CN1139614C - Epoxy resin solidified microsphere water-base system and its preparation method - Google Patents
Epoxy resin solidified microsphere water-base system and its preparation method Download PDFInfo
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- CN1139614C CN1139614C CNB001072161A CN00107216A CN1139614C CN 1139614 C CN1139614 C CN 1139614C CN B001072161 A CNB001072161 A CN B001072161A CN 00107216 A CN00107216 A CN 00107216A CN 1139614 C CN1139614 C CN 1139614C
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Abstract
The present invention relates to an epoxy resin solidified microsphere water-base system in which the weight ratio of epoxy resin solidified microspheres to the water is 1: 4 to 7: 3, wherein the particle diameter of the epoxy resin solidified microspheres is 10<2> nanometer to 10<1>micrometer. Epoxy resin and emulsifier are stirred uniformly according to the weight ratio of (10 to 99.9): (0.1 to 90), and a solidifying agent is added at 10 to 50 DEG C; then, solidifying reaction is carried out at 50 to 99 DEG C for 1 to 10 hours by stirring and adding water to prepare the epoxy resin compounded solidified microsphere water-base system. The epoxy resin solidified microsphere water-base system of the present invention has the characteristics of high strength, good heat resistance, etc., and the present invention can be used as a macromolecular modifier.
Description
The present invention relates to the polymeric hardener microballoon, particularly a kind of epoxy resin solidified microsphere and preparation method thereof.
The micron order polymer microsphere is in information industry, analytical chemistry, and biomedicine, many fields such as microelectronics all are with a wide range of applications.Because the size of micron order microballoon is between the product cut size (100-1000 μ m) that product cut size (0.1-0.7 μ m) that emulsion polymerization makes and suspension polymerization make, so the preparation of micron order polymer microsphere difficulty relatively.The traditional method for preparing this polymer microsphere is people such as Corner (Colloids Surf., 1981,3,119-129) people (Adv.Colloid Interface Sci. such as dispersion copolymerization method of Ti Chuing and Ugelstad, 1980,13,101-110) the seeding polymerization method of Ti Chuing.El-Aasser etc. (J.Polym.Sci., Polym.Chem.Ed., 1993,31,1393-1402) adopting diffuse-aggregate method to synthesize particle diameter is the poly (methyl methacrylate) micro-sphere of 2-10 μ m.Okubo M. etc. (ColloidPolym.Sci., 1991,269,222-226) adopt dynamic monomer swell method to carry out the substep seeding polymerization, synthesized the polystyrene microsphere of the about 7 μ m of particle diameter.But dispersion copolymerization method need make emulsion-stabilizing by dispersion stabilizer, seeding polymerization method long reaction time, and reaction conditions is wayward.And polymerization process generally is applicable to preparation addition polymer microballoon, and then experimental technique is loaded down with trivial details if be used for the preparation of polycondensate such as epoxide resin microballoon.
Polycondensate has excellent physicals, and the preparation of its aqueous based systems is the problem that people are concerned about always.Have good physicals such as Resins, epoxy, electrical insulation capability is good with the adhesiveproperties of various materials.Therefore, the research of aqueous epoxy resin dispersion system receives much attention in recent years.Recently, (Macromol.Chem.Phys. such as Katharina Landfester, 2000,201,1-5) adopt special letex polymerization (mini-emulsionpolymerization) method, under the ultrasonic wave effect with epoxy resin oligomer and diamines, the mixture of dithiol or bisphenol is prepared into emulsion by violent stirring in water, at high temperature carry out post polymerization then, make the particulate curing cross-linked, make the water-base emulsion that particle diameter is 30-600nm.But it is high that this method requires two components that polyaddition reaction takes place, and they should have low water-soluble, low viscosity, and also the emulsifying agent consumption is big.Different with aforesaid method; (Chem.J.Chin.Univ. such as Yang Zhenzhong; 1997; 18 (9), 1568-1570) propose to adopt phase inversion technique emulsification bisphenol A type epoxy resin, by controlling some parameters such as emulsifier type; concentration; emulsifying temperatures etc. can be controlled the degree of perfection of phase reversion, can obtain being of a size of nano level aqueous epoxy resin particulate or micron order Resins, epoxy porous microsphere respectively.But the above-mentioned system that adopts the phase reversion emulsifying technology to obtain is uncured crosslinked, still is the lower prepolymer of molecular weight.In some occasion, need with the Resins, epoxy in the particulate through polymerization be transformed into molecular weight higher until three-dimensional netted insoluble not clinkering structure, can present a series of good performances.
The present invention has overcome in the prior art, the uncured crosslinked aqueous epoxy resin dispersion system that adopts the phase reversion emulsifying technology to make, and a kind of aqueous based systems that contains epoxy resin solidified microsphere is provided.
In the epoxy resin solidified microsphere water-base system of the present invention, the weight ratio of epoxy resin solidified microsphere and water is 1: 4-7: 3.Described epoxy resin solidified microsphere is made up of following component and content: (weight part) Resins, epoxy: 10-99.9 emulsifying agent: 0.1-90 solidifying agent: in the solidifying agent in active group and the Resins, epoxy epoxide group mol ratio be controlled at 10: 1-1: 10 mentioned emulsifiers are Resins, epoxy/polyethyleneglycol block copolymer, the mol ratio of epoxide group is controlled at 10 in polyoxyethylene glycol terminal hydroxy group and the Resins, epoxy: 0.1-1: 4, above-mentioned Resins, epoxy is bisphenol A type epoxy resin, phenol aldehyde type epoxy resin, acrylic acid or the like Resins, epoxy, phenolic aldehyde epoxy type hexenyl ester resin, acrylic acid or the like epoxy type vinyl ester resin, or its mixture, molecular weight polyethylene glycol is 400-20000; Above-mentioned solidifying agent is the aliphatics amine, aromatic amine, tertiary amine class, imidazoles and derivative thereof, Versamid, organic acid anhydride etc.The preparation method of epoxy resin solidified microsphere water-base system of the present invention carries out in the following order:
1. Resins, epoxy and emulsifying agent are stirred under 30-150 ℃ by weight 10%-99.9%: 0.1%-90%, make mixed system; The mixed system temperature is reduced to 10-50 ℃, under agitation add solidifying agent, make the mixed system that contains solidifying agent; Above-mentioned curing dose is controlled at 10 by epoxide group mol ratio in active group in the solidifying agent and the Resins, epoxy: 1-1: 10;
2. under agitation, dropwise adding water in above-mentioned mixed system, is benchmark with the gross weight of all components in the system, when the weight content for the treatment of water reaches 20%-60%, the external phase of system is reversed to water by Resins, epoxy, has promptly realized phase reversion, has made aqueous epoxy resin dispersion system;
3. further thin up when solid weight content reaches 20%-70% in above-mentioned aqueous based systems, rises to 50-99 ℃ with system temperature and is cured reaction, and reaction continues 1-10 hour, obtains epoxy resin solidified microsphere, and microspherulite diameter is 10
2Nm-10
1μ m.
Above-mentioned Resins, epoxy is bisphenol A type epoxy resin or phenol aldehyde type epoxy resin; Mentioned emulsifier is cetomacrogol 1000 0/ bisphenol A type epoxy resin (mol ratio 1: 1) segmented copolymer or cetomacrogol 1000 0/ phenol aldehyde type epoxy resin (mol ratio 1: 1) segmented copolymer; Above-mentioned solidifying agent is an alkane diamines in the Meng, 4, and 4 '-diaminodiphenylmethane, N, N-dimethyl benzylamine, 2-ethyl 4-methylimidazole, dodecyl succinic anhydride or Versamid 200.
Preparation method's characteristics of the epoxy resin solidified microsphere water-base system that the present invention proposes are as follows:
1. with traditional seeding polymerization, dispersion polymerization, methods such as letex polymerization are compared, and adopt the phase reversion emulsifying technology to prepare epoxy resin solidified microsphere, do not need organic solvent, obtain aqueous based systems, and aftertreatment is simple, helps environment protection;
2. the size of solidified microsphere, structure and form are adjustable flexibly, can be by the feature materialization parameter such as the reactant ratio of system, system viscosity, emulsifying agent molecular structure and consumption, machined parameters such as temperature, controls such as rheology parameter.See Table I.When emulsifier concentration is 10%-90%, can obtain being of a size of nano level single solidified microsphere by complete phase reversion; When emulsifier concentration is 0.1%-10%, can obtain being of a size of micron-sized porous solidified microsphere by incomplete phase reversion.Proportioning by active group and epoxide group in the adjusting solidifying agent can obtain the different epoxy resin solidified microsphere of state of cure;
3. the experiment required equipment is simple, cheap, and experimental technique is safe and simple.
The present invention can obtain the different epoxy resin solidified microsphere water-base system of state of cure by the proportioning of epoxide group in active group and the Resins, epoxy in the adjusting solidifying agent.Completely crued epoxy resin solidified microsphere has the intensity height, good heat resistance, and characteristics such as chemical-resistant reagent can be widely used in fields such as analytical chemistry, biomedicine, electronics.Not exclusively the linear or branching shape epoxy resin solidified microsphere of solidified has active end group, and the active end group in this structure can further react with other materials and obtain novel product, can be used as polymer coupler, properties-correcting agent etc.
Table I
| Embodiment | Emulsifier concentration (%) | Fusing point (℃) | Solidified microsphere size (μ m) | The solidified microsphere form |
| 1 | 3 | 140 | 8 | Porous |
| 2 | 10 | 150 | 0.3 | Single |
| 3 | 5 | 95 | 4.5 | Porous |
| 4 | 11 | 90 | 0.4 | Single |
EXAMPLE Example 1: the preparation of the curing porous microballoon of bisphenol A type epoxy resin is with 3% emulsifying agent [cetomacrogol 1000 0/ bisphenol A type epoxy resin E-20 (mol ratio 1: 1) segmented copolymer], 24% bisphenol A type epoxy resin E-20 (oxirane value is 0.2), 73% bisphenol A type epoxy resin E-44 (oxirane value is 0.44), in the 250ml four-hole boiling flask, be mixed and heated to 120 ℃, fully stirred 1 hour, make mixed system.Then, be cooled to 30 ℃, drip 3.27 gram alkane diamines in the Meng (in the Meng alkane diamines in reactive hydrogen and the bisphenol A type epoxy resin epoxide group mol ratio be 1: 1), fully stirred 25 minutes, make the mixed system that contains solidifying agent.Afterwards, drip deionized water, descend suddenly, show that the phase reversion process realizes, has obtained corresponding aqueous based systems up to system resistance.Continuing to add deionized water, to be diluted to content of water in system be 70%, is warming up to 80 ℃ and is cured reaction, reacted 2 hours, obtains the water-based epoxy resin solidified microsphere.This microballoon still can being kept perfectly property under 140 ℃, melts, and illustrates that curing reaction finishes substantially.Scanning electron microscope result shows that this microballoon is a vesicular structure, and median size is 8 μ m, and the aperture is about 1 μ m.Embodiment 2: bisphenol A type epoxy resin solidifies the preparation of single microballoon with 10% emulsifying agent [cetomacrogol 1000 0/ bisphenol A type epoxy resin E-20 (mol ratio 1: 1) segmented copolymer], 90% bisphenol A type epoxy resin E-44 (oxirane value is 0.44), in the 250ml four-hole boiling flask, be mixed and heated to 100 ℃, fully stirred 1 hour, be cooled to 16 ℃, drip weight percent concentration and be 39% 4,4 '-diaminodiphenylmethane-acetone soln 14.88 grams, fully stirred 15 minutes, vacuumize acetone is removed, make the mixed system that contains solidifying agent.Afterwards, drip deionized water, descend suddenly, show that the phase reversion process realizes, has obtained corresponding aqueous based systems up to system resistance.Continuing to add deionized water, to be diluted to content of water in system be 60%, is warming up to 90 ℃ and is cured reaction, reacted 3 hours, obtains the water-based epoxy resin solidified microsphere.This microballoon still can being kept perfectly property under 135 ℃, melts, and illustrates that curing reaction finishes substantially.Scanning electron microscope result shows that this microballoon is single particulate, and median size is 200nm.Embodiment 3: the preparation of the curing porous microballoon of bisphenol A type epoxy resin is with 5% emulsifying agent [cetomacrogol 1000 0/ bisphenol A type epoxy resin E-20 (mol ratio 1: 1) segmented copolymer], 19% bisphenol A type epoxy resin E-20 (oxirane value is 0.2), 76% bisphenol A type epoxy resin E-44 (oxirane value is 0.44), in the 250ml four-hole boiling flask, be mixed and heated to 110 ℃, fully stirred 1 hour, be cooled to 19 ℃, drip 3.09 gram N, the N-dimethyl benzylamine, fully stir after 15 minutes, make the mixed system that contains solidifying agent.Afterwards, drip deionized water, descend suddenly, show that the phase reversion process realizes, has obtained corresponding aqueous based systems up to system resistance.Continuing to add deionized water, to be diluted to content of water in system be 60%, is warming up to 90 ℃ and is cured reaction, reacted 3 hours 30 minutes, obtains the water-based epoxy resin solidified microsphere.This microballoon still can being kept perfectly property under 150 ℃, melts, and illustrates that curing reaction finishes substantially.Scanning electron microscope result shows that this microballoon is a vesicular structure, and median size is 4.5 μ m, and the aperture is about 500nm.Embodiment 4: bisphenol A type epoxy resin solidifies the preparation of single microballoon with 10% emulsifying agent [cetomacrogol 1000 0/ bisphenol A type epoxy resin E-20 (mol ratio 1: 1) segmented copolymer], 10.8% bisphenol A type epoxy resin E-20 (oxirane value is 0.2), 79.2% bisphenol A type epoxy resin E-44 (oxirane value is 0.44), in the 250ml four-hole boiling flask, be mixed and heated to 120 ℃, fully stirred 1 hour, be cooled to 20 ℃, the dropping weight percent concentration is 50% the 2-ethyl 4-methyl miaow Cuo aqueous solution 2.13 grams, fully stir after 10 minutes, make the mixed system that contains solidifying agent.Afterwards, drip deionized water, descend suddenly, show that the phase reversion process realizes, has obtained corresponding aqueous based systems up to system resistance.Continuing to add deionized water, to be diluted to content of water in system be 70%, is warming up to 99 ℃ and is cured reaction, reacted 3 hours 30 minutes, obtains the water-based epoxy resin solidified microsphere.This microballoon still can being kept perfectly property under 150 ℃, melts, and illustrates that curing reaction finishes substantially.Scanning electron microscope result shows that this microballoon is single particulate, and median size is 300nm.Embodiment 5: the preparation of the curing porous microballoon of bisphenol A type epoxy resin is with 5% emulsifying agent [cetomacrogol 1000 0/ bisphenol A type epoxy resin E-20 (mol ratio 1: 1) segmented copolymer], 15.8% bisphenol A type epoxy resin E-20 (oxirane value is 0.2), 79.2% bisphenol A type epoxy resin E-44 (oxirane value is 0.44), in the 250ml four-hole boiling flask, be mixed and heated to 100 ℃, fully stirred 1 hour, be cooled to 20 ℃, drip 40 gram dodecyl succinic anhydrides, fully stir after 20 minutes, make the mixed system that contains solidifying agent.Afterwards, drip deionized water, descend suddenly, show that the phase reversion process realizes, has obtained corresponding aqueous based systems up to system resistance.Continuing to add deionized water, to be diluted to content of water in system be 70%, is warming up to 95 ℃ and is cured reaction, reacted 3 hours 30 minutes, obtains the water-based epoxy resin solidified microsphere.This microballoon still can being kept perfectly property under 140 ℃, melts, and illustrates that curing reaction finishes substantially.Scanning electron microscope result shows that this microballoon is a vesicular structure, and median size is 3 μ m, and the aperture is about 200nm.Embodiment 6: the preparation of the curing porous microballoon of bisphenol A type epoxy resin is with 5% emulsifying agent [cetomacrogol 1000 0/ bisphenol A type epoxy resin E-20 (mol ratio 1: 1) segmented copolymer], 15.8% bisphenol A type epoxy resin E-20 (oxirane value is 0.2), 79.2% bisphenol A type epoxy resin E-44 (oxirane value is 0.44), in the 250ml four-hole boiling flask, be mixed and heated to 100 ℃, fully stirred 1 hour, be cooled to 20 ℃, drip 36.43 gram Versamids 200, fully stir after 20 minutes, make the mixed system that contains solidifying agent.Afterwards, drip deionized water, descend suddenly, show that the phase reversion process realizes, has obtained corresponding aqueous based systems up to system resistance.Continuing to add deionized water, to be diluted to content of water in system be 70%, is warming up to 95 ℃ and is cured reaction, reacted 3 hours, obtains the water-based epoxy resin solidified microsphere.This microballoon still can being kept perfectly property under 150 ℃, melts, and illustrates that curing reaction finishes substantially.Scanning electron microscope result shows that this microballoon is a vesicular structure, and median size is 4 μ m, and the aperture is about 300nm.Embodiment 7: the preparation of the incomplete solidified microsphere of bisphenol A type epoxy resin is with 3% emulsifying agent [cetomacrogol 1000 0/ bisphenol A type epoxy resin E-20 (mol ratio 1: 1) segmented copolymer], 24% bisphenol A type epoxy resin E-20 (oxirane value is 0.2), 73% bisphenol A type epoxy resin E-44 (oxirane value is 0.44), in the 250ml four-hole boiling flask, be mixed and heated to 120 ℃, fully stirred 1 hour, make mixed system.Then, be cooled to 30 ℃, drip 1.07 gram alkane diamines in the Meng (in the Meng alkane diamines in reactive hydrogen and the bisphenol A type epoxy resin epoxide group mol ratio be 1: 10), fully stirred 25 minutes, make the mixed system that contains solidifying agent.Afterwards, drip deionized water, descend suddenly, show that the phase reversion process realizes, has obtained corresponding aqueous based systems up to system resistance.Continuing to add deionized water, to be diluted to content of water in system be 70%, is warming up to 80 ℃ and is cured reaction, reacted 2 hours, obtains the incomplete solidified microsphere of water-based epoxy resin.This microballoon melts down at 140 ℃, can not being kept perfectly property, under 90 ℃, do not melt, and illustrate that this moment, curing reaction was not exclusively curing.Scanning electron microscope result shows that this microballoon is a vesicular structure, and median size is 10 μ m, and the aperture is about 1 μ m.Embodiment 8: the preparation of the incomplete solidified microsphere of bisphenol A type epoxy resin is with 3% emulsifying agent [cetomacrogol 1000 0/ bisphenol A type epoxy resin E-20 (mol ratio 1: 1) segmented copolymer], 24% bisphenol A type epoxy resin E-20 (oxirane value is 0.2), 73% bisphenol A type epoxy resin E-44 (oxirane value is 0.44), in the 250ml four-hole boiling flask, be mixed and heated to 120 ℃, fully stirred 0.5 hour, make mixed system.Then, be cooled to 30 ℃, Dropwise 5 .63 gram alkane diamines in the Meng (in the Meng alkane diamines in reactive hydrogen and the bisphenol A type epoxy resin epoxide group mol ratio be 10: 1) fully stirred 25 minutes, made the mixed system that contains solidifying agent.Afterwards, drip deionized water, descend suddenly, show that the phase reversion process realizes, has obtained corresponding aqueous based systems up to system resistance.Continuing to add deionized water, to be diluted to content of water in system be 70%, is warming up to 80 ℃ and is cured reaction, reacted 2 hours, obtains the incomplete solidified microsphere of water-based epoxy resin.This microballoon melts down at 140 ℃, can not being kept perfectly property, under 90 ℃, do not melt, and illustrate that this moment, curing reaction was not exclusively curing.Scanning electron microscope result shows that this microballoon is a vesicular structure, and median size is 8 μ m, and the aperture is about 1 μ m.Embodiment 9: the preparation of the curing porous microballoon of phenol aldehyde type epoxy resin is with 5% emulsifying agent [cetomacrogol 1000 0/ phenol aldehyde type epoxy resin F-47 (mol ratio 1: 1) segmented copolymer], 95% phenol aldehyde type epoxy resin F-47 (oxirane value is 0.47), in the 250ml four-hole boiling flask, be mixed and heated to 100 ℃, fully stirred 1 hour, be cooled to 15 ℃, drip 3.46 gram alkane diamines in the Meng, fully stir 20 minutes after, make the mixed system that contains solidifying agent.Afterwards, drip deionized water, descend suddenly, show that the phase reversion process realizes, has obtained corresponding aqueous based systems up to system resistance.Continuing to add deionized water, to be diluted to content of water in system be 70%, is warming up to 90 ℃ and is cured reaction, reacted 3 hours, obtains the water-based epoxy resin solidified microsphere.This microballoon still can being kept perfectly property under 130 ℃, melts, and illustrates that curing reaction finishes substantially.Scanning electron microscope result shows that this microballoon is a vesicular structure, and median size is 5 μ m, and the aperture is about 800nm.Embodiment 10: phenol aldehyde type epoxy resin solidifies the preparation of single microballoon with 10% emulsifying agent [cetomacrogol 1000 0/ phenol aldehyde type epoxy resin F-47 (mol ratio 1: 1) segmented copolymer], 90% phenol aldehyde type epoxy resin F-47 (oxirane value is 0.47), in the 250ml four-hole boiling flask, be mixed and heated to 100 ℃, fully stirred 1 hour, be cooled to 15 ℃, drip 2.96 gram alkane diamines in the Meng, fully stir 20 minutes after, make the mixed system that contains solidifying agent.Afterwards, drip deionized water, descend suddenly, show that the phase reversion process realizes, has obtained corresponding aqueous based systems up to system resistance.Continuing to add deionized water, to be diluted to content of water in system be 70%, is warming up to 90 ℃ and is cured reaction, reacted 3 hours 30 minutes, obtains the water-based epoxy resin solidified microsphere.This microballoon still can being kept perfectly property under 130 ℃, melts, and illustrates that curing reaction finishes substantially.Scanning electron microscope result shows that this microballoon is single particulate, and median size is 100nm.
Claims (3)
1. an epoxy resin solidified microsphere water-base system is characterized in that in the described aqueous based systems, and the weight ratio of epoxy resin solidified microsphere and water is 1: 4-7: 3, and described epoxy resin solidified microsphere particle diameter is 10
2Nm-10
1μ m, form by following component and weight part content: bisphenol A type epoxy resin or phenol aldehyde type epoxy resin: 10-99.9 emulsifying agent bisphenol A type epoxy resin/polyethyleneglycol block copolymer or phenol aldehyde type epoxy resin/polyethyleneglycol block copolymer: the 0.1-90 solidifying agent: in the solidifying agent in active group and the Resins, epoxy epoxide group mol ratio be 10: 1-1: 10 above-mentioned solidifying agent are the aliphatics amine, aromatic amine, the tertiary amine class, imidazoles and derivative thereof, Versamid or organic acid anhydride.
2. epoxy resin solidified microsphere water-base system according to claim 1, the mol ratio that it is characterized in that epoxide group in described polyoxyethylene glycol terminal hydroxy group and the emulsifying agent Resins, epoxy/polyethyleneglycol block copolymer is 10: 0.1-1: 4.
3. the preparation method of epoxy resin solidified microsphere water-base system according to claim 1 is characterized in that carrying out in the following order:
(1) bisphenol A type epoxy resin or phenol aldehyde type epoxy resin and emulsifying agent bisphenol A type epoxy resin/polyethyleneglycol block copolymer or phenol aldehyde type epoxy resin/polyethyleneglycol block copolymer are stirred under 30-150 ℃ by weight 10-99.9: 0.1-90, make mixed system; The mixed system temperature is reduced to 10-50 ℃, under agitation add solidifying agent, make the mixed system that contains solidifying agent;
(2) under agitation, dropwise adding water in above-mentioned mixed system, is benchmark with the gross weight of all components in the system, when the weight content for the treatment of water reaches 20%-60%, has made aqueous based systems;
(3) thin up, solid weight content reaches 20%-70% in above-mentioned aqueous based systems, system temperature is risen to 50-99 ℃ be cured reaction, and reaction continues 1-10 hour, obtains epoxy resin solidified microsphere water-base system.
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| CN101003664B (en) * | 2006-01-16 | 2010-08-25 | 浙江安邦新材料发展有限公司 | Latex of epoxy resin of aqueous phenolic aldehyde, and preparation method |
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| CN102850521B (en) * | 2012-08-21 | 2014-08-20 | 西南科技大学 | Preparation method of epoxy resin hollow microsphere |
| CN105199322B (en) * | 2015-10-10 | 2017-03-22 | 苏州大学 | Epoxy resin microsphere and preparation method thereof |
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