CN101302317A - Nano-silicon dioxide particle modified polypropylene and preparation thereof - Google Patents
Nano-silicon dioxide particle modified polypropylene and preparation thereof Download PDFInfo
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- CN101302317A CN101302317A CNA2008103024267A CN200810302426A CN101302317A CN 101302317 A CN101302317 A CN 101302317A CN A2008103024267 A CNA2008103024267 A CN A2008103024267A CN 200810302426 A CN200810302426 A CN 200810302426A CN 101302317 A CN101302317 A CN 101302317A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/918—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling
- B29C48/9185—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling in the direction of the stream of the material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92904—Die; Nozzle zone
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Silicon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides nano silicon dioxide particle modified polypropylene and a method for preparing the same. The method uses high-concentration silica sol to replace nano silicon dioxides as filler; polypropylene, the high-concentration silica sol and auxiliary agent are uniformly mixed; and the modified polypropylene is obtained through extrusion, granulation and drying in a double-screw extruder according to the machine-shaping method of polymers. The method for adding the liquid silica sol into the polypropylene provided by the invention changes the prior single method by which nano particles can be only added into the polymers in the form of powder, and opens up a novel method for introducing the nano particles into the polymers; and the preparation method is simple in technical process and convenient in operation. By utilization of the high-concentration silica sol as the novel filler to modify the polypropylene, the prepared polypropylene composite materials have low cost, superior mechanical property and very good market application prospect.
Description
Technical field
The present invention relates to the modified polypropene technical field, particularly relate to a kind of nano-silicon dioxide particle modified polypropylene and preparation method thereof.
Background technology
With nanoparticle polymer materials being carried out modification can make composite modification material have high-strength, high-ductility performance simultaneously.The preparation method of existing inorganic nano-particle/polymer composites mainly contains three kinds: sol-gel method; Embedding inlay technique; Direct dispersion method or melt-blending process.Although preceding two kinds of methods can obtain the matrix material of nanostructure, processing condition complexity.The third method is the most practical and convenient, but in the melt blending process, limited shearing force is difficult to break up the nanoparticle coacervate.Therefore, need usually nanoparticle surface is carried out the graftomer modification, to strengthen particle and polymer bonding, to prevent to reunite.Existing inorganic nano particle modified polyacrylic preparation method needs it is carried out surface treatment earlier, and desired condition harshness, complex process, cost are higher.
Summary of the invention
Technical scheme to be solved by this invention is to overcome the deficiencies in the prior art, a kind of nano-silicon dioxide particle modified polypropylene and preparation method thereof is provided, this method uses cheap high density silicon sol as weighting material, replace nano-powder to improve polyacrylic mechanics and crystal property and the rigid particles dispersiveness in polypropylene as weighting material, changed in polymkeric substance and to have introduced the state of the art that nanoparticle can only enter with the powder form, a kind of new mode of introducing nanoparticle in polymkeric substance is provided.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme:
According to listed as parts by weight, nano-silicon dioxide particle modified polypropylene of the present invention is to add auxiliary agent for 0.15～4 part by 90～110 parts of polypropylene and high density silicon sol to be prepared from.A large amount of experimental results show that of contriver's process: when the add-on of high density silicon sol was higher than 4 parts, consumption was bigger than normal, bad dispersibility, reunion easily, and shock strength and degree of crystallinity descend; When high density silicon sol add-on was lower than 0.15 part, silicon sol content very little and degree of crystallinity improves not obviously influenced the raising of its mechanical property.
Preferably, nano-silicon dioxide particle modified polypropylene is to add auxiliary agent for 3 parts by 100 parts of polypropylene and high density silicon sol to be prepared from.
The mass percent concentration of nano silicon is 20～50% in the high density silicon sol in the aforementioned nano-silicon dioxide particle modified polypropylene.
Preferably, the concentration of high density silicon sol is chosen as 40%.Through studies have shown that in a large number of contriver, when silicon sol is higher than this concentration, its less stable, easily gel; When being lower than this concentration, the content of water in system height adds and easily produces bubble man-hour, and easily makes product surface produce the flyings phenomenon, so during with the silicon sol filled polypropylene, preferably selecting silicon-dioxide quality percentage concentration for use is 40% silicon sol.
The pH value of aforementioned high density silicon sol is 2～4 or 9～11.Such pH value can guarantee the stability of silicon sol.
The present invention also provides a kind of preferably preparation method of nano-silicon dioxide particle modified polypropylene: polypropylene, high density silicon sol and auxiliary agent are mixed, extrude in twin screw extruder according to the method for polymer processing moulding then and obtain polypropylene granules, pellet is dried to water content is promptly getting modified polypropene below 0.01%.
Wherein, the extruder temperature of twin screw extruder is: 165 ℃～175 ℃ in I district, 175 ℃～180 ℃ in II district, 180 ℃～185 ℃ in III district, 185 ℃～190 ℃ in IV district, 190 ℃～195 ℃ in V district, 195 ℃～200 ℃ in VI district, 200 ℃～205 ℃ in VII district, 205 ℃～215 ℃ in VIII district, 205 ℃～215 ℃ of head temperatures, screw speed is 180～240 rev/mins.
Preferably, the extruder temperature of twin screw extruder is: 170 ℃ in I district, 175 ℃ in II district, 180 ℃ in III district, 185 ℃ in IV district, 190 ℃ in V district, 195 ℃ in VI district, 200 ℃ in VII district, 205 ℃ in VIII district, 205 ℃ of head temperatures, screw speed is 200 rev/mins.
Mechanism of the present invention: silicon sol is that silicon dioxide microparticle is scattered in the colloidal solution in the water or in the organic solvent, has the dispersiveness of height.The high density silicon sol adds to and plays following effect in the polypropylene: (1) improves dispersed, compares with nano silicon, and silicon sol dispersion effect in polypropylene is better.(2) improve degree of crystallinity, and then improve the mechanical property of polypropylene material.(3) improve the crystalling propylene degree and optimize every performance as the heterogeneous nucleation agent.
Technical scheme of the present invention is that the contriver draws through a large amount of experiments, and is specific as follows:
One, high density silicon sol and nano silicon are to crystal property, mechanical property and dispersed influence
The high density silicon sol of interpolation different mass percentage concentration and the add-on of nano silicon research silicon sol and nano silicon are to crystalling propylene performance, mechanical property and dispersed influence.
The preparation of sample: polypropylene, (mass percent concentration of silicon-dioxide is 40% to silicon sol, 20nm) or nano silicon (20nm) and antioxidant 1010 (commercially available, technical grade) puts in the mixing equipment by the described proportioning of table 1 and mix, extrude in twin screw extruder according to the method for polymer processing moulding then and obtain polypropylene granules, the extruder temperature of control twin screw extruder is: 170 ℃ in I district, 175 ℃ in II district, 180 ℃ in III district, 185 ℃ in IV district, 190 ℃ in V district, 195 ℃ in VI district, 200 ℃ in VII district, 205 ℃ in VIII district, 205 ℃ of head temperatures, screw speed are 200 rev/mins.The polypropylene granules that makes is opened wide placement 48 hours in air, put into baking oven then and made its water content promptly get modified polypropene below 0.01% in dry 2 hours down at 75 ℃.Performance to each modified polypropene detects, and the result is shown in table 2 and table 3.
Each sample proportioning of table 1
| Sample | Polypropylene (g) | Silicon sol (g) | Nano silicon (g) | Oxidation inhibitor (g) |
| 1 | 2000 | - | - | 0.1 |
| 2 | 2000 | 50 | - | 0.1 |
| 3 | 2000 | 100 | - | 0.1 |
| 4 | 2000 | 150 | - | 0.1 |
| 5 | 2000 | 200 | - | 0.1 |
| 6 | 2000 | - | 20 | 0.1 |
| 7 | 2000 | - | 40 | 0.1 |
| 8 | 2000 | - | 60 | 0.1 |
| 9 | 2000 | - | 80 | 0.1 |
The result of the DSC melting curve of table 2 nucleation PP sample
| Sample | Melt temperature (℃) | Melting enthalpy (Jg -1) | Degree of crystallinity (%) |
| 1 | 170.64 | 70.47 | 51 |
| 2 | 169.28 | 76.35 | 55 |
| 3 | 171.43 | 81.11 | 59 |
| 4 | 169.63 | 85.06 | 62 |
| 5 | 170.65 | 73.29 | 53 |
| 6 | 169.3 | 82.16 | 59 |
| 7 | 170.2 | 83.14 | 60 |
| 8 | 169.6 | 85.94 | 62 |
| 9 | 169.51 | 78.33 | 57 |
As shown in Table 2, polyacrylic degree of crystallinity constantly increased when the silicon sol add-on was 50～150g, and this is that the nucleus number increases because silicon sol adds the back, refinement spherulite size, improved polyacrylic crystallization rate, degree of crystallinity improves, and polyacrylic degree of crystallinity diminishes when consumption surpasses 150g.Polyacrylic degree of crystallinity constantly increased when the nano silicon add-on was 20～60g, add-on reaches maximum value during for 60g, degree of crystallinity descends when consumption is 60～80g, this is because when the nano-powder consumption is too much, the reunion effect can appear, not only can not increase the nucleus number and reduce the nucleus number on the contrary, cause degree of crystallinity to reduce.
Table 3 silicon sol and nanometer titanium dioxide silicone content are to the influence of the mechanical property of PP
| Sample | Flexural strength (MPa) | Modulus in flexure (GPa) | Elongation at break (%) | Shock strength (KJ/M 2) | Tensile strength (MPa) | Tensile strength (GPa) |
| 1 | 29.8 | 1.02 | 60.3 | 3.8 | 30.7 | 0.278 |
| 2 | 36.3 | 1.29 | 39.64 | 4.06 | 33.7 | 0.293 |
| 3 | 36.4 | 1.27 | 36.65 | 4.12 | 33.8 | 0.287 |
| 4 | 37 | 1.18 | 52.01 | 4.49 | 33.4 | 0.293 |
| 5 | 37.2 | 1.28 | 40.15 | 4.16 | 33.5 | 0.283 |
| 6 | 35.3 | 1.24 | 45.98 | 4.06 | 33.5 | 0.28 |
| 7 | 35.6 | 1.25 | 42.37 | 4.1 | 33 | 0.273 |
| 8 | 34.7 | 1.2 | 36.34 | 4.432 | 33.4 | 0.281 |
| 9 | 35.1 | 1.21 | 34 | 4.24 | 33.4 | 0.291 |
As shown in Table 3, the shock strength of modified polypropene rises along with the increase of silicon sol and nano silicon consumption, when the add-on of silicon sol be the add-on of 150g or nano silicon when being 60g the polypropylene shock strength reach maximum value, silicon sol agglomeration occurred and makes the polypropylene shock strength begin to descend when the consumption that surpasses 150g or nano silicon when the consumption of silicon sol surpassed 60g in polypropylene.And the nano silicon consumption also agglomeration can occur after surpassing 60g.
After adding silicon sol and nano silicon in the polypropylene, tensile strength and flexural strength are greatly enhanced, and along with the increase of two kinds of additive consumptions is on a declining curve, but overall the variation not quite.After silicon sol and nano silicon added in the polypropylene, polyacrylic extension at break all descended to some extent.
From the back reflection electron image of each sample also as can be seen, when having added 50～150g silicon sol or 20～60g nano silicon in the polypropylene, its back reflection electron image is distributing more equably, and white bright size is uneven, the silicon-dioxide of disperse; Dose thing when the add-on that surpasses 150g or nano silicon when the add-on of silicon sol surpasses 60g and disperse inhomogeneously, agglomeration is more serious.
Compared with prior art, the present invention uses the high density silicon sol to fill thing replacement nano-powder silicon-dioxide as polypropylene, need not carry out surface treatment, adding technology is simple, the silicon sol cost is lower, not only can play the enhancing the same with nano silicon, toughness reinforcing effect, and good dispersity is in using nano silicon, be a kind of very worth in factory, the novel method that promote in the laboratory, prepared polyacrylic shock strength, tensile strength and flexural strength are all similar with the polypropylene that makes with usual way, and dispersing property has effectively improved the crystalling propylene performance than using nano silicon also to improve to some extent.Provided by the invention silica sol liquid is added in the polypropylene, having changed nanoparticle in the past can only be with the single method of powder form adding polymkeric substance, opened up the novel method of nanoparticle introducing polymkeric substance, and preparation method's technical process is simple, easy to operate, use the high density silicon sol as a kind of new weighting material polypropylene to be carried out modification, the polypropylene matrix material of preparation has low, the good mechanical performance of cost, has extraordinary market application foreground.
Embodiment
Preferred implementation of the present invention
Raw material: the mass percent concentration of polypropylene 2000g, silicon-dioxide is 40% high density silicon sol 100g and antioxidant 1010 (commercially available, technical grade) 0.1g.
Preparation method: will mix in polypropylene, high density silicon sol and the oxidation inhibitor input mixing equipment, extrude in twin screw extruder according to the method for polymer processing moulding then and obtain polypropylene granules, the extruder temperature of control twin screw extruder is: 170 ℃ in I district, 175 ℃ in II district, 180 ℃ in III district, 185 ℃ in IV district, 190 ℃ in V district, 195 ℃ in VI district, 200 ℃ in VII district, 205 ℃ in VIII district, 205 ℃ of head temperatures, screw speed is 200 rev/mins.The polypropylene granules that makes is opened wide placement 48 hours in air, put into baking oven then and made its water content promptly get modified polypropene below 0.01% in dry 2 hours down at 75 ℃.
Claims (8)
1. nano-silicon dioxide particle modified polypropylene is characterized in that: according to listed as parts by weight, it is to add auxiliary agent for 0.15～4 part by 90～110 parts of polypropylene and high density silicon sol to be prepared from.
2. according to the described nano-silicon dioxide particle modified polypropylene of claim 1, it is characterized in that: according to listed as parts by weight, it is to add auxiliary agent for 3 parts by 100 parts of polypropylene and high density silicon sol to be prepared from.
3. according to claim 1 or 2 described nano-silicon dioxide particle modified polypropylenes, it is characterized in that: the mass percent concentration of nano silicon is 20～50% in the described high density silicon sol.
4. according to the described nano-silicon dioxide particle modified polypropylene of claim 3, it is characterized in that: the mass percent concentration of nano silicon is 40% in the described high density silicon sol.
5. according to claim 1 or 2 described nano-silicon dioxide particle modified polypropylenes, it is characterized in that: the pH value of described high density silicon sol is 2～4 or 9～11.
6. the preparation method of the arbitrary described nano-silicon dioxide particle modified polypropylene of claim 1-5, it is characterized in that: polypropylene, high density silicon sol and auxiliary agent are mixed, extrude in twin screw extruder according to the method for polymer processing moulding then and obtain polypropylene granules, pellet is dried to water content is promptly getting modified polypropene below 0.01%.
7. according to the preparation method of the described nano-silicon dioxide particle modified polypropylene of claim 6, it is characterized in that: the extruder temperature of described twin screw extruder is: 165 ℃～175 ℃ in I district, 175 ℃～180 ℃ in II district, 180 ℃～185 ℃ in III district, 185 ℃～190 ℃ in IV district, 190 ℃～195 ℃ in V district, 195 ℃～200 ℃ in VI district, 200 ℃～205 ℃ in VII district, 205 ℃～215 ℃ in VIII district, 205 ℃～215 ℃ of head temperatures, screw speed is 180～240 rev/mins.
8. according to the preparation method of the described nano-silicon dioxide particle modified polypropylene of claim 6, it is characterized in that: the extruder temperature of described twin screw extruder is: 170 ℃ in I district, 175 ℃ in II district, 180 ℃ in III district, 185 ℃ in IV district, 190 ℃ in V district, 195 ℃ in VI district, 200 ℃ in VII district, 205 ℃ in VIII district, 205 ℃ of head temperatures, screw speed is 200 rev/mins.
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| CNA2008103024267A CN101302317A (en) | 2008-06-30 | 2008-06-30 | Nano-silicon dioxide particle modified polypropylene and preparation thereof |
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| CNA2008103024267A CN101302317A (en) | 2008-06-30 | 2008-06-30 | Nano-silicon dioxide particle modified polypropylene and preparation thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851374A (en) * | 2010-06-24 | 2010-10-06 | 华东理工大学 | Plasticized polypropylene/inorganic nanocomposite material and preparation method thereof |
| CN102827419A (en) * | 2011-06-14 | 2012-12-19 | 黑龙江鑫达企业集团有限公司 | Preparation method for easy-to-disperse and easy-to-process polypropylene composite material |
| CN107987393A (en) * | 2017-12-25 | 2018-05-04 | 桐城市祥泰塑业有限公司 | A kind of Nano sol composite polypropylene plastic material and preparation method thereof |
| CN109774001A (en) * | 2018-11-27 | 2019-05-21 | 江西势通钙业有限公司 | A kind of preparation method of high temperature hydrating apparatus and a kind of dedicated high filler loading capacity nanometer calcium carbonate master batch of transparent membrane |
-
2008
- 2008-06-30 CN CNA2008103024267A patent/CN101302317A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851374A (en) * | 2010-06-24 | 2010-10-06 | 华东理工大学 | Plasticized polypropylene/inorganic nanocomposite material and preparation method thereof |
| CN102827419A (en) * | 2011-06-14 | 2012-12-19 | 黑龙江鑫达企业集团有限公司 | Preparation method for easy-to-disperse and easy-to-process polypropylene composite material |
| CN107987393A (en) * | 2017-12-25 | 2018-05-04 | 桐城市祥泰塑业有限公司 | A kind of Nano sol composite polypropylene plastic material and preparation method thereof |
| CN109774001A (en) * | 2018-11-27 | 2019-05-21 | 江西势通钙业有限公司 | A kind of preparation method of high temperature hydrating apparatus and a kind of dedicated high filler loading capacity nanometer calcium carbonate master batch of transparent membrane |
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Open date: 20081112 |