CN1260309C - New method for superfine particle surface modification - Google Patents
New method for superfine particle surface modification Download PDFInfo
- Publication number
- CN1260309C CN1260309C CN 200410042527 CN200410042527A CN1260309C CN 1260309 C CN1260309 C CN 1260309C CN 200410042527 CN200410042527 CN 200410042527 CN 200410042527 A CN200410042527 A CN 200410042527A CN 1260309 C CN1260309 C CN 1260309C
- Authority
- CN
- China
- Prior art keywords
- carbon black
- nanometer
- grafted
- sio
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The present invention relates to a new method for the surface modification of superfine inorganic solid particles. The method comprises: polycondensation reaction is implemented between an ABx monomer or an AxB monomer and a superfine particle as a reaction central core in one step under the condition of the existence of certain temperature, mechanical stirring, nitrogen protection and a catalyst. A hyperbranched polymer is grafted on the surface of the superfine particle. The surface performance of the obtained superfine particle of hyperbranched polymer grafted modification is greatly changed to be well dispersed in various resin matrixes and solvent. The method can be completed in one step and is simple and practical. The modified inorganic solid particle can be widely applied to the fields of macromolecule composite material, electronic packaging material, plastics, paint, rubber, antibacterial material, etc. and has wide industrial application prospects.
Description
Technical field
The present invention relates to a kind of novel method of ultrafine particle surface modification.
Background technology
As everyone knows, the Application Areas of ultrafine particle is very extensive.With the nano silicon is example, and it can be widely used in electronic package material, polymer matrix composites, fields such as plastics, coating, rubber and anti-biotic material.But because the ultrafine particle surface energy is big, very easily reunite, make it to be difficult to be distributed in the polymeric matrix equably.Directly add the ultrafine particle that is untreated, generally at very low level (generally below 1%), the effect of ultrafine particle can not get demonstrating fully addition so.Therefore, solve the ultrafine particle agglomeration traits, improve its dispersiveness in matrix and become an important research direction.The method that solves ultrafine particle reunion and bad dispersibility is modification to be carried out on its surface handle.By modification, change the physico-chemical property of ultrafine particle, not only can significantly improve dispersiveness and the consistency of ultrafine particle in matrix, and can make the surface-functionalized of ultrafine particle, thus the over-all properties of raising material.
At present, the surface modifying method of ultrafine particle is a lot, comprises physical method and chemical process two classes.With nanometer SiO
2Be example, physical method such as silane coupler modified method, titanate coupling agent modification method, polymer overmold method, plasma surface treatment etc.It is inapt that these surface modifying methods belong to mostly, causes the nanometer SiO after the modification
2Still can not reach maximum effect; Chemical process such as surface grafting polymerization react, institute's grafted organic molecule can be the linear structure macromole, as utilize vinylbenzene and be grafted in advance that Raolical polymerizable has taken place two keys of silane coupling agent on the superfine silicon dioxide surface, thereby obtain the nanometer SiO of linear structure macromole graft modification
2Also can be the dendrimer of regular cladodification structure and highly branched hyperbranched polymer, as at first at nanometer SiO
2Initial group (NH is introduced on the surface
2), with the method for dispersing polyamide-based dendrimer (PAMAM) has been grafted to the surface of nano silicon then, improve greatly through the dispersion stabilization of the product after the modification in methyl alcohol; As utilizing at nanometer SiO
2Azo-group that introduce on the surface and vinyl monomer generation graft polymerization reaction arrive nanometer SiO with grafted by super branched polymer
2The surface; As can being that the polyethers dendrimer of carboxyl and polyarylester dendrimer have been grafted to the nanometer SiO through silane coupling agent pretreating surface band amino respectively with convergence method with interior end group
2Improve greatly through the dispersion stabilization of the product after the modification in organic solvent on the surface.But these graft-modification methods have common characteristic, all are at first at nanometer SiO
2Introduce initial group on the surface, and then polymerization reaction take place.Exist step various, severe reaction conditions, problems such as complex process.
Summary of the invention
1. goal of the invention: the present invention is intended to seek a kind of simple method of the ultrafine particle surface being carried out chemical modification grafting hyperbranched polymer, not only solve the ultrafine particle agglomeration traits, improve its dispersed and stable in matrix, and make the surface-functionalized of ultrafine particle, thereby improve the over-all properties of material.
2. summary of the invention: the present invention proposes a kind of is under the condition of 10h～12h in mechanical stirring, nitrogen protection, organic acid or organic alkali as a catalyst, temperature of reaction 120 ℃～140 ℃ and reaction times; the micron order or the nano level superfine particle that have hydroxyl or carboxyl or ester group with the surface are reactive center nuclear, with AB
xOr A
xThe B monomer is through the novel method of a step melt polymerization or solution polymerization grafting hyperbranched polymer chemical modification ultrafine particle.
3. invention is advanced:
This one step of method finishes simple, and the ultrafine particle surface properties of the grafted by super branched polymer modification that obtains has bigger change, can be dispersed in well in various resin matrixes and the solvent.。
Description of drawings
Fig. 1 (A) is engrafted nanometer SiO not
2Transmission electron microscope photo (AB
2Monomer)
Fig. 1 (B) is engrafted nanometer SiO
2Transmission electron microscope photo (AB
2Monomer)
Fig. 2 (A) is engrafted nanometer SiO not
2Transmission electron microscope photo (A
2The B monomer)
Fig. 2 (B) is engrafted nanometer SiO
2Transmission electron microscope photo (A
2The B monomer)
Fig. 3 (A) is engrafted nanometer carbon black transmission electron microscope photo (AB not
2Monomer)
Fig. 3 (B) is engrafted nanometer carbon black transmission electron microscope photo (AB
2Monomer)
Fig. 4 (A) is engrafted nanometer carbon black transmission electron microscope photo (A not
2The B monomer)
Fig. 4 (B) is engrafted nanometer carbon black transmission electron microscope photo (A
2The B monomer)
The AB that uses among the present invention
xOr A
xA in the B monomer and B can be hydroxyl, carboxyl, ester group or amido.As an example, the AB that uses among the present invention
2Monomer is with N, N-dihydroxy ethyl-3-amido-methyl propionate monomer and 3-carboxy-N, and N-dihydroxy ethyl propionic acid amide monomer is an example; A
2The B monomer is with N-hydroxyethyl-3-amido-N, N-dipropionic acid methyl esters) monomer and N-amine ethyl-3-amido-N, N-dipropionic acid methylmethacrylate monomer is an example; AB
3Monomer is with 3,3, and 3-trishydroxymethyl propionic acid monomer is an example.
The present invention illustrates with following embodiment, but the present invention is not limited to following embodiment, under the scope of described aim, changes and implements to be included in the technical scope of the present invention before and after not breaking away from.
Embodiment
Embodiment 1.
AB
2(A: ester group, B: monomer hydroxyl): N, N-dihydroxy ethyl-3-methyl propionate is monomeric synthetic:
Taking by weighing diethanolamine and acrylic acid methyl esters in 1: 1 in molar ratio, is solvent with methyl alcohol, in four-hole bottle at N
2Protection, 40 ℃, constant temperature 4h under the magnetic agitation, solvent methanol is removed in underpressure distillation, obtains a kind of faint yellow transparent liquid, is N, N-dihydroxy ethyl-3-methyl propionate monomer.
Nanometer SiO
2Modified-reaction (the AB of grafting hyperbranched poly (amine-ester)
2Monomer, melt polymerization):
Take by weighing 1g nanometer SiO
2, 0.023～0.0702molN, N-dihydroxy ethyl-3-methyl propionate monomer and 0.03～0.07g tosic acid in four-necked bottle, under nitrogen protection in 120 ℃ of violent stirring 10h.Get a pale yellow dope, with alcohol washing, centrifugation (1.5 * 10
4Rpm), throw out repeatedly repeats above-mentioned steps till detecting less than the unreacted matters existence again with centrifugal again after the hexanol washing in washings.30 ℃ of vacuum-drying 6h of throw out are got terminal hydroxy group hyperbranched poly (amine-ester) engrafted nanometer SiO
2
With engrafted nanometer SiO not
2Compare 1700cm on the FT-IR spectrogram of reacted product
-1C=O carbonyl charateristic avsorption band has just appearred; 2900cm
-1There is the charateristic avsorption band of c h bond at the place, illustrates that hyperbranched poly (amine-ester) has been grafted to SiO
2On the particle surface.
The performance test results:
1. nanometer SiO
2The dispersing property test
Take by weighing not grafted nanometer SiO of 0.05g
2With 0.05g engrafted nanometer SiO
2Place 50ml ethanol respectively, behind shake well, with 22PC type spectrophotometric determination transmittance, and the centrifugal settling certain hour is measured its transmittance again under the condition of 1500r/min.The results are shown in Table 1
Table 1 grafted nanometer SiO
2Grafted nanometer SiO not
2Transmittance
| Centrifugation time (s) | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 70 | 80 | 90 |
| Engrafted nanometer SiO not 2Transmittance | 48.6 | 79.3 | 85.9 | 94.9 | 96.1 | 98.8 | 99.3 | 99.4 | 99.6 | 99.6 |
| Engrafted nanometer SiO 2Transmittance | 31.1 | 37.4 | 40.2 | 46.9 | 53.0 | 57.8 | 60.2 | 62.6 | 63.9 | 64.1 |
As can be seen from Table 1, centrifugal before, grafted nanometer SiO
2The transmittance of-alcoholic dispersion system is well below grafted nanometer SiO not
2-alcoholic dispersion system, along with the increase of centrifugation time, grafted nanometer SiO
2-alcoholic dispersion system and grafted nanometer SiO not
2The transmittance of-alcoholic dispersion system increases gradually.But the degree that latter's transmittance increases is bigger.Obviously in alcohol solvent because nanometer SiO
2The volume sterically hindered effect of grafted hyperbranched poly (amine-ester) stops nanometer SiO on the surface
2Particle aggregation, thus nanometer SiO slowed down
2The decline of particle has improved nanometer SiO
2Particle is dispersion stabilization in solvent.
2.TEM analyze
With a certain amount of engrafted nanometer SiO
2Grafted nanometer SiO not
2Be placed on respectively in the ethanol, after CX-1 type Ultrasonic Cleaners fully disperses, drop in the Electronic Speculum copper mesh of carbon film support, then the H-700 type transmission electron microscope observing nanometer SiO that produces with HIT
2The pattern of particle.Can obviously find out not grafted nanometer SiO from Fig. 1
2Flock together and be difficult for disperseing.And grafted nanometer SiO
2Particles dispersed is better, nanometer SiO
2The particulate periphery has the cloud thing, and the surface is more plentiful, and particle diameter is in the nano level scope.This shows nanometer SiO
2Exist hyperbranched poly (amine-ester) grafts on the surface.
Embodiment 2
A
2Synthesizing of B monomer (A: ester group, B: hydroxyl): N-hydroxyethyl-3-amido-N, N-dipropionic acid methyl esters):
Taking by weighing thanomin and acrylic acid methyl esters in 1: 2 in molar ratio, is solvent with methyl alcohol, in four-hole bottle at N
2Protection, 40 ℃, constant temperature 4h under the magnetic agitation, solvent methanol is removed in underpressure distillation, obtains the transparent liquid of a kind of colorless chromogenic, is N-hydroxyethyl-3-amido-N, N-dipropionic acid methyl esters).
Nanometer SiO
2Modified-reaction (the A of grafting hyperbranched poly (amine-ester)
2B, solution polymerization):
Take by weighing 1g nanometer SiO
2, 0.01～0.0468mol 2-hydroxyethyl-N, N-two (methyl propionate) monomer and 0.01～0.04g tosic acid and 15ml naphthane in four-necked bottle, under nitrogen protection in 140 ℃, violent stirring 12h.Get a yellow dope, with chloroform washing, centrifugation (1.5 * 10
4Rpm), throw out repeatedly repeats above-mentioned steps till detecting less than the unreacted matters existence again with centrifugal again after the chloroform washing in washings.30 ℃ of vacuum-drying 6h of throw out are got poly-(amine-ester) engrafted nanometer SiO of ester terminal
2
With engrafted nanometer SiO not
2Compare 1700cm on the FT-IR spectrogram of reacted product
-1C=O carbonyl charateristic avsorption band has just appearred; 2900cm
-1There is the charateristic avsorption band of c h bond at the place, illustrates that hyperbranched poly (amine-ester) has been grafted to nanometer SiO
2On the particle surface.
The performance test results:
1. nanometer SiO
2The dispersing property test
Take by weighing not grafted nanometer SiO of 0.05g
2With 0.05g engrafted nanometer SiO
2Place the 50ml chloroform respectively, behind shake well, with 22PC type spectrophotometric determination transmittance, and the centrifugal settling certain hour is measured its transmittance again under the condition of 1500r/min.The results are shown in Table 2
Table 2 grafted nanometer SiO
2Grafted nanometer SiO not
2Transmittance
| Centrifugation time (s) | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 70 | 80 | 90 |
| Engrafted nanometer SiO not 2Transmittance | 48.6 | 79.3 | 85.9 | 94.9 | 96.1 | 98.8 | 99.3 | 99.4 | 99.6 | 99.6 |
| Engrafted nanometer SiO 2Transmittance | 33.1 | 37.4 | 41.2 | 45.9 | 52.0 | 57.8 | 60.1 | 62.8 | 64.6 | 65.2 |
As can be seen from Table 2, centrifugal before, grafted nanometer SiO
2The transmittance of-chloroform dispersion system is well below grafted nanometer SiO not
2-chloroform dispersion system, along with the increase of centrifugation time, grafted nanometer SiO
2-alcoholic dispersion system and grafted nanometer SiO not
2The transmittance of-chloroform dispersion system increases gradually.But the degree that latter's transmittance increases is bigger.Obviously in chloroform solvent because nanometer SiO
2The volume sterically hindered effect of grafted hyperbranched poly (amine-ester) stops nanometer SiO on the surface
2Particle aggregation, thus nanometer SiO slowed down
2The decline of particle has improved nanometer SiO
2Particle is dispersion stabilization in solvent.
2.TEM analyze
With a certain amount of engrafted nanometer SiO
2Grafted nanometer SiO not
2Be placed on respectively in the ethanol, after CX-1 type Ultrasonic Cleaners fully disperses, drop in the Electronic Speculum copper mesh of carbon film support, then the H-700 type transmission electron microscope observing nanometer SiO that produces with HIT
2The pattern of particle.Can obviously find out not grafted nanometer SiO from Fig. 2
2Flock together and be difficult for disperseing.And grafted nanometer SiO
2Particles dispersed is better, nanometer SiO
2The particulate periphery has the cloud thing, and the surface is more plentiful, and particle diameter is in the nano level scope.This shows nanometer SiO
2Exist hyperbranched poly (amine-ester) grafts on the surface.
Embodiment 3
Modified-reaction (the AB of nanometer carbon black surface grafting hyperbranched poly (amine-ester)
2Monomer, melt polymerization):
Take by weighing the 1g nanometer carbon black, 14g N, N-dihydroxy ethyl-3-methyl propionate monomer and 0.07g tosic acid in four-necked bottle, under nitrogen protection in 130 ℃ of violent stirring 10h.Get a black dope, with hexanol washing, centrifugation (1.5 * 10
4Rpm), throw out repeatedly repeats above-mentioned steps till detecting less than the unreacted matters existence again with centrifugal again after the hexanol washing in washings.30 ℃ of vacuum-drying 6h of throw out are got terminal hydroxy group hyperbranched poly (amine-ester) graft modification nanometer carbon black.
Compare 1700cm on the FT-IR spectrogram of reacted product with engrafted nanometer carbon black not
-1C=O carbonyl charateristic avsorption band is obviously strengthened; 2900cm
-1There is the charateristic avsorption band of c h bond at the place, illustrates that hyperbranched poly (amine-ester) has been grafted on the nanometer carbon black particle surface.The dispersed stability of nanometer carbon black after the graft modification in water, ethanol, acetone, butanone equal solvent increases greatly.
The performance test results:
1. nanometer carbon black dispersing property test
Take by weighing 0.05g not grafted nanometer carbon black and 0.05g engrafted nanometer carbon black place 50ml ethanol respectively, behind shake well, with 22PC type spectrophotometric determination transmittance, and the centrifugal settling certain hour is measured its transmittance again under the condition of 1500r/min.The results are shown in following table
Table 3 grafted nanometer carbon black and engrafted nanometer carbon black transmittance not
| Centrifugation time (s) | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 70 | 80 | 90 |
| Engrafted nanometer carbon black transmittance not | 46.6 | 76.7 | 86.9 | 94.1 | 95.4 | 99.2 | 99.4 | 99.5 | 99.6 | 99.6 |
| Engrafted nanometer carbon black transmittance | 31.2 | 34.4 | 39.9 | 44.6 | 51.0 | 57.0 | 62.3 | 63.8 | 64.9 | 65.3 |
As seen from Table 3, before centrifugal, the transmittance of grafted nanometer carbon black-alcoholic dispersion system is well below grafted nanometer carbon black-alcoholic dispersion system not, along with the increase of centrifugation time, grafted nanometer carbon black-alcoholic dispersion system and not the transmittance of grafted nanometer carbon black-alcoholic dispersion system increase gradually.But the degree that latter's transmittance increases is bigger.Obviously the volume sterically hindered effect of grafted hyperbranched poly (amine-ester) stops the nanometer carbon black particle aggregation in alcohol solvent because on the nanometer carbon black surface, thereby slowed down the decline of nanometer carbon black particle, improved nanometer carbon black particle dispersion stabilization in solvent.
2.TEM analyze
From the electromicroscopic photograph (see figure 3) as can be seen, the engrafted nanometer carbon black granules is not irregular spheroidal, and slick surface profile is arranged.Mutual gathering is arranged between the nanometer carbon black particle, present typical bead chain shape structure.The pattern of engrafted nanometer carbon black has had considerable change, nanometer carbon black particle homodisperse, and particle is more tiny; The circumference of nanometer carbon black particle is fuzzy.This be since a certain amount of grafted by super branched polymer due to the nanometer carbon black surface.
Embodiment 4
Modified-reaction (the A of nanometer carbon black surface grafting hyperbranched poly (amine-ester)
2The B monomer, solution polymerization):
Take by weighing 1g nanometer carbon black, 0.01mol N-hydroxyethyl-3-amido-N, N-dipropionic acid methyl esters) monomer and 0.01g tosic acid and 15ml naphthane in four-necked bottle, under nitrogen protection in 130 ℃, violent stirring 10h.Get a black dope, with chloroform washing, centrifugation (1.5 * 10
4Rpm), throw out repeatedly repeats above-mentioned steps till detecting less than the unreacted matters existence again with centrifugal again after the chloroform washing in washings.30 ℃ of vacuum-drying 6h of throw out are got ester terminal hyperbranched poly (amine-ester) graft modification nanometer carbon black.
Compare 1700cm on the FT-IR spectrogram of reaction back product with engrafted nanometer carbon black not
-1C=O carbonyl charateristic avsorption band is obviously strengthened; 2900cm
-1There is the charateristic avsorption band of c h bond at the place, illustrates that hyperbranched poly (amine-ester) has been grafted on the nanometer carbon black particle surface.
The performance test results:
1. nanometer carbon black dispersing property test
Take by weighing 0.05g not grafted nanometer carbon black and 0.05g engrafted nanometer carbon black place the 50ml chloroform respectively, behind shake well, with 22PC type spectrophotometric determination transmittance, and the centrifugal settling certain hour is measured its transmittance again under the condition of 1500r/min.The results are shown in following table
Table 4 grafted nanometer carbon black and engrafted nanometer carbon black transmittance not
| Centrifugation time (s) | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 70 | 80 | 90 |
| Engrafted nanometer carbon black transmittance not | 46.6 | 76.7 | 86.9 | 94.1 | 95.4 | 99.2 | 99.4 | 99.5 | 99.6 | 99.6 |
| Engrafted nanometer carbon black transmittance | 30.2 | 35.4 | 40.9 | 46.6 | 52.0 | 57.0 | 61.3 | 64.8 | 65.1 | 65.4 |
As seen from Table 4, before centrifugal, the transmittance of grafted nanometer carbon black-chloroform dispersion system is well below grafted nanometer carbon black-chloroform dispersion system not, along with the increase of centrifugation time, grafted nanometer carbon black-chloroform dispersion system and not the transmittance of grafted nanometer carbon black-chloroform dispersion system increase gradually.But the degree that latter's transmittance increases is bigger.Obviously the volume sterically hindered effect of grafted hyperbranched poly (amine-ester) stops carbon black particle to be reunited in chloroform solvent because on the nanometer carbon black surface, thereby the decline that has slowed down the nanometer carbon black particle has improved nanometer carbon black particle dispersion stabilization in solvent.
2.TEM analyze
From the electromicroscopic photograph (see figure 4) as can be seen, the engrafted nanometer carbon black granules is not irregular spheroidal, and slick surface profile is arranged.Mutual gathering is arranged between the nanometer carbon black particle, present typical bead chain shape structure.The pattern of engrafted nanometer carbon black has had considerable change, nanometer carbon black particle homodisperse, and particle is more tiny; The circumference of nanometer carbon black particle is fuzzy.This be since a certain amount of grafted by super branched polymer due to the nanometer carbon black surface.
Embodiment 5.
Micron SiO
2Modified-reaction (the AB of grafting hyperbranched poly (amine-ester)
2Monomer, melt polymerization):
Take by weighing 1g micron SiO
2, 0.023～0.0702mol N, N-dihydroxy ethyl-3-methyl propionate monomer and 0.03～0.07g tosic acid in four-necked bottle, under nitrogen protection in 120 ℃ of violent stirring 10h.Get a pale yellow dope, with hexanol washing, centrifugation (1.5 * 10
4Rpm), throw out repeatedly repeats above-mentioned steps till detecting less than the unreacted matters existence again with centrifugal again after the hexanol washing in washings.30 ℃ of vacuum-drying 6h of throw out are got terminal hydroxy group hyperbranched poly (amine-ester) grafting micron SiO
2
With grafting micron SiO not
2Compare 1700cm on the FT-IR spectrogram of reacted product
-1C=O carbonyl charateristic avsorption band has just appearred; 2900cm
-1There is the charateristic avsorption band of c h bond at the place, illustrates that hyperbranched poly (amine-ester) has been grafted to a micron SiO
2On the particle surface.
Micron SiO
2The dispersing property test
Take by weighing not grafted micron SiO of 0.05g
2With 0.05g grafting micron SiO
2Place 50ml ethanol respectively, behind shake well, with 22PC type spectrophotometric determination transmittance, and the centrifugal settling certain hour is measured its transmittance again under the condition of 1500r/min.The results are shown in Table 5
Table 5 grafted micron SiO
2Grafted micron SiO not
2Transmittance
| Centrifugation time (s) | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 70 | 80 | 90 |
| Grafting micron SiO not 2Transmittance | 48.6 | 79.3 | 85.9 | 94.9 | 96.1 | 98.8 | 99.3 | 99.4 | 99.6 | 99.6 |
| Grafting micron SiO 2Transmittance | 35.2 | 41.4 | 45.2 | 49.9 | 53.5 | 57.6 | 61.8 | 62.5 | 63.7 | 64.4 |
Embodiment 6
Micron SiO
2Modified-reaction (the A of grafting hyperbranched poly (amine-ester)
2B, solution polymerization):
Take by weighing 1g micron SiO
2, 0.01～0.0468mol 2-hydroxyethyl-N, N-two (methyl propionate) monomer and 0.01～0.04g tosic acid and 15ml naphthane in four-necked bottle, under nitrogen protection in 140 ℃, violent stirring 12h.Get a light yellow dope, with chloroform washing, centrifugation (1.5 * 10
4Rpm), throw out repeatedly repeats above-mentioned steps till detecting less than the unreacted matters existence again with centrifugal again after the chloroform washing in washings.30 ℃ of vacuum-drying 6h of throw out are got poly-(amine-ester) grafting micron SiO of ester terminal
2
With grafting micron SiO not
2Compare 1700cm on the FT-IR spectrogram of reacted product
-1C=O carbonyl charateristic avsorption band has just appearred; 2900cm
-1There is the charateristic avsorption band of c h bond at the place, illustrates that hyperbranched poly (amine-ester) has been grafted to a micron SiO
2On the particle surface.
Micron SiO
2The dispersing property test
Take by weighing not grafted micron SiO of 0.05g
2With 0.05g grafting micron SiO
2Place the 50ml chloroform respectively, behind shake well, with 22PC type spectrophotometric determination transmittance, and the centrifugal settling certain hour is measured its transmittance again under the condition of 1500r/min.The results are shown in Table 6
Table 6 grafted micron SiO
2Grafted micron SiO not
2Transmittance
| Centrifugation time (s) | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 70 | 80 | 90 |
| Grafting micron SiO not 2Transmittance | 50.2 | 80.3 | 85.6 | 94.5 | 97.3 | 98.2 | 98.7 | 99.0 | 99.4 | 99.6 |
| Grafting micron SiO 2Transmittance | 35.0 | 38.2 | 42.2 | 46.8 | 51.8 | 58.1 | 60.7 | 63.4 | 64.9 | 65.6 |
Modified-reaction (the AB of micron black carbon surface grafting hyperbranched poly (amine-ester)
2Monomer, melt polymerization):
Take by weighing 1g micron carbon black, 14g N, N-dihydroxy ethyl-3-methyl propionate monomer and 0.07g tosic acid in four-necked bottle, under nitrogen protection in 130 ℃ of violent stirring 10h.Get a black dope, with hexanol washing, centrifugation (1.5 * 10
4Rpm), throw out repeatedly repeats above-mentioned steps till detecting less than the unreacted matters existence again with centrifugal again after the hexanol washing in washings.30 ℃ of vacuum-drying 6h of throw out are got terminal hydroxy group hyperbranched poly (amine-ester) graft modification micron carbon black.
Compare 1700cm on the FT-IR spectrogram of reacted product with grafting micron carbon black not
-1C=O carbonyl charateristic avsorption band is obviously strengthened; 2900cm
-1There is the charateristic avsorption band of c h bond at the place, illustrates that hyperbranched poly (amine-ester) has been grafted on micron carbon black particle surface.The dispersed stability of micron carbon black in water, ethanol, acetone, butanone equal solvent after the graft modification increases greatly.
The test of micron carbon black dispersing property
Take by weighing 0.05g not grafted micron carbon black and 0.05g grafting micron carbon black place 50ml ethanol respectively, behind shake well, with 22PC type spectrophotometric determination transmittance, and the centrifugal settling certain hour is measured its transmittance again under the condition of 1500r/min.The results are shown in Table 7
Table 7 grafted micron carbon black and grafting micron carbon black transmittance not
| Centrifugation time (s) | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 70 | 80 | 90 |
| Grafting micron carbon black transmittance not | 48.6 | 77.6 | 87.5 | 93.9 | 96.3 | 98.5 | 98.9 | 99.3 | 99.5 | 99.7 |
| Grafting micron carbon black transmittance | 32.5 | 36.8 | 40.9 | 44.8 | 50.8 | 55.7 | 63.4 | 63.9 | 64.5 | 65.1 |
Embodiment 8
Modified-reaction (the A of micron black carbon surface grafting hyperbranched poly (amine-ester)
2The B monomer, solution polymerization):
Take by weighing 1g micron carbon black, 0.01mol N-hydroxyethyl-3-amido-N, N-dipropionic acid methyl esters) monomer and 0.01g tosic acid and 15ml naphthane in four-necked bottle, under nitrogen protection in 130 ℃, violent stirring 10h.Get a black dope, with chloroform washing, centrifugation (1.5 * 10
4Rpm), throw out repeatedly repeats above-mentioned steps till detecting less than the unreacted matters existence again with centrifugal again after the chloroform washing in washings.30 ℃ of vacuum-drying 6h of throw out are got ester terminal hyperbranched poly (amine-ester) graft modification micron carbon black.
Compare 1700crm on the FT-IR spectrogram of reaction back product with grafting micron carbon black not
-1C=O carbonyl charateristic avsorption band is obviously strengthened; 2900cm
-1There is the charateristic avsorption band of c h bond at the place, illustrates that hyperbranched poly (amine-ester) has been grafted on micron carbon black particle surface.
The test of micron carbon black dispersing property
Take by weighing 0.05g not grafted micron carbon black and 0.05g grafting micron carbon black place the 50ml chloroform respectively, behind shake well, with 22PC type spectrophotometric determination transmittance, and the centrifugal settling certain hour is measured its transmittance again under the condition of 1500r/min.The results are shown in Table 8
Table 8 grafted micron carbon black and grafting micron carbon black transmittance not
| Centrifugation time (s) | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 70 | 80 | 90 |
| Grafting micron carbon black transmittance not | 48.6 | 77.6 | 87.5 | 93.9 | 96.3 | 98.5 | 98.9 | 99.3 | 99.5 | 99.7 |
| Grafting micron carbon black transmittance | 34.1 | 35.8 | 39.9 | 45.7 | 50.5 | 55.7 | 62.2 | 63.6 | 64.8 | 66.7 |
AB
2Synthesizing of monomer (A: carboxyl, B: hydroxyl): 3-carboxy-N, N-dihydroxy ethyl propionic acid amide monomer)
Weighing Succinic anhydried and diethanolamine are dissolved among the DMAC fast, and room temperature magnetic agitation reaction 1h promptly gets the 3-carboxy-N, N-dihydroxy ethyl propionic acid amide monomer.
Nanometer SiO
2Modified-reaction (the AB of grafting hyperbranched poly esteramides
2Monomer, solution polymerization):
Take by weighing 1g nanometer SiO
2, 0.023～0.0702mol 3-carboxy-N, N-dihydroxy ethyl propionic acid amide monomer and 0.03～0.078 tosic acid and band aqua toluene are added under the nitrogen protection in 120 ℃ of violent stirring backflow 10h in four-necked bottle.Get a yellow dope, with hexanol washing, centrifugation (1.5 * 10
4Rpm), throw out repeatedly repeats above-mentioned steps till detecting less than the unreacted matters existence again with centrifugal again after the hexanol washing in washings.30 ℃ of vacuum-drying 6h get the acid amide-grafted nanometer SiO of terminal hydroxy group hyper-branched polyester with throw out
2
With engrafted nanometer SiO not
2Compare 1700cm on the FT-IR spectrogram of reacted product
-1C=O carbonyl charateristic avsorption band has just appearred; 1550cm
-1There is the charateristic avsorption band of C-N key at the place; 2900cm
-1There is the charateristic avsorption band of c h bond at the place, illustrates that super-branched polyesteramide has been grafted to nanometer SiO
2On the particle surface.Nanometer SiO
2Diffusing The performance test results:
Table 9 grafted nanometer SiO
2Grafted nanometer SiO not
2Transmittance
| Centrifugation time (s) | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 70 | 80 | 90 |
| Engrafted nanometer SiO not 2Transmittance | 48.6 | 79.3 | 85.9 | 94.9 | 96.1 | 98.8 | 99.3 | 99.4 | 99.6 | 99.6 |
| Engrafted nanometer | 35.2 | 39.1 | 43.2 | 47.9 | 51.8 | 56.3 | 59.0 | 61.9 | 62.6 | 62.8 |
| SiO 2Transmittance |
Embodiment 10
Modified-reaction (the AB of carbon black graft super-branched polyesteramide
2Monomer, solution polymerization):
Take by weighing 1g carbon black, (10～14) g 3-carboxy-N, N-dihydroxy ethyl propionic acid amide monomer and 0.03～0.07g tosic acid and band aqua toluene are added under the nitrogen protection in 120 ℃ of violent stirring backflow 10h in four-necked bottle.Get one
The black dope is with alcohol washing, centrifugation (1.5 * 10
4Rpm), throw out repeatedly repeats above-mentioned steps till detecting less than the unreacted matters existence again with centrifugal again after the hexanol washing in washings.30 ℃ of vacuum-drying 6h of throw out are got terminal hydroxy group super-branched polyesteramide engrafted nanometer carbon black particle.
Compare 1700cm on the FT-IR spectrogram of reacted product with engrafted nanometer carbon black not
-1C=O carbonyl charateristic avsorption band has just appearred; 1550cm
-1There is the charateristic avsorption band of C-N key at the place; 2900cm
-1There is the charateristic avsorption band of c h bond at the place, illustrates that super-branched polyesteramide has been grafted on the nanometer carbon black particle surface.
Nanometer carbon black dispersing property test result:
Table 10 grafted nanometer carbon black and engrafted nanometer carbon black transmittance not
| Centrifugation time (s) | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 70 | 80 | 90 |
| Engrafted nanometer carbon black transmittance not | 46.6 | 76.7 | 86.9 | 94.1 | 95.4 | 99.2 | 99.4 | 99.5 | 99.6 | 99.6 |
| Engrafted nanometer carbon black transmittance | 39.1 | 44.4 | 49.9 | 54.6 | 61.0 | 67.0 | 69.0 | 69.8 | 69.9 | 70.1 |
Embodiment 11
A
2The B monomer (A: ester group, B: amido): N-amine ethyl-3-amido-N, N-dipropionic acid methyl esters synthetic:
The methanol solution of methyl acrylate is added drop-wise to the methanol solution of quadrol, and room temperature magnetic agitation reaction 2h promptly gets N-amine ethyl-3-amido-N, N-dipropionic acid methylmethacrylate monomer under the nitrogen protection.
Nanometer SiO
2Modified-reaction (the A of grafting ultrabranching polyamide
2The B monomer, solution polymerization):
Take by weighing the 1g nanometer carbon black, 14g N-amine ethyl-3-amido-N, N-dipropionic acid methylmethacrylate monomer and 0.07g tosic acid in four-necked bottle, under nitrogen protection in 130 ℃ of violent stirring 12h.Get a black dope, with hexanol washing, centrifugation (1.5 * 10
4Rpm), throw out repeatedly repeats above-mentioned steps till detecting less than the unreacted matters existence again with centrifugal again after the hexanol washing in washings.30 ℃ of vacuum-drying 6h of throw out are got terminal hydroxy group ultrabranching polyamide graft modification nanometer carbon black.
Compare 1640cm on the FT-IR spectrogram of reacted product with engrafted nanometer carbon black not
-1C=O carbonyl charateristic avsorption band has just appearred; There is the charateristic avsorption band of C-N key at the 1550cm-1 place; 3300cm
-1There is the N-H charateristic avsorption band at the place; 2900cm
-1There is the charateristic avsorption band of c h bond at the place, illustrates that ultrabranching polyamide has been grafted on the nanometer carbon black particle surface.
Nanometer carbon black dispersing property test result:
Table 11 grafted nanometer carbon black and engrafted nanometer carbon black transmittance not
| Centrifugation time (s) | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 70 | 80 | 90 |
| Engrafted nanometer carbon black transmittance not | 46.6 | 76.7 | 86.9 | 94.1 | 95.4 | 99.2 | 99.4 | 99.5 | 99.6 | 99.6 |
| Graft black carbon nanometer transmittance | 38.3 | 46.2 | 50.1 | 53.7 | 60.8 | 67.1 | 69.4 | 69.6 | 69.8 | 70.0 |
Embodiment 12
AB
3Monomer: 3,3,3-trishydroxymethyl propionic acid
Nanometer SiO
2Modified-reaction (the AB of grafting hyper-branched polyester
3Monomer, solution polymerization):
Take by weighing 1g nanometer SiO
2, 0.023～0.0702mol AB
3Monomer and 0.03～0.07g tosic acid and band aqua toluene 15ml in four-necked bottle, under nitrogen protection in 120 ℃ of violent stirring 10h.Get a white dope, with hexanol washing, centrifugation (1.5 * 10
4Rpm), throw out repeatedly repeats above-mentioned steps till detecting less than the unreacted matters existence again with centrifugal again after the hexanol washing in washings.30 ℃ of vacuum-drying 6h of throw out are got terminal hydroxy group hyper-branched polyester engrafted nanometer SiO
2
With engrafted nanometer SiO not
2Compare 1735cm on the FT-IR spectrogram of reacted product
-1C=O carbonyl charateristic avsorption band has just appearred; 2900cm
-1There is the charateristic avsorption band of c h bond at the place; 1170～1260cm
-1There is the charateristic avsorption band of C-O key at the place, illustrates that hyper-branched polyester has been grafted to nanometer SiO
2On the particle surface.Nanometer SiO
2The dispersing property test result:
Table 12 grafted nanometer SiO
2Grafted nanometer SiO not
2Transmittance
| Centrifugation time (s) | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 70 | 80 | 90 |
| Engrafted nanometer SiO not 2Transmittance | 48.6 | 79.3 | 85.9 | 94.9 | 96.1 | 98.8 | 99.3 | 99.4 | 99.6 | 99.6 |
| Engrafted nanometer SiO 2Transmittance | 32.8 | 39.3 | 44.2 | 49.2 | 52.8 | 55.3 | 58.7 | 60.6 | 61.4 | 61.8 |
Embodiment 13
AB
3Monomer: 3,3,3-trishydroxymethyl propionic acid
Take by weighing the 1g nanometer carbon black, 14g 3,3,3-trishydroxymethyl propionic acid monomer and 0.07g tosic acid in four-necked bottle, under nitrogen protection in 130 ℃ of violent stirring 12h.Get a brown dope, with hexanol washing, centrifugation (1.5 * 10
4Rpm), throw out repeatedly repeats above-mentioned steps till detecting less than the unreacted matters existence again with centrifugal again after the hexanol washing in washings.30 ℃ of vacuum-drying 6h of throw out are got terminal hydroxy group hyper-branched polyester graft modification nanometer carbon black.
Compare 1735cm on the FT-IR spectrogram of reacted product with engrafted nanometer carbon black not
-1C=O carbonyl charateristic avsorption band has just appearred; 2900cm
-1There is the charateristic avsorption band of c h bond at the place; 1170～1260cm
-1There is the charateristic avsorption band of C-O key at the place, illustrates that hyper-branched polyester has been grafted on the nanometer carbon black particle surface.Nanometer carbon black dispersing property test result:
Table 13 grafted nanometer carbon black and engrafted nanometer carbon black transmittance not
| Centrifugation time (s) | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 70 | 80 | 90 |
| Engrafted nanometer carbon black transmittance not | 46.6 | 76.7 | 86.9 | 94.1 | 95.4 | 99.2 | 99.4 | 99.5 | 99.6 | 99.6 |
| Graft black carbon nanometer transmittance | 38.5 | 46.5 | 50.7 | 53.9 | 61.2 | 67.1 | 669.8 | 69.2 | 69.7 | 70.4 |
Embodiment 14
Nanometer SiO
2Modified-reaction (the AB of grafting hyperbranched poly (amine-ester)
2Monomer, melt polymerization):
Take by weighing 1g nanometer SiO
2(the about 0.0234mol of The adsorbed hydroxyl content), 0.0234molN, N-dihydroxy ethyl-3-methyl propionate monomer and 0.07g sodium methylate in four-necked bottle, under nitrogen protection in 120 ℃ of violent stirring 10h.Get a pale yellow dope, with hexanol washing, centrifugation (1.5 * 10
4Rpm), throw out repeatedly repeats above-mentioned steps till detecting less than the unreacted matters existence again with centrifugal again after the hexanol washing in washings.30 ℃ of vacuum-drying 6h of throw out are got terminal hydroxy group hyperbranched poly (amine-ester) engrafted nanometer SiO
2
With engrafted nanometer SiO not
2Compare 1700cm on the FT-IR spectrogram of reacted product
-1C=O carbonyl charateristic avsorption band has just appearred; 2900cm
-1There is the charateristic avsorption band of c h bond at the place, illustrates that hyperbranched poly (amine-ester) has been grafted to nanometer SiO
2On the particle surface.
Nanometer SiO
2The dispersing property test result:
Table 14 grafted nanometer SiO
2Grafted nanometer SiO not
2Transmittance
| Centrifugation time (s) | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 70 | 80 | 90 |
| Engrafted nanometer SiO not 2Transmittance | 48.6 | 79.3 | 85.9 | 94.9 | 96.1 | 98.8 | 99.3 | 99.4 | 99.6 | 99.6 |
| Engrafted nanometer SiO 2Transmittance | 33.2 | 38.2 | 43.2 | 49.9 | 53.8 | 59.3 | 62.0 | 64.9 | 65.0 | 65.3 |
Embodiment 15
Modified-reaction (the A of nanometer carbon black surface grafting hyperbranched poly (amine-ester)
2The B monomer, solution polymerization):
Take by weighing 1g nanometer carbon black, 0.01mol N-hydroxyethyl-3-amido-N; N-dipropionic acid methyl esters) monomer and 0.01g sodium methylate and 15ml naphthane are in four-necked bottle, and in 140 ℃, violent stirring 12h gets a black dope under nitrogen protection; with chloroform washing, centrifugation (1.5 * 10
4Rpm), throw out repeatedly repeats above-mentioned steps till detecting less than the unreacted matters existence again with centrifugal again after the chloroform washing in washings.30 ℃ of vacuum-drying 6h of throw out are got ester terminal hyperbranched poly (amine-ester) graft modification nanometer carbon black.
Compare 1700cm on the FT-IR spectrogram of reaction back product with engrafted nanometer carbon black not
-1C=O carbonyl charateristic avsorption band is obviously strengthened; 2900cm
-1There is the charateristic avsorption band of c h bond at the place, illustrates that hyperbranched poly (amine-ester) has been grafted on the nanometer carbon black particle surface
The test of nanometer carbon black dispersing property
Take by weighing 0.05g not grafted nanometer carbon black and 0.05g engrafted nanometer carbon black place the 50ml chloroform respectively, behind shake well, with 22PC type spectrophotometric determination transmittance, and the centrifugal settling certain hour is measured its transmittance again under the condition of 1500r/min.The results are shown in Table 15
Table 15 grafted nanometer carbon black and engrafted nanometer carbon black transmittance not
| Centrifugation time (s) | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 70 | 80 | 90 |
| Engrafted nanometer carbon black transmittance not | 46.6 | 76.7 | 86.9 | 94.1 | 95.4 | 99.2 | 99.4 | 99.5 | 99.6 | 99.6 |
| Engrafted nanometer carbon black transmittance | 31.3 | 35.4 | 41.5 | 46.9 | 52.3 | 57.4 | 61.7 | 64.7 | 65.0 | 65.3 |
Claims (5)
1. the novel method of a ultrafine particle surface modification is characterized in that it is included under the condition of certain temperature, mechanical stirring, nitrogen protection and catalyzer existence, and the ultrafine particle that has hydroxyl or carboxyl or ester group with the surface is a reactive center, with AB
xOr Ax
BThe reaction of one one-step polycondensation takes place in monomer, grafting hyperbranched polymer on the ultrafine particle surface, and wherein A and B are hydroxyl, carboxyl, ester group or amino in the monomer, X is 2 or 3.
2. the method for claim 1, the size that it is characterized in that described ultrafine particle is micron order or nano level.
3. method according to claim 1 is characterized in that described graft polymerization reaction comprises melt polymerization or solution polymerization.
4. method according to claim 1 is characterized in that described temperature of reaction at 120 ℃～140 ℃, and the reaction times is 10h～12h.
5. method according to claim 1 is characterized in that described catalyzer is organic acid or organic bases.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410042527 CN1260309C (en) | 2004-05-21 | 2004-05-21 | New method for superfine particle surface modification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410042527 CN1260309C (en) | 2004-05-21 | 2004-05-21 | New method for superfine particle surface modification |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1580137A CN1580137A (en) | 2005-02-16 |
| CN1260309C true CN1260309C (en) | 2006-06-21 |
Family
ID=34582167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410042527 Expired - Fee Related CN1260309C (en) | 2004-05-21 | 2004-05-21 | New method for superfine particle surface modification |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1260309C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104845412A (en) * | 2015-03-25 | 2015-08-19 | 西南石油大学 | Preparation method of hyperbranched polyamine-ester grafted nano Fe3O4 |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103849180B (en) * | 2014-03-20 | 2015-08-12 | 西北工业大学 | The preparation method of hyperbranched s-triazine engrafted nanometer particle |
| CN106366324B (en) * | 2016-08-23 | 2020-03-03 | 张家港康得新光电材料有限公司 | Hyperbranched polymer coated nano-particle, preparation method thereof, brightness enhancement composition containing hyperbranched polymer coated nano-particle, brightness enhancement film and LED display |
| CN107033632A (en) * | 2017-04-20 | 2017-08-11 | 安徽春辉仪表线缆集团有限公司 | A kind of hyper-branched polyester functional graft carbon black conductive filler and preparation method thereof |
| CN107129624A (en) * | 2017-04-20 | 2017-09-05 | 安徽春辉仪表线缆集团有限公司 | A kind of power cable peelable cross-linking type EVA semi-conductive shielding materials and preparation method thereof |
| CN107129779A (en) * | 2017-04-20 | 2017-09-05 | 安徽春辉仪表线缆集团有限公司 | A kind of pressure sensitive adhesive of SBS environment-friendly cables semi-conductive tape joint and preparation method thereof |
| CN114044950A (en) * | 2021-12-16 | 2022-02-15 | 东莞市百川新材料有限公司 | High-toughness oil-resistant rubber and preparation method thereof |
| CN114716715B (en) * | 2022-04-06 | 2023-09-22 | 江苏普非尔塑料科技有限公司 | Light wear-resistant PBT composite material and preparation method thereof |
| CN115806746A (en) * | 2022-08-18 | 2023-03-17 | 杭州应星新材料有限公司 | Method for modifying silicon dioxide by plasma in-situ polymerized silicone oil and application |
-
2004
- 2004-05-21 CN CN 200410042527 patent/CN1260309C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104845412A (en) * | 2015-03-25 | 2015-08-19 | 西南石油大学 | Preparation method of hyperbranched polyamine-ester grafted nano Fe3O4 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1580137A (en) | 2005-02-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1260309C (en) | New method for superfine particle surface modification | |
| CN1150270C (en) | Polymers of hydrophobic nature, filled with starch complexes | |
| CN100339766C (en) | Preparations of carbon nano tube layout film or composite material from polymerisable semgental surface modified carbon nano tubes | |
| CN1302061C (en) | Binder for mineral wool products | |
| CN1946750A (en) | Vinyl chloride resin composition and method for preparation thereof | |
| CN1653096A (en) | Diene rubber, process for production thereof, rubber compositions, process for producing the same, and crosslinked rubbers | |
| CN1898334A (en) | Inorganic-organic composite functional composition | |
| CN1922275A (en) | Organic and inorganic composite nanofiber, organic and inorganic composite structure and methods for producing the same | |
| CN1887716A (en) | Monodisperse micron level spherical vaterite-type calcium carbonate and its prepn process | |
| CN101037417A (en) | High stack-density sheet structural melamine cyanurate and production method and application for flame-resistant material | |
| CN1944478A (en) | Process for preparing acrylate resin for powder paint | |
| CN1289591C (en) | Antistatic flame-retardant polyethylene composition | |
| CN1861722A (en) | Process of preparing ester from rosin and acrylate | |
| CN1314729C (en) | Prepn process of copolymer of polyaspartic acid and chitosan | |
| CN1762571A (en) | Method for preparing surface patterned magnetic high molecular composite micriosphere | |
| CN1318964A (en) | Loudspeaker and its mfg. | |
| CN1908068A (en) | Heat-vulcanized silicone rubber containing nano montmorillonite and preparation method thereof | |
| CN1827669A (en) | Process for preparation of melamine polyphosphates and products thereof | |
| CN1856542A (en) | Spherical composite composition and process for producing spherical composite composition | |
| CN1171893C (en) | Microencapsulated lewis acid | |
| CN1084752C (en) | Natural rubber having a constant viscosity and production thereof | |
| CN1022417C (en) | Preparation of fast-dissolving anion type polyacrylamide | |
| US20090192255A1 (en) | Silica-polymeric resin composite and method for manufacturing the same | |
| CN1271123C (en) | Particle assembly, its prepn. method and photo diffusion agent | |
| CN1197902C (en) | Polyimide material filled with nano zinc oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060621 |