CN109517312B - Dual POSS polyether hybrid PMMA resin and preparation and forming methods thereof - Google Patents

Dual POSS polyether hybrid PMMA resin and preparation and forming methods thereof Download PDF

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CN109517312B
CN109517312B CN201811399115.7A CN201811399115A CN109517312B CN 109517312 B CN109517312 B CN 109517312B CN 201811399115 A CN201811399115 A CN 201811399115A CN 109517312 B CN109517312 B CN 109517312B
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CN109517312A (en
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安秋凤
王玉峰
吕竹筠
黄良仙
许伟
郝丽芬
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Shaanxi University of Science and Technology
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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Abstract

The invention discloses a double POSS polyether hybrid polymethyl methacrylate (PMMA) resin and a processing and forming method thereof. For this purpose, the invention firstly uses semi-closed cage-shaped oligomeric silsesquioxane trisilicol T7(OH)3And (2) carrying out polycondensation with a hexafunctional silane coupling agent-alpha, omega-bis (trialkoxy silicon propyl) polyether PECA under the action of an organic tin catalyst to obtain alpha, omega-bis POSS polyether (DPPE), then blending DPPE with methyl methacrylate MMA, an initiator, a plasticizer and the like, carrying out free radical copolymerization, and carrying out secondary reaction molding to obtain the double POSS polyether hybrid PMMA resin with transparent appearance. The application shows that compared with the unmodified PMMA resin, the scratch resistance and the heat resistance stability of the double POSS polyether hybrid PMMA resin are both improved beneficially.

Description

Dual POSS polyether hybrid PMMA resin and preparation and forming methods thereof
Technical Field
The invention belongs to the field of functional resin, and particularly relates to a double POSS polyether hybrid PMMA resin and preparation and forming methods thereof.
Background
Oligomeric silsesquioxanes having a skeleton comprising-RSiO3/2The chain link, structure can be in a net or cage shape, and is a typical semi-inorganic-semi-organic molecule. The cage-shaped oligomeric silsesquioxane (POSS) has the structural characteristics of oligomeric silsesquioxane, and organic groups are connected to corners, so that the cage-shaped oligomeric silsesquioxane has good compatibility with organic materials, good heat-resistant stability and chemical stability, is used for hybridization of the organic materials, and can improve the organic propertiesThe flame retardance and the heat-resistant stability of the material are improved, and the physical and mechanical properties and the hardness of the organic material are improved.
Polymethyl methacrylate (PMMA), commonly known as acrylic organic glass, is a thermoplastic organic resin material, has high light transmittance, good dielectric and electrical insulation properties, chemical stability, mechanical and weather resistance and easy processing performance, so that the PMMA material is widely applied or potentially applied in the fields of instrument panels, car lamps, optical lenses, learning products, lamp shades, artware, touch screens on curved surfaces, wearable electronic products and the like of high-grade instruments, but the PMMA material has low hardness and poor scratch resistance, thereby influencing the application of the material and requiring improvement urgently.
Using inorganic nano-materials such as nano-silicon oxide, nano-vanadium oxide, TiO2The hybrid PMMA resin (see CN107652604, CN106519527 and the like) can improve the hardness of resin materials and improve the scratch resistance of the materials, but inorganic nanoparticles or nano powder has poor compatibility with polymethyl methacrylate and is easy to agglomerate, so that when the hybrid PMMA resin is used for PMMA resin modification, the light transmittance of the resin is reduced, and the powder falling phenomenon can occur.
The cage-shaped organic oligomeric silsesquioxane has a skeleton similar to nano silicon oxide, but organic groups in molecules enable the silsesquioxane to be well miscible with PMMA and monomers, so that the cage-shaped organic oligomeric silsesquioxane becomes the first choice for PMMA resin modification.
In the literature, copolymerization of methacrylate-based POSS and acrylate is a common method for hybridization or modification of polyacrylic resin with POSS, and is also one of the current research hotspots, which can be found in chinese patent nos. CN106700809A, CN103304960A, CN107488244A, CN106752628A, etc. However, as can be seen from literature search, the oligomeric silsesquioxane used for acrylic resin hybridization is mainly cage-shaped methacrylate-based POSS (such as single-arm methacrylate-based POSS or eight-arm methacrylate-based POSS), vinyl POSS (such as octavinyl POSS), non-reactive methyl POSS or phenyl POSS, etc., while the properties of PMMA are improved by the novel structure of the bis-POSS polyether hybrid thermoplastic polymethyl methacrylate resin, which is not yet reported.
Disclosure of Invention
The invention aims to disclose a double POSS polyether hybrid PMMA resin and preparation and forming methods thereof. Firstly, carrying out polycondensation on alpha, omega-bis (trialkoxy silicon propyl) polyether which is a hexafunctional silane coupling agent and is synthesized by a hydrosilation reaction and semi-closed cage-shaped oligomeric silsesquioxane trisilanol under the action of an organic tin catalyst to synthesize alpha, omega-bis POSS polyether (DPPE); then, the POSS polyether is used as a nano reinforcing component, the DPPE and the methyl methacrylate are physically blended, then the body polymerization of MMA is initiated under the action of a free radical initiator, and the mixture is subjected to secondary reaction molding, so that the double POSS polyether hybrid thermoplastic polymethyl methacrylate resin with good transparency is prepared, and compared with unhybridized PMMA, the heat resistance stability, the hardness and the scratch resistance of the double POSS polyether hybrid PMMA resin prepared by the method are all beneficially improved.
The technical scheme adopted by the invention is as follows:
a double POSS polyether hybrid polymethyl methacrylate resin and a preparation and forming method thereof are characterized by comprising the following steps:
(1) synthesis of bis-POSS polyethers
Weighing semi-closed cage-shaped oligomeric silsesquioxane trisilicol [ T ]7(OH)3]Dissolving with solvent A to obtain 10-20% solution, stirring and heating to 20-60 deg.C, adding alpha, omega-bis (trialkoxy silicon propyl) Polyether (PECA) and organotin catalyst in catalytic amount, and regulating T7(OH)3The molar ratio of the POSA to PECA is 1:0.5, then the polycondensation reaction is carried out for 2-24h at the constant temperature of 20-60 ℃, the reaction is finished, the solvent is removed by evaporation under reduced pressure, the product is dried in vacuum, the alpha, omega-double POSS polyether with the structure shown in the formula (1) is obtained, the product is called DPPE, in the formula (1), R is isobutyl, isooctyl, octyl, phenyl and the like, a and b are respectively positive integers of 0, 1, 2, 3 … … and the like, and the value range of a + b is preferably selected to be 3-25.
Figure GDA0001933501690000021
(2) Preparation and molding of double POSS polyether hybrid polymethyl methacrylate resin
The preparation method comprises the following steps of weighing DPPE and MMA in sequence according to a mass ratio, adding 0.3-1.0% of free radical initiator and 1% of plasticizer in terms of the mass of MMA, uniformly stirring, heating to 50-80 ℃, carrying out prepolymerization reaction for 10-60min, cooling to room temperature after the viscosity of a system reaches 100-500mPa.s, putting the obtained viscous liquid into a polytetrafluoroethylene mold, heating to 80-90 ℃, keeping the temperature, carrying out secondary reaction molding for 2h, and cooling to room temperature after the reaction is finished to obtain a transparent solid sample, namely the dual-POSS polyether hybrid PMMA resin.
The semi-closed cage-shaped oligomeric silsesquioxane trisilicol T7(OH)3The structure is shown as (2), and the oligomeric silsesquioxane has seven same organic groups and three silicon hydroxyl groups connected in the molecule, wherein R in the formula (2) is the same as the formula (1), and can be synthesized by the hydrolytic polycondensation reaction of trialkoxysilane by the method of reference literature or directly purchased from Hybrid plastics of America.
Figure GDA0001933501690000031
The hexafunctional silane coupling agent alpha, omega-bis (trialkoxy silicon propyl) Polyether (PECA) has a molecular formula of (R' O)3SiC3H6O(C2H4O)a(C3H6O)bC3H6Si(OR′)3Wherein the value ranges of a, b and a + b are the same as formula (1), R ═ CH3Or C2H5Mainly comprises alpha, omega-bis (trimethoxysilylpropyl) polyoxyethylene polyoxypropylene ether, alpha, omega-bis (triethoxysilylpropyl) polyoxyethylene polyoxypropylene ether, alpha, omega-bis (trimethoxysilylpropyl) polyoxyethylene ether, alpha, omega-bis (triethoxysilylpropyl) polyoxypropylene ether, alpha, omega-bis (trimethoxysilylpropyl) polyoxypropylene ether and alpha, omega-bis (triethoxysilylpropyl) polyoxypropylene ether, and trialkoxyhydrosilane [ (R' O) under the action of platinum catalyst according to the reference method3SiH，TRS]And alpha, omega-diallyl polyether (alpha, omega-ViPE, structural formula CH)2＝CHCH2(C2H4O)a(C3H6O)bCH2CH＝CH2) The preparation method comprises the steps of carrying out hydrosilylation, wherein the molar ratio of TRS to alpha, omega-ViPE in the reaction is 2.1:1, the reaction temperature is 80 ℃, the reaction time is 2 hours, and the value ranges of a and b are the same as the formula (1).
The organic tin catalyst comprises dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dioctyltin diacetate and the like, and the dosage is [ T [ ]7(OH)3]+ 0.3-0.5% of the mass of PECA;
the solvent A is p-oligomeric silsesquioxane trisilicol T7(OH)3The alcohol, alcohol ether, halogenated hydrocarbon or hydrocarbon with good intersolubility mainly comprises ethanol, glycol dimethyl ether, tetrahydrofuran, chloroform, acetone, hexane, toluene and mixture of the ethanol, the glycol dimethyl ether, the tetrahydrofuran, the chloroform, the acetone, the hexane and the toluene in any proportion.
The oligomeric silsesquioxane trisilicol [ T ]7(OH)3]Polycondensation with a hexafunctional silane coupling agent alpha, omega-bis (trialkoxysilylpropyl) polyether PECA, T7(OH)3The mol ratio of the PECA to the PECA is 1:0.5, the reaction temperature is 20-60 ℃, and the reaction time is 2-24 h.
The preparation method and the molding of the double POSS polyether hybrid PMMA resin are characterized in that the mass ratio of the double POSS polyether to the methyl methacrylate MMA monomer is 5-25: 100.
The free radical initiator is generally a substance which can be decomposed by heating to release free radicals and has good intersolubility with oil-soluble monomers, and mainly comprises Azobisisobutyronitrile (AIBN), Benzoyl Peroxide (BPO), dimethyl Azobisisobutyrate (AIBME), tert-butyl peroxide, tert-butyl peroxycarbonate and the like, and the dosage of the free radical initiator is 0.3-1.0 percent of the total mass of MMA.
The plasticizer is one of dioctyl phthalate (DOP), dibutyl phthalate, tributyl phosphate, tributyl citrate and trioctyl citrate, and the dosage of the plasticizer is about 1% of the mass of monomer MMA.
The preparation method and secondary reaction forming of the double POSS polyether hybrid PMMA resin are characterized in that DPPE, MMA, a free radical initiator, a plasticizer and the like are stirred and uniformly mixed, then prepolymerization reaction is carried out for 10-60min at a lower temperature of 50-80 ℃, after the viscosity of a system is increased to 100-500mPa.s, the system is rapidly cooled to room temperature, then the system is placed into a polytetrafluoroethylene mold, and then the system is heated to 80-90 ℃ for heat preservation and reaction forming is carried out for 2 h.
The polytetrafluoroethylene mold is a square or rectangular mold hollowed out, and the depth of the groove is about 4 mm.
The application performance of the cured and molded dual POSS polyether hybrid PMMA resin sample is determined according to the following method: the appearance is evaluated by a visual method; the light transmittance (T%) is measured by using a Cary 5000 type ultraviolet-visible spectrophotometer, and the wavelength range is 200-800 nm; the glass transition temperature (Tg) was measured by a Differential Scanning Calorimeter (DSC) of Chi-Katsuki Kaisha, Germany, and the temperature rise rate was 10 ℃/min. Scratch or mar resistance: 0000 for reference to GB/T9279-1988 method#And (4) evaluating the scratch test of the steel wool on the surface of the resin.
The invention has the beneficial effects that: the invention uses semi-closed cage-shaped oligomeric silsesquioxane trisilicol [ T ]7(OH)3]As a rigid inorganic nano-source material, firstly, T is subjected to polycondensation reaction under the action of an organic tin catalyst by skillfully utilizing the reaction characteristic that silicon hydroxyl and siloxy can be subjected to polycondensation7(OH)3Carrying out polycondensation with alpha, omega-bis (trialkoxysilylpropyl) polyether (synthesized by hydrosilylation addition reaction in advance) which is a hexafunctional silane coupling agent in a dilute solution to prepare Double POSS Polyether (DPPE) with cage-shaped POSS suspended at two molecular ends; then, by utilizing the characteristic that the DPPE has good intersolubility with MMA and PMMA, firstly dissolving DPPE in MMA monomer in a true solution, then initiating the bulk polymerization among MMA molecules under the action of a free radical initiator, and synthesizing DPPE hybridized PMMA through secondary reaction molding; the method not only overcomes the foaming phenomenon generated by large exothermic effect and easy volatilization of monomers in the MMA polymerization process, but also ensures that the prepared target product, namely the double POSS polyether hybrid PMMA resin, has transparent appearance, increased glass transition temperature and obviously improved heat resistance and scratch resistance.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
Preparation of alpha, omega-bis (trialkoxy-silicon propyl) polyether as (mono) hexafunctional silane coupling agent
Trialkoxyhydrosilane (TRS) and diallyl polyether (alpha, omega-ViPE) are sequentially added into a three-necked bottle provided with a thermometer, a reflux condenser tube and a stirrer, the molar ratio of TRS to alpha to omega-ViPE is controlled to be 2.1:1, the mixture is uniformly stirred and heated to 80 ℃, 100ppm chloroplatinic acid catalyst is added for hydrosilylation reaction for 4 hours, and then pressure reduction and low boiling are carried out to obtain transparent liquid, namely a hexafunctional silane coupling agent, namely alpha, omega-bis (trialkoxysilylpropyl) Polyether (PECA), wherein the raw materials and the using amount used for synthesizing the PECA in each embodiment are detailed in Table 1.
TABLE 1 raw materials and amounts used for the preparation of the hexafunctional silane coupling agent PECA
Figure GDA0001933501690000051
TMS: trimethoxysilane; TES: triethoxysilane; alpha, omega-ViPE(1)：a＝0、b＝3、Mn＝272；α,ω-ViPE(2)：a＝18、b＝7、
Mn＝1296；α,ω-ViPE(3)：a＝7、b＝3、Mn＝580；α,ω-ViPE(4)：a＝10、b＝10、Mn＝1118；α,ω-ViPE(5)：a＝10、b＝0、
Mn＝538。
Example II
Example 1
(1) Preparation of bis-POSS polyether-bis (heptaisobutyl POSS) polyoxypropylene ether
In a 100mL three-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 3.95g (0.005mol) of semi-closed caged isobutylheptapolysilsesquioxane trisilol [ iBu-T ] was weighed in this order7(OH)3]And 35.55g of chloroform, and stirring and dissolving to prepare iBu-T7(OH)3A diluted solution having a mass concentration of 10% was added dropwise thereto 1.29g (0.0025mol) of a ═ 0, b ═ 3, a + b ═ 3, Mn ═ 516, and the formula (CH) synthesized in table 13O)3SiC3H6O(C3H6O)3C3H6Si(OCH3)3Alpha, omega-bis (trimethoxysilylpropyl) polyoxypropylene ether (PECA-1) and 2 drops of dibutyltin dilaurate catalyst in a system of iBu-T7(OH)3Stirring and uniformly mixing the mixture and PECA-1 according to the molar ratio of 1:0.5, then continuously carrying out polycondensation reaction for 24 hours at the temperature of 20 ℃, and evaporating the solvent under reduced pressure after the reaction is finished to obtain about 5.24g of the total compound, wherein the structure of the compound is shown as a formula (1), and R is i-C4H9Bis (heptaisobutyl POSS) polyoxypropylene ether (DPPE-1), a bis POSS polyether of (isobutyl), a ═ 0, b ═ 3, and a + b ═ 3.
(2) Preparation and molding of bis (heptaisobutyl POSS) polyoxypropylene ether hybrid PMMA resin
Weighing 2.5g of DPPE-1, 10g of MMA, 0.3% of free radical initiator BPO (about 0.03 g) and 0.1g of plasticizer dioctyl phthalate in sequence according to the mass ratio of DPPE-1 to MMA of 25:100, uniformly stirring, heating to 50 ℃ to react for 60min, wherein the viscosity of the system is about 112mPa.s, cooling to room temperature, pouring the obtained viscous liquid into a container (length, width and depth) with the volume of 10 x 0.4cm3The polytetrafluoroethylene mold (with the vent hole) is sealed, then the temperature is raised to 90 ℃ for secondary reaction forming for 2 hours, after the reaction is finished, the reaction product is cooled to room temperature, and the obtained transparent solid sample, namely the bis (heptaisobutyl POSS) polyoxypropylene ether hybrid PMMA resin, is marked as DPMA-1.
Example 2
(1) Preparation of bis POSS polyether-bis (heptaphenyl POSS) polyoxyethylene polyoxypropylene ether
In a 100mL three-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 3.73g (about 0.004mol) of half-closed caged phenyl heptasilsesquioxane trisilicol [ ph-T ] was weighed in this order7(OH)3]And 14.92g of tetrahydrofuran, and stirring to dissolve to prepare ph-T7(OH)3A diluted solution having a mass concentration of 20% was heated to 60 ℃, and then 3.18g (about 0.002mol) of a ═ 18, b ═ 7, a + b ═ 25, Mn ═ 1625, the molecular formula (C) synthesized in table 1 was added dropwise thereto2H5O)3SiC3H6O(C2H4O)18(C3H6O)7C3H6Si(OC2H5)3Alpha, omega-bis (triethoxysilylpropyl) polyoxyethylene polyoxypropylene ether (PECA-2) and 2 drops of dioctyltin dilaurate catalyst in a system of ph-T7(OH)3The molar ratio of the mixture to PECA-2 is 1:0.5, the mixture is stirred and mixed evenly, then the polycondensation reaction is continuously carried out for 2h under the temperature of 60 ℃, the reaction is finished, the solvent is evaporated under reduced pressure, and about 6.91g of bis (heptaphenyl POSS) polyoxyethylene polyoxypropylene ether (DPPE-2) which is a bis POSS polyether with the structure shown in formula (1) and has the structure of R ═ ph (phenyl), a ═ 18, b ═ 7 and a + b ═ 25 is obtained.
(2) Preparation and molding of bis (heptaphenyl POSS) polyoxyethylene polyoxypropylene ether hybrid PMMA resin
Weighing 0.5g of DPPE-2, 10g of MMA, 0.6% of free radical initiator AIBN accounting for the mass of MMA, 0.06g of plasticizer trioctyl citrate and 0.1g of plasticizer according to the mass ratio of DPPE-2 to MMA of 5:100 in sequence, stirring and uniformly mixing, heating to 80 ℃ to perform prepolymerization reaction for 10min, wherein the system viscosity is about 480mPa.s, cooling to room temperature, pouring the obtained viscous liquid into a container with the volume (length, width and depth) of 10 x 0.4cm3Sealing the polytetrafluoroethylene mold (leaving an exhaust hole), then heating to 80 ℃ for secondary reaction and molding for 2h, cooling to room temperature after the reaction is finished, and obtaining a transparent solid sample, namely the bis (heptaphenyl POSS) polyoxyethylene polyoxypropylene ether hybrid PMMA resin, which is recorded as DPMA-2.
Example 3
(1) Preparation of bis-POSS polyether-bis (heptaisooctyl POSS) polyoxyethylene polyoxypropylene ether
In a 100mL three-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 3.55g (0.003mol) of semi-closed caged isooctyl heptapolysilsesquioxane trisilicol [ iO-T ] were weighed in this order7(OH)3]And 20.12g of acetone, and stirring and dissolving to prepare iO-T7(OH)3A diluted solution having a mass concentration of 15% was heated to 30 ℃, and 1.24g (about 0.0015mol) of a ═ 7, b ═ 3, a + b ═ 10, Mn of about 824, and a molecular formula (CH) synthesized in table 1 was added dropwise thereto3O)3SiC3H6O(C2H4O)7(C3H6O)3C3H6Si(OCH3)3Alpha, omega-bis (trimethoxysilylpropyl) polyoxyethylene polyoxypropylene ether (PECA-3) and 1 drop of dibutyltin diacetate catalyst, in the system, iO-T7(OH)3Stirring and uniformly mixing the mixture and PECA-3 according to the molar ratio of 1:0.5, then continuously carrying out polycondensation reaction for 10 hours at the temperature of 30 ℃, and evaporating the solvent under reduced pressure after the reaction is finished to obtain about 5.55g of the total compound, wherein the structure of the compound is shown as the formula (1), and R is i-C8H17Bis (heptaisooctyl POSS) polyoxyethylene polyoxypropylene ether (DPPE-3) which is a bis POSS polyether of (isooctyl), a-7, b-3, a + b-10.
(2) Preparation and molding of bis (heptaisooctyl POSS) polyoxyethylene polyoxypropylene ether hybrid PMMA resin
Weighing 2.0g of DPPE-3, 10g of MMA, 1% of free radical initiator AIBME (1.1 g), and tributyl phosphate (0.1 g) plasticizer according to the mass ratio of DPPE-3 to MMA being 20:100, stirring and uniformly mixing, heating to 55 ℃ for reaction for 40min to obtain a system with the viscosity of about 392mPa.s, cooling to room temperature, pouring the obtained viscous liquid into the container with the volume (length, width and depth) of 10 x 0.4cm3Sealing the polytetrafluoroethylene mold (leaving an exhaust hole), then heating to 90 ℃ for secondary reaction and molding for 2h, cooling to room temperature after the reaction is finished, and obtaining a transparent solid sample, namely the bis (heptaisooctyl POSS) polyoxyethylene polyoxypropylene ether hybrid PMMA resin, which is recorded as DPMA-3.
Example 4
(1) Preparation of bis-POSS polyether-bis (heptaisobutyl POSS) polyoxyethylene polyoxypropylene ether
In a 100mL three-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 3.20g (0.004mol) of semi-closed caged isobutylheptapolysilsesquioxane trisilol [ iBu-T ] was weighed in this order7(OH)3]And 23.47g of a mixed solvent of ethylene glycol dimethyl ether/hexane (mass ratio: 2: 1) were stirred and dissolved to prepare iBu-T7(OH)3A diluted solution having a mass concentration of 12% was added, and then 2.72g (0.002mol) of a ═ 10, b ═ 10, a + b ═ 20, Mn about 1362, and a molecular formula of (CH) synthesized in table 1 were added3O)3SiC3H6O(C2H4O)10(C3H6O)10C3H6Si(OCH3)3Alpha, omega-bis (trimethoxysilylpropyl) polyoxyethylene polyoxypropylene ether (PECA-4) and 1 drop dioctyltin diacetate catalyst in the system iBu-T7(OH)3Stirring and uniformly mixing the mixture and PECA-4 according to the molar ratio of 1:0.5, then continuously carrying out polycondensation reaction for 16h at the temperature of 30 ℃, and evaporating the solvent under reduced pressure after the reaction is finished to obtain about 5.92g of the compound with the structure shown in formula (1) and R ═ i-C4H9Bis (heptaisobutyl POSS) polyoxyethylene polyoxypropylene ether (DPPE-4), a bis POSS polyether of (isobutyl), a 10, b 10, a + b 20.
(2) Preparation and molding of bis (heptaisobutyl POSS) polyoxyethylene polyoxypropylene ether hybrid PMMA resin
Weighing 1.8g of DPPE-4, 10g of MMA, 0.5% of free radical initiator BPO (0.05 g), and 0.1g of plasticizer dibutyl phthalate in sequence according to the mass ratio of DPPE-4 to MMA being 18:100, uniformly stirring, heating to 52 ℃ for reaction for 30min until the system viscosity is 210mPa.s, cooling to room temperature, pouring the obtained viscous liquid into a container with the volume (length, width and depth) of 10 x 0.4cm3Sealing the polytetrafluoroethylene mold (leaving an exhaust hole), then heating to 85 ℃ for secondary reaction molding for 2h, after the reaction is finished, cooling to room temperature to obtain a transparent solid sample, namely the bis (heptaisobutyl POSS) polyoxyethylene polyoxypropylene ether hybrid PMMA resin, which is recorded as DPMA-4.
Example 5
(1) Preparation of bis-POSS polyether-bis (heptaisobutyl POSS) polyoxyethylene ether
In a 100mL three-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 3.5g (0.0044mol) of a half-closed caged isobutylheptasilsesquioxane trisilol [ iBu-T ] was weighed in this order7(OH)3]And 19.83g of tetrahydrofuran/chloroform (mass ratio: 1) were added, and the mixture was dissolved by stirring to prepare iBu-T7(OH)3A diluted solution having a mass concentration of 15% was added, and then 1.72g (0.0022mol) of a ═ 10, b ═ 0, a + b ═ 10, Mn about 782, and a molecular formula (CH) synthesized in table 1 was added3O)3SiC3H6O(C2H4O)10C3H6Si(OCH3)3Alpha, omega-bis (trimethoxysilylpropyl) polyoxyethylene ether (PECA-5) and 1 drop of dioctyltin dilaurate catalyst in the system, iBu-T7(OH)3Stirring and uniformly mixing the mixture and PECA-5 according to the molar ratio of 1:0.5, then continuously carrying out polycondensation reaction for 15h at the temperature of 20 ℃, and evaporating the solvent under reduced pressure to obtain about 5.22g of the total compound, wherein the structural formula of the compound is shown in formula (1), and R is i-C4H9Bis (heptaisobutyl POSS) polyoxyethylene ether (DPPE-5), a bis POSS polyether of (isobutyl), a 10, b 0, a + b 10.
(2) Preparation and molding of bis (heptaisobutyl POSS) polyoxyethylene ether hybrid PMMA resin
Weighing 1.2g of DPPE-5, 10g of MMA and 0.44% of free radical initiator AIBN (about 0.044 g) in terms of the mass of the MMA in a mass ratio of the DPPE-5 to the MMA of 12:100 in sequence, stirring and uniformly mixing, heating to 57 ℃ for prepolymerization reaction for 35min to obtain a system with the viscosity of about 280mPa.s, cooling to room temperature, pouring the obtained viscous liquid into a container with the volume (length, width and depth) of 10 x 0.4cm3Sealing the polytetrafluoroethylene mold (leaving an exhaust hole), then heating to 80 ℃ for secondary molding reaction for 2h, cooling to room temperature after the reaction is finished, and obtaining a transparent solid sample, namely the bis (heptaisobutyl POSS) polyoxyethylene ether hybrid PMMA resin, which is recorded as DPMA-5.
The properties of the samples of DPMA solid resin prepared in examples 1 to 5 were measured as follows: the light transmittance (T%) of the resin is measured by using a Cary 5000 type ultraviolet-visible spectrophotometer, and the wavelength range is 200-800 nm; glass transition temperature (Tg) as measured by a Differential Scanning Calorimeter (DSC) of German Steady instruments manufacturing Ltd, and a temperature rise rate of 10 ℃/min; scratch or scratch resistance: 0000 for reference to GB/T9279-1988 method#The scratch test evaluation generated by 5 times of reciprocating friction of steel wool on the surface of the resin under the condition of 300g of load; in addition, PMMA resin which is not modified by the double polyether POSS and is prepared by only using MMA in the same way is used as the reference of the invention, and the measurement results are shown in the table 2.
TABLE 2 measurement results of Dual POSS polyether hybrid PMMA resin and reference Properties
Figure GDA0001933501690000091
● has a general scratch resistance, a good ¬ resistance, a good ═ major-.

Claims (7)

1. A preparation method of a double POSS polyether hybrid PMMA resin is characterized by comprising the following steps: the method comprises the following steps:
dissolving alpha, omega-bis POSS polyether DPPE into methyl methacrylate MMA monomer by using true solution, adding 0.3-1.0% of free radical initiator and 1% of plasticizer by mass of MMA, uniformly stirring, heating to 50-80 ℃, prepolymerizing for 10-60min, cooling to room temperature after the viscosity of the system reaches 100-500mPa.s, and carrying out secondary reaction forming at 80-90 ℃ to obtain bis POSS polyether hybrid PMMA resin;
the structural formula of the double POSS polyether DPPE is as follows:
Figure 453712DEST_PATH_IMAGE001
（Ⅰ）；
in the formula, R is one or more of isobutyl, isooctyl, octyl and phenyl; a + b = (3-25).
2. The method of claim 1, wherein: the mass ratio of the double POSS polyether DPPE to the methyl methacrylate monomer MMA is DPPE: MMA = (5-25): 100.
3. the method of claim 1, wherein: the bis POSS polyether DPPE is obtained by a process comprising the steps of:
semi-closed cage-shaped oligomeric silsesquioxane trisilicol T7(OH)3Carrying out polycondensation reaction with a hexafunctional silane coupling agent alpha, omega-bis (trialkoxy silicon propyl) polyether PECA to obtain alpha, omega-bis POSS polyether DPPE;
the hexafunctional silane coupling agent alpha, omega-bis (trialkoxysilylpropyl) polyether PECA is one or more of alpha, omega-bis (trimethoxysilylpropyl) polyoxyethylene polyoxypropylene ether, alpha, omega-bis (triethoxysilylpropyl) polyoxyethylene polyoxypropylene ether, alpha, omega-bis (trimethoxysilylpropyl) polyoxyethylene ether, alpha, omega-bis (triethoxysilylpropyl) polyoxyethylene ether, alpha, omega-bis (trimethoxysilylpropyl) polyoxypropylene ether and alpha, omega-bis (triethoxysilylpropyl) polyoxypropylene ether;
the semi-closed cage-shaped oligomeric silsesquioxane trisilicol T7(OH)3The oligomeric silsesquioxane has a molecular structure in which seven same organic groups and three silicon hydroxyl groups are connected, and the structural formula is as follows:
Figure 639974DEST_PATH_IMAGE002
（Ⅱ）；
in the formula, R is one or more of isobutyl, isooctyl, octyl or phenyl.
4. The method of claim 3, wherein: the alpha, omega-bis (trialkoxysilylpropyl) polyether PECA of the hexafunctional silane coupling agent is obtained by carrying out hydrosilylation addition reaction on trialkoxyhydrosilane TRS and diallyl polyether alpha, omega-ViPE, wherein the molar ratio of TRS to alpha to omega-ViPE in the reaction is 2.1: 1.
5. The method of claim 1, wherein: the method comprises the following specific steps:
weighing DPPE and methyl methacrylate MMA, adding 0.3-1.0% of free radical initiator and 1% of plasticizer by mass of MMA, uniformly stirring, heating to 50-80 ℃ for prepolymerization reaction for 10-60min, and cooling to room temperature after the viscosity of the system reaches 100-500 mPa.s.
6. The method of claim 5, wherein: the free radical initiator is azobisisobutyronitrile, benzoyl peroxide and dimethyl azobisisobutyrate; the plasticizer is dioctyl phthalate, dibutyl phthalate, tributyl phosphate, tributyl citrate and trioctyl citrate.
7. A bis POSS polyether hybrid PMMA resin prepared by the method of any one of claims 1-6.
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