CN103146146B - 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, particularly relate to a kind of epoxy nano composite material based on POSS with the controlled phase structure of reinforced effects, belong to 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 development in science and technology important directions.Under the promotion of this demand, increasing investigator illustrates huge research interest to organic-inorganic nanocomposite.Why organic-inorganic nanocomposite is subject to the favor of investigators, because it combines the advantage (as high-modulus, high rigidity, nonflammable) of the advantage (as low density, easily processing, toughness) of polymkeric substance and inorganic materials.
In recent years, the inorganic nano-particle cluster of controlled architecture, the such as preparation appearing as organic-inorganic nanocomposite of Polyhedral Oligomeric silsesquioxane (Polyhedral oligomeric silsesquioxanes is called for short POSS) provides a kind of effective way.Polyhedral Oligomeric silsesquioxane (POSS) Typical molecular formula is (RSiO
15)
n(n>=4, R=H, alkyl, aryl or organo-functional group), silicon and oxygen form its inorganic structure centre, structure centre peripheral surround by organic substituent.Silica cage modle skeleton gives the excellent properties of its inorganic materials, and peripheral organic group provides chance for it participates in building matrix material again.Based on POSS polymer based nanocomposites can by POSS and polymkeric substance or response type copolymerizing and blending system be directly blended obtains, also by POSS reactive organic group grafting, be copolymerized on polymer chain.
As everyone knows, epoxy resin has become one of commercial resin be most widely used, no matter is electronics, space flight or automatic field, and epoxy resin all plays very important effect.But, the fatal weakness such as cross-linked network structure enbrittles greatly, fracture toughness property is low that epoxy resin ossifys because of himself.In recent years, utilize the monomer of POSS or polymkeric substance and epoxy resin to construct organic-inorganic nanocomposite to be subject to paying close attention to more and more widely with the research realizing epoxy improvement in performance.Multicomponent mixture is utilized to construct in epoxy systems " nanostructure strengthening " that nanostructure effectively can realize epoxy resin.
Maria J.Abad etc. (Abad, M.J., et al., Macromolecules, 2003.36 (9): p.3128-3135.) by two-step approach, the POSS of high-content is successfully introduced in epoxy resin, POSS and diamines with the mol ratio complete reaction of 1:1.(the Zeng such as Zeng, K., et al., Polymer, 2009.50 (2): p.685-695.) synthesized PCL, PEO poly bisphenol ether of seven (trifluoro propyl) POSS end-blocking and they are used as epoxy resin modification agent have carried out original position and construct nano composite material.(the Ni C such as Ni, et al., Colloid & Polymer Science, 2009,288 (4): 469-477.) reacted by butylglycidyl ether and aminocarbonyl propyl POSS, obtain the POSS with 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, pipe 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.Li Qi sides etc. (Li Qifang, Lu Peng, Chinese patent, CN102815071A) adopt unique monoisocyanates base cage-type silsesquioxane (POSS) to carry out graft modification to epoxy molecule, obtain the epoxy resin of high heat-resisting, low dielectric.Octa-epoxy POSS monomer is incorporated in epoxy resin structural system by Zhang Chunling etc. (Zhang Chunling, Liu Bo, Sun Guoen, Bai Xuetao, Chinese patent, CN102492116A), defines network cross-linked structure, is not separated.At present, the research utilizing the monomer of POSS or polymkeric substance and epoxy resin to construct organic-inorganic nanocomposite obtains 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, effective consistency improving POSS monomer and epoxy resin, is 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, POSS component is dispersed in epoxy systems with the form of nanoparticle, realizes constructing of the controlled phase structure of epoxy systems nano level, can effective reinforced epoxy.This epoxy nano composite material preparation method is simple, workable, is easy to realize industrialization.
The present invention is by the following technical solutions: step one, the preparation of POSS group block copolymer, adopts reversible addition to rupture transferring free-radical polymerization (RAFT) legal system for POSS group block copolymer; Step 2, based on the preparation of the epoxy nano composite material of POSS, by POSS group block copolymer, POSS monomer and epoxy resin melt blending, add solidifying agent after stirring into homogeneous phase, pour 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-.
The di-block copolymer that POSS group block copolymer of the present invention is is block with polymethyl monomethacryloxypropyl isobutyl-Polyhedral Oligomeric silsesquioxane (PMAiBuPOSS) and polymethylmethacrylate (PMMA), i.e. polymethyl monomethacryloxypropyl isobutyl-Polyhedral Oligomeric silsesquioxane-b-polymethylmethacrylate (PMAiBuPOSS-b-PMMA), molecular weight of copolymer M
nbe 20000 ~ 100000, dispersion index PDI=M
n/ M
w=1.1 ~ 1.5, wherein M
wrepresent weight-average molecular weight, M
nrepresent number-average molecular weight.
In technique scheme, step one: details are as follows for the preparation method of POSS group block copolymer:
POSS monomer, chain-transfer agent and initiator are pressed the configuration of metering in tetrahydrofuran solution by step 1); argon shield reaction is filled with after solution being placed in degassed three to five times of reactor frozen-thawed; reaction terminates rear liquid nitrogen freezing stopped reaction; add tetrahydrofuran (THF) dilute and use methanol extraction; repeated precipitation is to existing without POSS monomer, and drying obtains pink colour PMAiBuPOSS.
Step 2) PMAiBuPOSS, methyl methacrylate monomer (MMA) and initiator are pressed the configuration of metering in tetrahydrofuran solution; argon shield reaction is filled with after solution being placed in degassed three to five times of reactor frozen-thawed; reaction terminates rear liquid nitrogen freezing stopped reaction; add tetrahydrofuran (THF) dilute and use methanol extraction; repeated precipitation is to existing without PMAiBuPOSS and monomer; drying obtains pale pink POSS group block copolymer, i.e. PMAiBuPOSS-b-PMMA.
In step 1), described temperature of reaction is 65 DEG C, and the reaction times is 24 ~ 48h, preferred 48h; The mol ratio of POSS monomer and chain-transfer agent is 10 ~ 50, preferably 20; The mol ratio of chain-transfer agent and initiator is 1 ~ 20, preferably 5.
In step 2) in, described temperature of reaction is 65 DEG C, and the reaction times is 12 ~ 24h, preferred 24h; The mol ratio of MMA and PMAiBuPOSS is 200 ~ 2000, preferably 800; The mol ratio of chain-transfer agent and initiator is 5 ~ 20, preferably 20.
Above-mentioned initiator is Diisopropyl azodicarboxylate (AIBN) or benzoyl peroxide BPO; Chain-transfer agent adopts dithiobenzoic acid cumyl ester (CDB) or benzyl dithiobenzoate 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) by POSS monomer, epoxy resin and above-mentioned prepare gained POSS group block copolymer by metering than being placed in reactor, melt blending, one-tenth homogeneous phase after continue stirring 2 ~ 4h, obtain POSS and the blended presoma of epoxy;
2) in POSS and the blended presoma of epoxy, solidifying agent is added, continue stirring 10 ~ 20min, after solidifying agent fully dissolves, blend is poured in mould, after temperature programming solidification, 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 Commercial epoxy E-51; Solidifying agent can be epoxy amine curing agent, and preferably 4,4 '-methylene radical-bis--(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, be, 1 ~ 100:100:1 ~ 100 in mass ratio.
Said procedure elevated cure temperature is set as: 135 DEG C of insulation 14h; Be warming up to 190 DEG C of insulation 4h.
The epoxy nano composite material tool with controlled phase structure based on POSS of the present invention has the following advantages:
1) the prepared epoxy nano composite material based on POSS of the present invention, have homodisperse nano grade inorganic phase, " nanometer enhancing " effectiveness provides good mechanical property based on the epoxy nano composite material of POSS polymer prepared by the present invention.POSS group block copolymer is using 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, PMMA block can dissolve each other with epoxy resin, therefore, POSS base prepared by the present invention is easy to form micella in the self-assembly of epoxy-resin systems situ, original position to be formed with POSS monomer and POSS block as core, take PMMA as the rich inorganic phase nanoparticle of hat, epoxy resin is played to the effectiveness of " nanometer enhancing ".Its principle schematic as shown in Figure 1.
2) the present invention adopts the common and blended preparation of epoxy systems of POSS group block copolymer and POSS monomer based on the epoxy nano composite material of POSS polymer, POSS group block copolymer in position self-assembly is formed while micella, compatibilization is played to POSS monomer and epoxy blend, effectively improves the simple problem using the poor compatibility occurred during the monomer modified epoxy resin of POSS.Meanwhile, POSS group block copolymer and POSS monomer are common blended with epoxy systems, 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, adopt direct melt-mixing method to prepare, preparation method is simple, is easy to industrialization, has larger prospect.
Accompanying drawing explanation
Fig. 1 is POSS group block copolymer primary reconstruction and the principle model schematic diagram of increase-volume POSS monomer and epoxy blend system, wherein, A) be the model of POSS group block copolymer and molecular structural formula; B) be model and the molecular structural formula of POSS monomer; C) be the microcosmic dispersion pattern model with the epoxy nano composite material of controlled phase structure based on POSS.
Fig. 2 is the epoxy nano composite material sample with controlled phase structure of embodiment 1 gained based on POSS, and scanning electron microscope (SEM) observes microsctructural photograph.Sample, with after methylene dichloride etching, is observed for SEM after metal spraying; In photo, shrinkage pool is the inorganic phase region etched by methylene dichloride.
In Fig. 3, a is that pure epoxy resin E-51 solidifies rear sample DMTA test result completely; B is the epoxy nano composite material sample with controlled phase structure of embodiment 1 gained based on POSS, and DMTA test result is.X-coordinate is temperature, and ordinate zou is mechanical loss angle tangent value, its peak value reflection glass transition temperature Tg.
Embodiment
Below provide the specific embodiment party with the epoxy nano composite material of 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 system; monomer concentration is 0.7mol/L; argon shield reaction 48h is filled with after solution being placed in degassed three to five times of reactor frozen-thawed; reaction terminates rear liquid nitrogen freezing stopped reaction; add the dilution of a small amount of tetrahydrofuran (THF); precipitate in instillation methyl alcohol; drying precipitate is sampled nuclear-magnetism test; repeat this step repeated precipitation to existing without POSS monomer, drying obtains pink colour PMAiBuPOSS.Measure than methyl methacrylate monomer (MMA): PMAiBuPOSS by mol: initiator (AIBN)=16000: 20: 1 configuration tetrahydrofuran solution system, monomer concentration is 4mol/L, argon shield reaction 20h is filled with after solution being placed in degassed three to five times of reactor frozen-thawed, reaction terminates rear liquid nitrogen freezing stopped reaction, add the dilution of a small amount of tetrahydrofuran (THF), precipitate in instillation methyl alcohol, drying precipitate is sampled nuclear-magnetism test, repeat this step repeated precipitation to existing without PMAiBuPOSS and monomer, drying obtains pale pink POSS group block copolymer, i.e. PMAiBuPOSS-b-PMMA.
By POSS monomer, epoxy resin with above-mentionedly prepare 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 stirring 2 ~ 4h after becoming homogeneous phase, obtain POSS and the blended presoma of epoxy.In blended presoma, add appropriate solidifying agent (as: in 100g epoxy E-51, adding MCDEA solidifying agent 48.45g), continue stirring 10 ~ 30min, after solidifying agent fully dissolves, blend is poured in mould, program Solidification: 135 DEG C of insulation 14h; Be warming up to 190 DEG C of insulation 4h.Obtain the epoxy nano composite material with controlled phase structure based on POSS of yellow transparent, for DMTA test, the performance test results is in table 1.
Embodiment 2
Preparation POSS monomer (MAiBuPOSS): chain-transfer agent (CDB): initiator (AIBN)=20: 1: 0.2 tetrahydrofuran solution system; monomer concentration is 0.7mol/L; argon shield reaction 48h is filled with after solution being placed in degassed three to five times of reactor frozen-thawed; reaction terminates rear liquid nitrogen freezing stopped reaction; add the dilution of a small amount of tetrahydrofuran (THF); precipitate in instillation methyl alcohol; drying precipitate is sampled nuclear-magnetism test; repeat this step repeated precipitation to existing without POSS monomer, drying obtains pink colour PMAiBuPOSS.Measure than methyl methacrylate monomer (MMA): PMAiBuPOSS by mol: initiator (AIBN)=16000: 20: 1 configuration tetrahydrofuran solution system, monomer concentration is 4mol/L, argon shield reaction 40h is filled with after solution being placed in degassed three to five times of reactor frozen-thawed, reaction terminates rear liquid nitrogen freezing stopped reaction, add the dilution of a small amount of tetrahydrofuran (THF), precipitate in instillation methyl alcohol, drying precipitate is sampled nuclear-magnetism test, repeat this step repeated precipitation to existing without PMAiBuPOSS and monomer, drying obtains pale pink POSS group block copolymer, i.e. PMAiBuPOSS-b-PMMA.All the other steps are with embodiment 1, and its performance test results is in table 1.
Embodiment 3
Preparation POSS monomer (MAiBuPOSS): chain-transfer agent (CDB): initiator (AIBN)=30: 1: 0.2 tetrahydrofuran solution system; monomer concentration is 0.7mol/L; argon shield reaction 48h is filled with after solution being placed in degassed three to five times of reactor frozen-thawed; reaction terminates rear liquid nitrogen freezing stopped reaction; add the dilution of a small amount of tetrahydrofuran (THF); precipitate in instillation methyl alcohol; drying precipitate is sampled nuclear-magnetism test; repeat this step repeated precipitation to existing without POSS monomer, drying obtains pink colour PMAiBuPOSS.Measure than methyl methacrylate monomer (MMA): PMAiBuPOSS by mol: initiator (AIBN)=16000: 20: 1 configuration tetrahydrofuran solution system, monomer concentration is 4mol/L, argon shield reaction 20h is filled with after solution being placed in degassed three to five times of reactor frozen-thawed, reaction terminates rear liquid nitrogen freezing stopped reaction, add the dilution of a small amount of tetrahydrofuran (THF), precipitate in instillation methyl alcohol, drying precipitate is sampled nuclear-magnetism test, repeat this step repeated precipitation to existing without PMAiBuPOSS and monomer, drying obtains pale pink POSS group block copolymer, i.e. PMAiBuPOSS-b-PMMA.All the other steps are with embodiment 1, and its performance test results is in table 1.
Embodiment 4
Similar to Example 1, its difference is POSS monomer, epoxy resin and prepares 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 is in table 1.
Embodiment 5
Similar to Example 1, its difference is POSS monomer, epoxy resin and prepares 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 is in table 1.
Embodiment 6
Similar to Example 1, its difference is POSS monomer, epoxy resin and prepares 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 is in table 1.
Table 1 is based on the performance test results with the epoxy nano composite material of controlled phase structure of POSS
| Sample | Inorganic domain size (nm) | Second-order transition temperature (DEG C) | 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 (8)
1. based on a preparation method for the epoxy nano composite material of POSS, it is characterized in that step one, the preparation of POSS group block copolymer, adopt reversible addition to rupture transferring free-radical polymerization (RAFT) legal system for POSS group block copolymer; Step 2, based on the preparation of the epoxy nano composite material of POSS, by POSS group block copolymer, POSS monomer and epoxy resin melt blending, add solidifying agent after stirring into homogeneous phase, pour mould program Solidification into, prepare the epoxy nano composite material based on POSS, described POSS monomer is methacryloxypropyl isobutyl-POSS (MAiBuPOSS), and its structural formula is as follows:
Wherein, R is-iBu, isobutyl-;
The di-block copolymer that described POSS group block copolymer is is block with polymethyl monomethacryloxypropyl isobutyl-Polyhedral Oligomeric silsesquioxane (PMAiBuPOSS) and polymethylmethacrylate (PMMA), i.e. polymethyl monomethacryloxypropyl isobutyl-Polyhedral Oligomeric silsesquioxane-b-polymethylmethacrylate (PMAiBuPOSS-b-PMMA), molecular weight of copolymer M
nbe 20000 ~ 100000, dispersion index PDI=M
n/ M
w=1.1 ~ 1.5, wherein M
wrepresent weight-average molecular weight, M
nrepresent number-average molecular weight.
2. the preparation method of a kind of epoxy nano composite material based on POSS according to claim 1, is characterized in that described step one: details are as follows for the preparation method of POSS group block copolymer:
Step 1) POSS monomer, chain-transfer agent and initiator are pressed the configuration of metering in tetrahydrofuran solution, argon shield reaction is filled with after solution being placed in degassed three to five times of reactor frozen-thawed, reaction terminates rear liquid nitrogen freezing stopped reaction, add tetrahydrofuran (THF) dilute and use methanol extraction, repeated precipitation is to existing without POSS monomer, and drying obtains pink colour PMAiBuPOSS;
Step 2) PMAiBuPOSS, methyl methacrylate monomer (MMA) and initiator are pressed the configuration of metering in tetrahydrofuran solution; argon shield reaction is filled with after solution being placed in degassed three to five times of reactor frozen-thawed; reaction terminates rear liquid nitrogen freezing stopped reaction; add tetrahydrofuran (THF) dilute and use methanol extraction; repeated precipitation is to existing without PMAiBuPOSS and monomer; drying obtains pale pink POSS group block copolymer, i.e. PMAiBuPOSS-b-PMMA.
3. the preparation method of a kind of epoxy nano composite material based on POSS according to claim 2, it is characterized in that in step 1) in, described temperature of reaction is 65 DEG C, and the reaction times is the mol ratio of 24 ~ 48h, POSS monomer and chain-transfer agent is 10 ~ 50; The mol ratio of chain-transfer agent and initiator is 1 ~ 20.
4. the preparation method of a kind of epoxy nano composite material based on POSS according to claim 2, is characterized in that in step 2) in, described temperature of reaction is 65 DEG C, and 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.
5. the preparation method of a kind of epoxy nano composite material based on POSS according to claim 2, is characterized in that described initiator is Diisopropyl azodicarboxylate (AIBN) or benzoyl peroxide BPO; Chain-transfer agent adopts dithiobenzoic acid cumyl ester (CDB) or benzyl dithiobenzoate BDB, and described CDB structural formula is as follows:
6. the preparation method of a kind of epoxy nano composite material based on POSS according to claim 2, is characterized in that described step 2: based on the preparation method of the epoxy nano composite material of POSS, details are as follows:
1) by POSS monomer, epoxy resin and gained POSS group block copolymer by metering than being placed in reactor, melt blending, one-tenth homogeneous phase after continue stirring 2 ~ 4h, obtain POSS and the blended presoma of epoxy;
2) in POSS and the blended presoma of epoxy, solidifying agent is added, continue stirring 10 ~ 20min, after solidifying agent fully dissolves, blend is poured in mould, after temperature programming solidification, obtain the epoxy nano composite material with controlled phase structure based on POSS of yellow transparent.
7. the preparation method of a kind of epoxy nano composite material based on POSS according to claim 6, is characterized in that described epoxy resin is bisphenol A type epoxy resin; Solidifying agent is epoxy amine curing agent.
8. the preparation method of a kind of epoxy nano composite material based on POSS according to claim 6, is characterized in that described POSS monomer, epoxy resin and POSS group block copolymer, is in mass ratio, 1 ~ 100:100:1 ~ 100; Elevated cure temperature is set as: 135 DEG C of insulation 14h; Be warming up to 190 DEG C 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 |
| 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 |
| 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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