CN100384941C - Resin/glass hollow microsphere composite material and preparation method thereof - Google Patents
Resin/glass hollow microsphere composite material and preparation method thereof Download PDFInfo
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- CN100384941C CN100384941C CNB2005100389487A CN200510038948A CN100384941C CN 100384941 C CN100384941 C CN 100384941C CN B2005100389487 A CNB2005100389487 A CN B2005100389487A CN 200510038948 A CN200510038948 A CN 200510038948A CN 100384941 C CN100384941 C CN 100384941C
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- 239000004793 Polystyrene Substances 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 15
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- 229910052799 carbon Inorganic materials 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
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Abstract
The invention discloses a resin/glass hollow microsphere composite material and a preparation method thereof. The material comprises glass hollow microspheres and thermoplastic resin coated outside the glass hollow microspheres, and particularly an interface layer which is compounded between the glass hollow microspheres and the thermoplastic resin and has the thickness of 20-100 nm and is formed by siloxane and a copolymer of three monomers, wherein the weight percentage of the interface layer to the copolymer is 10-60: 40-90%. The method comprises the following steps of mixing the glass hollow microspheres with the particle size of less than or equal to 20 mu m with thermoplastic resin: 1) spraying a siloxane solution containing amino or diamino or sulfydryl or epoxy on the surface of the glass hollow microsphere; 2) stirring the glass hollow microspheres and the graft copolymer wetted by the solvent for 5-20 minutes at 50-120 ℃; 3) and melting and blending the grafted glass hollow microspheres and thermoplastic resin at 160-280 ℃, wherein the weight percentage of the grafted glass hollow microspheres to the thermoplastic resin is 10-60: 40-90, and preparing the resin/glass hollow microsphere composite material. The tensile strength, modulus, bending strength, modulus and notch impact strength of the material are all greatly improved.
Description
Technical field
The present invention relates to a kind of cenosphere matrix material and method for making, especially resin/hollow glass bead composite material and preparation method thereof.
Background technology
By coal through 1500 ℃ of high-temp combustion fusions after rapidly cooling and the hollow glass bead that forms is the main composition of flyash, its chemical ingredients is mainly SiO
2, Al
2O
3, Fe
2O
3Deng, it is low that it has density, high ultimate compression strength, refractoriness, resistivity, corrosion-resistant rate, wear resistance, and characteristic such as low heat-conduction coefficient, percent thermal shrinkage.When with it during as the weighting material of macromolecular material and functional materials, it can make the cost of product reduce significantly, can also promote the multinomial performance that is filled thing simultaneously, makes it obtain good economic benefit in Application Areas.For this reason, people turn bane into boon, turn waste into wealth and weighting material and functional materials that desire utilizes hollow glass bead in the flyash to be used as macromolecular material have been done many trials and effort, as a kind of " manufacturing process of hollow micro bead filled resin base composite material " that discloses among the disclosed Chinese invention patent ublic specification of application CN 1339526A on March 13rd, 2002.It is intended to coal fly ash hollow micro bead is joined in the resin-based materials, to make hollow micro bead filled resin base composite material, realize resin-based materials had both been reached toughness reinforcing, enhanced purpose, the amount of inserting can both have mechanical property preferably at 20～30% o'clock, can improve its hardness, rigidity, wear resistance, erosion resistance and heat-proof quality etc. again, can also reduce the goods shrinking percentage, also can make anufacturability be able to obvious improvement simultaneously.Processing step is earlier by flyash being carried out classification, deironing, processing such as de-carbon and to obtain granularity be the cenosphere of 0.5～5 μ m, utilize aerosol processing to use treatment agent to carry out surface modification treatment again to cenosphere, wherein, treatment agent is silane coupling agent or titanate coupling agent or aluminate coupling agent or stearic acid, then hollow tiny pearl and polypropylene, polyvinyl chloride, polyethylene, polymeric amide, polyester, urethane, polyacrylic ester, polymethacrylate, ABS, one or more resin-based materials in ASA and the silicon rubber and auxiliary agent etc. mix, and injection moulding or laminating molding are made new matrix material again.But, this manufacturing process exists weak point, at first, the molecular weight of handling the treatment agent on cenosphere surface only is three, 400, be difficult to improve the combination between cenosphere and organic polymer, because of limited, so the combination at interface and enhancing toughening effect are all undesirable with the entanglement effect of macromolecular chain, make that finally the add-on of cenosphere only is 20～30%, and be difficult to improve again; Secondly, the price of used coupling agent is higher, causes the cost of modification excessive.
Summary of the invention
The technical problem to be solved in the present invention is for overcoming weak point of the prior art, and providing a kind of has higher hollow glass bead content and overall performance to be improved, and prepares easy resin/hollow glass bead composite material and preparation method thereof.
Resin/hollow glass bead composite material comprises hollow glass bead and its outer thermoplastic resin that is coating of granularity≤20 μ m, be compounded with interfacial layer between particularly said hollow glass bead and said thermoplastic resin, said interfacial layer is siloxanes and three monomeric multipolymers, said siloxanes is to contain amino or contain two amino or contain sulfydryl or contain the siloxanes of epoxy group(ing), said three monomers are respectively the above olefin(e) acid of hydroxyl 12 carbon or contain the vinylformic acid or the acrylate of epoxy group(ing), vinylbenzene, methacrylic ester or maleic anhydride, its bed thickness is 20～100nm, and the weight percent between said hollow glass bead and said thermoplastic resin is 10～60%: 40～90%.
As the further improvement of resin/hollow glass bead composite material, the granularity of described hollow glass bead is≤5 μ m; Described thermoplastic resin is polypropylene or polyethylene or polystyrene or polyacrylic ester or polymethacrylate or ABS or polyester or urethane or aforesaid mixture.
The preparation method of resin/hollow glass bead composite material comprises that the hollow glass bead with granularity≤20 μ m mixes mutually with thermoplastic resin, particularly it is finished according to the following steps: (1), will contain amino or contain the surface that solution two amino or that contain sulfydryl or contain the siloxanes of epoxy group(ing) is sprayed on hollow glass bead, wherein, contain amino or to contain consumption two amino or that contain sulfydryl or contain the siloxanes of epoxy group(ing) be 0.05～0.6wt% of hollow glass bead; (2), above-mentioned hollow glass bead and the graft copolymer of using wet with solvent were stirred 5～20 minutes down at 50～120 ℃, wherein, the consumption of graft copolymer is 0.2～10wt% of hollow glass bead, graft copolymer is made up of properties-correcting agent and thermoplastic resin, ratio therebetween is 4～25%: 75～96%, properties-correcting agent is made up of three monomers, said three monomers are respectively the above olefin(e) acid of hydroxyl 12 carbon or contain the vinylformic acid or the acrylate of epoxy group(ing), vinylbenzene, methacrylic ester or maleic anhydride, part by weight between said three monomers is 0.2～2: 1: 1～2.5, and the percentage of grafting of graft copolymer is 0.5～20%; (3), hollow glass bead that grafting was handled and thermoplastic resin be at 160～280 ℃ of following melt blendings, weight percent therebetween is 10～60%: 40～90%, makes resin/hollow glass bead composite material.
As the preparation method's of resin/hollow glass bead composite material further improvement, the solvent of described siloxanes is ethanol or the acetone or the aqueous solution; The solvent of described wetting graft copolymer is acetone or alcohol or dimethylbenzene or tetrahydrofuran (THF) or aforesaid mixed solution; Thermoplastic resin in the described graft copolymer, be polypropylene or polyethylene or polystyrene or polyacrylic ester or polymethacrylate or ABS or polyester or urethane or aforesaid mixture with the thermoplastic resin of hollow glass bead melt blending; The preparation method of described graft copolymer is solution method or extrusion by melting or gamma-ray irradiation method, and its percentage of grafting is 0.5～20%; The hollow glass bead that described elder generation handled grafting is mixed into the high density master batch mutually with big melting index thermoplastic resin, again it is mixed mutually with thermoplastic resin, afterwards, form through single screw rod or twin screw extruder melt blending extruding pelletization, or after the hollow glass bead that grafting was handled and thermoplastic resin directly mix, form through single screw rod or twin screw extruder melt blending extruding pelletization.
Beneficial effect with respect to prior art is, one, to its fracture of matrix material use emission scan electron microscope observation that makes, difference as can be known from the electromicroscopic photograph of different magnifications, each hollow glass bead all separately exists in the thermoplastic resin, be that hollow glass bead disperses very evenly in thermoplastic resin, its ratio between the two is about 10～60%: 40～90%.By fracture place hollow glass bead surface remaining the grafts resistates, hollow glass bead combines finely with grafts as can be seen.The long grafts molecular chain of macromolecule grafts makes and has formed thicker interfacial layer between hollow glass bead and the thermoplastic resin, its bed thickness is 20～100nm, and the polymkeric substance that grafts contains can participate in the thermoplastic resin, make the interface combine more firmly with thermoplastic resin, this point by the failure crack of matrix material all through or end at the hollow glass bead place and demonstrated fully, because the effect of hollow glass bead and interfacial layer, these all will be than the bigger energy of pure thermoplastic resin dissipation, and therefore mechanical properties such as the impact strength of matrix material and rigidity all can be improved; They are two years old, test with Fourier transformation infrared spectrometer to non-modified with through the hollow glass bead sample of graft modification, from infrared spectrum, can see that the graft modification sample is at 2800～3000cm through the unmodified and graft modification sample behind acetone three times and five washing and filterings of tetrahydrofuran (THF)
-1The characteristic peak of methyl, 1730cm have appearred in the place
-1V has appearred in the place
＞C=0Characteristic peak, 1500～1450cm
-1The skeletal vibration v that faint phenyl ring occurred
C=CCharacteristic peak (but 700 and 760cm
-1The strong characteristic peak of phenyl ring at place can't show because the covering of peak of microballon itself arranged), and this does not occur on the spectrogram of the hollow glass bead sample of non-modified, this explanation adopts grafting method to form the interfacial layer of chemical bonding on the hollow glass bead surface, and it is by siloxanes that contains amino or two amino or sulfydryl or epoxy group(ing) and the olefin(e) acid more than hydroxyl 12 carbon or contains the vinylformic acid of epoxy group(ing) or acrylate and vinylbenzene and methacrylic ester or maleic anhydride three monomeric multipolymers constitute; They are three years old, to the matrix material that makes behind melt blending extruding pelletization on the inferior company's T E-35 of the Nanjing section type twin screw extruder, again it (GB/T1039-92) is injection molded into the standard batten by " plastics mechanical test method general provisions " on day mechanical HTXF-150 of the company limited plastic injection moulding machine of sea, Ningbo, then, mechanical property to this standard batten is newly thought carefully the CMT4204 of measurement technology company limited type microcomputer control electronics universal testing machine and ZBC-15B type liquid crystal plastics balance weight impact testing machine with Shenzhen, respectively (GB/T1040-92) according to " plastic tensile method for testing performance ", " rigid plastics charpy impact test method " (GB/T1043-93), " plastics bending property test method " national standard (GB/T9341-2000) is tested, and its result is as shown in the table:
| Sample | Tensile strength (MPa) | Tensile modulus (MPa) | Bending strength (MPa) | Composite bending modulus (MPa) | Notched Izod impact strength (J/m 2) |
| PP | 36.596 | 1611.9 | 21.398 | 79.13 | 5.98 |
| PP-hollow tiny pearl-1# | 37.364 | 1851.52 | 22.594 | 94.978 | 10.62 |
| PP-hollow tiny pearl-2# | 35.896 | 2524.96 | 23.116 | 105.604 | 12.31 |
By finding out that the tensile strength of matrix material, tensile modulus, bending strength, composite bending modulus and notched Izod impact strength all have raising in various degree in the table, some index also has big or increases exponentially; They are four years old, thermoplastic resin can be selected polypropylene or polyethylene or polystyrene or polyacrylic ester or polymethacrylate or ABS or polyester or urethane or aforesaid mixture for use, both made the source of raw material than horn of plenty, made the easier enforcement of preparation technology and flexibly again; Its five, preparation method's reaction process is only carried out under normal pressure, temperature of reaction is not high yet, and just in stirring, finishes by mixing tank, so it is method is simpler, easy to operate, requirement to equipment is not high yet, applicable scope is wide, in addition, because modification all is lower than coupling agent with the reagent price, and consumption is also little, makes that the modification cost is lower.
Description of drawings
Below in conjunction with accompanying drawing optimal way of the present invention is described in further detail.
Fig. 1 be take the photograph after the fracture of matrix material is observed with Japanese JEOL SEM-6700F type field emission scanning electron microscope photo, by seeing the distribution situation of hollow glass bead in thermoplastic resin among the figure;
Fig. 2 be take the photograph after the fracture of matrix material is observed with Japanese JEOL SEM-6700F type field emission scanning electron microscope photo, by fracture place can see hollow glass bead surface also remaining the resistates of grafts;
Fig. 3 be take the photograph after the fracture of matrix material is observed with Japanese JEOL SEM-6700F type field emission scanning electron microscope photo, by finding out among the figure that failure crack is all by way of the hollow glass bead place;
Fig. 4 is the infrared spectrum that obtains after matrix material is detected with Nicolet Nexus 470 FTIR fourier transform infrared spectroscopies, and wherein, ordinate zou is a transmissivity, and X-coordinate is a wave number.
Embodiment
Embodiment 1: preparation process is as follows, 1), after siloxanes that 5 grams are contained amino (or two amino or sulfydryl or epoxy group(ing)) makes solvent furnishing solution with ethanol (or acetone or water), is sprayed on the surface of the hollow glass bead of 10 kilograms of granularities≤20 μ m.2), aforesaid hollow glass bead and the graft copolymer of using wet with solvent were stirred 20 minutes down at 50 ℃; Wherein, the consumption of graft copolymer is 400 grams, the solvent of wetting graft copolymer is acetone (or ethanol or dimethylbenzene or tetrahydrofuran (THF) or aforesaid mixed solution), graft copolymer is made up of properties-correcting agent and thermoplastic resin, prepare with solution method (or extrusion by melting or gamma-ray irradiation method), its percentage of grafting is 0.5%, properties-correcting agent wherein be 16 grams by the olefin(e) acid more than hydroxyl 12 carbon vinylformic acid or the acrylate of epoxy group(ing) (or contain) and vinylbenzene and methacrylic ester (or maleic anhydride three monomers) formation, thermoplastic resin is 384 gram polypropylene (or polyethylene or polystyrene or polyacrylic ester or polymethacrylate or ABS or polyester or urethane or aforesaid mixture), and the above olefin(e) acid of hydroxyl 12 carbon in the properties-correcting agent vinylformic acid or the acrylate of epoxy group(ing) (or contain): vinylbenzene: the part by weight of methacrylic ester (or maleic anhydride three monomers) is 0.2: 1: 2.5.3), hollow glass bead that grafting was handled and polypropylene (or polyethylene or polystyrene or polyacrylic ester or polymethacrylate or ABS or polyester or urethane or aforesaid mixture) thermoplastic resin is at 160 ℃ of following melt blendings, its weight percent between the two is 10%: 90%, makes to be similar to resin/hollow glass bead composite material as shown in Figure 1, Figure 2, Figure 3 and Figure 4 and that be similar to performance shown in 1# sample in the table.
Embodiment 2: preparation process is as follows, 1), after siloxanes that 8 grams are contained amino (or two amino or sulfydryl or epoxy group(ing)) makes solvent furnishing solution with ethanol (or acetone or water), is sprayed on the surface of the hollow glass bead of 10 kilograms of granularities≤20 μ m.2), aforesaid hollow glass bead and the graft copolymer of using wet with solvent were stirred 16 minutes down at 70 ℃; Wherein, the consumption of graft copolymer is 400 grams, the solvent of wetting graft copolymer is acetone (or ethanol or dimethylbenzene or tetrahydrofuran (THF) or aforesaid mixed solution), graft copolymer is made up of properties-correcting agent and thermoplastic resin, prepare with solution method (or extrusion by melting or gamma-ray irradiation method), its percentage of grafting is 5%, properties-correcting agent wherein be 40 grams by the olefin(e) acid more than hydroxyl 12 carbon vinylformic acid or the acrylate of epoxy group(ing) (or contain) and vinylbenzene and methacrylic ester (or maleic anhydride three monomers) formation, thermoplastic resin is 360 gram polypropylene (or polyethylene or polystyrene or polyacrylic ester or polymethacrylate or ABS or polyester or urethane or aforesaid mixture), and the above olefin(e) acid of hydroxyl 12 carbon in the properties-correcting agent vinylformic acid or the acrylate of epoxy group(ing) (or contain): vinylbenzene: the part by weight of methacrylic ester (or maleic anhydride three monomers) is 0.7: 1: 2.3.3), hollow glass bead that grafting was handled and polypropylene (or polyethylene or polystyrene or polyacrylic ester or polymethacrylate or ABS or polyester or urethane or aforesaid mixture) thermoplastic resin is at 190 ℃ of following melt blendings, its weight percent between the two is 26%: 74%, make be similar to as shown in Figure 1, Figure 2, Figure 3 and Figure 4 and in table the resin/hollow glass bead composite material of performance shown in the 1# sample.
Embodiment 3: preparation process is as follows, 1), after siloxanes that 10 grams are contained amino (or two amino or sulfydryl or epoxy group(ing)) makes solvent furnishing solution with ethanol (or acetone or water), is sprayed on the surface of the hollow glass bead of 10 kilograms of granularities≤20 μ m.2), aforesaid hollow glass bead and the graft copolymer of using wet with solvent were stirred 12 minutes down at 90 ℃; Wherein, the consumption of graft copolymer is 400 grams, the solvent of wetting graft copolymer is acetone (or ethanol or dimethylbenzene or tetrahydrofuran (THF) or aforesaid mixed solution), graft copolymer is made up of properties-correcting agent and thermoplastic resin, prepare with solution method (or extrusion by melting or gamma-ray irradiation method), its percentage of grafting is 11%, properties-correcting agent wherein be 80 grams by the olefin(e) acid more than hydroxyl 12 carbon vinylformic acid or the acrylate of epoxy group(ing) (or contain) and vinylbenzene and methacrylic ester (or maleic anhydride three monomers) formation, thermoplastic resin is 320 gram polypropylene (or polyethylene or polystyrene or polyacrylic ester or polymethacrylate or ABS or polyester or urethane or aforesaid mixture), and the above olefin(e) acid of hydroxyl 12 carbon in the properties-correcting agent vinylformic acid or the acrylate of epoxy group(ing) (or contain): vinylbenzene: the part by weight of methacrylic ester (or maleic anhydride three monomers) is 1: 1: 1.7.3), hollow glass bead that grafting was handled and polypropylene (or polyethylene or polystyrene or polyacrylic ester or polymethacrylate or ABS or polyester or urethane or aforesaid mixture) thermoplastic resin is at 220 ℃ of following melt blendings, its weight percent between the two is 35%: 65%, make as shown in Figure 1, Figure 2, Figure 3 and Figure 4 and in table the resin/hollow glass bead composite material of performance shown in the 2# sample.
Embodiment 4: preparation process is as follows, 1), after siloxanes that 30 grams are contained amino (or two amino or sulfydryl or epoxy group(ing)) makes solvent furnishing solution with ethanol (or acetone or water), is sprayed on the surface of the hollow glass bead of 10 kilograms of granularities≤20 μ m.2), aforesaid hollow glass bead and the graft copolymer of using wet with solvent were stirred 8 minutes down at 105 ℃; Wherein, the consumption of graft copolymer is 400 grams, the solvent of wetting graft copolymer is acetone (or ethanol or dimethylbenzene or tetrahydrofuran (THF) or aforesaid mixed solution), graft copolymer is made up of properties-correcting agent and thermoplastic resin, prepare with solution method (or extrusion by melting or gamma-ray irradiation method), its percentage of grafting is 16%, properties-correcting agent wherein be 60 grams by the olefin(e) acid more than hydroxyl 12 carbon vinylformic acid or the acrylate of epoxy group(ing) (or contain) and vinylbenzene and methacrylic ester (or maleic anhydride three monomers) formation, thermoplastic resin is 340 gram polypropylene (or polyethylene or polystyrene or polyacrylic ester or polymethacrylate or ABS or polyester or urethane or aforesaid mixture), and the above olefin(e) acid of hydroxyl 12 carbon in the properties-correcting agent vinylformic acid or the acrylate of epoxy group(ing) (or contain): vinylbenzene: the part by weight of methacrylic ester (or maleic anhydride three monomers) is 1.5: 1: 1.3.3), hollow glass bead that grafting was handled and polypropylene (or polyethylene or polystyrene or polyacrylic ester or polymethacrylate or ABS or polyester or urethane or aforesaid mixture) thermoplastic resin is at 250 ℃ of following melt blendings, its weight percent between the two is 44%: 56%, makes to be similar to resin/hollow glass bead composite material as shown in Figure 1, Figure 2, Figure 3 and Figure 4 and that be similar to performance shown in 2# sample in the table.
Embodiment 5: preparation process is as follows, 1), after siloxanes that 60 grams are contained amino (or two amino or sulfydryl or epoxy group(ing)) makes solvent furnishing solution with ethanol (or acetone or water), is sprayed on the surface of the hollow glass bead of 10 kilograms of granularities≤20 μ m.2), aforesaid hollow glass bead and the graft copolymer of using wet with solvent were stirred 5 minutes down at 120 ℃; Wherein, the consumption of graft copolymer is 400 grams, the solvent of wetting graft copolymer is acetone (or ethanol or dimethylbenzene or tetrahydrofuran (THF) or aforesaid mixed solution), graft copolymer is made up of properties-correcting agent and thermoplastic resin, prepare with solution method (or extrusion by melting or gamma-ray irradiation method), its percentage of grafting is 20%, properties-correcting agent wherein be 100 grams by the olefin(e) acid more than hydroxyl 12 carbon vinylformic acid or the acrylate of epoxy group(ing) (or contain) and vinylbenzene and methacrylic ester (or maleic anhydride three monomers) formation, thermoplastic resin is 300 gram polypropylene (or polyethylene or polystyrene or polyacrylic ester or polymethacrylate or ABS or polyester or urethane or aforesaid mixture), and the above olefin(e) acid of hydroxyl 12 carbon in the properties-correcting agent vinylformic acid or the acrylate of epoxy group(ing) (or contain): vinylbenzene: the part by weight of methacrylic ester (or maleic anhydride three monomers) is 2: 1: 1.3), hollow glass bead that grafting was handled and polypropylene (or polyethylene or polystyrene or polyacrylic ester or polymethacrylate or ABS or polyester or urethane or aforesaid mixture) thermoplastic resin is at 280 ℃ of following melt blendings, its weight percent between the two is 60%: 40%, makes to be similar to resin/hollow glass bead composite material as shown in Figure 1, Figure 2, Figure 3 and Figure 4 and that be similar to performance shown in 2# sample in the table.
The consumption of selecting graft copolymer more respectively for use is 20 grams, 100 grams, 700 grams and 1000 grams, and the consumption of definite thus properties-correcting agent and thermoplastic resin, repeat embodiment 1～5, made equally and be similar to resin/hollow glass bead composite material as shown in Figure 1, Figure 2, Figure 3 and Figure 4 and that be similar to performance shown in 1# or 2# sample in the table.
Also can be behind the third step among each embodiment, the hollow glass bead that grafting was handled is mixed into the high density master batch mutually with big melting index thermoplastic resin earlier, again it is mixed mutually with thermoplastic resin, make equally through single screw rod or twin screw extruder melt blending extruding pelletization then and be similar to resin/hollow glass bead composite material as shown in Figure 1, Figure 2, Figure 3 and Figure 4 and that be similar to performance shown in 1# or 2# sample in the table.
Obviously, those skilled in the art can carry out various changes and modification to resin/hollow glass bead composite material of the present invention and preparation method thereof and not break away from the spirit and scope of the present invention.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.
Claims (9)
1. resin/hollow glass bead composite material, the hollow glass bead and its outer thermoplastic resin that is coating that comprise granularity≤20 μ m, it is characterized in that being compounded with interfacial layer between said hollow glass bead and said thermoplastic resin, said interfacial layer is siloxanes and three monomeric multipolymers, said siloxanes is to contain amino or contain two amino or contain sulfydryl or contain the siloxanes of epoxy group(ing), said three monomers are respectively the above olefin(e) acid of hydroxyl 12 carbon or contain the vinylformic acid or the acrylate of epoxy group(ing), vinylbenzene, methacrylic ester or maleic anhydride, its bed thickness is 20～100nm, and the weight percent between said hollow glass bead and said thermoplastic resin is 10～60%: 40～90%.
2. resin/hollow glass bead composite material according to claim 1 is characterized in that the granularity of hollow glass bead is≤5 μ m.
3. resin/hollow glass bead composite material according to claim 1 is characterized in that thermoplastic resin is polypropylene or polyethylene or polystyrene or polyacrylic ester or polymethacrylate or ABS or polyester or urethane or aforesaid mixture.
4. the preparation method of resin/hollow glass bead composite material according to claim 1 comprises that the hollow glass bead with granularity≤20 μ m mixes mutually with thermoplastic resin, it is characterized in that finishing according to the following steps:
4.1, will contain amino or contain the surface that solution two amino or that contain sulfydryl or contain the siloxanes of epoxy group(ing) is sprayed on hollow glass bead, wherein, contain amino or to contain consumption two amino or that contain sulfydryl or contain the siloxanes of epoxy group(ing) be 0.05～0.6wt% of hollow glass bead;
4.2, above-mentioned hollow glass bead and the graft copolymer of using wet with solvent were stirred 5～20 minutes down at 50～120 ℃, wherein, the consumption of graft copolymer is 0.2～10wt% of hollow glass bead, graft copolymer is made up of properties-correcting agent and thermoplastic resin, ratio therebetween is 4～25%: 75～96%, properties-correcting agent is made up of three monomers, said three monomers are respectively the above olefin(e) acid of hydroxyl 12 carbon or contain the vinylformic acid or the acrylate of epoxy group(ing), vinylbenzene, methacrylic ester or maleic anhydride, part by weight between said three monomers is 0.2～2: 1: 1～2.5, and the percentage of grafting of graft copolymer is 0.5～20%;
4.3, hollow glass bead that grafting was handled and thermoplastic resin be at 160～280 ℃ of following melt blendings, weight percent therebetween is 10～60%: 40～90%, makes resin/hollow glass bead composite material.
5. the preparation method of resin/hollow glass bead composite material according to claim 4, the solvent that it is characterized in that siloxanes is ethanol or the acetone or the aqueous solution.
6. the preparation method of resin/hollow glass bead composite material according to claim 4, the solvent that it is characterized in that wetting graft copolymer is acetone or alcohol or dimethylbenzene or tetrahydrofuran (THF) or aforesaid mixed solution.
7. the preparation method of resin/hollow glass bead composite material according to claim 4, it is characterized in that in the graft copolymer thermoplastic resin, be polypropylene or polyethylene or polystyrene or polyacrylic ester or polymethacrylate or ABS or polyester or urethane or aforesaid mixture with the thermoplastic resin of hollow glass bead melt blending.
8. the preparation method of resin/hollow glass bead composite material according to claim 4, the preparation method who it is characterized in that graft copolymer is solution method or extrusion by melting or gamma-ray irradiation method, its percentage of grafting is 0.5～20%.
9. according to the preparation method of claim 4 or 7 described resin/hollow glass bead composite materials, it is characterized in that the hollow glass bead of earlier grafting being handled is mixed into the high density master batch mutually with big melting index thermoplastic resin, again it is mixed mutually with thermoplastic resin, afterwards, form through single screw rod or twin screw extruder melt blending extruding pelletization, or after the hollow glass bead that grafting was handled and thermoplastic resin directly mix, form through single screw rod or twin screw extruder melt blending extruding pelletization.
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| JP2019014798A (en) * | 2017-07-05 | 2019-01-31 | パナソニックＩｐマネジメント株式会社 | Polyolefin resin composition, polyolefin resin molding using the same, and vacuum cleaner using the same |
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| CN113321467B (en) * | 2021-06-01 | 2022-04-15 | 中铁大桥局集团有限公司 | Internal curing low-shrinkage lightweight aggregate ultrahigh-performance concrete and preparation method thereof |
| CN115612314B (en) * | 2022-11-11 | 2024-04-05 | 郑州圣莱特空心微珠新材料有限公司 | Surface treatment method of glass beads and polysulfide glue |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1082485A (en) * | 1992-06-19 | 1994-02-23 | 国际壳牌研究有限公司 | Polyolefin/filler composite materials and application thereof |
| US5384345A (en) * | 1991-12-17 | 1995-01-24 | Oatey Company | Compositions containing hollow microspheres |
| JPH07258542A (en) * | 1994-03-25 | 1995-10-09 | Nippon Oil Co Ltd | Resin composition for composite material, intermediate for composite material, and composite material |
| US5597522A (en) * | 1992-06-19 | 1997-01-28 | Shell Research Limited | Method of making polyolefin/filler composite materials |
| US6042936A (en) * | 1997-09-23 | 2000-03-28 | Fibermark, Inc. | Microsphere containing circuit board paper |
| CN1319623A (en) * | 2001-03-15 | 2001-10-31 | 刘星 | Hollow ball shape composite material and making method thereof |
| CN1332208A (en) * | 2001-08-28 | 2002-01-23 | 北京空心微珠技术发展中心 | Hollow microsphere composite material and preparation method thereof |
| CN1339526A (en) * | 2001-09-21 | 2002-03-13 | 刘承晖 | Process for producing hollow micro bead filled resin base composite material |
| JP2002296940A (en) * | 2001-03-29 | 2002-10-09 | Ge Toshiba Silicones Co Ltd | Silicone rubber composition for thermal fixing roll |
-
2005
- 2005-04-16 CN CNB2005100389487A patent/CN100384941C/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5384345A (en) * | 1991-12-17 | 1995-01-24 | Oatey Company | Compositions containing hollow microspheres |
| CN1082485A (en) * | 1992-06-19 | 1994-02-23 | 国际壳牌研究有限公司 | Polyolefin/filler composite materials and application thereof |
| US5597522A (en) * | 1992-06-19 | 1997-01-28 | Shell Research Limited | Method of making polyolefin/filler composite materials |
| JPH07258542A (en) * | 1994-03-25 | 1995-10-09 | Nippon Oil Co Ltd | Resin composition for composite material, intermediate for composite material, and composite material |
| US6042936A (en) * | 1997-09-23 | 2000-03-28 | Fibermark, Inc. | Microsphere containing circuit board paper |
| CN1319623A (en) * | 2001-03-15 | 2001-10-31 | 刘星 | Hollow ball shape composite material and making method thereof |
| JP2002296940A (en) * | 2001-03-29 | 2002-10-09 | Ge Toshiba Silicones Co Ltd | Silicone rubber composition for thermal fixing roll |
| CN1332208A (en) * | 2001-08-28 | 2002-01-23 | 北京空心微珠技术发展中心 | Hollow microsphere composite material and preparation method thereof |
| CN1339526A (en) * | 2001-09-21 | 2002-03-13 | 刘承晖 | Process for producing hollow micro bead filled resin base composite material |
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Application publication date: 20061018 Assignee: Hefei Cobayer New Material Co., Ltd. Assignor: Hefei Inst. of Matter Sciences, Chinese Academy of Sciences Contract record no.: 2012340000322 Denomination of invention: Resin/hollow glass bead composite material and its prepn process Granted publication date: 20080430 License type: Exclusive License Record date: 20120924 |
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