CN1098884C - Epoxy resin/microparticle composite solidified microsphere water base system and its preparation method - Google Patents
Epoxy resin/microparticle composite solidified microsphere water base system and its preparation method Download PDFInfo
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- CN1098884C CN1098884C CN00107215A CN00107215A CN1098884C CN 1098884 C CN1098884 C CN 1098884C CN 00107215 A CN00107215 A CN 00107215A CN 00107215 A CN00107215 A CN 00107215A CN 1098884 C CN1098884 C CN 1098884C
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 80
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000004005 microsphere Substances 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims description 44
- 238000002360 preparation method Methods 0.000 title claims description 24
- 239000011859 microparticle Substances 0.000 title claims description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 83
- 239000004593 Epoxy Substances 0.000 claims description 40
- 229920005989 resin Polymers 0.000 claims description 40
- 239000011347 resin Substances 0.000 claims description 40
- -1 phenol aldehyde Chemical class 0.000 claims description 35
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 6
- 239000010954 inorganic particle Substances 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229960001866 silicon dioxide Drugs 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims 4
- 125000003700 epoxy group Chemical group 0.000 claims 2
- 239000010419 fine particle Substances 0.000 abstract description 8
- 239000003607 modifier Substances 0.000 abstract 1
- 239000012763 reinforcing filler Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 26
- 239000008367 deionised water Substances 0.000 description 24
- 229910021641 deionized water Inorganic materials 0.000 description 24
- 229910004298 SiO 2 Inorganic materials 0.000 description 21
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 15
- 229920001577 copolymer Polymers 0.000 description 15
- IQXJCCZJOIKIAD-UHFFFAOYSA-N 1-(2-methoxyethoxy)hexadecane Chemical group CCCCCCCCCCCCCCCCOCCOC IQXJCCZJOIKIAD-UHFFFAOYSA-N 0.000 description 14
- 229950009789 cetomacrogol 1000 Drugs 0.000 description 14
- 238000010792 warming Methods 0.000 description 13
- 238000009835 boiling Methods 0.000 description 12
- 239000000155 melt Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 10
- 150000002924 oxiranes Chemical group 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 5
- 230000001804 emulsifying effect Effects 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 150000004662 dithiols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The present invention relates to an epoxy resin/fine particle compounded solidified microsphere water-base system in which the weight ratio of the epoxy resin/fine particle compounded solidified microspheres to the water is 1: 4 to 7: 3, wherein the particle diameter of the epoxy resin/fine particle compounded solidified microspheres is 10<2> nanometer to 10<1>micrometer. Epoxy resin, inorganic fine particles and emulsifier are stirred uniformly according to the weight ratio of (10 to 99.8): (0.1 to 40): (0.1 to 50), 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/fine particle compounded solidified microsphere water-base system. The epoxy resin/fine particle compounded solidified microsphere water-base system of the present invention has the characteristics of high strength, good heat resistance, etc., and the system can be uses as reinforcing filler, macromolecular modifier, etc.
Description
The present invention relates to the polymeric hardener microballoon, particularly a kind of Resins, epoxy/microparticle composite 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., 199l, 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 in post footpath.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.Recently, (Macromol.Chem.Phys. such as Katharina Landfester, 2000,201,1-5) adopt special letex polymerization (mini-emulsion polymerization) 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.In recent years, in the preparation of polymer composite, the polymer/particle composite material that adopts the method for emulsion polymerization preparation to have good clad structure causes everybody extensive concern day by day.Caris etc. (Br.Polym.J., 1989,21,133-140) adopt method of emulsion polymerization to make the polymethylmethacrylate of coated inorganic particulate.Although can the stable polymer/particulate compound system of processability with method of emulsion polymerization, its step that relates to be loaded down with trivial details, be not easy control, and solid content is lower, is about about 30%.If the bridging phenomenon can take place the system of preparation high solids content inevitably, cause problems such as particles agglomerate and rate of polymerization reduction.
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.Based on this, Yang Zhenzhong etc. (patent of invention, application number 99108085.8) further adopt the phase reversion emulsifying technology to prepare the composite aqueous dispersion system of the Resins, epoxy/particulate with good clad structure.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 composite aqueous dispersion system of Resins, epoxy/particulate that adopts the phase reversion emulsifying technology to make with good clad structure, and a kind of aqueous based systems that contains Resins, epoxy/microparticle composite solidified microsphere is provided.
In Resins, epoxy/microparticle composite solidified microsphere water base system of the present invention, the weight ratio of Resins, epoxy/microparticle composite solidified microsphere and water is 1: 4-7: 3.Described Resins, epoxy/microparticle composite solidified microsphere is made up of following component and content: (weight part) Resins, epoxy: 10-99.8 particulate: 0.1-40 emulsifying agent: 0.1-50 solidifying agent: in the solidifying agent in active group and the Resins, epoxy epoxide group mol ratio be controlled at 10: 1-1: 10 above-mentioned particulates comprise organic fine particles and inorganic particles, organic fine particles comprises graphite, carbon black etc.; Inorganic particles comprises lime carbonate, ferric oxide, and zinc oxide, titanium dioxide, talcum powder, silicon-dioxide, polynite etc., its particle diameter is 5-1000nm; Mentioned emulsifier is polyoxyethylene glycol/Resins, epoxy segmented 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 vinyl 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 Resins, epoxy/microparticle composite solidified microsphere water base system of the present invention carries out in the following order: 1. with Resins, epoxy, particulate and emulsifying agent stir under 30-150 ℃ by weight 10%-99.8%: 0.1%-40%: 0.1%-50%, 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 add water in above-mentioned mixed system, when treating that water-content reaches 20%-60%, the external phase of system is reversed to water by Resins, epoxy, has promptly realized phase reversion having made aqueous based systems; 3. further thin up, when the above-mentioned mixed system content that contains solidifying agent reaches 20%-70%, system temperature is risen to 50-99 ℃ be cured reaction, reaction continues 1-10 hour, obtain Resins, epoxy/microparticle composite solidified microsphere, microspherulite diameter is 10
2Nm-10
1μ m.Above-mentioned Resins, epoxy is bisphenol A type epoxy resin or phenol aldehyde type epoxy resin; Above-mentioned particulate is a ferric oxide, titanium dioxide, and talcum powder, silicon-dioxide, polynite or lime carbonate, its particle diameter are 5-1000nm; 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 Resins, epoxy/microparticle composite 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, adopt the phase reversion emulsifying technology to prepare Resins, epoxy/microparticle composite solidified microsphere, do not need organic solvent, obtain aqueous based systems, 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%-50%, 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 Resins, epoxy composite 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 Resins, epoxy/microparticle composite 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 Resins, epoxy/microparticle composite 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 Resins, epoxy/microparticle composite 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 | 7 | 140 | 5 | Porous |
| 2 | 10 | 150 | 0.4 | Single |
| 3 | 5 | 95 | 6.5 | Porous |
| 4 | 11 | 90 | 0.5 | Single |
EXAMPLE Example 1: bisphenol A type epoxy resin/SiO
2The preparation of composite curing porous microsphere is with 7% emulsifying agent [cetomacrogol 1000 0/ bisphenol A type epoxy resin E-20 (mol ratio 1: 1) segmented copolymer], 75% bisphenol A type epoxy resin E-44 (oxirane value is 0.44), 18%SiO
2Powder (median size is 5nm) is mixed and heated to 150 ℃ in the 250ml four-hole boiling flask, fully stirred 1 hour, makes mixed system.Then, be cooled to 15 ℃, drip 8.48 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 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 aqueous based systems up to system resistance.Continuing to add deionized water, to be diluted to content of water in system be 65%, is warming up to 80 ℃ and is cured reaction, reacted 3 hours, obtains water-based epoxy resin/SiO
2Composite 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 5 μ m, and the aperture is about 500nm.Embodiment 2: bisphenol A type epoxy resin/TiO
2The preparation of composite curing porous microsphere is with 5% emulsifying agent [cetomacrogol 1000 0/ bisphenol A type epoxy resin E-20 (mol ratio 1: 1) segmented copolymer], 85% bisphenol A type epoxy resin E-44 (oxirane value is 0.44), 10%TiO
2Powder (median size is 300nm), in the 250ml four-hole boiling flask, be mixed and heated to 90 ℃, fully stirred 1 hour, be cooled to 17 ℃, drip weight percent concentration and be 30% 4,4 '-diaminodiphenylmethane-acetone soln 19.33 grams fully stirred 20 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 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 75 ℃ and is cured reaction, reacted 1 hour 20 minutes, continues to be warming up to 90 ℃, reacted 1 hour 30 minutes, obtains water-based epoxy resin/TiO
2Composite 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 500nm.Embodiment 3: the preparation of bisphenol A type epoxy resin/talcum powder composite curing porous microsphere is with 6% emulsifying agent [cetomacrogol 1000 0/ bisphenol A type epoxy resin E-20 (mol ratio 1: 1) segmented copolymer], 74% bisphenol A type epoxy resin E-44 (oxirane value is 0.44), 20% talcum powder powder (median size is 600nm), in the 250ml four-hole boiling flask, be mixed and heated to 110 ℃, fully stirred 1 hour, be cooled to 20 ℃, drip 2.82 gram N, the N-dimethyl benzylamine, 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 aqueous based systems up to system resistance.Continuing to add deionized water, to be diluted to content of water in system 6 be 70%, is warming up to 90 ℃ and is cured reaction, reacted 3 hours, obtains water-based epoxy resin/talcum powder composite 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 6 μ m, and the aperture is about 1 μ m.Embodiment 4: the preparation of the curing porous microballoon of bisphenol A type epoxy resin/montmorillonite Composite is with 6% emulsifying agent [cetomacrogol 1000 0/ bisphenol A type epoxy resin E-20 (mol ratio 1: 1) segmented copolymer], 73.8% bisphenol A type epoxy resin E-44 (oxirane value is 0.44), 5.2% bisphenol A type epoxy resin E-20 (oxirane value is 0.2), 15% polynite powder (median size is 100nm), 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-methylimidazole aqueous solution 2.85 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 aqueous based systems up to system resistance.Continuing to add deionized water, to be diluted to content of water in system be 50%, is warming up to 95 ℃ and is cured reaction, reacted 5 hours, obtains water-based epoxy resin/montmorillonite Composite 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 6.5 μ m, and the aperture is about 1 μ m.Embodiment 5: bisphenol A type epoxy resin/CaCO
3The preparation of composite curing porous microsphere is with 6% emulsifying agent [cetomacrogol 1000 0/ bisphenol A type epoxy resin E-20 (mol ratio 1: 1) segmented copolymer], 71.8% bisphenol A type epoxy resin E-44 (oxirane value is 0.44), 7.2% bisphenol A type epoxy resin E-20 (oxirane value is 0.2), 15%CaCO
3Powder (median size is 1000nm) is mixed and heated to 120 ℃ in the 250ml four-hole boiling flask, fully stirred 1 hour, is cooled to 20 ℃, drips 33 gram dodecyl succinic anhydrides, fully stir 10 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 aqueous based systems up to system resistance.Continuing to add deionized water, to be diluted to content of water in system be 65%, is warming up to 95 ℃ and is cured reaction, reacted 3 hours, obtains water-based epoxy resin/CaCO
3Composite 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 7.5 μ m, and the aperture is about 1 μ m.Embodiment 6: bisphenol A type epoxy resin/Fe
2O
3The preparation of composite curing porous microsphere is with 7% emulsifying agent [cetomacrogol 1000 0/ bisphenol A type epoxy resin E-20 (mol ratio 1: 1) segmented copolymer], 73.8% bisphenol A type epoxy resin E-44 (oxirane value is 0.44), 4.2% bisphenol A type epoxy resin E-20 (oxirane value is 0.2), 15%Fe
2O
3Powder (median size is 2000nm) is mixed and heated to 120 ℃ in the 250ml four-hole boiling flask, fully stirred 1 hour, is cooled to 20 ℃, drips 33 gram Versamids 200, fully stir 10 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 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 water-based epoxy resin/Fe
2O
3Composite 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 8 μ m, and the aperture is about 1 μ m.Embodiment 7: bisphenol A type epoxy resin/SiO
2The preparation of the single microballoon of composite curing is with 10% emulsifying agent [cetomacrogol 1000 0/ bisphenol A type epoxy resin E-20 (mol ratio 1: 1) segmented copolymer], 80% bisphenol A type epoxy resin F-47 (oxirane value is 0.47), 10%SiO
2Powder (median size is 5nm) is mixed and heated to 100 ℃ in the 250ml four-hole boiling flask, fully stirred 1 hour, is cooled to 18 ℃, drips 2.76 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 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 water-based epoxy resin/SiO
2Composite 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 single particulate, and median size is 400nm.Embodiment 8: bisphenol A type epoxy resin/SiO
2The preparation of compound incomplete solidified microsphere is with 7% emulsifying agent [cetomacrogol 1000 0/ bisphenol A type epoxy resin E-20 (mol ratio 1: 1) segmented copolymer], 75% bisphenol A type epoxy resin E-44 (oxirane value is 0.44), 18%SiO
2Powder (median size is 5nm) is mixed and heated to 150 ℃ in the 250ml four-hole boiling flask, fully stirred 1 hour, makes mixed system.Then, be cooled to 15 ℃, drip 3.67 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 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 aqueous based systems up to system resistance.Continuing to add deionized water, to be diluted to content of water in system be 65%, is warming up to 80 ℃ and is cured reaction, reacted 3 hours, obtains water-based epoxy resin/SiO
2Compound incomplete solidified microsphere.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 6.5 μ m, and the aperture is about 900nm.Embodiment 9: bisphenol A type epoxy resin/SiO
2The preparation of compound incomplete solidified microsphere is with 7% emulsifying agent [cetomacrogol 1000 0/ bisphenol A type epoxy resin E-20 (mol ratio 1: 1) segmented copolymer], 75% bisphenol A type epoxy resin E-44 (oxirane value is 0.44), 18%SiO
2Powder (median size is 5nm) is mixed and heated to 150 ℃ in the 250ml four-hole boiling flask, fully stirred 1 hour, makes mixed system.Then, be cooled to 15 ℃, drip 8.87 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 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 aqueous based systems up to system resistance.Continuing to add deionized water, to be diluted to content of water in system be 65%, is warming up to 80 ℃ and is cured reaction, reacted 3 hours, obtains water-based epoxy resin/SiO
2Compound incomplete solidified microsphere.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 7.5 μ m, and the aperture is about 900nm.Embodiment 10: phenol aldehyde type epoxy resin/SiO
2The preparation of composite curing porous microsphere is with 7% emulsifying agent [cetomacrogol 1000 0/ phenol aldehyde type epoxy resin F-47 (mol ratio 1: 1) segmented copolymer], 78% phenol aldehyde type epoxy resin F-47 (oxirane value is 0.47), 15%SiO
2Powder (median size is 5nm) is mixed and heated to 150 ℃ in the 250ml four-hole boiling flask, fully stirred 1 hour, is cooled to 15 ℃, Dropwise 5 .71 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 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 water-based epoxy resin/SiO
2Composite 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 5.2 μ m, and the aperture is about 800nm.Embodiment 11: phenol aldehyde type epoxy resin/SiO
2The preparation of the single microballoon of composite curing is with 10% emulsifying agent [cetomacrogol 1000 0/ phenol aldehyde type epoxy resin F-47 (mol ratio 1: 1) segmented copolymer], 80% phenol aldehyde type epoxy resin F-47 (oxirane value is 0.47), 10%SiO
2Powder (median size is 5nm) is mixed and heated to 100 ℃ in the 250ml four-hole boiling flask, fully stirred 1 hour, is cooled to 15 ℃, drips 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 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 water-based epoxy resin/SiO
2Composite 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 500nm.Embodiment 12: phenol aldehyde type epoxy resin/SiO
2The preparation of compound incomplete solidified microsphere is with 7% emulsifying agent [cetomacrogol 1000 0/ phenol aldehyde type epoxy resin F-47 (mol ratio 1: 1) segmented copolymer], 75% phenol aldehyde type epoxy resin F-47 (oxirane value is 0.44), 18%SiO
2Powder (median size is 5nm) is mixed and heated to 150 ℃ in the 250ml four-hole boiling flask, fully stirred 1 hour, makes mixed system.Then, be cooled to 15 ℃, drip 4.28 gram alkane diamines in the Meng (in the Meng alkane diamines in reactive hydrogen and the phenol aldehyde type epoxy resin epoxide group mol ratio be 1: 5), fully stirred 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 aqueous based systems up to system resistance.Continuing to add deionized water, to be diluted to content of water in system be 65%, is warming up to 80 ℃ and is cured reaction, reacted 3 hours, obtains water-based epoxy resin/SiO
2Compound incomplete solidified microsphere.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 6.5 μ m, and the aperture is about 900nm.
Claims (4)
1. a Resins, epoxy/microparticle composite solidified microsphere water base system is characterized in that in the described aqueous based systems, and the weight ratio of Resins, epoxy/microparticle composite solidified microsphere and water is 1: 4-7: 3, and described Resins, epoxy/microparticle composite solidified microsphere particle diameter is 10
2Nm-10
1μ m, form by following component and content: (weight part) bisphenol A type epoxy resin or phenol aldehyde type epoxy resin: the 10-99.8 inorganic particles: 0.1-40 emulsifying agent bisphenol A type epoxy resin/polyethyleneglycol block copolymer or phenol aldehyde type epoxy resin/polyethyleneglycol block copolymer: the 0.1-50 solidifying agent: in the solidifying agent in active group and the Resins, epoxy epoxide group mol ratio be 10: 1-1: 10 above-mentioned inorganic particles are lime carbonate, ferric oxide, titanium dioxide, talcum powder, silicon-dioxide or polynite; Above-mentioned solidifying agent is the aliphatics amine, aromatic amine, tertiary amine class, imidazoles and derivative thereof, Versamid or organic acid anhydride.
2. Resins, epoxy/microparticle composite 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 Resins, epoxy is 10: 0.1-1: 4.
3. Resins, epoxy/microparticle composite solidified microsphere water base system according to claim 1, the particle diameter that it is characterized in that described inorganic particles is 5-1000nm.
4. the preparation method of Resins, epoxy/microparticle composite solidified microsphere water base system according to claim 1, it is characterized in that carrying out in the following order: (1) is with bisphenol A type epoxy resin or phenol aldehyde type epoxy resin, inorganic particles and emulsifying agent bisphenol A type epoxy resin/polyethyleneglycol block copolymer or phenol aldehyde type epoxy resin/polyethyleneglycol block copolymer stir under 30-150 ℃ by weight 10-99.8: 0.1-40: 0.1-50, 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 in above-mentioned mixed system, add water, when treating that water-content reaches 20%-60%, made aqueous based systems; (3) thin up when the above-mentioned mixed system content that contains solidifying agent reaches 20%-70%, rises to 50-99 ℃ with system temperature and is cured reaction, and reaction continues 1-10 hour, obtains Resins, epoxy/microparticle composite solidified microsphere water base system.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033062A (en) * | 1987-10-22 | 1989-05-24 | 中国科学院化学研究所 | High-resilient microballoon mother material and method for making thereof |
| CN1250061A (en) * | 1998-10-06 | 2000-04-12 | 中国科学院化学研究所 | Thermoplastic polymer microballoon and its preparation |
-
2000
- 2000-04-28 CN CN00107215A patent/CN1098884C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033062A (en) * | 1987-10-22 | 1989-05-24 | 中国科学院化学研究所 | High-resilient microballoon mother material and method for making thereof |
| CN1250061A (en) * | 1998-10-06 | 2000-04-12 | 中国科学院化学研究所 | Thermoplastic polymer microballoon and its preparation |
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