CN101033266A - Polymer/organic montmorillonite nano composite flame-proof masterbatch, its preparing method and application - Google Patents
Polymer/organic montmorillonite nano composite flame-proof masterbatch, its preparing method and application Download PDFInfo
- Publication number
- CN101033266A CN101033266A CN 200710027570 CN200710027570A CN101033266A CN 101033266 A CN101033266 A CN 101033266A CN 200710027570 CN200710027570 CN 200710027570 CN 200710027570 A CN200710027570 A CN 200710027570A CN 101033266 A CN101033266 A CN 101033266A
- Authority
- CN
- China
- Prior art keywords
- nano composite
- abs
- flame
- montmorillonite
- ommt
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
This invention relates to a polymer/organic montmorillonite nano-composite fire retardant material, its preparation and application, which takes water as the media, and under the condition of emulsifier, acrylic monomers or styrene monomers that enter organic montmorillonite layers through initiator conduct polymerization, obtaining the polymer/organic montmorillonite nano-composite fire retardant material. It can prepare flame-retardant plastic with good retardant and mechanical properties if this material is melt with acrylonitrile-butadiene-(ABS), HIPS or PP together.
Description
Technical field
The present invention relates to field of organic, specifically is a kind of polymkeric substance/organic montmorillonite nano composite flame-proof masterbatch and its production and application.
Background technology
In recent years, along with the enhancing of people's environmental consciousness and the appearance successively of strict environmental regulation more that some are relevant with fire retardant material, some traditional Halogen flame-retardant system uses in the macromolecular material flame retardant area have been subjected to increasing restriction, when burning, can produce a large amount of toxic smogs and corrosive gases because contain the macromolecular material of this class flame-retardant system, cause secondary pollution.The new way that the nano composite polymer/laminated silicate material of later 1980s rise has been opened up flame retarded polymeric material.In nano composite polymer/laminated silicate material, the addition of layered silicate only needs in 5% (massfraction, down together) flame retardant properties of polymer materials is significantly improved.
In recent years, both at home and abroad carried out more research at nano composite polymer/laminated silicate material aspect fire-retardant, and obtained gratifying progress, wherein using more layered silicate is polynite.Find that polynite content is that the heat release rate peak value (PHRR) of polystyrene/Nano composite material of montmorillonite of 2% is than pure polystyrene 55% (Flammabillty of polystyrene layered silicate (clay) the nanocomposites:carbonaceous char formation.Fire and materials that descended, 2002,26:247-253); The PHRR of ABS/ Nano composite material of montmorillonite that contains 5% polynite is than pure ABS 28% (the Preparation andcharacterization of flame retardant ABS/montmonrillonite nanocomposite.Applied clayscience that descended, 2004,25:49-55); The PHRR of urethane/Nano composite material of montmorillonite that contains 5% organic modification montmonrillonite is than pure urethane 57% (the Study on the properties of flame retardantpolyurethane/organoclay nanocomposite.Polymer degradation andstability that descended, 2005,87:111-116).Why nano composite polymer/laminated silicate material has flame retardant properties, be that it is in combustion processes, in polymeric matrix, be nano level dispersive layered silicate lamella and " caving in voluntarily " phenomenon can occur, the bigger layered silicate range of distribution of distribution density in burning surface forms than polymeric matrix, the polymeric matrix residue of these layered silicate lamellas and carbonization is closely linked, form fine and close barrier layer, play heat insulation, oxygen barrier and stop inner flammable volatile matter to effects such as burning surface migrations, thus play the incendiary effect that stops.
Can montmorillonite layer play fire retardation in polymkeric substance, key is how to make montmorillonite layer reach nano level in polymeric matrix to disperse.At present, the preparation method of nano composite polymer-montmorillonoid material mainly contains melt intercalated method, in-situ inserted method and solution intercalation method.Melt intercalated method be meant polymkeric substance under molten state by the direct intercalation of external force effect to the method between montmorillonite layer, this method technology is simple, is easy to industrialization; But because the compatibility problem between polynite and the polymeric matrix, the nano level that montmorillonite layer is difficult to reach real in the matrix material that melt intercalated method makes disperses, this has influenced flame retardant properties on the one hand, on the other hand, because the consistency between polymkeric substance and the polynite is relatively poor, may have influence on the mechanical property of some polymkeric substance, particularly compare specific polymers as aggregated structures such as ABS; In addition, the dispersion state of montmorillonite layer is subjected to the influence of fabrication process condition very big in this method, and the course of processing is wayward, because polynite directly adds with the powder form, causes dust from flying easily simultaneously, is unfavorable for large-scale industrial production.In-situ inserted method is to make nano composite polymer-montmorillonoid material by the initiator that enters between cheating engaging layer in the direct trigger monomer polymerization of interlayer, in-situ inserted method can guarantee that montmorillonite layer reaches nano level and disperses in polymeric matrix, and use a small amount of polynite (＜5%, massfraction), just can significantly improve every performance index of polymkeric substance, its shortcoming is to be applicable to that the polymer monomer kind of this method is less.The solution intercalation method has certain pollution owing to the use of solvent to environment, in addition, if directly use polymkeric substance to carry out the solution method intercalation, has limited the use of this method owing to some polymkeric substance is difficult to find suitable solvent.
Summary of the invention
The objective of the invention is to the defective that exists at prior art, provide a kind of to acrylonitrile-butadiene-styrene copolymer (ABS), high-impact polystyrene (HIPS), polypropylene (PP), etc. plastics have good fire retardation, polymkeric substance/organic montmorillonite nano composite flame-proof masterbatch easy to use.
The present invention also aims to provide the preparation method of described polymkeric substance/organic montmorillonite nano composite flame-proof masterbatch.
Purpose of the present invention also relates to the application of described polymkeric substance/organic montmorillonite nano composite flame-proof masterbatch in the preparation flame retardant plastics, this nano composite fire retardant parent material is joined in the resins such as ABS, HIPS, PP, by melt blending, can make flame retardant plastics with good flame-retardance energy and mechanical property.
The preparation method of polymkeric substance/organic montmorillonite nano composite flame-proof masterbatch of the present invention is to be medium with water, under the condition that emulsifying agent exists, causes the monomer generation polymerization that enters the organo montmorillonite interlayer by initiator and obtains.Described monomer comprises methyl acrylate, ethyl propenoate, butyl acrylate, butyl methacrylate or styrene monomer, organo montmorillonite comprises and utilizes palmityl trimethyl ammonium chloride (C16) or octadecyl trimethyl ammonium chloride (C18) that sodium-based montmorillonite is carried out the organically-modified organo montmorillonite that obtains, emulsifying agent comprises sodium soap, sodium lauryl sulphate, alkyl sodium sulfonate or rosined soap, and initiator comprises Potassium Persulphate or ammonium persulphate.
More specifically, the preparation method of polymkeric substance/organic montmorillonite nano composite flame-proof masterbatch of the present invention comprises the steps:
(1) organo montmorillonite, emulsifying agent, initiator are added in the entry, stirred 4-6 hour down, form uniform aqueous dispersions at 30-60 ℃;
(2) be warmed up to 50-90 ℃, under agitation condition, add monomer, and at 50-90 ℃ of following polyase 13-8 hour;
(3) reaction product is poured in the container, added a certain amount of distilled water, stir, leave standstill to the reactant layering;
(4) discard container clear water at the middle and upper levels, reaction product is carried out decompress filter;
(5) with the suction filtration products therefrom 50-90 ℃ of following vacuum-drying to constant weight, promptly make polymkeric substance/organic montmorillonite nano composite flame-proof masterbatch.
The parts by weight of above-mentioned raw materials are as follows:
Monomer 60
Organo montmorillonite 10-60
Emulsifying agent 1-5
Initiator 1-3
Water 200-700
The organo montmorillonite interlamellar spacing is 2.38 nanometers (nm), and in the nano composite fire retardant parent material of method for preparing, the interlamellar spacing of montmorillonite layer reaches 3.77nm, shows to have formed intercalation type nano composite material.
Described nano composite fire retardant parent material joins in the resins such as ABS, HIPS, PP, by melt blending, can prepare flame-proof ABS, HIPS, PP plastics with good mechanical property.For example, with organo montmorillonite content is that butyl polyacrylate/organic montmorillonite nano composite flame-proof masterbatch of 40% joins among the ABS, organo montmorillonite content in joining ABS is 3% o'clock, the PHRR of flame-proof ABS and evenly heat rate of release (mHRR) have descended 19% and 36% respectively than pure ABS, and have kept the good mechanical performance.
Particularly, the application of described nano composite fire retardant parent material in the preparation flame retardant plastics comprises the steps:
(1) is to add ABS, HIPS or PP on 170-190 ℃ the open warm-up mill earlier in the roller temperature, adds oxidation inhibitor and described polymkeric substance/organic montmorillonite nano composite flame-proof masterbatch behind the fusion bag roller;
(2) mixing even slice promptly makes the montmorillonite nano composite flame-proof plastics;
Described oxidation inhibitor is the general oxidation inhibitor in this area, as 1010, B215 etc.
The parts by weight of above-mentioned raw materials are as follows:
ABS or HIPS or PP resin 100
Polymkeric substance/organic montmorillonite nano composite flame-proof masterbatch 2-20
Oxidation inhibitor 0.001-0.003.
The present invention compared with prior art has following advantage:
(1) the present invention utilizes method of emulsion polymerization, make monomers such as acrylic ester monomer, vinylbenzene in organo montmorillonite interlayer generation polymerization, make polymkeric substance/organic montmorillonite nano composite flame-proof masterbatch, organo montmorillonite content can be up to more than 50% in this nano composite fire retardant parent material.When this masterbatch being added in other resin to the preparation flame retardant plastics, under the identical condition of final organo montmorillonite requirement, the masterbatch addition is less, can reduce the disadvantageous effect that the polymkeric substance in the masterbatch brings the flame retardant plastics performance.
(2) polymkeric substance/organic montmorillonite nano composite flame-proof masterbatch of the present invention is very easy to use, by common plastics melt blending processing units and method, organo montmorillonite is dispersed in the plastic substrates such as ABS, HIPS, PP preferably, complete processing is simple, control has good application and promotion prospect easily.
(3) polymkeric substance/organic montmorillonite nano composite flame-proof masterbatch of the present invention adds in the plastics such as ABS, HIPS, PP, can significantly improve the flame retardant of plastic performance.As being that butyl polyacrylate/organic montmorillonite nano composite flame-proof masterbatch of 40% joins among the ABS with organo montmorillonite content, organo montmorillonite content in joining ABS is 3% o'clock, the PHRR of ABS and mHRR have descended 19% and 36% respectively than pure ABS's, and have kept the good mechanical performance.
(4) preparation process of polymkeric substance/organic montmorillonite nano composite flame-proof masterbatch of the present invention does not have " three wastes " discharging, organo montmorillonite is added and be distributed in the plastics with the form of masterbatch, can effectively control dust pollution, the flame retardant plastics of preparation is except the organic intercalation agent that is used for modified montmorillonoid contains the minute quantity chlorion, do not contain halogenated flame retardant, belong to " green " fire retardant material of environment-friendly type.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) spectrogram of butyl polyacrylate/organo montmorillonite (PBA/OMMT) nano composite fire retardant parent material of sodium-based montmorillonite (MMT), octadecyl trimethyl ammonium chloride montmorillonite modified (OMMT) and different OMMT content.(a) is MMT among the figure; (b) be OMMT; (c) for OMMT content be 50% PBA/OMMT nano composite fire retardant parent material, note is made PBA/OMMT-50; (d) for OMMT content be 40% PBA/OMMT nano composite fire retardant parent material, note is made PBA/OMMT-40.
Fig. 2 is that to utilize the organo montmorillonite content of different methods preparation be the XRD spectra of 3% flame-proof ABS.(a) is the flame-proof ABS that OMMT is direct and ABS melt blending (being called for short the direct mixing method of OMMT) prepares among the figure; (b) for using the flame-proof ABS of PBA/OMMT-50 masterbatch dispersion method preparation; (c) for using the flame-proof ABS of PBA/OMMT-40 masterbatch dispersion method preparation.
Fig. 3 is that the direct mixing method preparation of pure ABS, OMMT reaches heat release rate (HRR) figure by the flame-proof ABS of masterbatch dispersion method preparation.(a) pure ABS among the figure; (b) ABS of direct mixing method preparation, OMMT content 3%; (c) be the flame-proof ABS that utilizes the OMMT content 3% of PBA/OMMT-50 masterbatch dispersion method preparation; (d)-(f): utilize PBA/OMMT-40 masterbatch dispersion method preparation, OMMT content to be respectively 3%, 5% and 7% flame-proof ABS.
Embodiment
The preparation of embodiment 1 PBA/OMMT nano composite fire retardant parent material
With 600 milliliters of (ml) water, 6.0 gram (g) sodium lauryl sulphate, 2.0g ammonium persulphate and 90g add in the there-necked flask through octadecyl trimethyl ammonium chloride montmorillonite modified (OMMT), 35 ℃ stirred in water bath 5 hours, bath temperature is increased to 80 ℃ then, the butyl acrylate that under agitation condition, in there-necked flask, adds 90g, 80 ℃ of following polymerizations after 6 hours, reaction product is poured in the beaker, add an amount of distilled water, stir, leave standstill to the reactant layering and discard the upper strata clear water, with lower floor's material decompress filter, the gained solid matter 60 ℃ of following vacuum-dryings to constant weight, promptly get OMMT content and be about butyl polyacrylate/organo montmorillonite (PBA/OMMT) nano composite fire retardant parent material of 50%, note is made PBA/OMMT-50.
The MMT sheet interlayer spacing is 1.23nm as seen from Figure 1, interlamellar spacing through the OMMT of C18 modification is increased to 2.38nm, and utilize the montmorillonite layer spacing among the PBA/OMMT-50 that the present invention makes to reach 3.77nm, the nano composite material that has made intercal type is described.
The application of nano composite fire retardant parent material (PBA/OMMT-50)
Be to add 188 gram ABS on 180 ℃ the open warm-up mill in the roller temperature, the oxidation inhibitor B215 of adding 0.2% and PBA/OMMT-50 masterbatch 12 grams behind the fusion bag roller, mixing even back slice, 180 ℃ of following hot pressing on vulcanizing press then, room temperature is colded pressing again, and the OMMT content that promptly obtains by the preparation of PBA/OMMT-50 masterbatch is 3% flame-proof ABS (being called for short the masterbatch dispersion method).
By Fig. 2 (b) as can be seen, utilize on the XRD spectra of the OMMT flame-proof ABS that the masterbatch dispersion method makes and can't see the obvious diffraction peak, showing that montmorillonite layer has reached in the ABS matrix peels off and with the nanoscale homodisperse, has made exfoliated ABS/OMMT nano composite material.
By Fig. 3 (a) as can be seen, pure ABS burning heat release concentrated in the short time, and its PHHR is 1023.5kW.m
-2, evenly heat rate of release (mHRR) is 564.6kW.m
-2Fig. 3 (c) is that to utilize the OMMT content of PBA/OMMT-50 masterbatch dispersion method preparation be 3% flame-proof ABS, and its PHRR is 807.9kW.m
-2, reduced by 21% than pure ABS; MHRR is 322.5kW.m
-2, descend 43% than pure ABS, illustrate with nanoscale to be dispersed in the burning that OMMT lamella among the ABS has delayed ABS.
By visual inspection; with respect to pure ABS; utilize the residue of combustion structure of the flame-proof ABS of PBA/OMMT-50 masterbatch dispersion method preparation to keep more complete; outside surface has formed fine and close protective layer; heat and mass transfer process in the combustion processes is produced certain barrier effect, improved the flame retardant resistance of ABS.
In addition, the OMMT content that utilizes the preparation of PBA/OMMT-50 nano composite fire retardant parent material is that the tensile strength of 3% flame-proof ABS is 46.4MPa, and shock strength is 6.3kJ.m
-2, kept the original mechanical property of ABS preferably.
The preparation method of PBA/OMMT nano composite fire retardant parent material of the present invention and reaction conditions such as embodiment 1 reduce to 60g with the OMMT consumption, promptly make OMMT content and are about 40% PBA/OMMT nano composite fire retardant parent material, and note is made PBA/OMMT-40.From Fig. 1 (d) as can be seen, the interlamellar spacing of polynite is 3.85nm, and is approaching with PBA/OMMT-50.
Fig. 2 (c) is that to utilize the OMMT content of PBA/OMMT-40 masterbatch dispersion method preparation be the XRD spectra of 3% flame-proof ABS.Result and Fig. 2 (b) are similar, show that montmorillonite layer has reached to peel off and with the nanoscale homodisperse, formed exfoliated ABS/OMMT nano composite material in ABS.
By Fig. 3 (d) as can be seen, be that the PHHR and the mHRR of 3% flame-proof ABS is respectively 825.2kW.m by the OMMT content of PBA/OMMT-40 masterbatch preparation
-2And 358.8Kw.m
-2, descended 19% and 36% respectively than pure ABS, suitable with the result of use PBA/OMMT-50 masterbatch among the embodiment 1.The tensile strength of the ABS that the PBA/OMMT-40 masterbatch is fire-retardant is 44.7MPa, and is low slightly during than use PBA/OMMT-50 masterbatch, but shock strength is 8.0kJ.m
-2, height about 27% during than use PBA/OMMT-50 masterbatch.When this may be to use PBA/OMMT-40, the butyl polyacrylate in the flame-proof ABS (PBA) content was higher, and system is had certain toughening effect.
Embodiment 3
According to method and the condition of embodiment 1, use the PBA/OMMT-40 nano composite fire retardant parent material and prepare flame-proof ABS.Change the consumption of PBA/OMMT-40, make OMMT content respectively and be 5% and 7% flame-proof ABS.
By Fig. 3 (d), 3 (e), 3 (f) as can be seen, along with OMMT content is increased to 5% and at 7% o'clock by 3%, the HRR curve of flame-proof ABS becomes gently gradually, and PHHR is by 825.2kW.m
-2Drop to 709.5kW.m respectively
-2And 710.8kW.m
-2, illustrate that the increase of OMMT content helps improving flame retardant effect, but after its content was increased to 5%, PHRR reduced no longer.In addition, when the OMMT consumption was increased to 5% and 7% by 3%, the tensile strength of obtained flame-retardant ABS dropped to 39.5MPa and 36.9MPa respectively by 44.7MPa, and shock strength is by 8.0kJ.m
-2Drop to 7.8kJ.m respectively
-2And 5.7kJ.m
-2, illustrating when the OMMT consumption is higher has bigger infringement to the mechanical property of ABS especially shock strength.Therefore, in order to obtain better comprehensive performance, the OMMT consumption should not surpass 5%.
Embodiment 4
Mixing and hot-press method and condition according to the preparation flame-proof ABS that provides among the embodiment 1, but not to adopt the masterbatch dispersion method, but OMMT is directly added on open warm-up mill among the ABS (being called for short direct mixing method), prepare the OMMT consumption and be 3% flame-proof ABS.
By Fig. 2 (a) as can be seen, can see the obvious diffraction peak in the XRD spectra of the flame-proof ABS of the direct mixing method preparation of OMMT, the interlamellar spacing of montmorillonite layer is 1.96nm, also has certain reducing than the interlamellar spacing 2.38nm of OMMT before mixing.This may be to have part organic modifiers C18 to deviate from from interlayer in the process of high-temperature mixing, and the ABS molecular chain fails to insert the OMMT interlayer, the dispersion of formation nano level.
From Fig. 3 (b) as can be seen, the PHRR of the flame-proof ABS of the direct mixing method preparation of OMMT is 849.4kW.m
-2, mHRR is 389.3kW.m
-2, all be higher than the identical flame-proof ABS of OMMT content that mother material prepares.In addition, the shock strength of the flame-proof ABS of the direct mixing method preparation of OMMT only is 2.7kJ.m
-2, be significantly less than the identical flame-proof ABS (8.0kJ.m of OMMT content by the mother material preparation of embodiment 2
-2).This further illustrates and utilizes masterbatch dispersion method of the present invention to help polynite to reach the nano level homodisperse in plastic substrate, thereby prepares the flame retardant plastics with excellent mechanical performances.
Claims (4)
1, a kind of preparation method of polymkeric substance/organic montmorillonite nano composite flame-proof masterbatch is characterized in that: be medium with water, under the condition that emulsifying agent exists, cause the monomer generation polymerization that enters the organo montmorillonite interlayer by initiator and obtain;
Described monomer is methyl acrylate, ethyl propenoate, butyl acrylate, butyl methacrylate or vinylbenzene;
Described organo montmorillonite is for to utilize palmityl trimethyl ammonium chloride (C16) or octadecyl trimethyl ammonium chloride (C18) that sodium-based montmorillonite is carried out the organically-modified organo montmorillonite that obtains;
Described emulsifying agent is sodium soap, sodium lauryl sulphate, alkyl sodium sulfonate or rosined soap;
Described initiator is Potassium Persulphate or ammonium persulphate.
2, the preparation method of polymkeric substance/organic montmorillonite nano composite flame-proof masterbatch according to claim 1 is characterized in that comprising the steps:
(1) organo montmorillonite, emulsifying agent, initiator are added in the distilled water, stirred 4-6 hour down, form uniform aqueous dispersions at 30-60 ℃;
(2) be warmed up to 50-90 ℃, under agitation condition, add monomer, and at 50-90 ℃ of following polyase 13-8 hour;
(3) reaction product is poured in the container, added a certain amount of distilled water, stir, leave standstill to the reactant layering;
(4) discard container clear water at the middle and upper levels, reaction product is carried out decompress filter;
(5) with the suction filtration products therefrom 50-90 ℃ of following vacuum-drying to constant weight;
The parts by weight of above-mentioned raw materials are as follows:
Monomer 60;
Organo montmorillonite 10-60;
Emulsifying agent 1-5;
Initiator 1-3;
Distilled water 200-700.
3, polymkeric substance/organic montmorillonite nano composite flame-proof masterbatch of preparing of claim 1 or 2 described methods.
4, the described polymkeric substance/organic montmorillonite nano composite flame-proof masterbatch of claim 3 is used to prepare the method for flame retardant plastics, it is characterized in that comprising the steps:
(1) is to add ABS, HIPS or PP resin on 170-190 ℃ the open warm-up mill earlier in the roller temperature, adds oxidation inhibitor and polymkeric substance/organic montmorillonite nano composite flame-proof masterbatch behind the fusion bag roller;
(2) mixing even back slice promptly makes the montmorillonite nano composite flame-proof plastics;
The parts by weight of above-mentioned raw materials are as follows:
ABS or HIPS or PP resin 100;
Polymkeric substance/organic montmorillonite nano composite flame-proof masterbatch 2-20;
Oxidation inhibitor 0.001-0.003.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200710027570XA CN100480278C (en) | 2007-04-13 | 2007-04-13 | Polymer/organic montmorillonite nano composite flame-proof masterbatch, and preparing method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200710027570XA CN100480278C (en) | 2007-04-13 | 2007-04-13 | Polymer/organic montmorillonite nano composite flame-proof masterbatch, and preparing method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101033266A true CN101033266A (en) | 2007-09-12 |
| CN100480278C CN100480278C (en) | 2009-04-22 |
Family
ID=38730025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200710027570XA Expired - Fee Related CN100480278C (en) | 2007-04-13 | 2007-04-13 | Polymer/organic montmorillonite nano composite flame-proof masterbatch, and preparing method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100480278C (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538396B (en) * | 2009-04-17 | 2011-01-19 | 浙江大学宁波理工学院 | Environment-friendly flame-resistant ABS resin |
| CN101851384B (en) * | 2009-04-03 | 2012-05-30 | 上海锦湖日丽塑料有限公司 | Fireproof anti-ultraviolet anti-static ABS material and preparation method thereof |
| CN102492079A (en) * | 2011-12-02 | 2012-06-13 | 陕西科技大学 | Method for preparing nano composite high-absorptivity chrome tanning auxiliary agent by combining polycarboxylic acid copolymer with montmorillonite |
| CN102504429A (en) * | 2011-12-02 | 2012-06-20 | 太原理工大学 | Flame-retardant polystyrene nano-composite material and preparation method thereof |
| CN103556505A (en) * | 2013-10-22 | 2014-02-05 | 常熟市启弘纺织实业有限公司 | Preparation method of dyeing assistant |
| CN104744842A (en) * | 2015-03-24 | 2015-07-01 | 合肥会通新材料有限公司 | Polystyrene composite material reinforced by in situ-polymerization of montmorillonite intercalation and preparation method of polystyrene composite material |
| CN105294911A (en) * | 2015-11-30 | 2016-02-03 | 桂林市和鑫防水装饰材料有限公司 | Preparation method of styrene-butyl acrylate/montmorillonoid composite emulsion |
| CN105315596A (en) * | 2015-12-01 | 2016-02-10 | 仇颖超 | Method for recycling polystyrene foams to prepare polystyrene foam flame-retardant plate |
| CN105482381A (en) * | 2015-11-30 | 2016-04-13 | 东华大学 | Method for preparing a phosphorus-containing polyethylene glycol terephthalate flame-retardant copolyester / organic intercalated alpha-ZrP nanocomposite |
| CN106167266A (en) * | 2016-07-11 | 2016-11-30 | 浙江青虹新材料有限公司 | One is prepared bentonite process by compound swelling agent |
| CN108250642A (en) * | 2017-12-23 | 2018-07-06 | 董晓 | A kind of preparation method of cable filler |
| CN108774380A (en) * | 2018-06-06 | 2018-11-09 | 汪涛 | A kind of preparation method of polymer matrix composites additive flame retardant |
| CN108774395A (en) * | 2018-06-06 | 2018-11-09 | 汪涛 | A kind of processing method of flame retarding type thermoplastic polyurethane elastomer |
| CN109438862A (en) * | 2018-12-04 | 2019-03-08 | 温州包鹿新材料有限公司 | The preparation method of high leakproofness water-proof sealing rubber strip |
| CN115612240A (en) * | 2022-11-04 | 2023-01-17 | 欣达瑞精密塑胶(苏州)股份有限公司 | Keycap and preparation method thereof |
| CN116285357A (en) * | 2021-12-13 | 2023-06-23 | 国网湖南省电力有限公司 | Montmorillonite/silicone rubber composite material based on electron beam radiation crosslinking, and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1224718C (en) * | 2004-01-12 | 2005-10-26 | 陕西科技大学 | Preparation technology of ving/polymer/modified montmorillonoid nano composite tanoing agent |
| CN1233729C (en) * | 2004-05-08 | 2005-12-28 | 河北工业大学 | Novel heat resistant transparent material and its making method |
-
2007
- 2007-04-13 CN CNB200710027570XA patent/CN100480278C/en not_active Expired - Fee Related
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851384B (en) * | 2009-04-03 | 2012-05-30 | 上海锦湖日丽塑料有限公司 | Fireproof anti-ultraviolet anti-static ABS material and preparation method thereof |
| CN101538396B (en) * | 2009-04-17 | 2011-01-19 | 浙江大学宁波理工学院 | Environment-friendly flame-resistant ABS resin |
| CN102492079B (en) * | 2011-12-02 | 2014-04-23 | 陕西科技大学 | Method for preparing nano composite high-absorptivity chrome tanning auxiliary agent by combining polycarboxylic acid copolymer with montmorillonite |
| CN102492079A (en) * | 2011-12-02 | 2012-06-13 | 陕西科技大学 | Method for preparing nano composite high-absorptivity chrome tanning auxiliary agent by combining polycarboxylic acid copolymer with montmorillonite |
| CN102504429A (en) * | 2011-12-02 | 2012-06-20 | 太原理工大学 | Flame-retardant polystyrene nano-composite material and preparation method thereof |
| CN103556505B (en) * | 2013-10-22 | 2016-04-27 | 常熟市启弘纺织实业有限公司 | The preparation method of dyeing assistant |
| CN103556505A (en) * | 2013-10-22 | 2014-02-05 | 常熟市启弘纺织实业有限公司 | Preparation method of dyeing assistant |
| CN104744842A (en) * | 2015-03-24 | 2015-07-01 | 合肥会通新材料有限公司 | Polystyrene composite material reinforced by in situ-polymerization of montmorillonite intercalation and preparation method of polystyrene composite material |
| CN105294911A (en) * | 2015-11-30 | 2016-02-03 | 桂林市和鑫防水装饰材料有限公司 | Preparation method of styrene-butyl acrylate/montmorillonoid composite emulsion |
| CN105482381A (en) * | 2015-11-30 | 2016-04-13 | 东华大学 | Method for preparing a phosphorus-containing polyethylene glycol terephthalate flame-retardant copolyester / organic intercalated alpha-ZrP nanocomposite |
| CN105315596A (en) * | 2015-12-01 | 2016-02-10 | 仇颖超 | Method for recycling polystyrene foams to prepare polystyrene foam flame-retardant plate |
| CN106167266A (en) * | 2016-07-11 | 2016-11-30 | 浙江青虹新材料有限公司 | One is prepared bentonite process by compound swelling agent |
| CN108250642A (en) * | 2017-12-23 | 2018-07-06 | 董晓 | A kind of preparation method of cable filler |
| CN108774395A (en) * | 2018-06-06 | 2018-11-09 | 汪涛 | A kind of processing method of flame retarding type thermoplastic polyurethane elastomer |
| CN108774380A (en) * | 2018-06-06 | 2018-11-09 | 汪涛 | A kind of preparation method of polymer matrix composites additive flame retardant |
| CN108774395B (en) * | 2018-06-06 | 2020-10-16 | 栖霞市兴邦新材料科技有限公司 | Processing method of flame-retardant thermoplastic polyurethane elastomer |
| CN108774380B (en) * | 2018-06-06 | 2020-12-22 | 惠州市志海新威科技有限公司 | Preparation method of additive type flame retardant for resin-based composite material |
| CN109438862A (en) * | 2018-12-04 | 2019-03-08 | 温州包鹿新材料有限公司 | The preparation method of high leakproofness water-proof sealing rubber strip |
| CN109438862B (en) * | 2018-12-04 | 2024-02-02 | 浙江博士龙密封科技有限公司 | Preparation method of waterproof sealing adhesive tape with high sealing performance |
| CN116285357A (en) * | 2021-12-13 | 2023-06-23 | 国网湖南省电力有限公司 | Montmorillonite/silicone rubber composite material based on electron beam radiation crosslinking, and preparation method and application thereof |
| CN115612240A (en) * | 2022-11-04 | 2023-01-17 | 欣达瑞精密塑胶(苏州)股份有限公司 | Keycap and preparation method thereof |
| CN115612240B (en) * | 2022-11-04 | 2024-02-27 | 欣达瑞精密塑胶(苏州)股份有限公司 | Key cap and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100480278C (en) | 2009-04-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101033266A (en) | Polymer/organic montmorillonite nano composite flame-proof masterbatch, its preparing method and application | |
| CN1850899A (en) | Nano kaoline fire-resistant synergistic halogen-free non-phosphor cable sheath material | |
| CN1948357A (en) | High oil absorption resin and its preparation method | |
| CN111592667B (en) | Reinforced antibacterial artificial granite waste residue-based plastic master batch and preparation method thereof | |
| CN1807497A (en) | Swell type combustion-proof glass fiber reinforced polypropylene composite material and its preparation method | |
| CN110372910B (en) | Attapulgite-based composite flame retardant and preparation method and use method thereof | |
| CN110079012B (en) | graphene/POSS composite synergistic halogen-free flame-retardant polypropylene composite material and preparation method thereof | |
| CN1293146C (en) | Nano calcium carbonate modified plant fiber powder and composite materials thereof with plastic | |
| CN111592707A (en) | Plastic product filled and modified by artificial granite waste residue and processing method thereof | |
| Chen et al. | Interfacial adhesion and mechanical properties of PMMA-coated CaCO3 nanoparticle reinforced PVC composites | |
| CN1194998C (en) | Nano-class rubber-laminated inorganic substance composition and its preparing process | |
| CN102558714B (en) | Polyvinyl chloride/modified nano montmorillonite compound material and preparation method thereof | |
| CN1958720A (en) | Composite flame retardant in bromine series, preparation method and application | |
| CN1216096C (en) | Polyiner/laminate inorganic nano composite material and its milling shearing preparation method | |
| CN1435437A (en) | Process for preparing graft polyolefin/lamellar silicate composite nanomaterial | |
| Shi et al. | Constructing Co-decorated layered double hydroxide via interfacial assembly and its application in flame-retardant epoxy resin | |
| CN105694239A (en) | Waste PCB (printed circuit board) nonmetal powder/EPDM rubber composite material and preparation method thereof | |
| CN102604205A (en) | Novel environment-friendly composite reinforced polypropylene building template | |
| CN1631962A (en) | Polyvinyl chloride plasticizing enhanced agglomerate and its preparation method and use | |
| CN111040355A (en) | Random stripping type polymethyl methacrylate/montmorillonite nano composite material and preparation method thereof | |
| CN115948002A (en) | Flame-retardant rubber material, preparation method thereof and sealing strip | |
| Sanetuntikul et al. | A Circular Economy Use of Post-Consumer Polypropylene Packaging for Low Thermal Conductive and Fire-Retardant Building Material Applications | |
| CN1760264A (en) | Nano composite fire retardant parent material, preparation method and application | |
| CN110746691A (en) | Modified polypropylene composite material for pipeline and preparation method and application thereof | |
| CN1482170A (en) | PVC/montmorillonite nanometer composite material and method for preparing the same |
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 | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Huizhou Huaju Plastics Technology Co., Ltd. Assignor: South China University of Technology Contract record no.: 2010440000495 Denomination of invention: Polymer/organic montmorillonite nano composite flame-proof masterbatch, its preparing method and application Granted publication date: 20090422 License type: Exclusive License Open date: 20070912 Record date: 20100517 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090422 Termination date: 20170413 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |