CN101824185B - 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
- Publication number
- CN101824185B CN101824185B CN200910073402.3A CN200910073402A CN101824185B CN 101824185 B CN101824185 B CN 101824185B CN 200910073402 A CN200910073402 A CN 200910073402A CN 101824185 B CN101824185 B CN 101824185B
- Authority
- CN
- China
- Prior art keywords
- polypropylene
- calcium carbonate
- nano
- microcrystal
- supercritical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 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 21
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 15
- -1 polypropylene Polymers 0.000 title claims abstract description 15
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 14
- 238000009792 diffusion process Methods 0.000 title claims abstract description 13
- 239000013081 microcrystal Substances 0.000 title claims abstract description 8
- 239000002131 composite material Substances 0.000 title claims description 6
- 239000012530 fluid Substances 0.000 title claims description 3
- 239000013078 crystal Substances 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 9
- 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
- 239000000203 mixture Substances 0.000 claims description 5
- 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
- 238000002156 mixing Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000007712 rapid solidification Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 230000007423 decrease Effects 0.000 claims 1
- 230000008595 infiltration Effects 0.000 claims 1
- 238000001764 infiltration Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 16
- 238000005516 engineering process Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 238000011049 filling Methods 0.000 abstract description 3
- 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
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 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
- 238000001746 injection moulding Methods 0.000 abstract 1
- 230000035699 permeability Effects 0.000 abstract 1
- 238000011160 research Methods 0.000 abstract 1
- 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
- 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
- 239000002114 nanocomposite Substances 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
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
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 Materials science, relate to microcrystal polypropylene composite material and advanced preparation method thereof that a kind of nano-calcium carbonate strengthens.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.The nano composite material of utilizing method that supercritical co sharply spreads to prepare, has good fluidity, and hardness is high, good stability of the dimension, the feature such as anti-scratch, is a kind of desirable high-grade automobile special material.
Background technology
In automobile modified plastics, the modified plastics taking polypropylene PP as matrix is the one that current application is the widest, in method of modifying, is modified as master again with inorganics filled.Along with the development of new technology, PP packing material is also fast-developing, and nano combinedization is one of its important development direction.Nanotechnology is the new technology growing up in the later stage eighties 20th century, is now applied in a lot of fields.In recent years, nano-calcium carbonate is also developed in succession, and it has obvious heterogeneous nucleating effect to the crystallization of PP, has improved 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.But due to reunion trend violent between nano particle, thereby how to make nano-calcium carbonate be uniformly distributed in to make in PP to fill to reach good with matrix engage, become a difficult point in current modified plastics field.At present the method for the most frequently used head it off is the stability that adds appropriate coupling agent, this method material between being difficult to ensure batch in twin screw extrusion, and the use of some organic solvents is also unfavorable for the theory that environmental protection is produced.Therefore in the situation that not adding any coupling agent, by a kind of novel environment friendly technique, nano-filled thing and resin matrix are realized and even mixing just highlighted its profound significance.
Summary of the invention
Patent exploitation supercritical CO of the present invention
2rapid diffusion technology is carried out filling-modified to PP, realized nano-calcium carbonate being uniformly distributed in PP, thereby greatly improves the stability of material after modification, and mechanical property.Supercritical co has the effect of plasticizing to PP with its unique gas-liquid two-phase in process of production, has reduced the melt temperature of PP, simultaneously supercritical CO
2height diffusion, perviousness makes CaCO
3be uniformly distributed in 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 sharply diffusion process from overcritical to normal temperature and pressure, make the nucleus of PP have little time to grow up just because of the sharply property changing, the significantly reduction of spherulite size, its optical property is improved, transparency increases greatly, and microlitic structure is conducive to reduce the contraction of final injecting products, has improved the dimensional stability of product.
Brief description of the drawings
Fig. 1 is supercritical co rapid diffusion process system schematic diagram, as shown in the figure, and by CO
2after gas and PP resin and filler blend, inject reactor (RV), through high temperature (HJ) high-pressure stirring (MS), form overcritical co-mixing system, afterwards critical blend system mixture is diffused to collection still (CV) through containing the ball valve of heated nozzle, it is material modified that final crystallization obtains PP.
Embodiment
The supercritical co rapid diffusion process quilt preparation technology as nano combined PP material in this invention.This system has adopted novel reactor to collect still vertical design (as shown in the figure), is conducive to the mass transfer of material, and has reduced the probability of plug nozzle.The working process of whole system can be summarized as: the CO that initial pressure is 5MPa
2(CO
2pressure in cylinder) inject reactor by syringe pump, covering on reactor heating unit around heats the first mixed system of the nano-calcium carbonate in reactor and PP, magnetic stirrer carries out rapid stirring to whole material system simultaneously, when the pressure of system and temperature reach predetermined numerical value, this numerical value is made as 25MPa and 200 DEG C in this invention.Mix with this understanding after 1 hour, open ball valve, make whole material system diffuse to and collect in still by nozzle rapidly, due to the sharply reduction of temperature and pressure, make the rapid solidification and crystallization of melting PP, because speed of cooling is fast, make the spherocrystal of PP have little time to grow up, be uniformly distributed in the nanometer CaCO in PP in addition
3pP is had to the effect of out-phase forming core, make the crystalline network of PP complete, degree of crystallinity is high, thereby has improved the mechanical property of material.Be not difficult to find out that application of the present invention is in fact very wide, 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.Also can prepare other inorganic nanoparticles by this technology and fill the PP of remodeling or engineering plastics as nylon etc. as nano ceramics/biological ceramics.
Claims (2)
1. one kind strengthens the method for microcrystal polypropylene composite material with supercritical fluid rapid diffusion method synthesis of nano calcium carbonate, wherein, the preparation method of described microcrystal polypropylene composite material comprises that step is as follows: (1) nano-calcium carbonate evenly mixes in supercritical co reactor with matrix resin polypropylene, wherein, described temperature in the kettle and pressure are respectively 200 DEG C and 25MPa, and described nano-calcium carbonate particles degree is 80-150 nm; (2) mixing reaction system after 1 hour diffuses to by reactor lower end nozzle in the collection still of normal temperature and pressure; (3) due to the sharply decline of pressure and temperature, the rapid crystallization of above-mentioned polypropylene and lattice have little time to grow up and form microlitic structure,
Wherein, described reactor be vertical setting with collecting still, and between two stills, with nozzle connection, and there is heating unit at nozzle place, this setting reduced mass diffusion apart from and nozzle be difficult for blockage phenomenon,
When the melt polypropylene of described nanon calcium carbonatefilled is that 500 μ m nozzles diffuse to while collecting in still through diameter, the rapid solidification and crystallization of above-mentioned polypropylene forms small spherulitic crystal structure, has greatly strengthened mobility and the mechanical property of polypropylene powder.
2. method according to claim 1, it is characterized in that, the height infiltration of described supercritical co, high resolution, make described nano-calcium carbonate in melt polypropylene, evenly mix, distribute, thereby need not any coupling agent in the situation that, solve a difficult problem for nano-calcium carbonate skewness in polypropylene.
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 CN101824185A (en) | 2010-09-08 |
| CN101824185B true CN101824185B (en) | 2014-08-27 |
Family
ID=42688365
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) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8603373B2 (en) * | 2010-11-04 | 2013-12-10 | Ricoh Company, Ltd. | 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 (2)
| 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》.2006,第22卷(第2期),第209-212页. |
| 成核剂的超临界分散及其效果的研究;刘颋等;《高分子材料科学与工程》;20060331;第22卷(第2期);第209-212页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101824185A (en) | 2010-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102108196B (en) | Method for preparing polylactic acid degradable material | |
| CN102241831B (en) | Preparation method of molded bodies of biodegradable polymer foamed particles | |
| CN101824185B (en) | Nano calcium carbonate strengthened microcrystal polypropylene composite material synthesized by supercritical fluid rapid diffusion method | |
| JP7288060B2 (en) | Manufacturing method for high-magnification polylactic acid foam sheet material | |
| CN103555471B (en) | Cleaning agent for screw extruder and preparation method thereof | |
| CN103057059B (en) | Injection molding device and injection molding method of online mixing and preparing high-performance microcellular foaming plastic | |
| CN101993086A (en) | Preparation method of mono-disperse silicon dioxide micro-spheres | |
| CN101456973A (en) | UPVC/grading complex formulation inorganic powder composite material and preparation method thereof | |
| CN102627837A (en) | Biodegradable polybutylene succinate (PBS) foaming material and preparation method thereof | |
| CN105623098A (en) | Preparation method of long-fiber reinforced polypropylene microcellular foam material | |
| CN104610654A (en) | Ultrafine talcum powder and polypropylene filling color masterbatch and preparation method thereof | |
| CN103205129B (en) | Old asphalt concrete regenerant and preparation method thereof | |
| CN101265343B (en) | Special-purpose material for high-strength high-ductility high-fluidity rotational molding and preparation method thereof | |
| CN207373611U (en) | Silicon rubber cold runner nozzle system | |
| CN203077566U (en) | Injection moulding device for on-line mixing preparation of high-performance microcellular foaming plastic | |
| CN106832860A (en) | A kind of preparation method of magnesium borate crystal whisker polycarbafil composite | |
| CN102626963B (en) | Preparation method of nanoscale functional masterbatches used for plastics modification | |
| CN107573660A (en) | A kind of low temperature FDM types biological medical degradable 3D printing material, preparation and application | |
| CN104672602B (en) | A kind of modified high filling color masterbatch and preparation method thereof | |
| CN102617946B (en) | Method for improving effective blending of polymers with different viscosities by aid of supercritical fluids | |
| CN101845165A (en) | Method for preparing flame-retardant wood-flour composite macromolecular thermoplastic resin material | |
| CN105382991A (en) | Water foaming injection molding method for PP/LDPE ultra-extension product | |
| CN104325615A (en) | Double screw extrusion foaming device for preparation of PET (polyethylene terephthalate) foamed plastic by use of supercritical CO2 | |
| CN102115556B (en) | Formula and manufacturing method for light plastic last | |
| CN204414515U (en) | A kind of injection machine injection screw |
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 |
|
| 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 |
|
| 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. |
|
| 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. |
|
| 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 |