CN101434683A - Polymer graft modification composite hollow micro-bead and preparation thereof - Google Patents
Polymer graft modification composite hollow micro-bead and preparation thereof Download PDFInfo
- Publication number
- CN101434683A CN101434683A CNA2007101773191A CN200710177319A CN101434683A CN 101434683 A CN101434683 A CN 101434683A CN A2007101773191 A CNA2007101773191 A CN A2007101773191A CN 200710177319 A CN200710177319 A CN 200710177319A CN 101434683 A CN101434683 A CN 101434683A
- Authority
- CN
- China
- Prior art keywords
- coupling agent
- cenosphere
- polymer
- composite hollow
- microballon
- 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.)
- Pending
Links
Images
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
The invention relates to a complex hollow microsphere of polymer grafting modification and a preparation method thereof, and pertains to the technical field of surface modification of hollow microsphere. The method provides the complex hollow microsphere of polymer grafting modification and the preparation method thereof aiming at the disadvantages that the surface properties and the compressive strength of the hollow microsphere up to now are hard to be improved simultaneouly. The complex hollow microsphere causes the compressive strength and the compatibility with matrix to be greatly improved by graft polymer on a surface, and can also inhibit defect structure in the surface of the complex hollow microsphere. The method is simple, easy to be operated, and low in cost. The complex hollow microsphere of polymer grafting modification is applied to complex material as light intensified filling.
Description
Technical field
The present invention relates to cenosphere process for modifying surface field, particularly relate to by obtaining composite hollow microballon and preparation method thereof at cenosphere surface grafting polymerization thing.
Background technology
Hollow glass or ceramic fine bead are a kind of inorganic non-metallic ball-shaped micro powder novel materials, have that granularity is little, spherical, light weight, heat insulation, sound insulation, multi-functional characteristic such as high temperature resistant, wear-resisting, therefore in aerospace industry and other civil area, purposes is widely arranged.
Hollow glass micropearl generally can be divided into two classes, and a class is that sorting obtains from flyash; Another kind of then is synthetic.Fly ash micro-sphere is that the flyash that produces in thermal power plant's power generation process obtains through sorting.This microballon is because sphericity is poor, purity is low, big (real density is generally greater than 0.6g/cm for density
3), so be of limited application, especially be unsuitable for preparing some low density foam matrix materials.By comparison, the artificial hollow glass microballon can be controlled composition, density and other various physical and chemical performances of microballon by adjusting conditions such as composition of raw materials, processing parameter, though price is higher, uses more wide model.For example, the advantage that density is little, specific tenacity is high makes it become the high-strength light filler of matrix material, is used to make storing box, creel, bathtub, car panel etc.; Ultralow heat conductivity then makes it become good thermal insulation material, is used to make that thermal isolation screen, computer console, artificial marble are poor, automobile sealed glue, diving outfit etc.
Hollow glass or ceramic fine bead are as the inorganic light weight strongthener, and being used to prepare foamed composite is one of its topmost purposes.Its distinctive feature is that it is the spherical hollow structure, has ideal light filler advantage, even the loading level height is also very little with mobile influence to the viscosity of matrix.These advantages also give cenosphere some uncommon characteristics, as reducing the density of matrix material, improve its rigidity, hardness, dimensional stability, and give material erosion resistance, flame retardant resistance and insulativity etc.However, cenosphere also should be noted that following problem when preparing composite foam material with the polymer-based carbon volume recombination:
(1) hollow glass or ceramic fine bead are a kind of ceramic, the alkalimetal oxide component that reduces free energy often concentrates on upper layer, adsorb the moisture in the surrounding environment easily, make cenosphere show as wetting ability, therefore when undressed cenosphere mixes with organic polymer, polar difference causes that consistency is bad between the two, cenosphere can not be in matrix material homodisperse.In addition, this situation has also caused can not forming the ideal interfacial layer between cenosphere and polymeric matrix, stress is difficult to transmit, directly or too much fill decline and the embrittlement that often easily causes some mechanical property of matrix material, thereby bring negative impact for the processing characteristics and the use properties of goods.
(2) for composite foam material, hollow glass or ceramic fine bead mainly play is lightweight and strengthens two kinds of effects, because the volume content of high-performance composite foam material hollow core microballon can be up to 40～70%, so cenosphere itself has the influence of highly significant to composite property.If cenosphere density is big, intensity difference so just can only slightly reduce the density of matrix material, and the intensity of the matrix material that might weaken.
(3) from composite foam material preparation technology, the technology of employing and cenosphere performance are closely related.Only have certain intensity, in the time of resisting certain shearing or compression, just may utilize moulding processs such as injection moulding, hot press molding, scale operation foamed composite at cenosphere itself.
In sum as can be known, the surface properties of cenosphere and compressive strength thereof are very important for the preparation of high-performance composite foam material, and especially its compressive strength has directly determined the preparation technology and the performance thereof of matrix material.
At present, the raising of the improvement of cenosphere surface properties, compressive strength is mainly undertaken by surface modification and two aspects of design of components thereof.The surface modification treatment of cenosphere mainly contains following several:
(1) surface ion exchange, by metal salt solution cenosphere is handled exactly, as United States Patent (USP) 4340642 (US Pat.NO.4340642, Surface modi fied hollow microsphres, 1982) and 4411847 (US Pat.NO.4411847, that Process for surface modified hollowmicrospheres, 1983) is reported impregnated in AlCl with hollow glass micropearl exactly
3, Al
2(SO
4)
3The aqueous solution in, make it to take place surface ion exchange, improve its surface appearance, improve water resistance.
(2) the coupling agent surface modification adds cenosphere in the coupling agent solution exactly, or the coupling agent solution atomizing is sprayed on the cenosphere surface, carries out follow-up drying treatment again.Through after this processing, the group of coupling agent molecule one end and cenosphere surface bonding, the other end group then can tangle or reaction with polymeric matrix, thereby improves the consistency between cenosphere and matrix.For example, Pang Longxing etc. have reported the employing silane coupling agent hollow glass micropearl have been carried out surface modification treatment (hollow glass micropearl Research on Surface Modification, Wuhan Polytechnical Univ's journal, 1998 on Wuhan Polytechnical Univ's journal in 1998,20 (2): 36-37,41.).
(3) surface coats and handles, and is exactly that polymer layer is coated on the cenosphere surface by more weak absorption or Intermolecular Forces etc., as (Polyami line coating on glass and PMMAmicrospheres, Reactive ﹠amp such as Rama; Functional Polymers, 2006,66:441-445) polyaniline is coated on bead surface, improve its electroconductibility.
Though these surface modifying methods can improve the consistency of cenosphere and polymeric matrix to a certain extent, and are little for its intensity effect.In order to improve the compressive strength of hollow glass micropearl, by adjusting the composition of cenosphere, insert components such as some Al, Ca therein often.But the introducing of these high melting point components can cause significantly improving of cenosphere melt temperature, the cost of cenosphere is risen, but also cause its preparation technology's difficulty to strengthen, and productive rate descends, even is difficult to obtain the ideal cenosphere.
From as can be known above-mentioned, these methods all have certain limitation, are difficult to simultaneously the surface properties and the compressive strength of cenosphere are improved significantly.Therefore, need the exploitation novel method to improve the surface properties and the compressive strength thereof of cenosphere simultaneously.
Summary of the invention
The objective of the invention is to provides a kind of composite hollow microballon of polymer graft modification at the surface properties of cenosphere and the disappearance that compressive strength is difficult to improve simultaneously thereof up to now.This composite hollow microballon makes compressive strength and obtain simultaneously to significantly improve with the consistency of matrix by the surface grafting polymerization thing, and also can suppress the defect structure on cenosphere surface.
The present invention also provides the preparation method of the composite hollow glass microballon of this polymer graft modification.This method is simple, easy handling, and cost is low.
Purpose of the present invention realizes in the following manner:
The composite hollow microballon of polymer graft modification provided by the invention comprises: the polymer layer of cenosphere, coupling agent layer and surface grafting.
Wherein, described cenosphere cavity diameter is 2～80 μ m, and inside is for vacuum or contain N
2Or CO
2Gas, cenosphere shell layer thickness are 0.2～5 μ m; Described coupling agent layer thickness is 10～50nm, by carrying out chemical bonds between Si-O-Si key and cenosphere housing; Described polymer layer of thickness is 0.1～2 μ m, carries out chemical bonds by double-bond polymerization and coupling agent layer.Accompanying drawing 1 is seen in the structural representation of composite hollow microballon, 1-cavity, 2-shell layer, 3-coupling agent layer, 4-polymer layer.
Described cenosphere is hollow ceramic microspheres and/or hollow glass micropearl; Described coupling agent is silane coupling agent, titanate coupling agent or aluminate coupling agent; Described polymkeric substance is polystyrene, polymethylmethacrylate, polyethyl acrylate or butyl polyacrylate.
The invention provides the preparation method of the composite hollow microballon of polymer graft modification, comprise the steps:
The first step cenosphere coupling processing: coupling agent and ethanol, water are mixed into solution, solution-stabilized for making, can use acid-conditioning solution pH value to 3～6 in advance, add cenosphere again, reacted 0.5～8 hour down at 25～80 ℃, preferred 50 ℃ were reacted 2 hours filtration, washing down, under 80～150 ℃, heat-treated 0.5～5 hour then, heat-treated 2～3 hours under preferred 120 ℃.
The second step coupling microballon graft polymerization: will add in the organic solvent through the cenosphere and the polymer monomer of coupling processing; under the initiator effect; protective atmosphere, 50～100 ℃ of following reactions 0.5～10 hour; preferred 80 ℃ were reacted 5～8 hours down; filter, wash, obtain the composite hollow microballon with toluene or dimethylbenzene.
If further handle, can also comprise the 3rd step drying treatment: will carry out drying at 50～80 ℃ through the composite hollow microballon that grafting is handled.
Wherein, described coupling agent is silane coupling agent, titanate coupling agent or aluminate coupling agent, the silane coupling agent that preferably has two keys, more preferably methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane or vinyltriethoxysilane, coupling agent content is 0.5～50% (weight).
Described water-content is 0.5～10% (weight), and described ethanol content is 50～99% (weight), and described acid is selected from hydrochloric acid, sulfuric acid or carboxylic acid.
Described polymer monomer is the polymer monomer that has two keys, be preferably vinylbenzene, vinylformic acid, methyl acrylate, ethyl propenoate, butyl acrylate or methyl methacrylate, or their mixture, polymer monomer content is 2～50% (weight).
Described initiator is a radical initiator, is preferably benzoyl peroxide, Diisopropyl azodicarboxylate, and initiator content is 0.2～10% (weight).
Described organic solvent is benzene, toluene or dimethylbenzene, and organic solvent content is 50～95% (weight).
Protective atmosphere in the described graft polymerization step is argon gas or nitrogen.
Described heat treating method and drying means are fluid-bed drying or air stream drying method.
Advantage of the present invention and beneficial effect:
The composite hollow microballon that surface aggregate thing grafting of the present invention is handled, by forming polymer layer in the cenosphere surface chemistry, the defect structure that not only can suppress the cenosphere surface, and because polymer layer is on the cenosphere surface by chemical bond linkage, has very strong reactive force between the two, can bear partial action power so be subjected to external pressure to make the time spent polymer layer, thereby significantly improve the compressive strength of composite hollow microballon.After polystyrene graft modification treatment of hollow glass bead, its percentage of damage under 12MPa 34.1% during by unmodified handle is reduced to 15.4%, and compressive strength is enhanced about more than once.
In addition, cenosphere finally all is to be filled in the polymeric matrix, at its surface grafting polymerization thing, can effectively regulate the interfacial layer characteristic by the different polymkeric substance of grafting, different percentage of grafting, not only can effectively improve both interface affinities, can also give full play to cenosphere and polymkeric substance advantage separately, realize optimization design.For example, behind polyethyl acrylate graft modification hollow glass micropearl, the 692mPas of the viscosity of microballon and polyethers system during by unmodified handle is reduced to 607mPas, and both consistencies have bigger improvement.Therefore, adopt the composite hollow glass microballon of this method preparation, not only have higher compressive strength, also good consistency is arranged with polymeric matrix, thereby expanded the means that cenosphere and polymeric matrix compound tense adopt, improved both blended homogeneities.
In addition, composite hollow glass microballon for this polymer graft modification, can also be by the selection of monomer or polymerizing condition, by the interfacial layer that artificially need between microballon and polymeric matrix, design different modulus, realize the control and the design of interfacial layer, prepare the high-performance composite foam material.For example, can improve interface rigidity between compounded microbeads and polymeric matrix, reach and improve the purpose that interfacial stress is transmitted, improve the intensity of matrix material by the strong polystyrene of grafting molecule segment rigidity; Also can improve interface flexibility between compounded microbeads and polymeric matrix, reach the purpose of toughening composition by the flexible good butyl polyacrylate of grafting molecule segment.
Method of the present invention is to carry out modification to handle on existing cenosphere basis, compares that to improve the method for cenosphere compressive strength by component modification more simple, and cost is lower, and operability is stronger.
The present invention is used for matrix material as lightweight, reinforcing filler.
Description of drawings
Fig. 1 is the structural representation of the composite hollow glass microballon of polymer graft modification.
Fig. 2 is the infrared diffuse reflectance spectroscopy figure of hollow glass micropearl of the coupling agent treatment of embodiment 1.
Fig. 3 is the infrared diffuse reflectance spectroscopy figure of hollow glass micropearl of the grafted polystyrene of embodiment 1.
Fig. 4 is the SEM figure of hollow glass micropearl of the grafted polystyrene of embodiment 1.
Fig. 5 is the SEM figure of hollow glass micropearl fragment section of the grafted polystyrene of embodiment 1.
Fig. 6 is the hollow glass micropearl infrared diffuse reflectance spectroscopy figure of the grafting polymethylmethacrylate of embodiment 2.
Fig. 7 is the SEM figure of hollow glass micropearl fragment section of the grafting polymethylmethacrylate of embodiment 2.
Fig. 8 is the hollow glass micropearl infrared diffuse reflectance spectroscopy figure of the graft polypropylene acetoacetic ester of embodiment 3.
Fig. 9 is the SEM figure of hollow glass micropearl of the graft polypropylene acetoacetic ester of embodiment 3.
Embodiment
Further specify the present invention below by specific embodiment, but these embodiment are used for limiting protection scope of the present invention.
The first step cenosphere coupling processing: earlier coupling agent methacryloxypropyl trimethoxy silane (KH570) is added in the ethanolic soln.Wherein, coupling agent content is 25%, and water-content is 5%, and ethanol content is 70%.For making coupling agent stable, the pH value of solution is adjusted to 4～5 with acetate in advance.Under magnetic agitation, hollow glass micropearl 10 grams are added in the above-mentioned ethanolic soln, 50 ℃ of reactions 1 hour.Filter, successively use ethanol and washing with acetone, put it in the hot-air drier under 120 ℃ thermal treatment then 2 hours, make the fully reaction of coupling agent and hollow glass micropearl surface, thereby introduce two keys on the cenosphere surface, obtain the hollow glass micropearl (being called for short HGM-KH570) of coupling agent treatment.
The second step coupling microballon graft polymerization: will add in the organic solvent toluene through the cenosphere and the polymer monomer vinylbenzene of coupling processing; under initiator Diisopropyl azodicarboxylate (AIBN) effect; under nitrogen protection, 80 ℃ of down reactions 5 hours; initiator content is 5%; styrene monomer content is 25%, and toluene solvant content is 70%, filters; use toluene wash, obtain the hollow glass micropearl (being called for short HGM-g-PS) of grafted polystyrene.
The 3rd step drying treatment: the second step gained composite hollow microballon is further dry with the air stream drying method at 50 ℃.
The HGM-KH570 product that obtains is white spherical powder, and its infrared casual emmission spectrum as shown in Figure 2.Microballon after handling as can be seen from Figure two charateristic avsorption band powders occurred at 2900cm-1,1700cm-1, corresponds respectively to-CH3, the absorption of vibrations of C=O group, shows that bead surface has chained silane coupling agent KH570.
Accompanying drawing 4 is the SEM photo of the hollow glass micropearl of surface grafting polystyrene.As can be seen, behind the surface grafting, hollow glass micropearl still is spherical, is monodisperse status.5 in accompanying drawing is the section of its part fragment, can know that observing the cenosphere surface is coated with one layer of polymeric.
For the compressive strength of hollow glass micropearl, represent with the percentage of damage of microballon under the static pressure such as 12MPa water.Deng the handtailor container of earlier microballon being packed in the static pressure test, place the equal pressing equipment pressure treatment.Because hollow glass micropearl is broken under pressure, cause the buoyancy of powder in water to descend, therefore can calculate percentage of damage according to container and the changes in weight of microballon powder in water before and after the pressurization.Percentage of damage variation before and after the polymer graft modification sees Table 1.By table as seen, the percentage of damage of the hollow glass micropearl of unmodified processing under 12MPa is 34.1%, though its percentage of damage is improved to some extent after the coupling agent treatment, changes not quite, reduces to 30%.After the polystyrene graft processing, its percentage of damage sharply is reduced to 15.4%, shows that its compressive strength has significant improvement.
In addition, by it being scattered in the polyethers system, the viscosity of test system changes the changing conditions of checking consistency between compounded microbeads and polymeric matrix.As can be seen from Table 2, hollow glass micropearl is through behind the grafted polystyrene, and the viscosity of compound system is reduced to 592mPas from 692mPas, shows that consistency is greatly improved between compounded microbeads and polymkeric substance.
The percentage of damage of table 1 polystyrene graft modification treatment of hollow glass bead under static pressure such as 12MPa
The viscosity change list of table 2 polystyrene graft modification hollow glass micropearl and polyether mixture (25 ℃)
Embodiment 2
The first step cenosphere coupling processing: earlier vinyltrimethoxy silane coupling agent (A-171) is added in the ethanolic soln.Wherein, coupling agent content is 0.5%, and water-content is 0.5%, and ethanol content is 99%.For making coupling agent stable, the pH value of solution is adjusted to 3～4 with hydrochloric acid in advance.Under magnetic agitation, hollow glass micropearl 10 grams are added in the above-mentioned ethanolic soln, 80 ℃ of reactions 8 hours.Filter, use washing with acetone, put it in the rotatory evaporator under 80 ℃ thermal treatment then 5 hours, make the fully reaction of coupling agent and glass microballon surface, thereby introduce two keys, obtain the hollow glass micropearl (being called for short HGM-A171) of coupling agent treatment in bead surface.
The second step coupling microballon graft polymerization: will add in the organic solvent-benzene through the cenosphere and the polymer monomer methyl methacrylate of coupling processing; under initiator benzoyl peroxide (BPO) effect; under argon shield, 50 ℃ of down reactions 10 hours; initiator content is 0.2%; methyl methacrylate monomer content is 49%, and benzene solvent content is 50.8%, filters; use toluene wash, obtain the hollow glass micropearl (being called for short HGM-g-PMMA) of grafting polymethylmethacrylate.
The 3rd step drying treatment: the second step gained composite hollow microballon is further dry in hot-air drier under 80 ℃.
Accompanying drawing 6 is the infrared diffuse reflectance spectroscopy of the hollow glass micropearl of grafting polymethylmethacrylate.As seen from the figure, except near the C 2900cm-1-H vibration peak, the stretching vibration peak of a tangible C=O also occurred on 1700cm-1, this is that the ester group of bead surface grafted esters of acrylic acid is caused.Accompanying drawing 7 is the SEM photo of its section of microballon of surface grafting polymethylmethacrylate.As can be seen, bead surface is coated with one layer of polymeric.
By table 3 as seen, through behind the grafting polymethylmethacrylate, its percentage of damage 34.1% during by unmodified processing is reduced to 19.4%, shows that its compressive strength has significant improvement really.In addition, can find out also that behind the hollow glass micropearl process grafting polymethylmethacrylate, the viscosity of compound system is reduced to 600mPas from 692mPas, shows that consistency is greatly improved between compounded microbeads and polymkeric substance from table 4.
The percentage of damage of table 3 polystyrene graft modification treatment of hollow glass bead under static pressure such as 12MPa
The viscosity change list of table 4 polystyrene graft modification hollow glass micropearl and polyether mixture (25 ℃)
The first step cenosphere coupling processing: earlier vinyltriethoxysilane coupling agent (A-151) is added in the ethanolic soln.Wherein, coupling agent content is 10%, and water-content is 10%, and ethanol content is 80%.For making coupling agent stable, the pH value of solution is adjusted to 5～6 with sulfuric acid in advance.Under magnetic agitation, hollow glass micropearl 10 grams are added in the above-mentioned ethanolic soln, 25 ℃ of reactions 5 hours.Filter, use washing with alcohol, put it in the ebullated dryer under 150 ℃ thermal treatment then 0.5 hour, make the fully reaction of coupling agent and hollow glass micropearl surface, thereby introduce two keys, obtain the hollow glass micropearl (being called for short HGM-A151) of coupling agent treatment on the cenosphere surface.
The second step coupling microballon graft polymerization: will add in the organic solvent dimethylbenzene through the cenosphere and the polymer monomer ethyl propenoate of coupling processing; under initiator benzoyl peroxide (BPO) effect; under argon shield, 100 ℃ of down reactions 0.5 hour; initiator content is 10%; the ethyl propenoate monomer content is 2%, and xylene solvent content is 88%, filters; with the dimethylbenzene washing, obtain the hollow glass micropearl (being called for short HGM-g-PEA) of graft polypropylene acetoacetic ester.
The 3rd step drying treatment: the second step gained composite hollow microballon is further dry in ebullated dryer under 50 ℃.
Accompanying drawing 8 is the infrared diffuse reflectance spectroscopy of the hollow glass micropearl of graft polypropylene acetoacetic ester.As seen from the figure, except near the C 2900cm-1-H vibration peak, the stretching vibration peak of a tangible C=O also occurred on 1700cm-1, this is that the ester group of bead surface grafted esters of acrylic acid is caused.Accompanying drawing 9 is the SEM photo of the compounded microbeads of surface grafting ethyl propenoate.
By table 5 as seen, through behind the graft polypropylene acetoacetic ester, its percentage of damage 34.1% during by unmodified processing is reduced to 17.7%, shows that its compressive strength has significant improvement really.In addition, can find out also that behind the hollow glass micropearl process graft polypropylene acetoacetic ester, the viscosity of compound system is reduced to 607mPas from 692mPas, shows that consistency is greatly improved between compounded microbeads and polymkeric substance from table 6.
The percentage of damage of table 5 polystyrene graft modification treatment of hollow glass bead under static pressure such as 12MPa
The viscosity change list of table 6 polystyrene graft modification hollow glass micropearl and polyether mixture (25 ℃)
Claims (10)
1. the composite hollow microballon of a polymer graft modification is characterized in that comprising: the polymer layer of cenosphere, coupling agent layer and surface grafting.
2. the composite hollow microballon of polymer graft modification according to claim 1 is characterized in that, described cenosphere cavity diameter is 2～80 μ m, and inside is for vacuum or contain N
2Or CO
2Gas, cenosphere shell layer thickness are 0.2～5 μ m; Described coupling agent layer thickness is 10～50nm, by carrying out chemical bonds between Si-O-Si key and cenosphere housing; Described polymer layer of thickness is 0.1～2 μ m, carries out chemical bonds by double-bond polymerization and coupling agent layer.
3. the composite hollow microballon of polymer graft modification according to claim 1 and 2 is characterized in that, described cenosphere is hollow ceramic microspheres and/or hollow glass micropearl; Described coupling agent is silane coupling agent, titanate coupling agent or aluminate coupling agent; Described polymkeric substance is polystyrene, polymethylmethacrylate, polyethyl acrylate or butyl polyacrylate.
4. the preparation method of the composite hollow microballon of a polymer graft modification is characterized in that comprising the steps:
The first step cenosphere coupling processing: coupling agent and ethanol, water are mixed into solution, add cenosphere again, reacted 0.5～8 hour down, filter, wash, under 80～150 ℃, heat-treated 0.5～5 hour then at 25～80 ℃;
Second step coupling microballon graft polymerization: will add in the organic solvent with polymer monomer through the cenosphere of coupling processing, under the initiator effect,, filtration, wash, obtain the composite hollow microballon in protective atmosphere, 50～100 ℃ reaction 0.5～10 hour down.
5. the preparation method of the composite hollow microballon of polymer graft modification according to claim 4 is characterized in that comprising the 3rd step drying treatment: will carry out drying at 50～80 ℃ through the composite hollow microballon that grafting is handled.
6. the preparation method of the composite hollow microballon of polymer graft modification according to claim 4 is characterized in that in the first step that coupling agent and ethanol, water are mixed into behind the solution with acid-conditioning solution pH value to 3～6.
7. the preparation method of the composite hollow microballon of polymer graft modification according to claim 4 is characterized in that described coupling agent is silane coupling agent, titanate coupling agent or aluminate coupling agent, and coupling agent content is 0.5～50wt%; Described polymer monomer is the polymer monomer that has two keys, and polymer monomer content is 2～50wt%; Described initiator is a radical initiator; Described organic solvent is benzene, toluene or dimethylbenzene; Protective atmosphere in the described graft polymerization step is argon gas or nitrogen.
8. according to the preparation method of the composite hollow microballon of claim 4 or 7 described polymer graft modifications, it is characterized in that described coupling agent is the silane coupling agent that has two keys; Described polymer monomer is vinylbenzene, vinylformic acid, methyl acrylate, ethyl propenoate, butyl acrylate or methyl methacrylate, or their mixture; Described initiator is benzoyl peroxide, Diisopropyl azodicarboxylate.
9. the preparation method of the composite hollow microballon of polymer graft modification according to claim 8 is characterized in that the described silane coupling agent that has two keys is methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane or vinyltriethoxysilane.
10. according to the preparation method of the composite hollow microballon of any one described polymer graft modification in the claim 4 to 9, it is characterized in that described heat treating method and drying means are fluid-bed drying or air stream drying method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101773191A CN101434683A (en) | 2007-11-14 | 2007-11-14 | Polymer graft modification composite hollow micro-bead and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101773191A CN101434683A (en) | 2007-11-14 | 2007-11-14 | Polymer graft modification composite hollow micro-bead and preparation thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101434683A true CN101434683A (en) | 2009-05-20 |
Family
ID=40709328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101773191A Pending CN101434683A (en) | 2007-11-14 | 2007-11-14 | Polymer graft modification composite hollow micro-bead and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101434683A (en) |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020877A (en) * | 2010-10-13 | 2011-04-20 | 天津大学 | Rear-earth surface-modified hollow glass microsphere and preparation method thereof |
| CN102321394A (en) * | 2011-09-28 | 2012-01-18 | 蚌埠玻璃工业设计研究院 | Method for producing hollow glass microspheres on large scale through surface modification |
| CN102604439A (en) * | 2012-01-19 | 2012-07-25 | 蚌埠华洋粉体技术有限公司 | Surface modification method of hollow glass beads |
| CN103709540A (en) * | 2012-10-09 | 2014-04-09 | 中国石油化工股份有限公司 | Organic hollow microspheres, preparation method thereof, and drilling fluid |
| CN105294959A (en) * | 2015-07-31 | 2016-02-03 | 泰山玻璃纤维有限公司 | Preparation method of anti-static organic glass |
| CN105754054A (en) * | 2016-05-06 | 2016-07-13 | 南通南京大学材料工程技术研究院 | Flexible resin modified hollow microbead and modification method thereof |
| CN106634137A (en) * | 2016-12-30 | 2017-05-10 | 山西长达交通材料科技股份有限公司 | Preparation method of glass micro-beads used for road marking line |
| CN106830667A (en) * | 2015-12-03 | 2017-06-13 | 中国石油天然气股份有限公司 | The method of modifying of hollow glass micropearl and its application |
| CN108034154A (en) * | 2017-12-06 | 2018-05-15 | 胡旺 | A kind of copolymer-modified Polystyrene heat insulation material and preparation method thereof |
| CN108164832A (en) * | 2017-12-25 | 2018-06-15 | 广州科苑新型材料有限公司 | PP composite materials with negative ion-releasing function and preparation method and application |
| CN108797143A (en) * | 2018-07-27 | 2018-11-13 | 加通汽车内饰(常熟)有限公司 | A kind of automobile-used artificial leather of lightweight and preparation method thereof with wear-resisting epidermis |
| CN109535432A (en) * | 2018-10-10 | 2019-03-29 | 万华化学（宁波）有限公司 | A kind of hollow glass micropearl surface modifying method and a kind of low-density high durable PP composite material and preparation method thereof |
| CN109722062A (en) * | 2018-12-21 | 2019-05-07 | 英德科迪颜料技术有限公司 | A kind of preparation method of core-shell structure transparent ferric oxide coated pigment |
| CN111876129A (en) * | 2020-09-05 | 2020-11-03 | 深圳市宝力新材料有限公司 | Low-density high-heat-conductivity pouring sealant |
| CN112893866A (en) * | 2021-01-13 | 2021-06-04 | 中国科学院金属研究所 | Photocuring 3D printing metal-ceramic composite material part and preparation method thereof |
| CN113149546A (en) * | 2021-03-24 | 2021-07-23 | 浙江瑞联节能材料有限公司 | Inorganic lightweight aggregate insulation board and preparation method thereof |
| CN113821066A (en) * | 2021-10-19 | 2021-12-21 | 中国工程物理研究院激光聚变研究中心 | Device and method for reducing influence of dynamic protective gas on temperature control in heat treatment process |
| CN114437567A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Metal oxide/hollow microsphere and preparation method thereof |
| CN114507066A (en) * | 2022-02-24 | 2022-05-17 | 新化县正能精细陶瓷有限公司 | Ceramic base material for aromatherapy machine |
| CN115029017A (en) * | 2022-06-28 | 2022-09-09 | 万华化学集团股份有限公司 | Titanium dioxide coated hollow glass bead composite material and preparation method thereof |
| CN115594918A (en) * | 2022-10-09 | 2023-01-13 | 山东龙腾新材料有限公司（Cn） | Light odorless polypropylene composite material and preparation method thereof |
-
2007
- 2007-11-14 CN CNA2007101773191A patent/CN101434683A/en active Pending
Cited By (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020877A (en) * | 2010-10-13 | 2011-04-20 | 天津大学 | Rear-earth surface-modified hollow glass microsphere and preparation method thereof |
| CN102020877B (en) * | 2010-10-13 | 2013-02-27 | 天津大学 | Rear-earth surface-modified hollow glass microsphere and preparation method thereof |
| CN102321394A (en) * | 2011-09-28 | 2012-01-18 | 蚌埠玻璃工业设计研究院 | Method for producing hollow glass microspheres on large scale through surface modification |
| CN102604439A (en) * | 2012-01-19 | 2012-07-25 | 蚌埠华洋粉体技术有限公司 | Surface modification method of hollow glass beads |
| CN103709540A (en) * | 2012-10-09 | 2014-04-09 | 中国石油化工股份有限公司 | Organic hollow microspheres, preparation method thereof, and drilling fluid |
| CN103709540B (en) * | 2012-10-09 | 2016-04-27 | 中国石油化工股份有限公司 | A kind of organic tiny balloon and preparation method thereof and drilling fluid |
| CN105294959A (en) * | 2015-07-31 | 2016-02-03 | 泰山玻璃纤维有限公司 | Preparation method of anti-static organic glass |
| CN106830667B (en) * | 2015-12-03 | 2020-05-08 | 中国石油天然气股份有限公司 | Modification method of hollow glass beads and application thereof |
| CN106830667A (en) * | 2015-12-03 | 2017-06-13 | 中国石油天然气股份有限公司 | The method of modifying of hollow glass micropearl and its application |
| CN105754054A (en) * | 2016-05-06 | 2016-07-13 | 南通南京大学材料工程技术研究院 | Flexible resin modified hollow microbead and modification method thereof |
| CN106634137A (en) * | 2016-12-30 | 2017-05-10 | 山西长达交通材料科技股份有限公司 | Preparation method of glass micro-beads used for road marking line |
| CN106634137B (en) * | 2016-12-30 | 2019-05-31 | 山西中涂交通科技股份有限公司 | A kind of preparation method of roadmarking glass microballoon |
| CN108034154A (en) * | 2017-12-06 | 2018-05-15 | 胡旺 | A kind of copolymer-modified Polystyrene heat insulation material and preparation method thereof |
| CN108164832A (en) * | 2017-12-25 | 2018-06-15 | 广州科苑新型材料有限公司 | PP composite materials with negative ion-releasing function and preparation method and application |
| CN108797143A (en) * | 2018-07-27 | 2018-11-13 | 加通汽车内饰(常熟)有限公司 | A kind of automobile-used artificial leather of lightweight and preparation method thereof with wear-resisting epidermis |
| CN109535432A (en) * | 2018-10-10 | 2019-03-29 | 万华化学（宁波）有限公司 | A kind of hollow glass micropearl surface modifying method and a kind of low-density high durable PP composite material and preparation method thereof |
| CN109535432B (en) * | 2018-10-10 | 2021-06-29 | 万华化学（宁波）有限公司 | Surface modification method for hollow glass beads, low-density high-weather-resistance polypropylene composite material and preparation method thereof |
| CN109722062A (en) * | 2018-12-21 | 2019-05-07 | 英德科迪颜料技术有限公司 | A kind of preparation method of core-shell structure transparent ferric oxide coated pigment |
| CN111876129A (en) * | 2020-09-05 | 2020-11-03 | 深圳市宝力新材料有限公司 | Low-density high-heat-conductivity pouring sealant |
| CN114437567A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Metal oxide/hollow microsphere and preparation method thereof |
| CN114437567B (en) * | 2020-10-31 | 2023-07-04 | 中国石油化工股份有限公司 | Metal oxide/hollow microsphere and preparation method thereof |
| CN112893866A (en) * | 2021-01-13 | 2021-06-04 | 中国科学院金属研究所 | Photocuring 3D printing metal-ceramic composite material part and preparation method thereof |
| CN113149546A (en) * | 2021-03-24 | 2021-07-23 | 浙江瑞联节能材料有限公司 | Inorganic lightweight aggregate insulation board and preparation method thereof |
| CN113821066A (en) * | 2021-10-19 | 2021-12-21 | 中国工程物理研究院激光聚变研究中心 | Device and method for reducing influence of dynamic protective gas on temperature control in heat treatment process |
| CN113821066B (en) * | 2021-10-19 | 2022-07-15 | 中国工程物理研究院激光聚变研究中心 | Device and method for reducing influence of dynamic protective gas on temperature control in heat treatment process |
| CN114507066A (en) * | 2022-02-24 | 2022-05-17 | 新化县正能精细陶瓷有限公司 | Ceramic base material for aromatherapy machine |
| CN115029017A (en) * | 2022-06-28 | 2022-09-09 | 万华化学集团股份有限公司 | Titanium dioxide coated hollow glass bead composite material and preparation method thereof |
| CN115029017B (en) * | 2022-06-28 | 2024-02-02 | 万华化学集团股份有限公司 | Titanium dioxide coated hollow glass bead composite material and preparation method thereof |
| CN115594918A (en) * | 2022-10-09 | 2023-01-13 | 山东龙腾新材料有限公司（Cn） | Light odorless polypropylene composite material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101434683A (en) | Polymer graft modification composite hollow micro-bead and preparation thereof | |
| Sengupta et al. | Furfuryl palmitate coated fly ash used as filler in recycled polypropylene matrix composites | |
| CN107099869B (en) | A kind of modified polypropylene fiber and preparation method thereof and modified polypropylene fiber reinforced mortar concrete | |
| US5532295A (en) | Thermoplastic syntactic foams and their preparation | |
| CN107324834A (en) | It is a kind of that there is imitative shell laminar composite of regular bridged linkage and preparation method thereof | |
| JP2008537570A (en) | A process for producing monolithic xerogels and aerogels composed of silica / latex hybrids modified with alkoxysilane groups under subcritical conditions. | |
| Ciardiello et al. | Effects of carbon black and graphene nano-platelet fillers on the mechanical properties of syntactic foam | |
| CN102358799A (en) | Unsaturated polyester molding compound and preparation method thereof | |
| CN105038161B (en) | A kind of modified galapectite/PLA composite foam material and its preparation and application | |
| WO2004058471A1 (en) | Near net shape prepreg | |
| CN1256373C (en) | Preparation technology for composite of epoxy resin nano silicon dioxide | |
| KR20190022664A (en) | Compositions comprising fiber materials, multistage polymers and (meth) acrylic polymers, processes for their preparation, and uses thereof | |
| CN104945571B (en) | The preparation method of pH responsive polymer base Janus hollow nanospheres | |
| JPS62108782A (en) | Glass fiber-reinforced cement press formed body | |
| JP2009242477A (en) | Fiber-reinforced plastic | |
| CN116903929A (en) | Surface modification method of basalt fiber | |
| Nguyen et al. | Novel core–shell (dendrimer) epoxy tougheners: Processing and hot–wet performance | |
| Ji et al. | Opal gel templated synthesis of oblate titania opal materials | |
| CN109486120B (en) | Dispersing method and application of basalt chopped fiber for vinyl resin | |
| CN113894894A (en) | Bamboo wood modifier and preparation method and application thereof | |
| KR102009811B1 (en) | Composite material preform board and method for preparing the same | |
| CN113897049A (en) | Damping material containing pore embedded particles and preparation method thereof | |
| Zhang et al. | Optimizing interfacial interactions between functionalized graphene and chitosan for enhanced strength and toughness of composite films | |
| Fu et al. | Fabrication and characterization of nanocomposites with high-impact polystyrene and hydroxyapatite with well-defined polystyrene via ATRP | |
| CN110283278B (en) | Polydicyclopentadiene composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20090520 |