CN1063190C - Cross-linked hard core-shell copolymerized particle - Google Patents
Cross-linked hard core-shell copolymerized particle Download PDFInfo
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- CN1063190C CN1063190C CN97106348A CN97106348A CN1063190C CN 1063190 C CN1063190 C CN 1063190C CN 97106348 A CN97106348 A CN 97106348A CN 97106348 A CN97106348 A CN 97106348A CN 1063190 C CN1063190 C CN 1063190C
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Abstract
The present invention relates to crosslinking core-shell copolymerized particles, each particle comprises a core and a shell, wherein the core contains an alkenyl arene chain segment and a crosslinking agent; the shell contains an alkenyl arene chain segment; the chain segment of the shell is connected with the core through one end of the core with the crosslinking agent. When crosslinking core-shell copolymerized particles are used for toughening of cross blend cross blending of pure polystyrene, the shock strength can be increased by about one time without influencing the dtransparence of the pure polystyrene; the particles can be used for toughening and modifying the transparent polystyrene.
Description
The present invention relates to cross-linked core-shell copolymerized particle, particularly about being used for the cross-linked hard core-shell copolymerized particle of transparent polystyrene blending toughening.
Styrene is the most facile kind in the transparent plastic, but owing to himself fragility shortcoming, is very limited in the application, only is used at present low grade products.P-poly-phenyl ethene toughness reinforcing has several different methods, as: with the graft copolymerization (high-impact polystyrene) of divinyl; With vinyl cyanide, butadiene copolymer (ABS); With other polymer blending etc.But the difficult toughening modifying that is used for transparent polystyrene of these methods.Because the composite emulsion polymerization technology can design the macromolecule emulsion microballoon from microcosmic, regulate copolymer component, the refraction index of nucleocapsid and base material is complementary, when changing simultaneously the composite emulsion polymerization condition and making the core-shell particle size be lower than 0.1 μ m, can not affected the modifier of the base material transparency.Desirable nucleocapsid structure polymer particles should be that the shell polymer chain is related with nuclear phase to guarantee energy transmission between layers, and such core-shell polymer must have following polymerizing condition: monomer is the swelling polymer particle not: the shell polymer is at the nuclear Surface Creation: not phase counterdiffusion between nuclear and the shell.Along with going deep into that core-shell particle is studied, people have developed multiple structure core-shell particle, are used for the blending and modifying to various polymkeric substance.Japan's military field pharmaceutical industries (strain) changes into that the big island of product institute is pure to be controlled etc. at " polymer collection of thesis " Vol.52 in June nineteen ninety-five, No.l, p.17-24 reported with the butyl polyacrylate to be nuclear in, polymethylmethacrylate is a shell, and with allyl methacrylate(AMA) and 1,4-butyleneglycol double methacrylate is the synthetic core-shell copolymerized particle with crosslinked soft nuclear of linking agent.Its particle diameter can only be suitable for the blending and modifying to nontransparent resin about 0.3 μ m.
In order to overcome the shortcoming that exists in the above-mentioned document, the purpose of this invention is to provide a kind of new cross-linked hard core-shell copolymerized particle, this particulate can be fit to the blending toughening modification of transparent resin, especially the blending toughening modification of transparent polystyrene, when not influencing light transmission, shock strength can increase nearly 1 times after the modification.
The objective of the invention is to realize: a kind of cross-linked hard core-shell copolymerized particle by following technical scheme, comprise nuclear, shell, nuclear contains alkenyl arene segment and linking agent, shell contains the alkenyl arene segment, the segment of shell connects by an end and the nuclear phase of linking agent, the weight ratio of its center and shell is 1: 1.09～1.96, and the particle diameter of copolymerized particle is 90～129 nanometers.
In the technique scheme, alkenyl arene can be vinylbenzene, alpha-methyl styrene, p-methylstyrene, and its preferred version is a vinylbenzene.Linking agent can be two methacryloxypropyl phenyl-propanes, polyethersulfone diene macromonomer or its mixture.In copolymerized particle in the parts by weight linking agent: nuclear is 0.1～10: 90～99.9.
In the core-shell particle of above-mentioned cross-linked hard, the structural formula of two methacryloxypropyl phenyl-propanes (BVA) of linking agent or polyethersulfone diene macromonomer (BVPES) is:
The preparation method of cross-linked hard core-shell particulate of the present invention adopts the composite emulsion method, is polymerized by two-step approach.Its concrete steps are as follows:
The first step: with deionized water, emulsifying agent (oleate) and small amount of N aHCO
3Place three mouthfuls of reaction flasks, feed nitrogen.Stirring fully disperses emulsifying agent, with raw material alkenyl arene monomer and crosslinking agent and initator (K
2S
2O
8) mixed liquor add in the reaction bulb, 80～120 ℃ of lower polymerizations.With the fritted sand funnel a small amount of block condensation product in the system is filtered.
Second step: drip simultaneously alkenyl arene monomer and acetone mixed liquor and add emulsifying agent and initator, continue again reaction 0.2～2 hour, reaction is stopped.
Crosslinking agent adds copolymerization in this technology in first step reaction, can prevent core shell reverse. and increase the hardness of examining, thus prepared the nucleocapsid structure particulate with crosslinked centronucleus.This particulate is applicable to the toughening modifying of transparent polystyrene, has obtained effect preferably.
[embodiment 1]
Enuatrol 1 gram is put into there-necked flask, add 1 gram sodium acid carbonate and letting nitrogen in and deoxidizing.Add 140 gram deionized water dissolving and turn on agitator, treat that emulsifying agent enuatrol and sodium acid carbonate dissolve be uniformly dispersed rear (about 20 minutes), add first monomer mixture (styrene 50 grams, bismethacryloyloxyphenyl propane 0.82 gram), after continuing to stir 20 minutes abundant dispersions, move in 95 ℃ of water-baths, add initator K
2S
2O
8(with 20 ml deionized water dissolving, 0.16 gram) reaction 1 hour, this moment, system was blue look, was cooled to 80 ℃.Suction filtration is removed condensation product, adds 0.1 gram enuatrol again, simultaneously drip styrene (65 gram), acetone (7.5ml) mixture and enuatrol (0.5 gram), K
2S
2O
8(0.2 gram), H
2The mixture of O (25 gram) continues reaction 2～2.5 hours, stops namely to get the cross-linked core-shell copolymerized particle emulsion.
Above-mentioned emulsion is diluted to solid content about 5% through methyl alcohol, with 5% salt naphtenic acid, adds altogether about 580 milliliters, solidifyingization of heating 10～20 minutes, precipitation is through methanol wash centrifugal sedimentation, prior to 70 ℃ of forced air dryings, in 40 ℃ of vacuum drying 24 hours, namely get fine-particle powder again.[embodiment 2]
Enuatrol 1 gram is put into there-necked flask, add 1 gram sodium acid carbonate and letting nitrogen in and deoxidizing.Add 140 gram deionized water dissolving and turn on agitator, treat that emulsifying agent enuatrol and sodium acid carbonate dissolve be uniformly dispersed rear (about 20 minutes), add first monomer mixture (styrene 35 grams, bismethacryloyloxyphenyl propane 0.82 gram), after continuing to stir 20 minutes abundant dispersions, move in 95 ℃ of water-baths, add initator (NH
4)
2S
2O
8(with 20 ml deionized water dissolving, 0.16 gram) reaction 1 hour, this moment, system was blue look, was cooled to 80 ℃.Suction filtration is removed condensation product, adds 0.1 gram enuatrol again, simultaneously drip styrene (65 gram), acetone (7.5ml) mixture and enuatrol (0.5 gram), (NH
4)
2S
2O
8(0.2 gram), H
2The mixture of O (25 gram) continues reaction 2～2.5 hours, stops namely to get the cross-linked core-shell copolymerized particle emulsion.
Above-mentioned emulsion is diluted to solid content about 5% through ethanol.With 5% salt naphtenic acid, add altogether about 580 milliliters, solidifyingization of heating 10～20 minutes, precipitation prior to 70 ℃ of forced air dryings, in 40 ℃ of vacuum drying 24 hours, namely gets fine-particle powder through methanol wash centrifugal sedimentation again.[embodiment 3]
Enuatrol 1.5 grams are put into there-necked flask, add 1 gram sodium acid carbonate and letting nitrogen in and deoxidizing.Add 180 gram deionized water dissolving and turn on agitator, treat that emulsifying agent enuatrol and sodium acid carbonate dissolve be uniformly dispersed rear (about 20 minutes), add first monomer mixture (styrene 40 grams, bismethacryloyloxyphenyl propane 1.0 grams), after continuing to stir 20 minutes abundant dispersions, move in 95 ℃ of water-baths, add initator K
2S
2O
80.2 gram, FeSO
40.10 gram (with 20 ml deionized water dissolving, 0.20 gram) reaction 1 hour, this moment, system was blue look, was cooled to 80 ℃.Suction filtration is removed condensation product, adds 0.2 gram enuatrol again, simultaneously drip styrene (65 gram), acetone (7.5ml) mixture and enuatrol (0.3 gram), K
2S
2O
8(0.3 gram), H
2The mixture of O (30 gram) continues reaction 2～2.5 hours, stops namely to get the cross-linked core-shell copolymerized particle emulsion.
Above-mentioned emulsion is diluted to solid content about 5% through methyl alcohol, with 5% salt naphtenic acid, adds altogether about 580 milliliters, solidifyingization of heating 10～20 minutes, precipitation is through methanol wash centrifugal sedimentation, prior to 70 ℃ of forced air dryings, in 40 ℃ of vacuum drying 24 hours, namely get fine-particle powder again.[embodiment 4]
Enuatrol 2 grams are put into there-necked flask, add 1 gram sodium acid carbonate and letting nitrogen in and deoxidizing.Add 180 gram deionized water dissolving and turn on agitator, treat that emulsifying agent enuatrol and sodium acid carbonate dissolve be uniformly dispersed rear (about 20 minutes), add first monomer mixture (styrene 40 grams, polyether sulfone double methyl methacrylate 2.5 grams), after continuing to stir 20 minutes abundant dispersions, move in 95 ℃ of water-baths, add initator K
2S
2O
8(with 20 ml deionized water dissolving, 0.30 gram) reaction 1 hour, this moment, system was blue look, was cooled to 80 ℃.Suction filtration is removed condensation product, adds 0.40 gram enuatrol again, simultaneously drip styrene (80 gram), acetone (10ml) mixture and enuatrol (0.8 gram), K
2S
2O
8(0.5 gram), H
2The mixture of O (20 gram) continues reaction 2～2.5 hours, stops namely to get the cross-linked core-shell copolymerized particle emulsion.
Above-mentioned emulsion is diluted to solid content about 5% through methyl alcohol, with 5% salt naphtenic acid, adds altogether about 580 milliliters, solidifyingization of heating 10～20 minutes, precipitation is through methanol wash centrifugal sedimentation, prior to 70 ℃ of forced air dryings, in 40 ℃ of vacuum drying 24 hours, namely get fine-particle powder again.[embodiment 5]
Enuatrol 5 grams are put into there-necked flask, add 1 gram sodium acid carbonate and letting nitrogen in and deoxidizing.Add 250 gram deionized water dissolving and turn on agitator, treat that the dissolving of emulsifying agent enuatrol and sodium acid carbonate is uniformly dispersed rear (about 20 minutes), add first monomer mixture (styrene 45 grams, bismethacryloyloxyphenyl propane 0.82 gram).After continuing to stir 20 minutes abundant dispersions, move in 95 ℃ of water-baths, add initator K
2S
2O
8(going from restraining in water-soluble solution 0.50 with 20 milliliters) reaction 1 hour, this moment, system was blue look, was cooled to 80 ℃.Suction filtration is removed condensation product, adds 0.20 gram enuatrol again, simultaneously drip styrene (50 gram), acetone (5ml) mixture and enuatrol (0.5 gram), K
2S
2O
8(0.2 gram), H
2The mixture of O (25 gram) continues reaction 2～2.5 hours, stops namely to get the cross-linked core-shell copolymerized particle emulsion.
Above-mentioned emulsion is diluted to solid content about 5% through methyl alcohol, with 5% salt naphtenic acid, adds altogether about 580 milliliters, solidifyingization of heating 10～20 minutes, precipitation is through methanol wash centrifugal sedimentation, prior to 70 ℃ of forced air dryings, in 40 ℃ of vacuum drying 24 hours, namely get fine-particle powder again.[embodiment 6]
Enuatrol 1.5 grams are put into there-necked flask, add 1 gram sodium acid carbonate and letting nitrogen in and deoxidizing.Add 140 gram deionized water dissolving and turn on agitator, treat that emulsifying agent enuatrol and sodium acid carbonate dissolve be uniformly dispersed rear (about 20 minutes), add first monomer mixture (styrene 40 grams, bismethacryloyloxyphenyl propane 1.0 grams), after continuing to stir 20 minutes abundant dispersions, move in 95 ℃ of water-baths, add initator K
2S
2O
8(with 20 ml deionized water dissolving, 0.1 gram) reaction 1 hour, this moment, system was blue look, was cooled to 80 ℃.Suction filtration is removed condensation product, adds 0.10 gram enuatrol again, simultaneously drip styrene (80 gram), acetone (7.5ml) mixture and enuatrol (0.8 gram), K
2S
2O
8(0.5 gram), H
2The mixture of O (20 gram) continues reaction 2～2.5 hours, stops namely to get the cross-linked core-shell copolymerized particle emulsion.
Above-mentioned emulsion is diluted to solid content about 5% through methyl alcohol, with 5% salt naphtenic acid, adds about 580 milliliters altogether, and heating is changed 10～20 minutes with fixed attention, and precipitation is through methanol wash centrifugal settling, prior to 70 ℃ of forced air dryings, again in 40 ℃ of vacuum-dryings 24 hours.Promptly get fine-particle powder.[embodiment 7]
Enuatrol 1.5 grams are put into there-necked flask, add 1 gram sodium acid carbonate and letting nitrogen in and deoxidizing.Add 140 gram deionized water dissolving and turn on agitator, treat that emulsifying agent enuatrol and sodium acid carbonate dissolve be uniformly dispersed rear (about 20 minutes), add first monomer mixture (styrene 40 grams, bismethacryloyloxyphenyl propane 1.0 grams), after continuing to stir 20 minutes abundant dispersions, move in 95 ℃ of water-baths, add initator K
2S
2O
8(with 20 ml deionized water dissolving, 0.16 gram) reaction 1 hour, this moment, system was blue look, was cooled to 80 ℃.Suction filtration is removed condensation product. add again 0.10 gram enuatrol, simultaneously drip styrene (70 gram), acetone (7.5ml) mixture and enuatrol (0.5 gram), K
2S
2O
8(0.4 gram), H
2The mixture of O (20 gram) continues reaction 2～2.5 hours, stops namely to get the cross-linked core-shell copolymerized particle emulsion.
Above-mentioned emulsion is diluted to solid content about 5% through methyl alcohol, with 5% salt naphtenic acid, adds altogether about 580 milliliters, solidifyingization of heating 10～20 minutes, precipitation is through methanol wash centrifugal sedimentation, prior to 70 ℃ of forced air dryings, in 40 ℃ of vacuum drying 24 hours, namely get fine-particle powder again.[embodiment 8]
Enuatrol 1.5 grams are put into there-necked flask, add 1 gram sodium acid carbonate and letting nitrogen in and deoxidizing.Add 140 gram deionized water dissolving and turn on agitator, treat that emulsifying agent enuatrol and sodium acid carbonate dissolve be uniformly dispersed rear (about 20 minutes), add first monomer mixture (AMS 40 grams, bismethacryloyloxyphenyl propane 0.8 gram), after continuing to stir 20 minutes abundant dispersions, move in 95 ℃ of water-baths, add initator K
2S
2O
8(with 20 ml deionized water dissolving, 0.16 gram) reaction 1 hour, this moment, system was blue look, was cooled to 80 ℃.Suction filtration is removed condensation product, adds 0.10 gram enuatrol again, simultaneously drip styrene (70 gram), acetone (7.5ml) mixture and enuatrol (0.5 gram), K
2S
2O
8(0.4 gram, H
2The mixture of O (20 gram) continues reaction 2～2.5 hours, stops namely to get the cross-linked core-shell copolymerized particle emulsion.
Above-mentioned emulsion is diluted to solid content about 5% through methyl alcohol, with 5% salt naphtenic acid, adds altogether about 580 milliliters, solidifyingization of heating 10～20 minutes, precipitation is through methanol wash centrifugal sedimentation, prior to 70 ℃ of forced air dryings, in 40 ℃ of vacuum drying 24 hours, namely get fine-particle powder again.[embodiment 9]
Enuatrol 1.5 grams are put into there-necked flask, add 1 gram sodium acid carbonate and letting nitrogen in and deoxidizing.Add 140 gram deionized water dissolving and turn on agitator, treat that emulsifying agent enuatrol and sodium acid carbonate dissolve be uniformly dispersed rear (about 20 minutes), add first monomer mixture (p-methylstyrene 45 grams, bismethacryloyloxyphenyl propane 1.0 grams), after continuing to stir 20 minutes abundant dispersions, move in 95 ℃ of water-baths, add initator K
2S
2O
8(with 20 ml deionized water dissolving, 0.20 gram) reaction 1 hour, this moment, system was blue look, was cooled to 80 ℃.Suction filtration is removed condensation product, adds 0.10 gram enuatrol again, simultaneously drip styrene (70 gram), acetone (7.5ml) mixture and enuatrol (0.5 gram), K
2S
2O
8(0.4 gram), H
2The mixture of O (20 gram) continues reaction 2～2.5 hours, stops namely to get the cross-linked core-shell copolymerized particle emulsion.
Above-mentioned emulsion is diluted to solid content about 5% through methyl alcohol, with 5% salt naphtenic acid, adds altogether about 580 milliliters. solidifyingization of heating 10～20 minutes, precipitation is through methanol wash centrifugal sedimentation, prior to 70 ℃ of forced air dryings, in 40 ℃ of vacuum drying 24 hours, namely get fine-particle powder again.[embodiment 10]
Enuatrol 1.5 grams are put into there-necked flask, add 1 gram sodium acid carbonate and letting nitrogen in and deoxidizing.Add 140 gram deionized water dissolving and turn on agitator, treat that the dissolving of emulsifying agent enuatrol and sodium acid carbonate is uniformly dispersed rear (about 20 minutes), add first monomer mixture (AMS 40 grams, bismethacryloyloxyphenyl propane 1.0 grams).After continuing to stir 20 minutes abundant dispersions, move in 95 ℃ of water-baths, add initator K
2S
2O
8(with 20 ml deionized water dissolving, 0.18 gram) reaction 1 hour, this moment, system was blue look, was cooled to 80 ℃.Suction filtration is removed condensation product, adds 0.10 gram enuatrol again, simultaneously drip styrene (75 gram), acetone (7.5ml) mixture and enuatrol (0.5 gram), K
2S
2O
8(0.4 gram), H
2The mixture of O (20 gram).Continue reaction 2～2.5 hours, stop namely to get the cross-linked core-shell copolymerized particle emulsion.
Above-mentioned emulsion is diluted to solid content about 5% through methyl alcohol, with 5% salt naphtenic acid, adds altogether about 580 milliliters, solidifyingization of heating 10～20 minutes, precipitation is through methanol wash centrifugal sedimentation, prior to 70 ℃ of forced air dryings, in 40 ℃ of vacuum drying 24 hours, namely get fine-particle powder again.[embodiment 11]
Enuatrol 1.5 grams are put into there-necked flask, add 1 gram sodium acid carbonate and letting nitrogen in and deoxidizing.Add 140 gram deionized water dissolving and turn on agitator, treat that emulsifying agent enuatrol and sodium acid carbonate dissolve be uniformly dispersed rear (about 20 minutes), add first monomer mixture (p-methylstyrene 40 grams, bismethacryloyloxyphenyl propane 1.0 grams), after continuing to stir 20 minutes abundant dispersions, move in 95 ℃ of water-baths, add initator K
2S
2O
8(with 20 ml deionized water dissolving, 0.16 gram) reaction 1 hour, this moment, system was blue look, was cooled to 80 ℃.Suction filtration is removed condensation product, adds 0.10 gram enuatrol again, simultaneously drip styrene (70 gram), acetone (7.5ml) mixture and enuatrol (0.5 gram), K
2S
2O
8(0.4 gram), H
2The mixture of O (20 gram) continues reaction 2～2.5 hours, stops namely to get the cross-linked core-shell copolymerized particle emulsion.
Above-mentioned emulsion is diluted to solid content about 5% through methyl alcohol, with 5% salt naphtenic acid, adds altogether about 580 milliliters, solidifyingization of heating 10～20 minutes, precipitation is through methanol wash centrifugal sedimentation, prior to 70 ℃ of forced air dryings, in 40 ℃ of vacuum drying 24 hours, namely get fine-particle powder again.[embodiment 12]
Enuatrol 1.5 grams are put into there-necked flask, add 1 gram sodium acid carbonate and letting nitrogen in and deoxidizing.Add 140 gram deionized water dissolving and turn on agitator, treat emulsifying agent enuatrol and sodium acid carbonate dissolved fraction evenly rear (about 20 minutes), add first monomer mixture (AMS 40 grams, bismethacryloyloxyphenyl propane 1.5 grams), after continuing to stir 20 minutes abundant dispersions, move in 95 ℃ of water-baths, add initator K
2S
2O
8(with 20 milliliter deionized water dissolvings, 0.16 gram) reaction 1 hour, this moment, system was blue look, was cooled to 80 ℃.Suction filtration is removed condensation product, adds 0.10 gram enuatrol again, simultaneously drip styrene (70 gram), acetone (7.5ml) mixture and enuatrol (0.5 gram), K
2S
2O
8(0.3 gram), H
2The mixture of O (20 gram) continues reaction 2～2.5 hours, stops namely to get the cross-linked core-shell copolymerized particle emulsion.
Above-mentioned emulsion is diluted to solid content about 5% through methyl alcohol, with 5% salt naphtenic acid, adds altogether about 580 milliliters, solidifyingization of heating 10～20 minutes, precipitation is through methanol wash centrifugal sedimentation, prior to 70 ℃ of forced air dryings, in 40 ℃ of vacuum drying 24 hours, namely get fine-particle powder again.[embodiment 13]
Enuatrol 1.5 grams are put into there-necked flask, add 1 gram sodium acid carbonate and letting nitrogen in and deoxidizing.Add 140 gram deionized water dissolving and turn on agitator, treat that emulsifying agent enuatrol and sodium acid carbonate dissolve be uniformly dispersed rear (about 20 minutes), add first monomer mixture (styrene 40 grams, bismethacryloyloxyphenyl propane 1.5 grams), after continuing to stir 20 minutes abundant dispersions, move in 95 ℃ of water-baths, add initator K
2S
2O
8(with 20 ml deionized water dissolving, 0.20 gram) reaction 1 hour, this moment, system was blue look, was cooled to 80 ℃.Suction filtration is removed condensation product, adds 0.10 gram enuatrol again, simultaneously drip styrene (70 gram), acetone (7.5ml) mixture and enuatrol (0.5 gram), K
2S
2O
8(0.4 gram), H
2The mixture of O (20 gram) continues reaction 2～2.5 hours, stops namely to get the cross-linked core-shell copolymerized particle emulsion.
Above-mentioned emulsion is diluted to solid content about 5% through methyl alcohol, with 5% salt naphtenic acid, adds altogether about 580 milliliters, solidifyingization of heating 10～20 minutes, precipitation is through methanol wash centrifugal sedimentation, prior to 70 ℃ of forced air dryings, in 40 ℃ of vacuum drying 24 hours, namely get fine-particle powder again.[embodiment 14]
Enuatrol 1.5 grams are put into there-necked flask, add 1 gram sodium acid carbonate and letting nitrogen in and deoxidizing.Add 140 gram deionized water dissolving and turn on agitator, treat that emulsifying agent enuatrol and sodium acid carbonate dissolve be uniformly dispersed rear (about 20 minutes), add first monomer mixture (AMS 45 grams, bismethacryloyloxyphenyl propane 1.2 grams), after continuing to stir 20 minutes abundant dispersions, move in 95 ℃ of water-baths, add initator K
2S
2O
8(with 20 ml deionized water dissolving, 0.2 gram) reaction 1 hour, this moment, system was blue look, was cooled to 80 ℃.Suction filtration is removed condensation product, adds 0.10 gram enuatrol again, simultaneously drip styrene (75 gram), acetone (7.5ml) mixture and enuatrol (0.5 gram), K
2S
2O
8(0.5 gram), H
2The mixture of O (20 gram). continue reaction 2～2.5 hours, stop namely to get the cross-linked core-shell copolymerized particle emulsion.
Above-mentioned emulsion is diluted to solid content about 5% through methyl alcohol, with 5% salt naphtenic acid, adds altogether about 580 milliliters, solidifyingization of heating 10～20 minutes, precipitation is through methanol wash centrifugal sedimentation, prior to 70 ℃ of forced air dryings, in 40 ℃ of vacuum drying 24 hours, namely get fine-particle powder again.[embodiment 15]
Get 80 milliliters of toluene, chloroform is mixed in the beaker for 20 milliliters, and the core-shell copolymerized particle 1 that add transparent polystyrene pellet 20 grams, makes with embodiment 1 restrains particle size 90nm.Low-grade fever to 40～50 ℃, treat solid dissolve fully mix after, desolventizing namely gets modification transparent polystyrene material.Light transmission is 90% (wavelength 700nm), and shock strength is 5.57KJ/m
2, be equivalent to pure polystyrene shock strength 3.14KJ/m
21.77 times.[embodiment 16]
Get 60 milliliters of toluene, chloroform is mixed in the beaker for 40 milliliters, and the core-shell copolymerized particle 0.5 that add transparent polystyrene pellet 25 grams, makes with embodiment 2 restrains particle size 129nm.Low-grade fever to 40～50 ℃, treat solid dissolve fully mix after, desolventizing namely gets modification transparent polystyrene material.Light transmission is 88% (wavelength 700nm), and shock strength is 6.30KJ/m
2, be pure polystyrene shock strength 3.14KJ/m
22.01 times.[embodiment 17]
Get 50 milliliters of toluene, chloroform is mixed in the beaker for 50 milliliters, and the core-shell copolymerized particle 2 that add transparent polystyrene pellet 20 grams, makes with embodiment 3 restrains particle size 129nm.Low-grade fever to 40～50 ℃, treat solid dissolve fully mix after, desolventizing namely gets modification transparent polystyrene material.Light transmission is 89% (wavelength 700nm), and shock strength is 6.28KJ/m
2, be pure polystyrene shock strength 3.14KJ/m
22.0 times.[comparative example]
Behind pure polystyrene processing batten, measuring its light transmission is 88～89% (wavelength 700nm), and shock strength is 3.14KJ/m
2
Claims (5)
1, a kind of cross-linked hard core-shell copolymerized particle, comprise nuclear, shell, it is characterized in that nuclear is for containing alkenyl arene segment and linking agent, shell is the segment that contains alkenyl arene, the segment of shell connects by an end and the nuclear phase of linking agent, the weight ratio of its center and shell is 1: 1.09～1.96, and the particle diameter of copolymerized particle is 90～129 nanometers.
2,, it is characterized in that alkenyl arene is vinylbenzene, alpha-methyl styrene, p-methylstyrene according to the described cross-linked hard core-shell copolymerized particle of claim 1.
3,, it is characterized in that alkenyl arene is a vinylbenzene according to the described cross-linked hard core-shell copolymerized particle of claim 2.
4,, it is characterized in that linking agent is two methacryloxypropyl phenyl-propanes, polyethersulfone diene macromonomer or its mixture according to the described cross-linked hard core-shell copolymerized particle of claim 1.
5, according to the described cross-linked hard core-shell copolymerized particle of claim 1, it is characterized in that in the copolymerized particle in the parts by weight linking agent: nuclear is 0.1～10: 90～99.9.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106348A CN1063190C (en) | 1997-04-03 | 1997-04-03 | Cross-linked hard core-shell copolymerized particle |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106348A CN1063190C (en) | 1997-04-03 | 1997-04-03 | Cross-linked hard core-shell copolymerized particle |
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| CN1063190C true CN1063190C (en) | 2001-03-14 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4681915A (en) * | 1985-12-20 | 1987-07-21 | General Electric Company | Impact modified polyphenylene ether-polyamide compositions |
| EP0300212A2 (en) * | 1987-07-21 | 1989-01-25 | General Electric Company | Impact modified poly(alkenyl aromatic) resin compostions |
-
1997
- 1997-04-03 CN CN97106348A patent/CN1063190C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4681915A (en) * | 1985-12-20 | 1987-07-21 | General Electric Company | Impact modified polyphenylene ether-polyamide compositions |
| EP0300212A2 (en) * | 1987-07-21 | 1989-01-25 | General Electric Company | Impact modified poly(alkenyl aromatic) resin compostions |
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| Publication number | Publication date |
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| CN1194990A (en) | 1998-10-07 |
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