CN103146146A - Epoxy nanocomposite with controllable phase structure and based on polyhedral oligomeric silsesquioxanes (POSS) - Google Patents
Epoxy nanocomposite with controllable phase structure and based on polyhedral oligomeric silsesquioxanes (POSS) Download PDFInfo
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Abstract
The invention discloses an epoxy nanocomposite based on polyhedral oligomeric silsesquioxanes (POSS) and a preparation method of the epoxy nanocomposite based on the POSS and relates to the epoxy nanocomposite with a controllable phase structure capable of improving effect and based on the POSS. The preparation method includes the following steps of allocating a POSS monomer, a chain transfer agent and an initiating agent in a solution according to the measuring amount through a reversible addition-fragmentation chain transfer (RAFT) method, conducting freeze thaw and degassing through liquid nitrogen, charging argon shield to enable the mixture to react, and obtaining PMAiBuPOSS; further allocating PMAiBuPOSS, Methl Methacrylate monomer (MMA) and an initiating agent in a solution, and obtaining POSS base block copolymer , namely, PMAiBuPOSS-b-PMMA, through the RAFT; conducting melt blending on the POSS monomer, epoxy resin, the prepared POSS base block copolymer to obtain blend precursor of the POSS and the epoxy, adding in a curing agent, fully stirring, dissolving the mixture the curing agent, pouring the blend into a die, conducting temperature programming and curing, and obtaining the nanocomposite with the controllable phase structure and based on the POSS.
Description
Technical field
The present invention relates to a kind of epoxy nano composite material based on POSS and preparation method thereof, relate in particular to a kind of epoxy nano composite material based on POSS with controlled phase structure of reinforced effects, belong to the organic polymer material field.
Background technology
Along with develop rapidly and the progress of society, the functional novel material with multiple excellent properties has become the development in science and technology important directions.Under the promotion of this demand, increasing investigator has represented huge research interest to organic-inorganic nanocomposite.Why organic-inorganic nanocomposite is subject to investigators' favor, because it combines the advantage (as low density, easy processing, toughness) of polymkeric substance and the advantage (as high-modulus, high rigidity, nonflammable) of inorganic materials.
In recent years, the inorganic nano-particle cluster of controlled architecture, for example the preparation that appears as organic-inorganic nanocomposite of polyhedron oligomeric silsesquioxanes (Polyhedral oligomeric silsesquioxanes is called for short POSS) provides a kind of effective way.The typical molecular formula of polyhedron oligomeric silsesquioxanes (POSS) is (RSiO
15)
n(n 〉=4, R=H, alkyl, aryl or organo-functional group), silicon and oxygen consist of its inorganic structure centre, and the structure centre periphery is surrounded by organic substituent.Silica cage modle skeleton is given the excellent properties of its inorganic materials, and peripheral organic group provides chance for it participates in building matrix material again.Can obtain by POSS and polymkeric substance or the direct blend of response type copolymerizing and blending system based on the polymer based nanocomposites of POSS, reactive organic group grafting that also can be by POSS, be copolymerized on polymer chain.
As everyone knows, epoxy resin has become one of commercialization resin that is most widely used, no matter is electronics, space flight or automatic field, and epoxy resin is all being brought into play very important effect.Yet epoxy resin is because of fatal weakness such as the cross-linked network structure that himself ossifys enbrittle greatly, fracture toughness property is low.In recent years, utilizing the monomer of POSS or polymkeric substance and epoxy resin to construct organic-inorganic nanocomposite is subject to paying close attention to more and more widely with the research that realizes the epoxy improvement in performance.Utilize multicomponent mixture to construct " nanostructure reinforcement " that nanostructure can effectively realize epoxy resin in epoxy systems.
Maria J.Abad etc. (Abad, M.J., et al., Macromolecules, 2003.36 (9): p.3128-3135.) successfully introduce in epoxy resin by the POSS of two-step approach with high-content, POSS and diamines are with the mol ratio complete reaction of 1:1.(Zeng, K., et al., Polymer, 2009.50 (2): p.685-695.) synthesized PCL, the PEO poly bisphenol ether of seven (trifluoro propyl) POSS end-blocking and come them original position to construct nano composite material as the epoxy resin modification agent such as Zeng.(Ni C, et al., the Colloid﹠amp such as Ni; Polymer Science, 2009,288 (4): 469-477.) by butylglycidyl ether and aminocarbonyl propyl POSS reaction, obtained having the POSS of reactive hydroxyl and amido, it joins in epoxy resin, can improve mechanical property and the thermal characteristics of epoxy resin.Open and increase equality (Zhang Zengping, Liang Guozheng, Liu Jisan, Xie Jianqiang, Guan Xinghua, cage-type silsesquioxane POSS-epoxy hybrid resins system curing reaction Kinetics and performance study, China's tackiness agent, 2007,16(9): 1-4) adopt cage modle oligomeric silsesquioxanes (POSS) modified bisphenol A type epoxy resin E51, obtain the organic inorganic hybridization resin that thermotolerance improves.(Chinese patent CN102815071A) adopts unique monoisocyanates base cage-type silsesquioxane (POSS) to carry out graft modification to the epoxy molecule, obtains the epoxy resin of high heat-resisting, low dielectric for Li Qifang, Lu Peng in Li Qi sides etc.Zhang Chunling etc. (Zhang Chunling, Liu Bo, Sun Guoen, Bai Xuetao, Chinese patent CN102492116A) is incorporated into octa-epoxy POSS monomer in the epoxy resin structural system, has formed the network cross-linked structure, is not separated.At present, the research that utilizes the monomer of POSS or polymkeric substance and epoxy resin to construct organic-inorganic nanocomposite has obtained greater advance, but above-mentioned research report does not all relate to a kind of increase-volume POSS monomer of POSS group block copolymer and the epoxy nano composite material of epoxy direct physical co-mixing system.
Summary of the invention
The present invention aims to provide a kind ofly has epoxy nano composite material of controlled phase structure and preparation method thereof based on POSS.
A kind of epoxy nano composite material with controlled phase structure based on POSS involved in the present invention adopts POSS group block copolymer increase-volume POSS monomer and the direct co-mixing system of epoxy resin, effectively improve the consistency of POSS monomer and epoxy resin, be prepared into the epoxy nano composite material based on POSS with the controlled phase structure of nano level.In above-mentioned epoxy nano composite material, the POSS component is dispersed in epoxy systems with the form of nanoparticle, realizes constructing of the controlled phase structure of epoxy systems nano level, effectively reinforced epoxy.The preparation method is simple for this epoxy nano composite material, and is workable, is easy to realize industrialization.
The present invention is by the following technical solutions: step 1, and the standby POSS group block copolymer of reversible addition fracture transferring free-radical polymerization (RAFT) legal system is adopted in the preparation of POSS group block copolymer; Step 2 is based on the preparation of the epoxy nano composite material of POSS, with the POSS group block copolymer, POSS monomer and epoxy resin melt blending, add solidifying agent after stirring into homogeneous phase, pour the mould program Solidification into, prepare the epoxy nano composite material based on POSS.
POSS monomer of the present invention is methacryloxypropyl isobutyl-POSS(MAiBuPOSS), its structural formula is as follows:
Wherein, R is-iBu, isobutyl-.
POSS group block copolymer of the present invention is the di-block copolymer take polymethyl acyl-oxygen propyl group isobutyl-polyhedron oligomeric silsesquioxanes (PMAiBuPOSS) and polymethylmethacrylate (PMMA) as block, be polymethyl acyl-oxygen propyl group isobutyl-polyhedron oligomeric silsesquioxanes-b-polymethylmethacrylate (PMAiBuPOSS-b-PMMA), molecular weight of copolymer M
nBe 20000～100000, dispersion index PDI=M
n/ M
w=1.1～1.5, M wherein
wRepresent weight-average molecular weight, M
nRepresent number-average molecular weight.
In technique scheme, step 1: details are as follows for the preparation method of POSS group block copolymer:
Step 1) is pressed the configuration of metering in tetrahydrofuran solution with POSS monomer, chain-transfer agent and initiator; solution is placed in reactor with being filled with the argon shield reaction after degassed three to five times of frozen-thawed; after finishing, reaction uses the liquid nitrogen freezing stopped reaction; add tetrahydrofuran (THF) to dilute and use methanol extraction; till repeated precipitation extremely existed without the POSS monomer, drying obtained pink colour PMAiBuPOSS.
Step 2) PMAiBuPOSS, methyl methacrylate monomer (MMA) and initiator are pressed the configuration of metering in tetrahydrofuran solution; solution is placed in reactor with being filled with the argon shield reaction after degassed three to five times of frozen-thawed; after finishing, reaction uses the liquid nitrogen freezing stopped reaction; add tetrahydrofuran (THF) to dilute and use methanol extraction; repeated precipitation is extremely without till PMAiBuPOSS and monomer existence; drying obtains pale pink POSS group block copolymer, i.e. PMAiBuPOSS-b-PMMA.
In step 1), described temperature of reaction is 65 ℃, and the reaction times is 24～48h, preferred 48h; The mol ratio of POSS monomer and chain-transfer agent is 10～50, preferred 20; The mol ratio of chain-transfer agent and initiator is 1～20, preferred 5.
In step 2) in, described temperature of reaction is 65 ℃, the reaction times is 12～24h, preferred 24h; The mol ratio of MMA and PMAiBuPOSS is 200～2000, preferred 800; The mol ratio of chain-transfer agent and initiator is 5～20, preferred 20.
Above-mentioned initiator is Diisopropyl azodicarboxylate (AIBN) or benzoyl peroxide BPO; Chain-transfer agent adopts dithiobenzoic acid cumyl ester (CDB) or dithiobenzoic acid benzyl ester BDB, preferred CDB, and its structural formula is as follows:
In technical scheme of the present invention, step 2: details are as follows based on the preparation method of the epoxy nano composite material of POSS:
1) with POSS monomer, epoxy resin and above-mentioned preparation gained POSS group block copolymer by metering than being placed in reactor, melt blending continues stirring 2～4h after becoming homogeneous phase, obtains POSS and epoxy blend presoma;
2) add solidifying agent in POSS and epoxy blend presoma, continue to stir 10～20min, after solidifying agent fully dissolves, blend is poured in mould, after temperature programming is solidified, obtain the epoxy nano composite material with controlled phase structure based on POSS of yellow transparent.
Above-mentioned epoxy resin can be bisphenol A type epoxy resin, preferred commercially available epoxy E-51; Solidifying agent can be the epoxy amine curing agent, preferred 4,4 '-methylene radical-two-(3-chloro-2,6-diethyl aniline) (MCDEA), hardener dose calculates according to epoxy resin quality and epoxy equivalent (weight).
Above-mentioned POSS monomer, epoxy resin and POSS group block copolymer are 1～100:100:1～100 in mass ratio.
Said procedure intensification solidification value is set as: 135 ℃ of insulation 14h; Be warming up to 190 ℃ of insulation 4h.
The epoxy nano composite material with controlled phase structure based on POSS of the present invention has following advantage:
1) the prepared epoxy nano composite material based on POSS of the present invention, have homodisperse nano grade inorganic phase, and " nanometer enhancing " effectiveness provides mechanical property preferably for the prepared epoxy nano composite material based on the POSS polymkeric substance of the present invention.The POSS group block copolymer with PMAiBuPOSS and PMMA as block; According to " similar person is compatible " principle, PMAiBuPOSS block and POSS monomer have excellent compatibility, simultaneously, because PMMA and epoxy resin have close solubility parameters, the PMMA block can dissolve each other with epoxy resin, therefore, the prepared POSS base of the present invention is easy to form micella in the self-assembly of epoxy-resin systems situ, original position forms take POSS monomer and POSS block as core, take the rich inorganic phase nanoparticle of PMMA as hat, epoxy resin is played the effectiveness of " nanometer enhancing ".Its principle schematic as shown in Figure 1.
2) the present invention adopts that POSS group block copolymer and POSS monomer are common prepares epoxy nano composite material based on the POSS polymkeric substance with the epoxy systems blend, the POSS group block copolymer is when self-assembly forms micella in position, POSS monomer and epoxy blend are played compatibilization, the poor problem of consistency that has occured when effectively having improved the monomer modified epoxy resin of simple use POSS.Simultaneously, POSS group block copolymer and POSS monomer common with the epoxy systems blend, for the preparation of the organic-inorganic epoxy nano composite material of the larger inorganic component content of realization provides new way.
3) the prepared epoxy nano composite material based on POSS of the present invention adopts direct melt-mixing method preparation, and the preparation method is simple, is easy to industrialization, has larger prospect.
Description of drawings
Fig. 1 is the principle model schematic diagram of the original position self-assembly of POSS group block copolymer and increase-volume POSS monomer and epoxy blend system, wherein, A) is model and the molecular structural formula of POSS group block copolymer; B) be model and the molecular structural formula of POSS monomer; C) disperse the pattern model for the microcosmic based on the epoxy nano composite material with controlled phase structure of POSS.
Fig. 2 be embodiment 1 gained based on the epoxy nano composite material sample with controlled phase structure of POSS, scanning electron microscope (SEM) is observed the microtexture photo.After sample is used the methylene dichloride etching, be used for SEM after metal spraying and observe; In photo, shrinkage pool is by the inorganic phase region of methylene dichloride etching.
In Fig. 3, a is that pure epoxy resin E-51 solidifies rear sample DMTA test result fully; B be embodiment 1 gained based on the epoxy nano composite material sample with controlled phase structure of POSS, the DMTA test result is.X-coordinate is temperature, and ordinate zou is the mechanical loss angle tangent value, its peak value reflection glass transition temperature Tg.
Embodiment
Below provide the specific embodiment party of the epoxy nano composite material with controlled phase structure based on POSS of the present invention
Embodiment 1
Preparation POSS monomer (MAiBuPOSS): chain-transfer agent (CDB): initiator (AIBN)=20: 1: 0.2 tetrahydrofuran solution systems; monomer concentration is 0.7mol/L; solution is placed in reactor with being filled with argon shield reaction 48h after degassed three to five times of frozen-thawed; after finishing, reaction uses the liquid nitrogen freezing stopped reaction; add a small amount of tetrahydrofuran (THF) dilution; splash in methyl alcohol and precipitate; with take a sample nuclear-magnetism test of drying precipitate; repeat this step repeated precipitation extremely without till the existence of POSS monomer, drying obtains pink colour PMAiBuPOSS.measure by mol than methyl methacrylate monomer (MMA): PMAiBuPOSS: initiator (AIBN)=16000: 20: 1 configuration tetrahydrofuran solution systems, monomer concentration is 4mol/L, solution is placed in reactor with being filled with argon shield reaction 20h after degassed three to five times of frozen-thawed, after finishing, reaction uses the liquid nitrogen freezing stopped reaction, add a small amount of tetrahydrofuran (THF) dilution, splash in methyl alcohol and precipitate, with take a sample nuclear-magnetism test of drying precipitate, repeat this step repeated precipitation extremely without till PMAiBuPOSS and monomer existence, drying obtains pale pink POSS group block copolymer, be PMAiBuPOSS-b-PMMA.
With POSS monomer, epoxy resin and above-mentioned preparation gained POSS group block copolymer POSS monomer in mass ratio: epoxy resin: POSS group block copolymer=5:100:1 is placed in reactor, melt blending, continue to stir 2～4h after becoming homogeneous phase, obtain POSS and epoxy blend presoma.Add appropriate solidifying agent (as: in 100g epoxy E-51, adding MCDEA solidifying agent 48.45g) in the blend presoma, continue to stir 10～30min, after solidifying agent fully dissolves, blend is poured in mould into program Solidification: 135 ℃ of insulation 14h; Be warming up to 190 ℃ of insulation 4h.Obtain the epoxy nano composite material with controlled phase structure based on POSS of yellow transparent, be used for the DMTA test, the performance test results sees Table 1.
Embodiment 2
Preparation POSS monomer (MAiBuPOSS): chain-transfer agent (CDB): initiator (AIBN)=20: 1: 0.2 tetrahydrofuran solution systems; monomer concentration is 0.7mol/L; solution is placed in reactor with being filled with argon shield reaction 48h after degassed three to five times of frozen-thawed; after finishing, reaction uses the liquid nitrogen freezing stopped reaction; add a small amount of tetrahydrofuran (THF) dilution; splash in methyl alcohol and precipitate; with take a sample nuclear-magnetism test of drying precipitate; repeat this step repeated precipitation extremely without till the existence of POSS monomer, drying obtains pink colour PMAiBuPOSS.measure by mol than methyl methacrylate monomer (MMA): PMAiBuPOSS: initiator (AIBN)=16000: 20: 1 configuration tetrahydrofuran solution systems, monomer concentration is 4mol/L, solution is placed in reactor with being filled with argon shield reaction 40h after degassed three to five times of frozen-thawed, after finishing, reaction uses the liquid nitrogen freezing stopped reaction, add a small amount of tetrahydrofuran (THF) dilution, splash in methyl alcohol and precipitate, with take a sample nuclear-magnetism test of drying precipitate, repeat this step repeated precipitation extremely without till PMAiBuPOSS and monomer existence, drying obtains pale pink POSS group block copolymer, be PMAiBuPOSS-b-PMMA.All the other steps are with embodiment 1, and its performance test results sees Table 1.
Embodiment 3
Preparation POSS monomer (MAiBuPOSS): chain-transfer agent (CDB): initiator (AIBN)=30: 1: 0.2 tetrahydrofuran solution systems; monomer concentration is 0.7mol/L; solution is placed in reactor with being filled with argon shield reaction 48h after degassed three to five times of frozen-thawed; after finishing, reaction uses the liquid nitrogen freezing stopped reaction; add a small amount of tetrahydrofuran (THF) dilution; splash in methyl alcohol and precipitate; with take a sample nuclear-magnetism test of drying precipitate; repeat this step repeated precipitation extremely without till the existence of POSS monomer, drying obtains pink colour PMAiBuPOSS.measure by mol than methyl methacrylate monomer (MMA): PMAiBuPOSS: initiator (AIBN)=16000: 20: 1 configuration tetrahydrofuran solution systems, monomer concentration is 4mol/L, solution is placed in reactor with being filled with argon shield reaction 20h after degassed three to five times of frozen-thawed, after finishing, reaction uses the liquid nitrogen freezing stopped reaction, add a small amount of tetrahydrofuran (THF) dilution, splash in methyl alcohol and precipitate, with take a sample nuclear-magnetism test of drying precipitate, repeat this step repeated precipitation extremely without till PMAiBuPOSS and monomer existence, drying obtains pale pink POSS group block copolymer, be PMAiBuPOSS-b-PMMA.All the other steps are with embodiment 1, and its performance test results sees Table 1.
Embodiment 4
Similar to Example 1, its difference is POSS monomer, epoxy resin and preparation gained POSS group block copolymer POSS monomer in mass ratio: epoxy resin: POSS group block copolymer=10:100:1 is placed in reactor, melt blending.All the other steps are with embodiment 1, and its performance test results sees Table 1.
Embodiment 5
Similar to Example 1, its difference is POSS monomer, epoxy resin and preparation gained POSS group block copolymer POSS monomer in mass ratio: epoxy resin: POSS group block copolymer=20:100:1 is placed in reactor, melt blending.All the other steps are with embodiment 1, and its performance test results sees Table 1.
Embodiment 6
Similar to Example 1, its difference is POSS monomer, epoxy resin and preparation gained POSS group block copolymer POSS monomer in mass ratio: epoxy resin: POSS group block copolymer=10:100:5 is placed in reactor, melt blending.All the other steps are with embodiment 1, and its performance test results sees Table 1.
Table 1 is based on the performance test results of the epoxy nano composite material with controlled phase structure of POSS
| Sample | Inorganic phase region size (nm) | Second-order transition temperature (℃) | Storage modulus (dyn/cm 2,25℃） |
| Embodiment 1 | 50～100 | 193.4 | 2.43×10 10 |
| Embodiment 2 | 50～100 | 192.6 | 2.40×10 10 |
| Embodiment 3 | 100～200 | 189.7 | 2.55×10 10 |
| Embodiment 4 | 700～1000 | 188.1 | 2.64×10 10 |
| Embodiment 5 | 1000～1500 | 182.5 | 2.68×10 10 |
| Embodiment 6 | 100～200 | 193.1 | 2.70×10 10 |
| Pure epoxy resin E-51 | -------------- | 187.6 | 2.02×10 10 |
Claims (10)
1. one kind based on epoxy nano composite material of POSS and preparation method thereof, it is characterized in that step 1, and the standby POSS group block copolymer of reversible addition fracture transferring free-radical polymerization (RAFT) legal system is adopted in the preparation of POSS group block copolymer; Step 2 is based on the preparation of the epoxy nano composite material of POSS, with the POSS group block copolymer, POSS monomer and epoxy resin melt blending, add solidifying agent after stirring into homogeneous phase, pour the mould program Solidification into, prepare the epoxy nano composite material based on POSS.
2. the preparation method of a kind of epoxy nano composite material based on POSS according to claim 1, is characterized in that described POSS monomer is methacryloxypropyl isobutyl-POSS(MAiBuPOSS), its structural formula is as follows:
Wherein, R is-iBu, isobutyl-.
3. the preparation method of a kind of epoxy nano composite material based on POSS according to claim 1, it is characterized in that described POSS group block copolymer is the di-block copolymer take polymethyl acyl-oxygen propyl group isobutyl-polyhedron oligomeric silsesquioxanes (PMAiBuPOSS) and polymethylmethacrylate (PMMA) as block, be polymethyl acyl-oxygen propyl group isobutyl-polyhedron oligomeric silsesquioxanes-b-polymethylmethacrylate (PMAiBuPOSS-b-PMMA), molecular weight of copolymer M
nBe 20000～100000, dispersion index PDI=M
n/ M
w=1.1～1.5, M wherein
wRepresent weight-average molecular weight, M
nRepresent number-average molecular weight.
4. the preparation method of a kind of epoxy nano composite material based on POSS according to claim 1, it is characterized in that described step 1: details are as follows for the preparation method of POSS group block copolymer:
Step 1) is pressed the configuration of metering in tetrahydrofuran solution with POSS monomer, chain-transfer agent and initiator, solution is placed in reactor with being filled with the argon shield reaction after degassed three to five times of frozen-thawed, after finishing, reaction uses the liquid nitrogen freezing stopped reaction, add tetrahydrofuran (THF) to dilute and use methanol extraction, till repeated precipitation extremely existed without the POSS monomer, drying obtained pink colour PMAiBuPOSS;
Step 2) PMAiBuPOSS, methyl methacrylate monomer (MMA) and initiator are pressed the configuration of metering in tetrahydrofuran solution; solution is placed in reactor with being filled with the argon shield reaction after degassed three to five times of frozen-thawed; after finishing, reaction uses the liquid nitrogen freezing stopped reaction; add tetrahydrofuran (THF) to dilute and use methanol extraction; repeated precipitation is extremely without till PMAiBuPOSS and monomer existence; drying obtains pale pink POSS group block copolymer, i.e. PMAiBuPOSS-b-PMMA.
5. the preparation method of a kind of epoxy nano composite material based on POSS according to claim 4, is characterized in that in step 1), and described temperature of reaction is 65 ℃, and the reaction times is 24～48h, and the mol ratio of POSS monomer and chain-transfer agent is 10～50; The mol ratio of chain-transfer agent and initiator is 1～20.
6. the preparation method of a kind of epoxy nano composite material based on POSS according to claim 4, is characterized in that in step 2) in, described temperature of reaction is 65 ℃, the reaction times is 12～24h; The mol ratio of MMA and PMAiBuPOSS is 200～2000; The mol ratio of chain-transfer agent and initiator is 5～20.
7. the preparation method of a kind of epoxy nano composite material based on POSS according to claim 4, is characterized in that described initiator is Diisopropyl azodicarboxylate (AIBN) or benzoyl peroxide BPO; Chain-transfer agent adopts dithiobenzoic acid cumyl ester (CDB) or dithiobenzoic acid benzyl ester BDB, and its structural formula is as follows:
8. the preparation method of a kind of epoxy nano composite material based on POSS according to claim 1 is characterized in that described step 2: details are as follows based on the preparation method of the epoxy nano composite material of POSS:
1) with POSS monomer, epoxy resin and above-mentioned preparation gained POSS group block copolymer by metering than being placed in reactor, melt blending continues stirring 2～4h after becoming homogeneous phase, obtains POSS and epoxy blend presoma;
2) add solidifying agent in POSS and epoxy blend presoma, continue to stir 10～20min, after solidifying agent fully dissolves, blend is poured in mould, after temperature programming is solidified, obtain the epoxy nano composite material with controlled phase structure based on POSS of yellow transparent.
9. the preparation method of a kind of epoxy nano composite material based on POSS according to claim 8, is characterized in that described epoxy resin is bisphenol A type epoxy resin; Solidifying agent can be the epoxy amine curing agent.
10. the preparation method of a kind of epoxy nano composite material based on POSS according to claim 8, is characterized in that described POSS monomer, epoxy resin and POSS group block copolymer, is in mass ratio 1～100:100:1～100; The intensification solidification value is set as: 135 ℃ of insulation 14h; Be warming up to 190 ℃ of insulation 4h.
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| CN105037607A (en) * | 2015-06-12 | 2015-11-11 | 四川凯美克科技有限公司 | Cage oligomeric silsesquioxane modified polymethyl methacrylate |
| US11512339B2 (en) | 2016-12-22 | 2022-11-29 | Illumina, Inc. | Arrays including a resin film and a patterned polymer layer |
| US11932900B2 (en) | 2016-12-22 | 2024-03-19 | Illumina, Inc. | Arrays including a resin film and a patterned polymer layer |
| CN109786823A (en) * | 2019-01-22 | 2019-05-21 | 广东天劲新能源科技股份有限公司 | A kind of PMMA base method for preparing gel polymer electrolyte |
| CN112250878A (en) * | 2020-09-28 | 2021-01-22 | 厦门大学 | Thermally self-repairing recyclable epoxy resin and preparation method thereof |
| CN112250878B (en) * | 2020-09-28 | 2022-03-15 | 厦门大学 | Thermally self-repairing recyclable epoxy resin and preparation method thereof |
| CN113999614A (en) * | 2021-11-29 | 2022-02-01 | 国网山东省电力公司电力科学研究院 | High-solid anticorrosive paint with adjustable film forming property, and preparation method and application thereof |
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