CN101824185A - Nano calcium carbonate strengthened microcrystal polypropylene composite material synthesized by supercritical fluid rapid diffusion method - Google Patents
Nano calcium carbonate strengthened microcrystal polypropylene composite material synthesized by supercritical fluid rapid diffusion method Download PDFInfo
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- CN101824185A CN101824185A CN200910073402A CN200910073402A CN101824185A CN 101824185 A CN101824185 A CN 101824185A CN 200910073402 A CN200910073402 A CN 200910073402A CN 200910073402 A CN200910073402 A CN 200910073402A CN 101824185 A CN101824185 A CN 101824185A
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- supercritical
- calcium carbonate
- nano
- microcrystal
- performance
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 43
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 18
- 238000009792 diffusion process Methods 0.000 title claims abstract description 15
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 13
- 239000013081 microcrystal Substances 0.000 title claims abstract description 7
- -1 polypropylene Polymers 0.000 title claims abstract description 7
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 7
- 239000002131 composite material Substances 0.000 title claims description 5
- 239000012530 fluid Substances 0.000 title claims description 4
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000005516 engineering process Methods 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims abstract description 3
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 3
- 230000004927 fusion Effects 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000002114 nanocomposite Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000007712 rapid solidification Methods 0.000 claims description 2
- 230000007423 decrease Effects 0.000 claims 1
- 230000008595 infiltration Effects 0.000 claims 1
- 238000001764 infiltration Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 238000011049 filling Methods 0.000 abstract description 4
- 230000008602 contraction Effects 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- 235000010216 calcium carbonate Nutrition 0.000 abstract 3
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000001746 injection moulding Methods 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 230000035699 permeability Effects 0.000 abstract 1
- 238000011160 research Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention realizes the even distribution of nano calcium carbonate in PP (Polypropylene) by carrying out filling modification on the PP through applying a supercritical CO2 rapid diffusion technology, thereby greatly improving the stability and the mechanical performance of the modified material. The supercritical CO2 plays a role of plasticization on the PP by unique gas-liquid two-phase performance in the production process, the melting temperature of the PP is reduced, and meanwhile, CaCO3 is uniformly distributed in the PP by the high diffusion and permeability of supercritical CO2. The invention researches a high-performance nano CaCO3 filled microcrystal PP powder. The effect of a microcrystal attributes to the sharp diffusion process from a supercritical state to normal temperature and normal pressure of the whole system; a crystal nucleus of the PP is too late to grow due to the sharp performance of conversion; the optical performance and the transparency are greatly improved by great reduction of the sphaerocrystal size, and the microcrystal structure is beneficial to reducing the contraction of a final injection molding product; and the invention improves the size stability of products and is an ideal high-grade automobile special material.
Description
Technical field
The invention belongs to the polymer composite field in the Materials science, relate to a kind of nano-calcium carbonate enhanced microcrystal polypropylene composite material and advanced preparation method thereof.The present invention has improved the diffusion difficult problem of micro-nano filler particles in polypropylene matrix, and has improved polyacrylic crystal habit, and spherulite size is reduced greatly.Utilize the sharply nano composite material prepared of the method for diffusion of supercritical co, have good fluidity, characteristics such as hardness height, dimensional stability are good, anti-scratch are the high-grade automobile special materials of a kind of ideal.
Background technology
In the automobile modified plastics, be that the modified plastics of matrix is the widest a kind of of current application with polypropylene PP, in method of modifying, be modified as the master with inorganics filled again.Along with the development of new technology, the PP packing material is also fast-developing, and nano combinedization is one of its important development direction.Nanotechnology is the later stage eighties 20th century new developing technology, now is applied in a lot of fields.In recent years, nano-calcium carbonate is also developed in succession, and it has tangible heterogeneous nucleation effect to the crystallization of PP, has improved the crystallization integrity and the heat-drawn wire of material, mechanical property to material also improves significantly, and low temperature and normal temperature impact property all improve.Yet because violent reunion trend between nano particle, engage, become a difficult point in current modified plastics field thereby nano-calcium carbonate is uniformly distributed in make among the PP to fill to reach preferably with matrix.The method of at present the most frequently used head it off is to add an amount of coupling agent in the twin screw extrusion, the stability of the material between this method is difficult to guarantee batch, and the use of some organic solvents also is unfavorable for the theory that environmental protection is produced.Therefore under the situation that does not add any coupling agent, make nano-filled thing and resin matrix realize that uniform mixing has just highlighted its profound significance with a kind of novel environment friendly technology.
Summary of the invention
Patent utilization supercritical CO of the present invention
2The rapid diffusion technology is carried out filling-modified to PP, realized the uniform distribution of nano-calcium carbonate in PP, thereby improves the stability of material after the modification greatly, and mechanical property.Supercritical co has the plastifying effect with its unique gas-liquid two phasic properties to PP in process of production, has reduced the melt temperature of PP, simultaneously supercritical CO
2Height diffusion, perviousness makes CaCO
3Be uniformly distributed among the PP.The present invention has developed a kind of high performance nanometer CaCO
3The crystallite PP powder of filling, the effect of crystallite will be owing to whole system the rapid diffusion process from overcritical to normal temperature and pressure, make the nucleus of PP have little time to grow up just because of the rapid property that changes, the reduction significantly of spherulite size, its optical property is improved, transparency increases greatly, and microlitic structure helps reducing the contraction of final injecting products, has improved the dimensional stability of product.
Description of drawings
Fig. 1 is a supercritical co rapid diffusion process system synoptic diagram, as shown in the figure, and with CO
2Inject reactor (RV) after gas and PP resin and the filler blend, stir (MS) through high temperature (HJ) high pressure, form overcritical co-mixing system, the ball valve of the critical system mixture of blend through containing heated nozzle diffused to collect still (CV) afterwards, it is material modified that final crystallization obtains PP.
Embodiment
Supercritical co rapid diffusion process quilt is with in this invention as the preparation technology of nano combined PP material.This system has adopted novel reactor to collect still vertical design (as shown in the figure), helps the mass transfer of material, and has reduced the probability of plug nozzle.The whole system operation process can be summarized as: initial pressure is the CO of 5MPa
2(CO
2Pressure in cylinder) inject reactor by syringe pump, the heating unit that covers on around the reactor heats the first mixed system of nano-calcium carbonate in the reactor and PP, magnetic stirrer stirs fast to whole material system simultaneously, when the pressure and the temperature of system reaches predetermined numerical value, this numerical value is made as 25MPa and 200 ℃ in this invention.After mixing 1 hour with this understanding, open ball valve, whole material system is diffused to by nozzle rapidly to be collected in the still, because the rapid reduction of temperature and pressure, make the rapid solidification and crystallization of fusion PP, because speed of cooling is fast, makes the spherocrystal of PP have little time to grow up, and is uniformly distributed in the nanometer CaCO among the PP in addition
3PP there is the effect of out-phase forming core, makes the crystalline network of PP complete, the degree of crystallinity height, thus improved the mechanical property of material.Be not difficult to find out that application of the present invention is very wide in fact, except can directly generating MODIFIED PP, by changing CaCO
3Also can be made into filling master batch with the proportioning of PP, because the granularity of its goods is little, good fluidity, thus make its being evenly distributed in matrix resin.PP or the engineering plastics such as the nylon etc. that also can prepare other inorganic nanoparticles such as nano ceramics/biological ceramics filling remodeling by this technology.
Claims (6)
1. one kind with supercritical fluid rapid diffusion method synthetic nano-calcium carbonate enhanced microcrystal polypropylene composite material, is a kind of novel high-grade automobile special material.
2. according to claim 1, described nano-calcium carbonate particles degree is 80-150nm.
3. according to claim 1, preparation technology's supercutical fluid diffusion process of a kind of advanced person is used for preparing nano composite material, comprise that step is as follows: (1) nano-calcium carbonate and matrix resin (PP) carry out uniform mixing in the supercritical co reactor, and temperature in the kettle and pressure are respectively 200 ℃ and 25MPa; (2) mixing 1 hour afterreaction system diffuses in the collection still of normal temperature and pressure by reactor lower end nozzle; (3) owing to the rapid decline of pressure and temperature, rapid crystallization of PP and lattice have little time to grow up and form microlitic structure.
4. according to claim 3, it is characterized in that two reactors (reactor and collect still) are vertical settings, with the nozzle connection, and there is heating unit at the nozzle place between two stills, this setting reduced mass diffusion apart from and nozzle be difficult for blockage phenomenon.
5. according to claim 3, it is characterized in that height infiltration, the high resolution of supercritical co, make nanometer CaCO
3Uniform mixing, distribution in fusion PP, thus under need not the situation of any coupling agent, have solved the difficult problem of nano-filled thing skewness in PP.
6. according to claim 3, when calcium carbonate-filled fusion PP diffuses to for the 500um nozzle when collecting in the still through diameter, the rapid solidification and crystallization of PP forms small spherulitic crystal structure, has strengthened the flowability and the mechanical property of PP powder greatly.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910073402.3A CN101824185B (en) | 2009-12-11 | 2009-12-11 | Nano calcium carbonate strengthened microcrystal polypropylene composite material synthesized by supercritical fluid rapid diffusion method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910073402.3A CN101824185B (en) | 2009-12-11 | 2009-12-11 | Nano calcium carbonate strengthened microcrystal polypropylene composite material synthesized by supercritical fluid rapid diffusion method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101824185A true CN101824185A (en) | 2010-09-08 |
| CN101824185B CN101824185B (en) | 2014-08-27 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910073402.3A Expired - Fee Related CN101824185B (en) | 2009-12-11 | 2009-12-11 | Nano calcium carbonate strengthened microcrystal polypropylene composite material synthesized by supercritical fluid rapid diffusion method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101824185B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102455613A (en) * | 2010-11-04 | 2012-05-16 | 株式会社理光 | Method for producing particles, method for producing toner, and apparatus for producing particles |
| CN112427646A (en) * | 2020-12-02 | 2021-03-02 | 山东理工大学 | Method for preparing magnetic abrasive material by supercritical carbon dioxide assisted plasma spray |
| CN113549314A (en) * | 2021-08-11 | 2021-10-26 | 深圳市久信达科技有限公司 | Anti-static degradable film for electronic packaging and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1607212A (en) * | 2003-10-16 | 2005-04-20 | 华东理工大学 | Method for preparing crystalline polypropylene by supercritical CO2 |
-
2009
- 2009-12-11 CN CN200910073402.3A patent/CN101824185B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1607212A (en) * | 2003-10-16 | 2005-04-20 | 华东理工大学 | Method for preparing crystalline polypropylene by supercritical CO2 |
Non-Patent Citations (1)
| Title |
|---|
| 刘颋等: "成核剂的超临界分散及其效果的研究", 《高分子材料科学与工程》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102455613A (en) * | 2010-11-04 | 2012-05-16 | 株式会社理光 | Method for producing particles, method for producing toner, and apparatus for producing particles |
| CN102455613B (en) * | 2010-11-04 | 2014-11-05 | 株式会社理光 | Method for producing particles, method for producing toner, and apparatus for producing particles |
| CN112427646A (en) * | 2020-12-02 | 2021-03-02 | 山东理工大学 | Method for preparing magnetic abrasive material by supercritical carbon dioxide assisted plasma spray |
| CN113549314A (en) * | 2021-08-11 | 2021-10-26 | 深圳市久信达科技有限公司 | Anti-static degradable film for electronic packaging and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101824185B (en) | 2014-08-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| ASS | Succession or assignment of patent right |
Owner name: HEILONGJIANG XINDA ENTERPRISE GROUP CO., LTD. Free format text: FORMER OWNER: HARBIN XINDA POLYMER MATERIAL CO., LTD. Effective date: 20120521 |
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| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 150078 HARBIN, HEILONGJIANG PROVINCE TO: 150060 HARBIN, HEILONGJIANG PROVINCE |
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| TA01 | Transfer of patent application right |
Effective date of registration: 20120521 Address after: Haping Road Development Zone in Harbin City, Heilongjiang province 150060 District Dalian Road No. 9 Applicant after: Heilongjiang Xinda Enterprise Group Co.,Ltd. Address before: 150078 No. 9, Qinling Mountains Road, Yingbin Road, Harbin Development Zone, Heilongjiang, China Applicant before: Harbin Xinda Polymer Materials Co.,Ltd. |
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| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: Pingfang District Road 150060 Heilongjiang Hanan city of Harbin Province, No. 9 Applicant after: Heilongjiang Xinda Enterprise Group Co.,Ltd. Address before: Haping Road Development Zone in Harbin City, Heilongjiang province 150060 District Dalian Road No. 9 Applicant before: Heilongjiang Xinda Enterprise Group Co.,Ltd. |
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140827 Termination date: 20181211 |