CN1246355C - Core-shell particles with acroleic acid esterified polyurethane as main body of core and making method and use thereof - Google Patents
Core-shell particles with acroleic acid esterified polyurethane as main body of core and making method and use thereof Download PDFInfo
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- CN1246355C CN1246355C CN 200310112355 CN200310112355A CN1246355C CN 1246355 C CN1246355 C CN 1246355C CN 200310112355 CN200310112355 CN 200310112355 CN 200310112355 A CN200310112355 A CN 200310112355A CN 1246355 C CN1246355 C CN 1246355C
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Abstract
The present invention relates to a core-shell particle using acroleic acid esterified polyurethane as a main body, and a preparing method thereof and application thereof. The core-shell particle uses the copolymer of an acroleic acid esterified polyurethane monomer and an acroleic acid ester type soft monomer as a core, and uses an acroleic acid ester type hard monomer on an external connection branch as a shell. The preparing method of the core-shell particle comprising the following steps: 1) preparing acroleic acid esterified polyurethane; 2) emulsionizing the acroleic acid esterified polyurethane to obtain aqueous acroleic acid esterified polyurethane emulsion; 3) A: the acroleic acid ester type soft monomer is added in the emulsion to react to obtain seed emulsion; B: the acroleic acid ester type hard monomer is added in the seed emulsion to react to obtain core-shell emulsion; 4) the emulsion is broken by sodium chloride saturated solution, is frozen, and is pumped and filtered, and the emulsion is washed, dried and ground to obtain the core-shell particle using acroleic acid esterified polyurethane as a main body. The core-shell particle can be used as a toughening agent in epoxy resin so that the glass transition temperature can not be greatly reduced, and has good interface compatibility with the epoxy resin. The preparing method has the advantage of environmental protection.
Description
Technical field
The present invention relates to of core-shell particles and method for making and the application of a kind of Acrylated urethanes for the nuclear main body.
Technical background
Resins, epoxy has good physical strength and adhesiveproperties, thermotolerance, electric property and moulding processability are good, and shrinking percentage is little, and resistance to medium is good, and cost is lower, is widely used in fields such as Aeronautics and Astronautics, electronics, machinery as semiconductor sealing material and adhesive substrate material.It is higher that but the greatest drawback of Resins, epoxy is an internal stress, and fragility is big, and impact resistance is poor, thereby hindered its application.Therefore, toughening modifying becomes Resins, epoxy one of urgent problem in actual applications.
Liquid polyurethane is a kind of macromolecular material of excellent property, has the characteristics of snappiness, high bonding force, can combine with epoxy in a variety of forms, forms the material of various excellent propertys.The bibliographical information liquid polyurethane is all arranged as toughner both at home and abroad, be used for the modification of Resins, epoxy, develop products such as successful polyurethane modified epoxy resin sqtructural adhesive, composite matrix resin as U.S. Dow Chemical company at first and be used for aerospace industry.
There is following shortcoming but liquid polyurethane is epoxy resin toughened: in the epoxy resin cure process, increase along with molecular weight, liquid polyurethane and epoxy resin compatibility reduction, progressively be separated, but because the two is separated not exclusively, have small amount of liquid urethane remain in Resins, epoxy mutually in, cause second-order transition temperature to reduce by a relatively large margin.It is unsaturated two strong polymerizable liquid urethane that the present invention has synthesized a kind of end group by polystep reaction, examine with itself and the copolymerization of esters of acrylic acid soft monomer, make shell with the esters of acrylic acid hard monomer then, prepared a kind of novel core-shell particles, is to be structure and performance in order to regulate nuclear in order to improve the consistency of particle and resin matrix, to add a spot of esters of acrylic acid soft monomer and urethane copolymerization with the acrylic acid or the like hard monomer as shell.
Summary of the invention
Purpose of the present invention provides the core-shell particles of a kind of Acrylated urethanes for the nuclear main body, and it uses as epoxy resin toughener, can not cause second-order transition temperature to reduce by a relatively large margin, has the good interface consistency with Resins, epoxy.
Another object of the present invention provides the preparation method of this core-shell particles, and this method adopts emulsion method, has avoided the environmental pollution and the toxic action that are with an organic solvent caused, the tool feature of environmental protection.
A further object of the present invention provides the application of this core-shell particles as toughner in the Resins, epoxy, and it can solve the problem that exists in the epoxy resin toughened technology of liquid polyurethane preferably.
The present invention adopts seeded emulsion polymerization technology, and the Acrylated urethanes monomer of employing energy self-crosslinking prepares a kind of core-shell particles of excellent performance, and this core-shell particles is suitable for use as neo-epoxy resin toughner.
Core-shell particles provided by the invention, its multipolymer with Acrylated urethanes monomer and esters of acrylic acid soft monomer is a nuclear, the esters of acrylic acid hard monomer is a shell in the grafting outward again.
Wherein in the multipolymer of Acrylated urethanes monomer and esters of acrylic acid soft monomer, the mass ratio of Acrylated urethanes monomer and esters of acrylic acid soft monomer be 2: 1～4: 1 (based on the Acrylated urethanes monomer, so claim with the Acrylated urethanes to be the nuclear main body), the nucleocapsid mass ratio is 1: 2～2: 1.
The particle diameter of this core-shell particles is generally 40～80nm.
The preparation method of this core-shell particles comprises the steps:
1), the preparation of Acrylated urethanes: with the number-average molecular weight of 30-40% is that 300-3000, hydroxyl value are that the polyhydric alcohol polymer of 50-200mgKOH/g is earlier through decompression dehydration, diisocyanate monomer with 10-30% reacts 1-3h at 70-75 ℃ again, be warming up to 80-90 ℃ then, add the organic tin catalyzer, reaction 1-2h obtains base polyurethane prepolymer for use as; The polyvalent alcohol that contains carboxyl that adds 4-10% in above-mentioned performed polymer is made hydrophilic chain extender, in 60-80 ℃ of reaction 4-7h; The unsaturated monohydroxy-alcohol end-capping reagent and the 0.001-0.05% stopper that contain ethylene linkage that add 8-20% then in 50-70 ℃ of reaction 5-8h, get the Acrylated urethanes monomer;
2), aforesaid propylene acid esters urethane adds the ammoniacal liquor neutralization, stirred 5-30 minute, the adding deionized water, emulsify at a high speed obtains the Acrylated urethanes emulsion of water-based;
3), Acrylated urethanes is the preparation of the core-shell particles of nuclear:
A: the esters of acrylic acid soft monomer of adding 10-20% in above-mentioned emulsion, logical nitrogen stirs, and is warming up to 70-8O ℃, adds the water soluble starter of 0.2-1%, and reaction 5-6h gets seed emulsion;
B: in above-mentioned seed emulsion, add the 0.5-2.0% linking agent, add the water soluble starter of 0.2-1%, be incubated 70-80 ℃, slowly drip the esters of acrylic acid hard monomer of 20-50% and the emulsifying agent of adding 0-1%, the dropping time is 2-3h, dropwises reaction 2-3h, cooling discharge gets the core-shell emulsion of Acrylated urethanes for the nuclear main body;
4), with above-mentioned core-shell emulsion sodium chloride saturated solution breakdown of emulsion ,-1--10 ℃ is freezing, decompress filter, washing, drying is ground, Acrylated urethanes is the core-shell particles of nuclear main body;
More than all consumptions be benchmark all in the core-shell particles total mass.
Wherein polyhydric alcohol polymer can be polyether glycol, polyester polyol, castor-oil plant wet goods, also can be one or more the mixture in polyester-polyether glycol, polycarbonate polyol, polytetrahydrofuran polyvalent alcohol, polyurethane polyol, the polycaprolactone polyol, the preferred, polyethers polyvalent alcohol.
Diisocyanate monomer can be tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), six cyclohexyl diisocyanate (H
6MDI) and one or more mixture of xylylene diisocyanate, preferred tolylene diisocyanate, diphenylmethanediisocyanate (MDI).
The polyvalent alcohol chainextender that contains carboxyl can be one or more the mixture in dimethylol propionic acid (DMPA), dimethylolpropionic acid (DMBA), dihydroxymethyl valeric acid, the tartrate.
The unsaturated monohydroxy-alcohol end-capping reagent that contains ethylene linkage can be one or more the mixture in hydroxyethyl methylacrylate, Propylene glycol monoacrylate, the glycidyl methacrylate.
Stopper can be MEHQ, Resorcinol, 2,6-di-tert-butyl hydroquinone, 2, the mixture of one or more in 6-dinitrobenzene p-cresol, p-ten.-butylcatechol, the thiodiphenylamine.Preferred MEHQ, Resorcinol.
Esters of acrylic acid soft or hard monomer is divided with the second-order transition temperature of its superpolymer, and the present invention selects second-order transition temperature to surpass 50 ℃ monomer as the shell hard monomer, is lower than-20 ℃ as the nuclear soft monomers.The esters of acrylic acid soft monomer that uses among the present invention, can be one or more the mixture in butyl acrylate, ethyl propenoate, isobutyl acrylate, Isooctyl acrylate monomer, Isooctyl methacrylate, the Ethyl acrylate etc., preferred butyl acrylate, ethyl propenoate.
The esters of acrylic acid hard monomer, can be methyl methacrylate, Jia Jibingxisuanyizhi, can also add function monomer such as methacrylic acid, vinylformic acid, dimethylaminoethyl methacrylate, methylacryoyloxyethyl trimethyl ammonium chloride, or one or more the mixture in the phosphoric acid ester function monomer of Rhodia (as PAM 100 and PAM 200), allyloxy hydroxypropyl azochlorosulfonate acid sodium, methallylsulfonic acid sodium, β-propyloic acrylic ester, allyl urea monomer etc. is to improve the wetting ability of shell monomer, preferable methyl methyl acrylate.
Water soluble starter can be persulphate such as Potassium Persulphate, ammonium persulphate, also can be one or more the mixture in redox system such as Potassium Persulphate-sodium bisulfite, Potassium Persulphate-iron protochloride, hydrogen peroxide-iron protochloride, the isopropyl benzene hydroperoxide-iron protochloride.
Linking agent can be Vinylstyrene, methylene-bisacrylamide, N, the mixture of one or more in N '-methylene-bisacrylamide, methacrylate glycol ester, the tripropylene glycol diacrylate.
Emulsifying agent can be nonionic emulsifier such as ethers, ester class, amine, amides, also can be one or more the mixture in anionic emulsifier such as Sulfates, metal carboxylate, Sulfonates, the phosphoric acid salt.Have the particular monomers of hydrophilic radical as the esters of acrylic acid shell monomer, then need not add emulsifying agent.
Core-shell particles provided by the invention can be used as toughner in the Resins, epoxy.
Wherein Resins, epoxy can be one or more the mixture in bisphenol A type epoxy resin, bisphenol f type epoxy resin, the bisphenol-s epoxy resin.
The consumption mass ratio of Resins, epoxy and core-shell particles is preferably 10: 1-30: 1.
Above-mentioned core-shell particles can be added in the Resins, epoxy in the use, add quantitative defoamer, dispersed with stirring is even, then in be ground on the three-roller obtain translucent liquid azury till.The solidifying agent of Jia Ruing again, self-vulcanizing after one week, is measured shearing resistance and shock strength.
Acrylated urethanes of the present invention is compared with existing liquid polyurethane epoxy resin toughener for the core-shell particles of nuclear, has the following advantages:
1, method for making provided by the invention is started with from the angle of environmental protection, adopts the preparation water-based emulsion, and emulsion belongs to nontoxicity liquid,
Nonflammable, there are not artificial interpolation benzene,toluene,xylene, formaldehyde and polymkeric substance thereof and the compound of heavy metal,
Avoided the environmental pollution and the toxic action that are with an organic solvent caused.
2, relate to urethane and acrylic ester monomer simultaneously in the preparation process of this toughner, this just makes is selecting raw material
The time have wideer range of choice, building-up process is more changeable, is convenient to design the core-shell particles of multiple structure.
3, this core-shell particles after the grinding, is white powder through seasoning, and is not perishable, is convenient to deposit for a long time.
4, this toughner is grafted to acrylic ester monomer on the polyurethane molecular chain by radical polymerization, has nucleocapsid structure.
5, this core-shell particles is soft nuclear main body with Acrylated urethanes, guaranteed when epoxy resin toughened, to have good result, when core-shell particles is epoxy resin toughened, before solidifying, be separated fully, can not cause the second-order transition temperature religion to reduce significantly, adopt acrylic ester monomer to do duricrust, can increase the interface compatibility of core-shell particles and Resins, epoxy.
Description of drawings
Fig. 1 is the transmission electron microscope picture (* 80000) of the core-shell particles emulsion of embodiment 1 preparation;
Fig. 2 is the profile scanning Electronic Speculum figure of embodiment 1 Resins, epoxy after core-shell particles is toughness reinforcing.
Embodiment
Embodiment 1
In three mouthfuls of round-bottomed flasks of the 500ml that is equipped with agitator, thermometer and prolong, add 200g polyoxygenated third rare-ethylene oxide dibasic alcohol (M=1000) and the 69.61g tolylene diisocyanate (TDI), logical nitrogen, stir on the limit, heat up in the limit, to 75 ℃, reaction 2h is warming up to 80 ℃, add 5 catalyzer dibutyl tin laurates, reaction 1h.Be cooled to 70 ℃, add 13.41g dimethylol propionic acid (DMPA), reaction 6h, add 50ml acetone viscosity reduction, be cooled to 60 ℃ then, add 26.10g hydroxyethyl methylacrylate (HEMA), 0.31g the stopper MEHQ, reaction 7h gets Acrylated urethanes.
Get the Acrylated urethanes 30g of above-mentioned preparation, the ammoniacal liquor neutralization was stirred 5 minutes, added the 270ml deionized water, and high-speed stirring emulsification gets the Acrylated urethanes emulsion.
Add above-mentioned emulsion and 15g butyl acrylate in being equipped with the 500ml four-hole round-bottomed flask of agitator, thermometer and prolong, logical nitrogen stirs and disperseed 30 minutes, is warming up to 80 ℃, adds initiator 0.5gK
2S
2O
8And 0.2gNaHSO
3, reaction 6h reaches more than 98% to the transformation efficiency of acrylate butyl ester, seed emulsion.
Add 5g linking agent tripropylene glycol diacrylate (TPGDA) in seed emulsion, stir, logical nitrogen is incubated 80 ℃, adds initiator 0.5g K
2S
2O
8And 0.2gNaaHSO
3Slowly drip monomers methyl methacrylate (MMA) 30g and nonionic emulsifier sim alkylphenol Soxylat A 25-7 (OPE-10), the dropping time is 2 hours, after dropwising, reaction 3h, cooling discharge, get the core-shell emulsion band, being detected by JEM-100CXII type transmission electron microscope, see Fig. 1, is tangible nucleocapsid structure as can be seen.
With above-mentioned core-shell emulsion, use the saturated aqueous sodium chloride breakdown of emulsion ,-5 ℃ are freezing, decompress filter, washing, drying is ground, and gets white powder.
Get the above-mentioned core-shell particles powder of 8g, 100g Resins, epoxy 828, the defoamer BYK-141 that 1.1g Bi Ke chemistry company limited produces stirs, and grinds on three-roller, gets blue translucent liquid.
In the Resins, epoxy of above-mentioned grinding, add solidifying agent: 33.3g modification mixed amine (aromatic amine and modified fatty amine), 1.40g 2,4,6,-three (dimethylamino methyl) phenol (DMP-30), 2.40g coupling agent Racemic glycidol oxygen propyl trimethoxy silicane (KH-560), ambient cure, after one week, measure its shearing resistance and shock strength and be respectively 31.63MPa and 7.67KJ/m
2, be respectively 2.21 times and 3.30 times of unmodified epoxy resin, its anti-impact section is seen Fig. 2, among the figure significantly groove and crackle can absorb impact energy, thereby reach toughness reinforcing effect.
Embodiment 2
In three mouthfuls of round-bottomed flasks of the 500ml that is equipped with agitator, thermometer and prolong, add 250g polyethylene glycol adipate glycol (PEA, M=2000) and 62.51g ditan-4,4 '-vulcabond (MDI), logical nitrogen, stir on the limit, heat up in the limit, to 75 ℃, reaction 2h is warming up to 80 ℃, add 5 catalyzer dibutyl tin laurates, reaction 1h.Be cooled to 70 ℃, adding 9.30g dimethylolpropionic acid (DMBA), reaction 5h adds 40ml acetone viscosity reduction, is cooled to 60 ℃ then, adds the 18.17g Rocryl 410, the 0.40g hydroquinone of polymerization retarder, reaction 6h gets Acrylated urethanes.
Get the Acrylated urethanes 30g of above-mentioned preparation, the ammoniacal liquor neutralization was stirred 5 minutes, added the 300ml deionized water, and high-speed stirring emulsification gets the Acrylated urethanes emulsion.
In being equipped with the 500ml four-hole round-bottomed flask of agitator, thermometer and prolong, add above-mentioned emulsion and 15g butyl methacrylate, logical nitrogen, stir and disperseed 30 minutes, be warming up to 80 ℃, add initiator 0.5g ammonium persulphate, reaction 6h reaches more than 98% to the transformation efficiency of methacrylic ester butyl ester, seed emulsion.
In seed emulsion, add the 5g Vinylstyrene, stir, logical nitrogen, be incubated 80 ℃, add initiator 0.5g ammonium persulphate, slowly drip monomer Jia Jibingxisuanyizhi 20g and emulsifier sodium lauryl sulfate 0.5g, the dropping time is 2 hours, after dropwising, reaction 2h, cooling discharge gets core-shell emulsion, being detected by JEM-100CXII type transmission electron microscope, is tangible nucleocapsid structure as can be seen.
With above-mentioned core-shell emulsion, use the saturated aqueous sodium chloride breakdown of emulsion ,-6 ℃ are freezing, decompress filter, washing, drying is ground, and gets white powder.
Get the above-mentioned core-shell particles powder of 5g, 100g Resins, epoxy 828, the defoamer BYK-141 that 1.10g Bi Ke chemistry company limited produces stirs, and grinds on three-roller, gets blue translucent liquid.
Add as embodiment 1 described solidifying agent, ambient cure after one week, is measured its shearing resistance and shock strength and is respectively 25.10Mpa and 5.89KJ/m
2, be respectively 1.75 times and 2.53 times of unmodified epoxy resin.
Embodiment 3
Be equipped with agitator, (PCL M=1000) with 88.92g isophorone diisocyanate (IPDI), leads to nitrogen to add 200g poly-epsilon-caprolactone glycol in three mouthfuls of round-bottomed flasks of the 500ml of thermometer and prolong, stir on the limit, heat up in the limit, to 75 ℃, and reaction 2h, be warming up to 80 ℃, add the inferior tin of 5 octoate catalysts, reaction 2h is cooled to 70 ℃, add 15.01g tartrate, reaction 5h adds 50ml acetone viscosity reduction, is cooled to 60 ℃ then, add 26.10g hydroxyethyl methylacrylate (HEMA), 0.31g stopper 2,6-di-tert-butyl hydroquinone, reaction 8h, get Acrylated urethanes
Get the Acrylated urethanes 30g of above-mentioned preparation, the ammoniacal liquor neutralization was stirred 5 minutes, added the 200ml deionized water, and high-speed stirring emulsification gets the Acrylated urethanes emulsion.
Add above-mentioned emulsion and 15g ethyl propenoate in being equipped with the 500ml four-hole round-bottomed flask of agitator, thermometer and prolong, logical nitrogen stirs and disperseed 30 minutes, is warming up to 80 ℃, adds initiator 0.5gK
2S
2O
8, reaction 6h reaches more than 98% to the transformation efficiency of acrylate ethyl ester, seed emulsion.
Add 3g linking agent methylene-bisacrylamide in seed emulsion, stir, logical nitrogen is incubated 80 ℃, adds initiator 0.5g K
2S
2O
8, slowly dripping monomers methyl methacrylate (MMA) 30g and 0.4g Sodium dodecylbenzene sulfonate, the dropping time is 2 hours, after dropwising, reaction 3h, cooling discharge, getting the core-shell emulsion band, detected by JEM-100CXII type transmission electron microscope, is tangible nucleocapsid structure as can be seen.
With above-mentioned core-shell emulsion, use the saturated aqueous sodium chloride breakdown of emulsion ,-10 ℃ are freezing, decompress filter, washing, drying is ground, and gets white powder.
Get the above-mentioned core-shell particles powder of 10g, 100g Resins, epoxy 828, the defoamer BYK-141 that 1.10g Bi Ke chemistry company limited produces stirs, and grinds on three-roller, gets blue translucent liquid.
Add as embodiment 1 described solidifying agent, ambient cure after one week, is measured its shearing resistance and shock strength and is respectively 24.82Mpa and 5.24KJ/m
2, be respectively 1.73 times and 2.25 times of unmodified epoxy resin.
Claims (10)
1, a kind of core-shell particles, its multipolymer with Acrylated urethanes monomer and esters of acrylic acid soft monomer is a nuclear, the esters of acrylic acid hard monomer is a shell in the grafting outward again.
2, the core-shell particles of claim 1, wherein in the multipolymer of Acrylated urethanes monomer and esters of acrylic acid soft monomer, the mass ratio of Acrylated urethanes monomer and esters of acrylic acid soft monomer is 2: 1～4: 1, the nucleocapsid mass ratio is 1: 2～2: 1.
3, claim 1 or 2 core-shell particles, its particle diameter is 40～80nm.
4, the preparation method of the arbitrary core-shell particles of claim 1～3 comprises the steps:
1), the preparation of Acrylated urethanes: with the number-average molecular weight of 30-40% is that 300-3000, hydroxyl value are that the polyhydric alcohol polymer of 50-200mgKOH/g is earlier through decompression dehydration, diisocyanate monomer with 10-30% reacts 1-3h at 70-75 ℃ again, be warming up to 80-90 ℃ then, add the organic tin catalyzer, reaction 1-2h obtains base polyurethane prepolymer for use as; The polyvalent alcohol that contains carboxyl that adds 4-10% in above-mentioned performed polymer is made hydrophilic chain extender, in 60-80 ℃ of reaction 4-7h; The unsaturated monohydroxy-alcohol end-capping reagent and the 0.001-0.05% stopper that contain ethylene linkage that add 8-20% then, in 50-70 ℃ of reaction 5-8h, the Acrylated urethanes monomer, the said unsaturated monohydroxy-alcohol end-capping reagent that contains ethylene linkage is one or more the mixture in hydroxyethyl methylacrylate, Propylene glycol monoacrylate, the glycidyl methacrylate;
2), aforesaid propylene acid esters urethane adds the ammoniacal liquor neutralization, stirred 5-30 minute, the adding deionized water, emulsify at a high speed obtains the Acrylated urethanes emulsion of water-based;
3), Acrylated urethanes is the preparation of the core-shell particles of nuclear:
A: the esters of acrylic acid soft monomer of adding 10-20% in above-mentioned emulsion, logical nitrogen stirs, and is warming up to 70-80 ℃, adds the water soluble starter of 0.2-1%, and reaction 5-6h gets seed emulsion;
B: in above-mentioned seed emulsion, add the 0.5-2.0% linking agent, add the water soluble starter of 0.2-1%, be incubated 70-80 ℃, slowly drip the esters of acrylic acid hard monomer of 20-50% and the emulsifying agent of adding 0-1%, the dropping time is 2-3h, dropwises reaction 2-3h, cooling discharge gets the core-shell emulsion of Acrylated urethanes for the nuclear main body;
4), with above-mentioned core-shell emulsion sodium chloride saturated solution breakdown of emulsion ,-1--10 ℃ is freezing, decompress filter, washing, drying is ground, Acrylated urethanes is the core-shell particles of nuclear main body;
More than all consumptions be benchmark all in the core-shell particles total mass.
5, the method for claim 4, wherein polyhydric alcohol polymer is a polyether glycol.
6, claim 4 or 5 method, wherein diisocyanate monomer is selected from tolylene diisocyanate, diphenylmethanediisocyanate.
7, claim 4 or 5 method, wherein the esters of acrylic acid soft monomer is selected from butyl acrylate, ethyl propenoate, and the esters of acrylic acid hard monomer is a methyl methacrylate.
8, arbitrary core-shell particles is used as toughner in the Resins, epoxy in the claim 1～3.
9, the application of claim 8, wherein Resins, epoxy is selected from one or more the mixture in bisphenol A type epoxy resin, bisphenol f type epoxy resin, the bisphenol-s epoxy resin.
10, claim 8 or 9 application, wherein the consumption mass ratio of Resins, epoxy and core-shell particles is 10: 1-30: 1.
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