CN1329111A - Polyamide/silicate nanometer composite material and its preparation method - Google Patents
Polyamide/silicate nanometer composite material and its preparation method Download PDFInfo
- Publication number
- CN1329111A CN1329111A CN 01129634 CN01129634A CN1329111A CN 1329111 A CN1329111 A CN 1329111A CN 01129634 CN01129634 CN 01129634 CN 01129634 A CN01129634 A CN 01129634A CN 1329111 A CN1329111 A CN 1329111A
- Authority
- CN
- China
- Prior art keywords
- silicate
- polyamide
- family
- monomer
- polymerization
- 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.)
- Granted
Links
Images
Abstract
The present invention relates to a polyamide/silicate nanometer compousite material, and is characterized by that firstly, using high-shearing emulsification equipment to treat silicate, dispersing medium and composite organic compound, then vacuum-suction filtering, dewatering, ultrasonic dispersing and continuously polymerizing so as to obtain the invented required composite material. As compared with the existent technology, the said invention is low in production cost, less in additive nanometer material, and can raise its product performance, and is suitable for large-scale production.
Description
The present invention relates to the polyamide nylon matrix material, more particularly, is the nylon nano matrix material that a kind of polymeric amide and silicate are formed.
The nylon nano matrix material is not good enough at pure nylon shock resistance under dry state and low temperature, and a kind of high performance composite developed not enough in some Application Areas heat-drawn wire, U.S. Pat 4,739,007 adopts two step method production, promptly earlier with after the silicate ion exchange, after filtration, washing, dry, pulverize, mix with monomer of polyamide again, be polymerized under certain condition, this complex technical process, imperceptible organic exsiccant silicate dust easily causes environmental pollution, and simultaneously, the ultrafine powder surface adsorption after drying is pulverized can be big, easily reunite the nylon nano composite property shakiness of production again, addition is big.Chinese invention patent application CN1138593A and 9710836.8 adopts single stage method directly to prepare the nylon nano matrix material, though overcome drying, pulverizing process, but because the existence of a large amount of dispersion medium water, must in reactive system, heat distillation dehydration in advance, like this, power consumption is big, whole polymerization cycle is prolonged greatly, simultaneously, in removing the process of big water gaging, can lose partially polymerized monomer again, in addition, usage ratio of equipment is very low, and therefore, single stage method only is suitable for the interstitial polymerization method and produces.Chinese patent application CN1206028A and US4,739,007 is similar substantially, and only the polymer matrix material that adopts is different different with the equipment that adopts.What the former adopted is that polyamide polymer is extruded with twin screw, and the latter adopts monomer of polyamide to produce with polymeric kettle.But the two common weak point is the particle aggregation problem can not get fine solution, and the nano material content that matrix material added of preparation is higher relatively, is difficult to the serialization industrial production.
The objective of the invention is to overcome the deficiency of prior art, propose a kind of continous vacuum suction strainer dehydration, continuous polymerization technique is prepared high performance nm-class composite polyamide/silicate material under the less relatively situation of the nano material content that adds then.
Main technical schemes of the present invention: the high-shear emulsifying device processes is used earlier in silicate, dispersion medium water, the compound agent that organises, vacuum suction filter dehydration then, ultrasonic dispersing, successive polymerization make excellent performance and stable nm-class composite polyamide/silicate material.
Raw material that matrix material of the present invention is used and content thereof (in parts by weight)
100 parts of monomer of polyamide, silicate 0.01-30 part, dispersion medium 1-800 part, the compound agent 5-30 part that organises.
Described monomer of polyamide comprises hexanolactam, butyrolactam, spicy inner formyl amine, ω oenantholactam 11 lactan, laurolactam and their open-loop products amino acid.
Described silicate is feldspar family, zeolite family and the ultramarine family silicate of the pyroxene family that comprises mica family, clay family, chlorite and chain-like structure with laminate structure, amphibole family, frame shape structure, its cation exchange capacity (CEC) 100-400meq/100g, the cation exchange capacity (CEC) of silicate is by the atomic spectroscopy test, with K
+, Na
+, Ca
2+, Mg
2+The total yield numerical table shows.Silicate should be crushed to more than 200 orders in advance.
The described compound agent that organises comprises two or more the mixture in the proton compound of long alkyl chain length quaternary ammonium salt, nylon 1010, nylon 1212 salt and above-mentioned monomer of polyamide.The sulfuric acid proton compound of caprolactam is preparation like this among the present invention: be added to the hexanolactam and the sulfuric acid of equivalent in the reactor jointly, add the water that is doubled in hexanolactam and sulfuric acid gross weight then, got final product in 1～3 hour 105 ℃～110 ℃ following back flow reaction.
All raw materials of the present invention market at home are all available, are industrial goods.
Preparation method of the present invention may further comprise the steps:
(1) silicate 0.01-30 part of laminate structure, dispersion medium water 1-800 part, compound organising the mixing of agent 5-30 part, at 25-105 ℃ down with high-shear emulsifying device processes 0.5-2 hour, then with the continous vacuum suction strainer pressure filter moisture 40-50% of reaching to the filter cake that dewaters.
(2) filter cake that step (1) is made joins in 100 parts of (weight) monomer of polyamide, under its melting temperature, disperseed 30-60 minute with ultrasonic generator, enter then in the VK polymerizing pipe, at first enter the pre-polymerization pipe: controlled temperature 230-275 ℃, pressure 0.2-1.0Mpa, arrheaed time 4-8 hour, enter again post polymerization pipe: temperature 275-245 ℃, pressure-0.05～-0.01Mpa, arrheaed time 5-10 hour, after pelletizing, extract, be drying to obtain required nm-class composite polyamide/silicate material.
The described high-shear emulsifying plant capacity of step (1) is 0.3-15KW, and stirring-head speed is 3000-200000rpm.High-shear emulsifying equipment is Shanghai sino-america joint-venture prestige space Mechanical and Electrical Equipment Company, stroke productions such as Lu Ke Mechanical and Electrical Equipment Company.
The described continous vacuum suction strainer of step (1) pressure-filteration drying machine is productions such as Xiang Tan whizzer factory.
The described ultrasonic generator of step (2), its frequency are that 25-80KHz, power are 0.3-60KW.Shape designs as required, and the new power ultrasonic device in Shanghai ultrasonic device company limited and Guangdong company limited can produce.
Poly-(2) described VK of step (comes from German: Vereinfacht Kontinuierlich, promptly vertical tower meaning) polymerizing pipe, wherein pre-polymerization length of tube and diameter ratio are 2: 1.0～12: 1.5, post polymerization length of tube and diameter ratio are 3: 1.0～13: 1.2, the polymerizing pipe internal upper part is laid the straight line stainless steel tube, polymerization single polymerization monomer and melt are walked tube side, walk thermal oil in the shell side.The VK pipe can design according to the output needs, and Ba Ling petro-chemical corporation of SINOPEC and Italian NORY company etc. all can design production, and thermal oil is heated to earlier in preheater behind the assigned temperature with recycle pump reach the last polymerizing pipe and post polymerization pipe.Pre-polymerization pipe temperature is controlled at 230～275 ℃, carries out the control of multistage temperature, and the temperature ladder raises from top to bottom, 275～245 ℃ of post polymerization pipe temperature controls, and the temperature ladder reduces from top to bottom.Adopt the control of DCS system, heat-up rate is 0.5～2.0 ℃/min.
Advantage of the present invention and effect:
The present invention compared with prior art has following remarkable advantage;
(1) the invention provides a kind of continous vacuum suction strainer dehydration equipment and prepare nano-organosilicon hydrochlorate technology, and the method for the continuous production nm-class composite polyamide/silicate material poly-before a kind of the pressurization, that the decompression back is poly-, compare with twin screw extruding polymerization technology with interstitial polymerization, production cost is lower, and quality is more stable.
(2) owing to adopted ultrasonic wave and high-shear emulsifying equipment among the present invention, just silicate disperses more even in polymerization single polymerization monomer, particle is littler, in nm-class composite polyamide/silicate material, only need to add small amounts of silicate and can reach good enhancing, toughening effect, the heat-drawn wire of product is further enhanced, and is compared with the prior art data such as table 1.Find out by table 1: under the clay situation of same amount, adopt tensile strength, the thermal denaturation temperature of the matrix material of the present invention's preparation all to improve a lot;
(3) owing to adopted the compound agent that organises among the present invention, organosilicate is convenient to continuously dehydrating, thereby the industrialization that makes successive polymerization produce nm-class composite polyamide/silicate material becomes possibility.
Example 1
This example prepares nm-class composite polyamide/silicate material in conjunction with Fig. 1 flowchart text by method of the present invention.The high-shear emulsifying still that 1 clay dispersion is used among the figure, 2 for clay organise exchange usefulness the high-shear emulsifying still, 3 for the organized clay middle vessel, 4 for continous vacuum suction strainer pressure-filteration drying machine, 5 for hexanolactam melt basin, 6 for moisture content regulate still, 7 for the performed polymer basin, 8 for preceding poly-pipe, 9 for the poly-pipe in back, 10 for extraction tower, 11 be drying tower.
Concrete preparation process: with the cationic exchange total amount is 160meq/100g, particle diameter 220 purpose clay 5kg, it is 3KW that deionized water 500Kg joins power, rotating speed 3000rpm high-shear emulsifying still 1 high speed is sheared and was disperseed 30 minutes, squeezing into power through volume pump then is 5KW, in the high-shear emulsifying still 2 of rotating speed 4000rpm, be heated to 65 ℃, add dodecyl benzyl dimethyl ammonium chloride 220 grams again, sulfuric acid proton compound 17000 grams of hexanolactam, the high-shear exchange is after 2 hours, squeeze into the middle vessel 3 that organises, dewater through continous vacuum suction strainer pressure-filteration drying machine machine again, filter cake enters power 5KW is housed, frequency is to handle 60 minutes in the ultrasonic generator hexanolactam melt jar 5 of 35KHz, obtains stably dispersing, uniform clay caprolactam solution; Entering moisture content then regulates in the still 6, being adjusted to content of water in system is 1% o'clock, enter homo(io)thermism again in 195 ℃ performed polymer basin 7, in volume pump is reached the last polymerizing pipe 8 continuously, pre-polymerization pipe length-to-diameter ratio is 3.5: 1.05, temperature ladder from top to bottom rises, and span of control is 220-265 ℃, 7 hours residence time; In the back poly-pipe 9 that enters length-to-diameter ratio again and be 3.5: 0.95, temperature ladder from top to bottom descends, scope is 265-245 ℃, 9 hours residence time, extrude pelletizing through toothed gear pump, go into drying tower 11 dryings, packing after entering extraction tower 10 extractions, obtain good, the stay-in-grade nm-class composite polyamide/silicate material of performance.Product detects the d of dispersive layered silicate in the polyamide substrate through X-ray diffractometer and transmission electron microscope
001Face is 165 , and interlamellar spacing is 25-40nm, is evenly distributed, and performance sees Table 2.
Example 2-10
The clay amount of example 2-7 is respectively 20kg, 30kg, 40kg, 50kg, 200kg, 300kg, and dispersion medium water is respectively 1000kg, 3000kg, 4000kg, 1335kg, 4000kg, 3500kg preparation technology with example 1, product performance such as table 2.
Example 8-10 is a comparative example, and its clay amount is respectively 0.15kg, 0.2kg, 0.25kg, hexanolactam 5kg, and preparation technology presses CN1138593A method, performance such as table 2.
Example 11-15
Example 11-15 adopts the different compound agent that organises to prepare nm-class composite polyamide/silicate material by method of the present invention.Compound agent kind, quantity such as the table 3 of organising.Composite property such as table 4.
Example 16-18
Example 16-18 adopts different monomer of polyamide under the identical situation of clay amount, adopts the nm-class composite polyamide/silicate material of method preparation of the present invention.Polymerization single polymerization monomer kind, quantity and composite property such as table 5.
Example 19-22
Example 19-22 is the nm-class composite polyamide/silicate material that different types of clay adopts method of the present invention to make.The kind and the composite property of clay see Table 6.
Can be seen and be found out by table 2～6 results: adopt nm-class composite polyamide/silicate material that the inventive method produces to account under 0.5% the situation of hexanolactam amount at the layered silicate addition, every mechanical property and thermotolerance are significantly increased.Adopt the inventive method can prepare comprehensive mechanical property nano composite material preferably with organise agent, different polyamide monomer of different composite.
Table 1
| Project | Clay content (%) | Tensile strength (MPa) | Elongation at break (%) | Thermal denaturation temperature (℃/1.82MPa) | d 001Interplanar distance |
| CN1138593A | ????3.0 | ????78 | ????30 | ????140 | ＞100 |
| CN1206028A | ????3.0 | ????86 | ????96 | ＞100 | |
| 97108360.8 | ????3.3 | ????90.5 | ????120 | ????143 | |
| The present invention | ????3.0 | ????95 | ????33 | ????148 | ??155 |
Table 2
| Example | Clay amount (kg) | Hexanolactam amount (kg) | ?d 001Interplanar distance () | Clay layer spacing (nm) | Tensile strength (MPa) | Elongation at break (%) | Flexural strength (MPa) | Modulus in flexure (GPa) | Notched Izod impact strength (kj/m2 | Heat-drawn wire (℃/1.82MPa) |
| ?1 | ?5 | ?1000 | ?163 | ?35 | ?97 | ?65 | ?108.2 | ?2.83 | ?7.8 | ?105 |
| ?2 | ?20 | ?1000 | ?159 | ?29 | ?94 | ?47 | ?127 | ?3.43 | ?8.9 | ?135 |
| ?3 | ?30 | ?1000 | ?155 | ?27 | ?95 | ?33 | ?135 | ?3.75 | ?9.5 | ?148 |
| ?4 | ?40 | ?1000 | ?143 | ?23 | ?96 | ?21 | ?149 | ?4.46 | ?9.6 | ?163 |
| ?5 | ?50 | ?1000 | ?139 | ?21 | ?96.5 | ?17 | ?153 | ?4.85 | ?9.7 | ?163.5 |
| ?6 | ?200 | ?1000 | ?129 | ?16 | ?98.9 | ?11 | ?156 | ?4.95 | ?8.7 | ?153.5 |
| ?7 | ?300 | ?1000 | ?126 | ?12 | ?97.5 | ?8 | ?152 | ?5.05 | ?8.3 | ?156.5 |
| ?8 | ?0.15 | ?5.0 | ?125 | ?19.5 | ?81 | ?25 | ?102 | ?2.45 | ?7.8 | ?128.8 |
| ?9 | ?0.2 | ?5.0 | ?118 | ?17.3 | ?78.3 | ?18.9 | ?98 | ?2.38 | ?7.6 | ?129.5 |
| ?10 | ?0.25 | ?5.0 | ?107 | ?17.1 | ?76.5 | ?17.5 | ?92 | ?2.12 | ?6.9 | ?132 |
Table 3
| Example | The compound agent kind that organises | The compound dosage that organises (g) |
| ?11 | Tetradecyl dimethyl benzyl ammonium chloride+nylon 1010 salt | 630＋70 |
| ?12 | Cetalkonium chloride+nylon 1010 salt | 650＋50 |
| ?13 | Stearyl dimethyl benzyl ammonium chloride+nylon 1212 salt | 680＋20 |
| ?14 | Cetalkonium chloride+nylon 1010 salt | 650＋50 |
| ?15 | The sulfuric acid proton compound of tetradecyl dimethyl benzyl ammonium chloride+hexanolactam | 630＋70 |
Table 4
| Example | Clay amount (kg) | Hexanolactam amount (kg) | ?d 001Interplanar distance () | Clay layer spacing (nm) | Tensile strength (MPa) | Elongation at break (%) | Flexural strength (MPa) | Modulus in flexure (GPa) | Notched Izod impact strength (KJ/m 2) | Heat-drawn wire (℃/1.824Pa) |
| ?11 | ????30 | ?1000 | ?163.8 | ????35 | ????97.8 | ????35 | ?118.2 | ????3.83 | ????8.8 | ?155 |
| ?12 | ????30 | ?1000 | ?157.9 | ????25 | ????94.9 | ????57 | ?123 | ????3.63 | ????8.6 | ?158 |
| ?13 | ????30 | ?1000 | ?155.3 | ????23 | ????95.3 | ????43 | ?135 | ????3.95 | ????9.5 | ?153 |
| ?14 | ????30 | ?1000 | ?135.8 | ????28 | ????95.8 | ????53 | ?145 | ????3.55 | ????8.5 | ?148.8 |
| ?15 | ????30 | ?1000 | ?145.6 | ????29 | ????95.6 | ????23 | ?155 | ????4.26 | ????9.4 | ?158.5 |
Table 5
| Example | Clay amount (kg) | Monomeric species | Hexanolactam amount (kg) | d 001Interplanar distance () | Clay layer spacing (nm) | Tensile strength (MPa) | Elongation at break (%) | Flexural strength (MPa) | Modulus in flexure (GPa) | Notched Izod impact strength (KJ/m 2) | Heat-drawn wire (℃/1.82MPa) |
| 16 | ????30 | Laurolactam | 1000 | ?173.8 | ?55 | ?87.8 | ?75 | ?108.2 | ?3.53 | ?9.8 | ?135 |
| 17 | ????30 | 6-aminocaprolc acid | 1000 | ?159.9 | ?45 | ?84.9 | ?57 | ?153 | ?3.83 | ?8.6 | ?148 |
| 18 | ????30 | Butyrolactam | 1000 | ?135.3 | ?33 | ?85.3 | ?43 | ?135 | ?3.65 | ?7.5 | ?143 |
Table 6
| Embodiment | Clay amount (kg) | Clay types | Hexanolactam amount (kg) | d 001Interplanar distance () | Clay layer spacing (nm) | Tensile strength (MPa) | Elongation at break (%) | Flexural strength (MPa) | Modulus in flexure (GPa) | Notched Izod impact strength (KJ/m 2) | Heat-drawn wire (℃/1.82MPa) |
| ?19 | ????30 | Muscovitum | 1000 | ?153.8 | ?35 | ?89.8 | ?45 | ?148.2 | ????4.10 | ???9.6 | ?155 |
| ?20 | ????30 | Chlorite | 1000 | ?149.5 | ?45 | ?88.6 | ?37 | ?143 | ????4.02 | ???9.1 | ?159 |
| ?21 | ????30 | The pyroxene ore deposit | 1000 | ?145.3 | ?38 | ?85.9 | ?34 | ?152 | ????4.15 | ???8.5 | ?163 |
| ?22 | ????30 | Zeolite | 1000 | ?135.8 | ?48 | ?87.3 | ?38 | ?147 | ????4.35 | ???8.9 | ?156 |
Claims (8)
1. nm-class composite polyamide/silicate material is characterized in that used feed composition and content thereof (in parts by weight):
100 parts of monomer of polyamide, silicate 0.01-30 part, dispersion medium water 1-800 part, the compound agent 5-30 part that organises.
2. according to the described matrix material of claim 1, it is characterized in that described monomer of polyamide comprises hexanolactam, butyrolactam, ω-oenantholactam, 11 lactan, laurolactam and their open-loop products amino acid.
3. according to the described matrix material of claim 1, it is characterized in that described silicate comprises pyroxene family, the amphibole family of mica family, clay family, chlorite and chain-like structure, feldspar family, zeolite family and the ultramarine family silicate of frame shape structure, its cation exchange capacity (CEC) is 100-400meq/100g.
4. according to the described matrix material of claim 1, it is characterized in that the described compound agent that organises comprises two or more the mixture in the proton compound of long alkyl chain length quaternary ammonium salt, nylon 1010 salt, nylon 1212 salt, monomer of polyamide.
5. the preparation method of the described nm-class composite polyamide/silicate material of claim 1 may further comprise the steps:
(1) silicate 0.01-30 part of laminate structure, dispersion medium water 1-800 part, compound organising the mixing of agent 5-30 part, use high-shear emulsifying device processes 0.5-2 hour down at 25-105 ℃, dewater to the moisture 40-50% of being of filter cake with continous vacuum suction strainer pressure filter then.
(2) filter cake that step (1) is made joins in 100 parts of monomer of polyamide, under its melting temperature, disperseed 30-60 minute with ultrasonic generator, enter then in the VK polymerizing pipe, at first enter the pre-polymerization pipe: controlled temperature 230-275 ℃, pressure 0.2-1.0Mpa, arrheaed time 4-8 hour, enter again post polymerization pipe: temperature 275-245 ℃, pressure-0.05～-0.01Mpa, arrheaed time 5-10 hour, after pelletizing, extract, be drying to obtain required nm-class composite polyamide/silicate material.
6. in accordance with the method for claim 5, it is characterized in that the described high-shear emulsifying plant capacity of step (1) is 0.3-15KW, stirring-head speed is 3000-200000rpm.
7. in accordance with the method for claim 5, the frequency that it is characterized in that the described ultrasonic generator of step (2) is that 25-80KHz, power are 0.3-60KW.
8. in accordance with the method for claim 5, it is characterized in that the described VK polymerizing pipe of step (2), the pre-polymerization length of tube is 2 with the diameter ratio: 1.0-12: 1.5, and the post polymerization length of tube is 3 with the diameter ratio: 1.0-13: 12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01129634 CN1127534C (en) | 2001-06-25 | 2001-06-25 | Polyamide/silicate nanometer composite material and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01129634 CN1127534C (en) | 2001-06-25 | 2001-06-25 | Polyamide/silicate nanometer composite material and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1329111A true CN1329111A (en) | 2002-01-02 |
| CN1127534C CN1127534C (en) | 2003-11-12 |
Family
ID=4669326
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01129634 Expired - Fee Related CN1127534C (en) | 2001-06-25 | 2001-06-25 | Polyamide/silicate nanometer composite material and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1127534C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003040026A2 (en) * | 2001-11-02 | 2003-05-15 | The Government Of The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Electrically conductive, optically transparent polymer/carbon nanotube composites and process for preparation thereof |
| CN103012775A (en) * | 2012-12-03 | 2013-04-03 | 合肥杰事杰新材料股份有限公司 | Cast nylon 6 composite and preparation method thereof |
| CN105295367A (en) * | 2014-06-27 | 2016-02-03 | 上海凯赛生物技术研发中心有限公司 | Toughened polyamide resin composite material and preparation method therefor |
| CN108384228A (en) * | 2018-02-12 | 2018-08-10 | 广东新会美达锦纶股份有限公司 | A kind of preparation method for exempting to spray 6 composite material of nano-nylon |
-
2001
- 2001-06-25 CN CN 01129634 patent/CN1127534C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003040026A2 (en) * | 2001-11-02 | 2003-05-15 | The Government Of The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Electrically conductive, optically transparent polymer/carbon nanotube composites and process for preparation thereof |
| WO2003040026A3 (en) * | 2001-11-02 | 2003-10-23 | Nasa | Electrically conductive, optically transparent polymer/carbon nanotube composites and process for preparation thereof |
| US7588699B2 (en) | 2001-11-02 | 2009-09-15 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Electrically conductive, optically transparent polymer/carbon nanotube composites and process for preparation thereof |
| US7906043B2 (en) | 2001-11-02 | 2011-03-15 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Electrically conductive, optically transparent polymer/carbon nanotube composites and process for preparation thereof |
| US7972536B2 (en) | 2001-11-02 | 2011-07-05 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Electrically conductive, optically transparent polymer/carbon nanotube composites |
| CN103012775A (en) * | 2012-12-03 | 2013-04-03 | 合肥杰事杰新材料股份有限公司 | Cast nylon 6 composite and preparation method thereof |
| CN103012775B (en) * | 2012-12-03 | 2017-08-01 | 合肥杰事杰新材料股份有限公司 | A kind of composite of nylon monomer-cast nylon 6 and preparation method thereof |
| CN105295367A (en) * | 2014-06-27 | 2016-02-03 | 上海凯赛生物技术研发中心有限公司 | Toughened polyamide resin composite material and preparation method therefor |
| CN108384228A (en) * | 2018-02-12 | 2018-08-10 | 广东新会美达锦纶股份有限公司 | A kind of preparation method for exempting to spray 6 composite material of nano-nylon |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1127534C (en) | 2003-11-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103113666B (en) | Polypropylene composite material filter plate and preparation method thereof | |
| WO2005118474A1 (en) | Silicon and method for producing the same | |
| WO2005118272A1 (en) | Compacting device | |
| CN1686794A (en) | Material of composite modified bentonite and production method | |
| CN1258231A (en) | Method for compacting aerogels | |
| CN1127534C (en) | Polyamide/silicate nanometer composite material and its preparation method | |
| CN1081207C (en) | Nanometer composite polyamide-clay material and its preparation | |
| CN101565512A (en) | Nanometer rare-earth calcium-zinc-magnesium-aluminum PVC composite stabilizer | |
| CN100503727C (en) | Nylon/attapulgite composites and their preparing process | |
| CN1257103C (en) | Method for preparing inorganic gel of aluminium magnesium silicate in high purity | |
| CN115888236A (en) | Waste liquid recycling equipment for calcium stearate production | |
| CN104974404A (en) | Preparation method of wood-plastic composite material | |
| CN107216122A (en) | A kind of ecological porcelain mud and its production method | |
| CN1239620C (en) | Nylon/bentonite nano composite material | |
| CN1626494A (en) | Method for recovering acetic acid from wastewater generated in production of furfural | |
| CN1285533C (en) | Method for preparing high efficient concrete water reducing agent using heavy washing oil | |
| CN106832670A (en) | High-strength PVC heat-conductive composite material and preparation method thereof | |
| CN116657406B (en) | Oil-water separation material based on polyester bottle flake regenerated fiber and preparation method thereof | |
| CN1011879B (en) | Prepn. of sodium-base bentonite from calcium-base bentonite | |
| CN1136232C (en) | Switching method between incompatible polymerizatino catalysts | |
| CN1651500A (en) | Preparation method of special resin for making high filling high permeable unidirection stretching film | |
| CN1187409C (en) | Method for preparing composite phenolic resin/phyllosilicate nano material | |
| CN1809579A (en) | Method for the agglomeration of used material or fines from the production of organohalosilanes | |
| EP2748119B1 (en) | Titanium diboride granules as erosion protection for cathodes | |
| CN1052492C (en) | Process and equipment for prodn. of homogeneous phase solution polymerization of rubber-rubber latex |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: CHINA PETROCHEMICAL CORPORATION; BALING PETROCHEM Free format text: FORMER OWNER: YUEYANG PETROCHEMICAL PLANT, BALING PETROCHEMICAL CORP. Effective date: 20070622 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20070622 Address after: 100029 No. 6, Xin Xin Street East, Beijing, Chaoyang District Co-patentee after: Baling Petrochemical Co., Ltd., SINOPEC Patentee after: China Petrochemical Group Corp. Address before: 414014 technical development department, Yueyang Petrochemical General Plant, Hunan Patentee before: Yueyang Chemical General Plant, Baling Petrochemical |
|
| 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: 20031112 Termination date: 20200625 |