jointly form an aliphatic polyester type polyurethane acrylate with excellent toughness, excellent anti-fracture and anti-deformation ability; the six-membered ring space has large occupation, which can reduce the volume shrinkage rate after curing, and has excellent anti-deformation ability. Although the aliphatic polyester type polyurethane acrylate disclosed in the patent can be applied to 3D printing photocurable materials, it does not solve the problem of poor self-repairing and self-reinforcing performance of the material.

[0004] The Chinese invention patent with the patent publication number CN117720705A discloses a photocurable polyurethane acrylate with self-healing property and a preparation method thereof. A photosensitive group and a dynamic bond are introduced into a polyester or ether terminated by isocyanate group, and a polyurethane acrylate with self-healing property and high mechanical property is obtained after photocuring. The polyurethane acrylate has a dynamic crosslinking bond, can realize self-healing property after curing, and also has high transparency and flexibility. Although the patent introduces a disulfide dynamic bond into the polyurethane acrylate to improve its self-repairing performance, the initial fracture toughness thereof is not high enough, limiting its application in high-end fields (such as denture materials). SUMMARY

[0005] To solve the above problems, the application provides a polyurethane acrylate with a spirothiopyran group. Under the action of external stress, the polymer network is easy to form cracks and quickly expand, eventually leading to material failure. The application introduces a self-reinforced material design strategy based on weak covalent bond and mechanical chemical synergy, introduces the C-S weak covalent bond of spirothiopyran (STP) into the polyurethane acrylate main chain, utilizes the characteristics of easy homolysis under external force to dissipate energy, and realizes inter-chain crosslinking through free radical mediated click reaction, thereby enhancing the mechanical strength, and making it suitable for the fields of denture base, oral prostheses, biomedical implants and the like.

[0006] The first aspect of the application provides a polyurethane acrylate with a spirothiopyran group, and the structural general formula of the polyurethane acrylate with the spirothiopyran group satisfies any one or more of the following formula I-III:

[0007]

[0008] In formula I, r1, r2, r3, r4, r6, r7, r8, r9 are independently selected hydrocarbon groups or heteroatom-containing hydrocarbon groups;

[0009] r5, r 10 are H or methyl;

[0010] X is NH or O;

[0011] STP is a spirothiopyran group;

[0012]

[0013] In formula II, Z1, Z2, Z3, Z4, Z6, Z7, Z8 are independently selected hydrocarbon groups or heteroatom-containing hydrocarbon groups;

[0014] Z9, Z5 are H or methyl;

[0015] X is NH or O;

[0016] STP is a spirothiopyran group;

[0017]

[0018] In formula III, R, R1, R2, R4, R5, R7, R8 are independently selected hydrocarbon groups or heteroatom-containing hydrocarbon groups;

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

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

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

[0022] Optionally, the spirothiopyran group has the structure: wherein C1, C2 are selected from C1-C4 alkyl groups.

[0023] Optionally, the spirothiopyran group has the structure:

[0024] Optionally, R1, R2, R3, R4, R5, R6, R7, R8, R9 are selected from one of

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

[0026] Optionally, r2, r7, Z1 are selected from one of

[0027] Optionally, r2, r7, Z1 are selected from one of Optionally, r2, r7, Z1 are selected from one of

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

[0029] Optionally, r4, r9, Z4, Z8, R2, R5, R8 are selected from one of

[0030] Optionally, R is selected from one of wherein B1, B2, B3 are selected from C1-C7 hydrocarbon groups.

[0031] The polyurethane acrylate is the base that constitutes the final material, which determines the physical and chemical properties of the final product. The polyurethane acrylate is prepared by polymerization of a polyol and a polyisocyanate to form a polyurethane prepolymer, and then polymerization of the polyurethane prepolymer with a hydroxyl-containing acrylate or methacrylate monomer.

[0032] The polyurethane acrylate can include at least one polyisocyanate oligomer, i.e., the polyurethane acrylate can include one polyisocyanate oligomer or a plurality of polyisocyanate oligomers. It can be understood that the polyurethane prepolymer contains a plurality of isocyanate groups (-NCO). Specifically, the polyurethane prepolymer includes a polyisocyanate oligomer generated by reaction of at least one polyisocyanate and at least one polyol. The polyisocyanate includes a diisocyanate or a polyisocyanate, i.e., the polyurethane prepolymer can include a polyurethane oligomer generated by reaction of at least one diisocyanate or polyisocyanate and at least one polyol.

[0033] The polyurethane prepolymer can be a polyisocyanate oligomer generated from the reaction of a polyisocyanate and a polyol. In the above reaction process, the polyisocyanate can also be of various types, such as hexamethylene diisocyanate trimer (HDI trimer), isophorone diisocyanate trimer (IPDI trimer). The polyisocyanate contains diisocyanate. The diisocyanate can be of various types, such as diisocyanate including 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 polyol can also be of various types, such as polyol including but not limited to polyether polyol and polyester polyol, such as polybutylene glycol (PTMG). Due to the various types of diisocyanate, the various types of polyisocyanate, and the various types of polyol, the polyurethane prepolymer generated from the reaction of diisocyanate or polyisocyanate and polyol can also be of various types. Therefore, the polyurethane prepolymer can contain at least one diisocyanate or at least one polyisocyanate oligomer generated from the reaction of at least one polyisocyanate and at least one polyol. For example, the polyurethane prepolymer can also contain one polyisocyanate oligomer generated from the reaction of one diisocyanate or one polyisocyanate and one polyol, and one polyisocyanate oligomer generated from the reaction of another diisocyanate or another polyisocyanate and another polyol, and so on.

[0034] Optionally, the acrylic or methacrylic monomer with hydroxyl group is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate (HEMA), hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate.

[0035] Optionally, the polyol is one or more of polyether polyol, polyester polyol, polycarbonate polyol, acrylate-modified polyol, or bio-based polyol. Further, the polyether polyol can be polypropylene oxide glycol (PPG), a linear chain formed by ring-opening polymerization of propylene oxide (PO), with hydroxyl groups at both ends. Or the polyether polyol can be polytetramethylene ether glycol (PTMEG), which is polymerized from tetrahydrofuran (THF) and contains regular ether bonds.

[0036] Optionally, the polyester polyol can be polybutylene adipate (PBA), which is polycondensed from adipic acid and butanediol. Or the polyester polyol can be polycaprolactone polyol (PCL), which is generated by ring-opening polymerization of ε-caprolactone and contains terminal hydroxyl groups.

[0037] Optionally, the polycarbonate polyol can be a polycarbonate diol (PCDL) having aliphatic segments (e.g., hexamethylene carbonate) connected by carbonate linkages.

[0038] Optionally, the acrylate-modified polyol can be a hydroxyl-containing acrylate oligomer having hydroxyl groups incorporated into the acrylate segments (e.g., HEMA or HPA copolymer).

[0039] Optionally, the bio-based polyol can be a vegetable oil derivative polyol, which can further be a castor oil or soybean oil, etc. chemically modified (e.g., epoxidized, hydroxylated).

[0040] Optionally, the catalysts required for the synthesis of the polyurethane acrylate can be one or more of dioctyl dilauryl phosphate, stannous octoate, dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin mercaptide, dibutyl tin thioacetate, dibutyl tin dimaleate, dioctyl tin mercaptide, dioctyl tin thioacetate, lead 2-ethylhexanoate, tetraalkyl titanates such as tetrabutyl titanate, triethylamine, N,N-dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, N,N-dimethyl-p-toluidine, β-(dimethylamino)propionitrile, N-methylpyrrolidine, 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(amino-propyl)piperazine, N-(N,N'-dimethylaminoethyl)morpholine, bis(morpholinoethyl)ether, 1,2-dimethylimidazole, N-methylimidazole, 1,4-diformamidine, 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-[5.4.0]-undec-7-ene, and phenolate, salts (such as octoate), 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 one exemplary embodiment of the present application, the method of preparing a polyurethane acrylate with spirothiopyran groups includes the steps of:

[0042] Mixing the polyisocyanate and the derivative with the spirothiopyran group, adding a catalyst, reacting at a certain temperature, and then adding the polyol, the polyisocyanate, the hydroxyl-containing acrylate or methacrylate monomer by polymerization reaction in sequence to obtain.

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

[0044] Mixing the polyisocyanate and the hydroxyl-containing acrylate or methacrylate monomer, adding a catalyst, reacting at a certain temperature, and then adding the derivative with the spirothiopyran group to continue the reaction to obtain a preliminary mixture, and then adding the polyurethane prepolymer to continue the reaction.

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

[0046] Mixing the polyisocyanate and the derivative with the spirothiopyran group, adding a catalyst, reacting at a certain temperature, and then adding the polyisocyanate, the hydroxyl-containing acrylate or methacrylate monomer to obtain.

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

[0048] Optionally, the reaction temperature in the method for preparing the polyurethane acrylate with the spirothiopyran group is 50-80℃.

[0049] In the method for preparing the polyurethane acrylate with the spirothiopyran group in the present application, the C-S weak covalent bond of the spirothiopyran is introduced into the main chain of the polyurethane acrylate, which utilizes the characteristics of the easy homolysis of the spirothiopyran under external force to dissipate energy, and realizes the inter-chain crosslinking through the free radical-mediated click reaction, thereby enhancing the mechanical strength, and making it suitable for the fields of denture base, oral prostheses, biomedical implants, etc. The method for preparing the polyurethane acrylate with the spirothiopyran group is not limited to this, and the person skilled in the art can introduce the spirothiopyran group on the basis of the synthesis route of the polyurethane acrylate.

[0050] Optionally, the derivative with the spirothiopyran group has the structural formula wherein A1 and A2 are selected from the alcohol group, and the alcohol group can be one of the group consisting of

[0051] Optionally, the derivative structure of the spirothiopyran group is

[0052] The second aspect of the present application provides a photocured denture base material, the photocured denture base material comprising:

[0053] 5-70 wt% polyurethane acrylate with a spirothiopyran group;

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

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

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

[0057] Optionally, the photoinitiator can be 1 -hydroxy cyclohexyl phenyl ketone (OMNIRAD 184), 2,2-dimethoxy-1,2-diphenylethan-1 -one (OMNIRAD 651 ), bis(2,4,6- trimethylbenzoyl)phenylphosphine oxide (OMNIRAD 819), 1 -[4-(2- hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1 -propane-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 S.p.A., Gallarate, Italy), 2-hydroxy-2-methyl-1 -phenylpropan-1 -one (DAROCUR 1173), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (OMNIRAD TPO) and 2,4,6-trimethylbenzoylphenylphosphinic acid ester (OMNIRAD TPO-L), benzyl dimethyl ketal, 2-methyl-2-hydroxyphenylpropanone, benzoin methyl ether, benzoin isopropyl ether, anisoin methyl ether, aromatic sulfonyl chlorides or photoactive oximes and combinations thereof.

[0058] The monomeric acrylic ester can be one or more of methyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, fluoroalkyl (meth)acrylate, 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-triazin-2-yl)-5-hexyloxyphenol, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, poly(butylene succinate) (2,2,6,6-tetramethyl-4-piperidyl).

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

[0061] The above raw materials are mixed, and photocuring 3D printing is carried out at room temperature (for example, 20-35℃) to obtain the photocurable denture base material.

[0062] The third aspect of the present application provides the use of polyurethane acrylate with a spirothiopyran group in a denture base material.

[0063] The fourth aspect of the present application provides the use of polyurethane acrylate with a spirothiopyran group in an oral prosthesis material.

[0064] The fifth aspect of the present application provides the use of polyurethane acrylate with a spirothiopyran group in a 3D printing photocurable material.

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

[0066] (1) The present application provides a polyurethane acrylate with a spirothiopyran group, which introduces a C-S weak covalent bond of spirothiopyran into the main chain of polyurethane acrylate, utilizes the characteristics of easy homolysis under external force to dissipate energy, and realizes inter-chain crosslinking through a free radical-mediated click reaction, thereby enhancing the mechanical strength and endowing the material with self-repairing and self-reinforcing capabilities.

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

[0068] (3) The present application provides a photocuring denture base material, which is endowed with self-repairing and self-reinforcing capabilities by adding a polyurethane acrylate with a spirothiopyran group. BRIEF DESCRIPTION OF DRAWINGS

[0069] The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:

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

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

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

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

[0074] In order to more clearly illustrate the overall concept of the present application, the following detailed description is given with reference to the accompanying drawings.

[0075] In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application. However, it will be apparent to one skilled in the art that the present application can be practiced without the specific details given in this description.

[0076] Example 1 Synthesis of STP derivatives

[0077] Referring to the following reaction flow, the STP derivatives are prepared:

[0078]

[0079] Specifically, the preparation process of 3-methacryloyloxy methyl-5-nitrosalicylaldehyde (b) includes the following steps:

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

[0081] The preparation of 3-methacryloyloxymethyl-2-O-(N,N-dimethylthiocarbamoyl)-5- nitrosalicylaldehyde (c) involved 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. Filtration, evaporation, dissolution in ethyl acetate, washing with saturated aqueous sodium chloride solution and drying over anhydrous magnesium sulfate. Evaporation of the solution to dryness gave red-brown tar c in 90% yield.

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

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

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

[0086] 486.5 mg (1.38 mmol) of compound d was dissolved in 50 mL of methanol and 0.7 M aqueous sodium hydroxide solution was added dropwise. The mixture was stirred at 20°C for 10 minutes. 1 M aqueous hydrochloric acid solution was added and the product was extracted with diethyl ether. The extract was washed with saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate. Evaporation of the solution to dryness gave light yellow powder e in 81% yield.

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

[0088] A mixture of 318.5 mg of 2,3,3-trimethylindoline and 250 mg of 2-bromoethanol was dissolved in toluene. The reaction mixture was heated to 80°C under a nitrogen (N2) atmosphere. After stirring for 2 hours, the toluene was evaporated to dryness to give 1-(2-hydroxyethyl)-2,3,3-trimethyl-3H-indole bromide (f) in 99% yield.

[0089] 9,9,9a-trimethyl-2,3,9,9a-tetrahydro-oxazolo[3,2-a]indole (g) was synthesized as follows:

[0090] A mixture of 318.5 mg of 2,3,3-trimethylindoline and 250 mg of 2-bromoethanol was dissolved in toluene. The reaction mixture was heated to 80°C under a nitrogen (N2) atmosphere. After stirring for 2 hours, the toluene was evaporated to dryness to give 1-(2-hydroxyethyl)-2,3,3-trimethyl-3H-indole bromide (f) in 99% yield.

[0091] The preparation of the STP derivative included the following steps:

[0092] A mixture of 355.7 mg (2.06 mmol) of product g was dissolved in 10 mL of 2-butanone, then 610.0 mg (2.17 mmol) of product e and 50 mg of potassium bicarbonate powder were added to the solution. The reaction mixture was heated at 70°C for 20 hours in the dark. After evaporation of the solvent, the resulting red waxy material was purified by column chromatography on silica gel (eluted with benzene / hexane in a 1 / 1 ratio). The resulting yellow solid was recrystallized from a benzene / hexane (1 / 1) mixture to give yellow cubic crystals of the STP derivative in 41% yield.

[0093] wherein the compound e has 1 The H-NMR spectrum (CDCl3, 500 MHz) of the compound e is referenced Figure 1 The mass spectrum of the compound e is referenced Figure 2 The H-NMR spectrum (CDCl3, 500 MHz) of the compound e is referenced 1 The mass spectrum of the compound e is referenced Figure 3 The mass spectrum of the compound e is referenced Figure 4 The H-NMR spectrum (CDCl3, 500 MHz) of the compound e is referenced

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

[0095] First step: IPDI and BDO were mixed and added into a 500 mL three-neck flask with overhead stirrer, nitrogen protection and thermometer at a molar ratio of 2:1. Then 200 μΐ^of catalyst dibutyltin dilaurate (DBTL) was added into the flask and stirred, and heated to 70 °C, and IPDI-BDO-IPDI was obtained after 4 hours of reaction;

[0096] Second step: PTMG1000 was added into the above three-neck flask at a molar ratio of 2, stirred at 70 °C, and PTMG-IPDI-BDO-IPDI-PTMG was obtained after 4 hours of reaction;

[0097] Third step: IPDI was added into the above three-neck flask at a molar ratio of 2, stirred at 70 °C, and IPDI-PTMG-IPDI-BDO-IPDI-PTMG-IPDI was obtained after 4 hours of reaction;

[0098] Fourth step: 100 ppm of hydroquinone and HEMA were added into the above three-neck flask at a molar ratio of 2, stirred at 70 °C, and HEMA-IPDI-PTMG-IPDI-BDO-IPDI-PTMG-IPDI-HEMA (prepolymer 1) was obtained after 4 hours of reaction. The following is a reaction scheme of the 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 replaced 1,4-butanediol (BDO) with the STP derivative prepared in Example 1, and other steps were similar to the preparation process of the prepolymer 1.

[0102] First step: IPDI and STP were mixed at a molar ratio of 2:1, a catalyst was added, and IPDI-STP-IPDI was obtained after reaction at the reaction temperature;

[0103] Second step: PTMG1000 was added under stirring at a molar ratio of 2, a catalyst was added, and PTMG-IPDI-STP-IPDI-PTMG was obtained after reaction at the reaction temperature;

[0104] Third step: IPDI was added under stirring at a molar ratio of 2, a catalyst was added, and IPDI-PTMG-IPDI-STP-IPDI-PTMG-IPDI was obtained after reaction at the reaction temperature;

[0105] Step 4: 2 mole ratio of HEMA was added under stirring, catalyst was added, and the reaction was carried out 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: Formulations were prepared using Prepolymer 1 of Example 2 and Prepolymer 2 of Example 3, and light-curing 3D printing tests were carried out.

[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, respectively, 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 strips 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 strips were cured with a light intensity of 80000 uW / cm2for 45 minutes. The total breaking work and maximum stress intensity factor of the cured strips were tested according to the YY 0270.1-2011 standard using an Instron tensile testing machine. 2

[0109] The weight fractions of the components and the test results are shown in Table 1 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.

[0110] Table 1

[0111]

[0112]

[0113] Example 4: Synthesis of polyurethane acrylate 3 without STP groups (Prepolymer 3)

[0114] Step 1: IPDI and HEMA were mixed in a 1:1 mole ratio and added to a 500 mL three-necked flask with an overhead stirrer, nitrogen protection, and a thermometer. Then 200 μL of catalyst dibutyltin dilaurate (DBTL) was added to the flask and stirred, and the temperature was raised to 70°C. After 4 hours of reaction, HEMA-IPDI was obtained;

[0115] ​Second step: 1 mole ratio of BDO was added to the above three-neck flask, stirred at 70 °C, and HEMA-IPDI-BDO was obtained after 4 hours of reaction;

[0116] Third step: IPDI and PTMG1000 were mixed in a 2: 1 mole ratio and added to a 500 mL three-neck flask with an overhead stirrer, nitrogen protection, and a thermometer. Then 200 μL of catalyst dibutyltin dilaurate (DBTL) was added to the flask and stirred, and the temperature was raised to 70 °C, and IPDI-PTMG-IPDI was obtained after 4 hours of reaction;

[0117] Fourth step: 100 ppm of hydroquinone and 2 mole ratio of HEMA-IPDI-BDO were added to the above three-neck flask, stirred at 70 °C, and HEMA-IPDI-BDO-IPDI-PTMG-IPDI-BDO-IPDI-HEMA (Prepolymer 3) was obtained after 4 hours of reaction. The synthesis route of Prepolymer 3 is shown below.

[0118]

[0119] Example 5: Synthesis of polyurethane acrylate 4 (Prepolymer 4) with STP group

[0120] First step: IPDI and HEMA were mixed in a 1: 1 mole ratio and added to a 500 mL three-neck flask with an overhead stirrer, nitrogen protection, and a thermometer. Then 200 μL of catalyst dibutyltin dilaurate (DBTL) was added to the flask and stirred, and the temperature was raised to 70 °C, and HEMA-IPDI was obtained after 4 hours of reaction.

[0121] Second step: 1 mole ratio of STP was added to the above three-neck flask, stirred at 70 °C, and HEMA-IPDI-STP was obtained after 4 hours of reaction.

[0122] Third step: IPDI and PTMG1000 were mixed in a 2: 1 mole ratio and added to a 500 mL three-neck flask with an overhead stirrer, nitrogen protection, and a thermometer. Then 200 μL of catalyst dibutyltin dilaurate (DBTL) was added to the flask and stirred, and the temperature was raised to 70 °C, and IPDI-PTMG-IPDI was obtained after 4 hours of reaction.

[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 Maximum stress intensity factor / MPa m 1 / 2 ]] 1.8 3.7 Total work to break / 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 testing 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 significantly increase the maximum stress intensity factor and total breaking work.

[0153] Table 3

[0154]

[0155] Example 9

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

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

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

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

[0160] On the basis of prepolymer 2, methylene bis-cyclohexyl isocyanate (HMDI) was used to replace IPDI, and 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 other steps were similar to the preparation process of prepolymer 2, to obtain prepolymer 13.

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

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

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

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

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

[0167] Test Example 4: The prepolymer 8-18 was formulated into a formulation, and based on the test example 1, the photocuring 3D printing test was carried out, and the results are shown in Table 4.

[0168] Table 4

[0169]

[0170]

[0171] Referring to Tables 1-4, it can be seen that the polyurethane acrylate with a spirothiopyran group in the present application has a maximum stress intensity factor Kmax of not less than 2.5 MPa m 1 / 2 , and a total breaking work W of not less than 1200 J / m 2 when subjected to 3D photocuring printing material test. To some extent, it proves that the introduction of the spirothiopyran group into the polyurethane acrylate endows the material with good self-repairing and self-reinforcing capabilities.

[0172] The above description is merely illustrative of the embodiments of the present application and is not used to limit the present application. The present application can have various modifications and changes for those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the scope of claims of the present application.

Claims

1. A polyurethane acrylate with a spirothiopyran group, characterized in that, The general structure of the polyurethane acrylate with spirothiopyran group satisfies any one or more of the following formula I-III: Formula I, In formula I, r1, r2, r3, r4, r6, r7, r8, r9 are independently selected hydrocarbon group or heteroatom-containing hydrocarbon group; r5, r 10 is H or methyl; X is NH or O; STP is a spirothiopyran group; Formula II, In formula II, Z1, Z2, Z3, Z4, Z6, Z7, Z8 are independently selected hydrocarbon group or heteroatom-containing hydrocarbon group; Z9, Z5 are H or methyl; X is NH or O; STP is a spirothiopyran group; Formula III, In formula III, R, R1, R2, R4, R5, R7, R8 are independently selected hydrocarbon group or heteroatom-containing hydrocarbon group; R3, R6, R9 are H or methyl; At least one of W1, W2, W3 is a spirothiopyran group, and the other two are independently selected hydrocarbon group or heteroatom-containing hydrocarbon group.

2. The polyurethane acrylate with spirothiopyran group according to claim 1, characterized in that, The structure of the spirothiopyran group is as follows: 。 3. The polyurethane acrylate with spirothiopyran group according to claim 1, characterized in that, r1, r3, r6, r8, Z2, Z3, Z6, Z7, R1, R4, R7are selected from one of , , , , , , , , or .

4. The polyurethane acrylate with spirothiopyran group according to claim 1, characterized in that, r2, r7, Z1 are selected from one of the following: the residual part of polytetrahydrofuran ether diol after removing the two end hydroxyl groups, the residual part of polybutylene adipate after removing the two end hydroxyl groups, or the residual part of polycaprolactone polyol after removing the two end hydroxyl groups.

5. The polyurethane acrylate with spirothiopyran group according to claim 1, characterized in that, r4, r9, Z4, Z8, R2, R5, R8 are selected from C2-C4 hydrocarbon group.

6. The polyurethane acrylate with spirothiopyran group according to claim 5, characterized in that, r4, r9, Z4, Z8, R2, R5, R8 are each selected from or .

7. A photocured denture base material, characterized by, The light-cured denture base material comprises: 5-70wt% of the polyurethane acrylate with spirothiopyran group according to any one of claims 1-6; 25-90wt% of at least one monomeric acrylate; 0.1-5wt% of at least one photoinitiator; and 0.05-2wt% of at least one light stabilizer.

8. Use of the polyurethane acrylate with spirothiopyran group according to any one of claims 1-6 in a denture base material.

9. Use of the polyurethane acrylate with spirothiopyran group according to any one of claims 1-6 in an oral prosthetic material.

10. Use of the polyurethane acrylate with spirothiopyran group according to any one of claims 1-6 in a 3D printing light-cured material.

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