CN102068387A - Methyl acrylate (MA)-methyl methacrylate (MMA) copolymer-base denture base material as well as preparation method and application thereof - Google Patents
Methyl acrylate (MA)-methyl methacrylate (MMA) copolymer-base denture base material as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a methyl acrylate (MA)-methyl methacrylate (MMA) copolymer-base denture base material as well as a preparation method and application thereof. The preparation method comprises the following steps: toughening a first monomer-MMA by a second monomer-MA; copolymerizing the two monomers in a suspension polymerization manner, wherein the MA monomer and the MMA monomer form an oil phase, the amount of the MA monomer is 1-10wt% of the mass of the oil phase, and the amount of the MMA monomer is 90-99wt% of the mass of the oil phase; evenly mixing the obtained copolymerization product with the heat-cured liquid for denture acrylic; and finally heating for curing. The MA-MMA copolymer-base denture base material is applied to the field of a denture base material; and compared with a purer PMMA (polymethylmethacrylate) material, the denture base material has the advantages of greatly improved bending strength, greatly improved impact strength and slightly improved tensile strength, thus successfully solving the problems of the PMMA denture base material in mechanical strength and particularly in impact strength.
Description
Technical field
The invention belongs to the prosthetic dentistry field, more particularly, the denture base material that relates to the toughness reinforcing polymethyl methacrylate of a kind of copolymerization (PMMA) particularly is matrix with PMMA, is toughness reinforcing denture base material of the second monomeric copolymerization and its production and application with acrylic acid methyl ester. (MA).
Background technology
Along with the progress and the growth in the living standard of society, people are strong day by day to the requirement of aesthetic reparation, and are also more and more higher to the requirement of oral cavity material, and simultaneously, retaining of tooth makes the spectrum of disease in oral cavity that change take place.According to the interrelated data measuring and calculating, China's population dental caries sickness rate is 37%, and on average everyone has 2.47 of dental caries, by 1,200,000,000 populations, and nearly 500,000,000 people of national eurodonticus, the dental caries sum is more than 1,000,000,000.In the adult, periodontal disease patient is about 80%, and this all can cause very a high proportion of dentition defect.11 of the average agomphosis of over-65s elderly population.These all need to use dental prosthetic material reparation, and the market of visible China dental prosthetic material is very wide.
Adopt natural and artificial material to make the application of basal seat area, existing long history in the prosthetic dentistry field.Adopting hardwood, animal bone, Dens Elephatis etc. to do the embedding base the earliest decorates, adopted thiorubber. in 1885, nineteen thirty-seven, Germany Kulzer company released heat-curing type PMMA denture base material " Paladan " first, started new era of prosthetic dentistry, because its superior performance, easy and simple to handle, the bio-compatible performance is good, so far still as the first-selection of clinical practice.But, because the existence of internal stress in the not good enough and solidification process of the intensity of PMMA resin own, the toughness of resin material and intensity are all lower, the vertical easily folding of artificial tooth on causing in clinical repair, the phenomenon of rupture of base often takes place during interlock, therefore the mechanical performance of PMMA can not satisfy the requirement of Oral Repair fully, even if best clinical experience is arranged, the selection of indication, artificial tooth's arrangement and the most rational operating process, still there is the problem of mechanical strength aspect in the PMMA base material, particularly impact strength is relatively poor, often causes fractureing of base, and causes that dysbacteriosis causes denture stomatitis.
In the last few years, modification field at the PMMA base material, appear in the PMMA substrate and add SiO2, nanoparticles such as TiO2 carry out compound and adopting montmorillonite carries out the intercalation composite methods, can strengthen some performance of matrix significantly, especially significantly improved the intensity of material, but improved its toughness, improving that effect also is not very desirable aspect the impact strength.
Summary of the invention
The objective of the invention is to overcome the deficiency of PMMA base material in the prior art, the deficiency that especially exists on toughness provides a kind of acrylic acid methyl ester .-methylmethacrylate copolymer base denture base material and preparation method thereof.
The present invention also aims to provide of the application of a kind of acrylic acid methyl ester .-methylmethacrylate copolymer material as denture base material.
Purpose of the present invention is achieved by following technical proposals:
A kind of acrylic acid methyl ester .-methylmethacrylate copolymer base denture base material, carry out toughness reinforcing with the second monomer acrylic acid methyl ester. to first monomers methyl methacrylate, two monomers carry out copolymerization by the suspension polymerisation mode, two kinds of monomers of described acrylic acid methyl ester. and methyl methacrylate are formed oil phase, the methacrylate monomer consumption is 1～10wt% of oil phase quality, the consumption of methyl methacrylate monomer is 90～99wt% of oil phase quality, copolymerization product coagulates type dental base acrylic resin liquid mix homogeneously with heat, is heating and curing.
A kind of method for preparing acrylic acid methyl ester .-methylmethacrylate copolymer base denture base material, carry out according to following step:
(1) be comonomer with acrylic acid methyl ester. and methyl methacrylate, make by suspension polymerisation, in suspension polymerization system, the volume ratio of water and oil phase is 1～5, described oil phase is made up of acrylic acid methyl ester. and two kinds of monomers of methyl methacrylate, the consumption of methacrylate monomer is 1～10wt% of oil phase quality, and the consumption of methyl methacrylate monomer is 90～99wt% of oil phase quality; Described water is made up of water, dispersant and surfactant, wherein the consumption of dispersant be two kinds of monomer masses and 3～3.5wt%, the consumption of surfactant be two kinds of monomer masses and 0.1～0.2wt%
(2) oil phase and water are added in the reactor, stir, feeding noble gas is in the inert gas atmosphere in course of reaction to remain on whole reactor, be warming up on the initiation temperature of initiator, add initiator simultaneously with initiated polymerization, obtain acrylic acid methyl ester .-methylmethacrylate copolymer A
(3) copolymer A of step (2) preparation is filtered and washed, obtain copolymer powder B after the oven dry
(4) copolymer powder B and heat are coagulated the type dental base acrylic resin liquid according to mass ratio (1～2): 1, carry out mix homogeneously
(5) mixture for the treatment of step (4) mix homogeneously enters the dough after date and is taken out, and is filled in the mould, and pressure is 2～4MPa
(6) mould after the filling is heating and curing, in 70～80 ℃ water, heats 1.5～3.5h, be warming up to 90～100 ℃ again, keep leaving standstill cooling, die sinking behind 1～3h.
In the suspension polymerization system of the present invention, described dispersant is a kind of in basic magnesium carbonate, calcium hydroxy phosphate (HAP), hydroxyethyl-cellulose (HEC) or the tricalcium phosphate, preferred hydroxyethyl-cellulose (HEC); The volume ratio of described water and oil phase is preferably 3; Described surfactant is a kind of in dodecylbenzene sodium sulfonate (SDBS), sodium lauryl sulphate (SDS) or the sodium glycocholate, is preferably dodecylbenzene sodium sulfonate (SDBS); Described initiator is a kind of in azodiisobutyronitrile (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN), benzoyl peroxide (BPO) or peroxy dicarbonate two (2-ethyl) the own ester (EHP), preferred azodiisobutyronitrile (AIBN) or benzoyl peroxide (BPO); Described noble gas is a kind of in nitrogen, helium or the argon; In the time of on being heated to the initiation temperature of initiator, according to what of reactant, realize higher conversion ratio to guarantee two kinds of monomers when the copolymerization, the preferred reaction time is 3-10 hour sufficiently long time of needs polyreaction.
In the preparation method of the present invention, in the described step (4), copolymer powder B coagulates the type dental base acrylic resin liquid with heat and is preferably 1.5: 1 according to mass ratio; In the described step (5), the preferred 3Mpa of pressure; In the described step (6), preferably in 70 ℃ water, heat 1.5h, be warming up to 100 ℃ again, leave standstill cooling, die sinking after the maintenance 1.
In many denture base materials, small bead polymer (the pearl PMMA powder of making by the process suspension polymerisation of methyl methacrylate (MMA) monomer, be dental base acrylic resin powder) be the main component of denture base material, weight average molecular weight is 60～1,000,000, particle diameter is 40～70 μ m, transmittance is more than 90%, and density is about 1.19g/cm
3The pearl PMMA powder of monomer polymerization preparation exists a lot of not enough on mechanical property.The present invention introduces the PMMA denture base material from the free-radical polymerized mode of the toughness reinforcing angle Selection of macromolecule with second monomer, thereby realizes the raising of flexible improvement and impact property.The present invention is when selecting second monomer, and consider that emphatically second monomer should give satisfied: (1) contains two keys, can with the MMA polymerization; (2) contain gentle chain, increase toughness; (3) can be crosslinked, do not reduce the strength of materials; (4) nontoxic, or toxicity is lower.Select the MA monomer to contain two keys, polymerizable can be crosslinked, has flexible side-chains, can be toughness reinforcing, and little with the transparency influence to material after the MMA copolymerization, and toxicity is lower.P of the present invention (MMA-co-MA) copolymer first Application is to the denture base material field, after being prepared into the artificial tooth base resin powder and being made into standard specimen, purer PMMA resin material, bending strength and impact strength all are greatly improved, the hot strength of resin also slightly improves simultaneously, has successfully solved the problem that the PMMA denture base material particularly exists aspect impact strength aspect mechanical strength.
Method of the present invention is simple to operate, and is with low cost, and experiment condition is easily controlled, and the operation cycle is shorter, and effect toughness reinforcing under the prerequisite that does not reduce resin matrix intensity is fairly obvious.Meanwhile, copolymer resins has all obtained improvement in various degree at aspects such as hot property, anti-saliva performance, hygroscopicity value, solubility value and residual monomer contents, so the denture base material of Using such method preparation has good application prospects in the Oral Repair field.
The specific embodiment
Further specify technical scheme of the present invention below in conjunction with specific embodiment.The heat that embodiment selects for use is coagulated the artificial tooth base resin that the type dental base acrylic resin liquid is Dentistry Material Plant, Shanghai Medical Machinery Co., Ltd. (I type), and composition is as shown in the table:
Embodiment 1
(1) MA with 1wt% mixes with the MMA monomer of 99wt% in the back adding there-necked flask (the monomer total amount is 60mL), in the 170ml deionized water, add 1.8g hydroxyethyl-cellulose (HEC) and 0.074g dodecylbenzene sodium sulfonate (SDBS) simultaneously, be poured in the there-necked flask after preliminary the stirring, continue stirring at low speed.Logical N
2Behind the protection 40min, be warming up to 90 ℃, and continue to keep inert atmosphere, add 0.4g initiator B PO initiated polymerization.Reaction 9h, with the reaction system cold filtration, the cyclic washing filtration product.Vacuum drying is to constant weight, obtain corresponding copolymerization crude product, again copolymerization crude product P (MMA-co-MA) is dissolved in 50-80 ℃ the n-butyl alcohol, is cooled to-20 ℃, make PMMA homopolymer precipitation, filter, washing splashes into methanol down until methanol/total pure 0.5-2 that is in stirring in filtrate, precipitation is P (MMA-co-MA) copolymer, continue to add methanol, then can precipitate and separate out the PMA homopolymer.Just can obtain purified P (MMA-co-MA) copolymerization product with this method;
(2) purified P (MMA-co-MA) copolymerization product (powder) and heat are coagulated the type dental base acrylic resin liquid and carry out mix homogeneously according to 1: 1 mass ratio, thing to be mixed enters the dough after date and is taken out, and is filled in the mould, and pressure is 4Mpa;
(3) mould after the filling is heating and curing, in 70 ℃ water, heats 1.5h, be warming up to 100 ℃ again, keep leaving standstill cooling, die sinking behind the 1h.
Embodiment 2
(1) MA with 1.5wt% mixes with the MMA monomer of 98.5wt% in the back adding there-necked flask (the monomer total amount is 50mL), in the 250ml deionized water, add 1.8g hydroxyethyl-cellulose (HEC) and 0.074g dodecylbenzene sodium sulfonate (SDBS) simultaneously, be poured in the there-necked flask after preliminary the stirring, continue stirring at low speed.Behind the logical argon shield 40min, be warming up to 90 ℃, and continue to keep inert atmosphere, add 0.4g initiator azodiisobutyronitrile initiated polymerization.Reaction 5h, with the reaction system cold filtration, the cyclic washing filtration product.Vacuum drying is to constant weight, obtain corresponding copolymerization crude product, again copolymerization crude product P (MMA-co-MA) is dissolved in 50-80 ℃ the n-butyl alcohol, is cooled to-20 ℃, make PMMA homopolymer precipitation, filter, washing splashes into methanol down until methanol/total pure 0.5-2 that is in stirring in filtrate, precipitation is P (MMA-co-MA) copolymer, continue to add methanol, then can precipitate and separate out the PBA homopolymer.Just can obtain purified P (MMA-co-MA) copolymerization product with this method;
(2) purified P (MMA-co-MA) copolymerization product (powder) and heat are coagulated the type dental base acrylic resin liquid and carry out mix homogeneously according to 2: 1 mass ratio, thing to be mixed enters the dough after date and is taken out, and is filled in the mould, and pressure is 2Mpa;
(3) mould after the filling is heating and curing, in 80 ℃ water, heats 2h, be warming up to 90 ℃ again, keep leaving standstill cooling, die sinking behind the 3h.
Embodiment 3
(1) MA with 3wt% mixes with the MMA monomer of 97wt% in the back adding there-necked flask (the monomer total amount is 50mL), in the 200ml deionized water, add 1.8g calcium hydroxy phosphate and 0.074g sodium lauryl sulphate simultaneously, be poured in the there-necked flask after preliminary the stirring, continue stirring at low speed.Behind the helium injection gas shiled 40min, be warming up to 90 ℃, and continue to keep inert atmosphere, add 0.4g initiator 2,2'-Azobis(2,4-dimethylvaleronitrile) initiated polymerization.Reaction 3h, with the reaction system cold filtration, the cyclic washing filtration product.Vacuum drying is to constant weight, obtain corresponding copolymerization crude product, again copolymerization crude product P (MMA-co-MA) is dissolved in 50-80 ℃ the n-butyl alcohol, is cooled to-20 ℃, make PMMA homopolymer precipitation, filter, washing splashes into methanol down until methanol/total pure 0.5-2 that is in stirring in filtrate, precipitation is P (MMA-co-MA) copolymer, continue to add methanol, then can precipitate and separate out the PMA homopolymer.Just can obtain purified P (MMA-co-MA) copolymerization product with this method;
(2) purified P (MMA-co-MA) copolymerization product (powder) and heat are coagulated the type dental base acrylic resin liquid and carry out mix homogeneously according to 1: 1 mass ratio, thing to be mixed enters the dough after date and is taken out, and is filled in the mould, and pressure is 3Mpa;
(3) mould after the filling is heating and curing, in 75 ℃ water, heats 3.5h, be warming up to 95 ℃ again, keep leaving standstill cooling, die sinking behind the 2h.
Embodiment 4
(1) MA with 5wt% mixes with the MMA monomer of 95wt% in the back adding there-necked flask (the monomer total amount is 50mL), in the 100ml deionized water, add 1.8g basic magnesium carbonate and 0.074g sodium glycocholate simultaneously, be poured in the there-necked flask after preliminary the stirring, continue stirring at low speed.Logical N
2Behind the protection 40min, be warming up to 90 ℃, and continue to keep inert atmosphere, add 0.4g initiator B PO initiated polymerization.Reaction 5h, with the reaction system cold filtration, the cyclic washing filtration product.Vacuum drying is to constant weight, obtain corresponding copolymerization crude product, again copolymerization crude product P (MMA-co-MA) is dissolved in 50-80 ℃ the n-butyl alcohol, is cooled to-20 ℃, make PMMA homopolymer precipitation, filter, washing splashes into methanol down until methanol/total pure 0.5-2 that is in stirring in filtrate, precipitation is P (MMA-co-MA) copolymer, continue to add methanol, then can precipitate and separate out the PMA homopolymer.Just can obtain purified P (MMA-co-MA) copolymerization product with this method;
(2) purified P (MMA-co-MA) copolymerization product (powder) and heat are coagulated the type dental base acrylic resin liquid and carry out mix homogeneously according to 1.5: 1 mass ratio, thing to be mixed enters the dough after date and is taken out, and is filled in the mould, and pressure is 3Mpa;
(3) mould after the filling is heating and curing, in 75 ℃ water, heats 3.5h, be warming up to 95 ℃ again, keep leaving standstill cooling, die sinking behind the 3h.
Embodiment 5
(1) MA with 10wt% mixes with the MMA monomer of 90wt% in the back adding there-necked flask (the monomer total amount is 50mL), in the 150ml deionized water, add 1.8g hydroxyethyl-cellulose (HEC) and 0.074g dodecylbenzene sodium sulfonate (SDBS) simultaneously, be poured in the there-necked flask after preliminary the stirring, continue stirring at low speed.Logical N
2Behind the protection 40min, be warming up to 90 ℃, and continue to keep inert atmosphere, add 0.4g initiator B PO initiated polymerization.Reaction 5h, with the reaction system cold filtration, the cyclic washing filtration product.Vacuum drying is to constant weight, obtain corresponding copolymerization crude product, again copolymerization crude product P (MMA-co-MA) is dissolved in 50-80 ℃ the n-butyl alcohol, is cooled to-20 ℃, make PMMA homopolymer precipitation, filter, washing splashes into methanol down until methanol/total pure 0.5-2 that is in stirring in filtrate, precipitation is P (MMA-co-MA) copolymer, continue to add methanol, then can precipitate and separate out the PMA homopolymer.Just can obtain purified P (MMA-co-MA) copolymerization product with this method;
(2) purified P (MMA-co-MA) copolymerization product (powder) and heat are coagulated the type dental base acrylic resin liquid and carry out mix homogeneously according to 1.5: 1 mass ratio, thing to be mixed enters the dough after date and is taken out, and is filled in the mould, and pressure is 2Mpa;
(3) mould after the filling is heating and curing, in 70 ℃ water, heats 1.5h, be warming up to 100 ℃ again, keep leaving standstill cooling, die sinking behind the 2h.
Comparative Examples
(1) 60mL MMA monomer is added in the there-necked flask, in the 190ml deionized water, add 1.9g hydroxyethyl-cellulose (HEC) and 0.075g dodecylbenzene sodium sulfonate (SDBS) simultaneously, be poured in the there-necked flask after preliminary the stirring, continue stirring at low speed.Logical N
2Behind the protection 10min, be warming up to 100 ℃, add 0.5g initiator B PO initiated polymerization.10h is with the reaction system cold filtration in reaction, the cyclic washing filtration product.Vacuum drying obtains PMMA artificial tooth base resin powder to constant weight.
(2) PMMA artificial tooth base resin powder and heat are coagulated the type dental base acrylic resin liquid and carry out mix homogeneously according to 1.5: 1 mass ratio, thing to be mixed enters the dough after date and is taken out, and is filled in the mould, and pressure is 2Mpa;
(3) mould after the filling is heating and curing, in 70 ℃ water, heats 1.5h, be warming up to 100 ℃ again, keep leaving standstill cooling, die sinking behind the 2h.
Test implementation example 1-5 product is learnt weight average molecular weight 60-80 ten thousand, and particle diameter is at 40～70 μ m, and it is as follows to utilize the omnipotent mechanical test machine of M350-20KN type of Britain Testometric company to carry out measuring mechanical property:
1, bending property test: three-point bending specimen size 64 * 10 * 3.3mm, load until sample fracture, test fulcrum span is 50mm, loading velocity is 5mm/min.
2, tensile property test: mechanics tensile sample size 50 * 7 * 2mm, rate of extension is 2mm/min.
3, impact property test: impact specimen size 80 * 10 * 4mm, breach keeps thickness 8mm, loads until sample fracture, and test fulcrum span is 50mm.
The mechanical performance of PMMA copolymer resin during difference MA content
More than the present invention has been done exemplary description; should be noted that; under the situation that does not break away from core of the present invention, the replacement that is equal to that any simple distortion, modification or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.
Claims (8)
1. acrylic acid methyl ester .-methylmethacrylate copolymer base denture base material, it is characterized in that, carry out toughness reinforcing with the second monomer acrylic acid methyl ester. to first monomers methyl methacrylate, two monomers carry out copolymerization by the suspension polymerisation mode, two kinds of monomers of described acrylic acid methyl ester. and methyl methacrylate are formed oil phase, the methacrylate monomer consumption is 1～10wt% of oil phase quality, the consumption of methyl methacrylate monomer is 90～99wt% of oil phase quality, copolymerization product coagulates type dental base acrylic resin liquid mix homogeneously with heat, is heating and curing.
2. a method for preparing acrylic acid methyl ester .-methylmethacrylate copolymer base denture base material is characterized in that, carries out according to following step:
(1) be comonomer with acrylic acid methyl ester. and methyl methacrylate, make by suspension polymerisation, in suspension polymerization system, the volume ratio of water and oil phase is 1～5, described oil phase is made up of acrylic acid methyl ester. and two kinds of monomers of methyl methacrylate, the consumption of methacrylate monomer is 1～10wt% of oil phase quality, and the consumption of methyl methacrylate monomer is 90～99wt% of oil phase quality; Described water is made up of water, dispersant and surfactant, wherein the consumption of dispersant be two kinds of monomer masses and 3～3.5wt%, the consumption of surfactant be two kinds of monomer masses and 0.1～0.2wt%
(2) oil phase and water are added in the reactor, stir, feeding noble gas is in the inert gas atmosphere in course of reaction to remain on whole reactor, be warming up on the initiation temperature of initiator, add initiator simultaneously with initiated polymerization, obtain acrylic acid methyl ester .-methylmethacrylate copolymer A
(3) copolymer A of step (2) preparation is filtered and washed, obtain copolymer powder B after the oven dry
(4) copolymer powder B and heat are coagulated the type dental base acrylic resin liquid according to mass ratio (1～2): 1, carry out mix homogeneously
(5) mixture for the treatment of step (4) mix homogeneously enters the dough after date and is taken out, and is filled in the mould, and pressure is 2～4MPa
(6) mould after the filling is heating and curing, in 70～80 ℃ water, heats 1.5～3.5h, be warming up to 90～100 ℃ again, keep leaving standstill cooling, die sinking behind 1～3h.
3. a kind of method for preparing acrylic acid methyl ester .-methylmethacrylate copolymer base denture base material according to claim 2, it is characterized in that described dispersant is a kind of in basic magnesium carbonate, calcium hydroxy phosphate, hydroxyethyl-cellulose or the tricalcium phosphate; Described surfactant is a kind of in dodecylbenzene sodium sulfonate, sodium lauryl sulphate or the sodium glycocholate; Described initiator is a kind of in the own ester of azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide or peroxy dicarbonate two (2-ethyl); Described noble gas is a kind of in nitrogen, helium or the argon.
4. a kind of method for preparing acrylic acid methyl ester .-methylmethacrylate copolymer base denture base material according to claim 3 is characterized in that described dispersant is a hydroxyethyl-cellulose; Described surfactant is a dodecylbenzene sodium sulfonate; Described initiator is azodiisobutyronitrile or benzoyl peroxide.
5. a kind of method for preparing acrylic acid methyl ester .-methylmethacrylate copolymer base denture base material according to claim 2 is characterized in that the volume ratio of described water and oil phase is 3.
6. a kind of method for preparing acrylic acid methyl ester .-methylmethacrylate copolymer base denture base material according to claim 2 is characterized in that two kinds of monomeric copolyreaction times are 3-10 hour.
7. a kind of method for preparing acrylic acid methyl ester .-methylmethacrylate copolymer base denture base material according to claim 2 is characterized in that, in the described step (4), it is 1.5: 1 according to mass ratio that copolymer powder B coagulates the type dental base acrylic resin liquid with heat; In the described step (5), pressure is 3Mpa; In the described step (6), in 70 ℃ water, heat 1.5h, be warming up to 100 ℃ again, leave standstill cooling, die sinking after the maintenance 1.
8. the application of acrylic acid methyl ester .-methylmethacrylate copolymer as claimed in claim 1 in denture base material.
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| CN104231507A (en) * | 2013-06-10 | 2014-12-24 | 贺利氏古萨有限公司 | Moulded parts made of pmma powder as simple dosing aid in the manufacture of dental prostheses |
| CN107875027A (en) * | 2017-11-27 | 2018-04-06 | 东莞市爱嘉义齿有限公司 | A kind of artificial tooth material and preparation method thereof |
| CN115400269A (en) * | 2022-08-16 | 2022-11-29 | 武汉理工大学 | Injectable bone cement and preparation method and application thereof |
| CN115637012A (en) * | 2022-10-21 | 2023-01-24 | 苏州双象光学材料有限公司 | Polymethyl methacrylate alloy resin composition and preparation method thereof |
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