CN100352859C - Nano composite fire retardant parent material, preparation method and application - Google Patents
Nano composite fire retardant parent material, preparation method and application Download PDFInfo
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Abstract
The present invention relates to a fire-retardant nanometer composite base material of epoxy phenolic resin and organic montmovillonite, and a preparation process thereof. In the preparation process, a silane coupling agent is added so that the epoxy phenolic resin is combined between sodium base montmovillonite layers, and the fire-retardant nanometer composite base material is obtained; when the fire-retardant nanometer composite base material is combined with organic phosphate, fire-retardant plastics with fine performance of fire retardance and mechanical properties can be prepared.
Description
Technical field
The present invention relates to organism and inorganics compound field of nanocomposite materials, in more detail novolac epoxy/organic montmorillonite nano composite flame-proof masterbatch.
The invention still further relates to the preparation method of described nano composite fire retardant parent material.
The invention still further relates to the application of described nano composite fire retardant parent material in the preparation flame retardant plastics.
Background technology
Flourish along with macromolecular material, plastics obtain increasingly extensive application in the national economy every field, but most of plastics are all more inflammable, have hidden fire-fighting danger, thereby limited their use.Therefore, the research and development flame retardant plastics has become a heat subject.Traditional Halogen flame-retardant system can produce a large amount of poisonous smogs in the time of incendiary, cause secondary pollution, therefore uses to be subjected to increasing restriction; Dispersiveness and the consistencies of inorganic combustion inhibitor in plastics such as magnesium hydroxide commonly used, aluminium hydroxide are poor, need bigger consumption could satisfy fire-retardant requirement, and this often causes the processing of plastic degradation, the remarkable deterioration of mechanical property, particularly shock strength.Therefore, research and develop halogen-free flame-retardant system efficiently, the preparation halogen-free fire retardant plastic is the target that scientific circles and industry member are pursued.The new way that the nano composite polymer/laminated silicate material of later 1980s rise has been opened up flame retarded polymeric material is described as the revolution of macromolecular material flame-retarded technology.In nano composite polymer/laminated silicate material, the addition of layered silicate only needs 3%-5%, the flame retardant properties that just can make polymer materials especially self-extinguishing can be significantly improved, and can keep even improve the original excellent properties of polymeric substrate, recovery and regeneration are also very convenient, are a kind of ideal " green " fire retardant materials.
In recent years, both at home and abroad aspect nano composite polymer/laminated silicate material fire-retardant, carried out more research and inquirement, and obtained gratifying progress.Discovery contains the heat release rate peak value (PHRR) of nylon-6/Nano composite material of montmorillonite of 5% polynite than pure nylon-6 63% (the Ray S S et al.Polymer/layered silicate nanocomposites:a review from preparation to processing.Progress in polymer science that descended, 2003,28:1539-1641); The PHRR of composite nanometer-level polypropylene/montmorillonoid material that contains 2% polynite is than pure PP 70% (Gilman J W.Flammability andthermalstability studies of polymer-layered silicate (clay) the nanocomposites.Applied ClayScience that descended, 1999,15 (9): 31-49); The PHRR of polystyrene/Nano composite material of montmorillonite that contains 3% polynite is than pure polystyrene 48% (the Zhu J et al.Thermal and fire studies on polystyreneclay nanocomposites.Polymer International that descended, 2000,49:1158-1163).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.
Have ubiquity though nano level dispersive layered silicate can significantly improve the flame retardant properties of polymkeric substance, the dispersing morphology of layered silicate lamella in polymeric matrix is very big to the flame retardant properties influence of polymer materials.Yet, with polynite or even through layered silicate and the direct blend of plastics such as montmorillonite modified, adopt traditional plastic working method to be difficult to guarantee that layered silicate reaches the nano level homodisperse in polymeric matrix, and dispersion state influenced by fabrication process condition very big.In addition, to major part plastic material commonly used, only rely on and laminar silicic acid salt formation nano composite material, flame retardant properties also can't reach the requirement of actual use.Oxygen index as composite nanometer-level polypropylene/montmorillonoid material only is about 23.These problems have all limited nano composite polymer/laminated silicate material as the large-scale promotion application of a kind of fire retardant material in engineering reality.
In recent years, the research about the synergistic effect of layered silicate and conventional flame retardants has caused people's attention again.Promptly in the fire-retardant plastics system of conventional flame retardants, again by with the nanometer composite technology of layered silicate, reach at plastics under the situation of desired flame retardant properties, can reduce the consumption of conventional flame retardants significantly.Can on the plastic substrate burning surface, form coking charcoal layer as phosphorus flame retardant, stop the transmission of heat and the invasion of oxygen, suppress the decomposition of polymkeric substance and the effusion of flammable volatility product and burn with termination.Montmorillonite layer in the nano composite polymer-montmorillonoid material can delay the thermal destruction of polymkeric substance, increases the barrier property of charcoal layer and strengthens the stability of charcoal layer in when burning.Therefore phosphorus flame retardant and polynite is composite will have synergistic preferably.Fusing point such as phosphorus flame retardant at present relatively more commonly used such as triphenylphosphate, triphenyl phosphite, triethyl phosphate and boiling point are all lower, the volatilization of in the course of processing, being heated easily, and the mechanical property influence to plastic basis material is bigger during large usage quantity, is very limited in the use.
Summary of the invention
The objective of the invention is to defective, a kind of novolac epoxy/organic montmorillonite nano composite flame-proof masterbatch that polypropylene (PP), acrylonitrile-butadiene-styrene copolymer plastics such as (ABS) is had good fire retardation is provided at the prior art existence.
The present invention also aims to provide the preparation method of described nano composite fire retardant parent material.
The invention still further relates to the application of described nano composite fire retardant parent material in the preparation flame retardant plastics, carry out this nano composite fire retardant parent material and organophosphate composite, join in the plastics such as polypropylene, ABS, preparation has the flame retardant plastics of good flame-retardance energy and mechanical property.
The preparation method of nano composite fire retardant parent material of the present invention adds silane coupling agent, novolac epoxy (NER) is entered through the organically-modified sodium-based montmorillonite of chain alkyl ammonium salt (being called for short organo montmorillonite OMMT) interlayer, obtain novolac epoxy/organic montmorillonite nano composite flame-proof masterbatch (NER/OMMT).Described chain alkyl ammonium salt comprises octadecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride or dodecyl dimethyl Bian ammonium chloride, and silane coupling agent comprises KH550, KH560 or KH570.
Described organically-modified sodium-based montmorillonite (being called for short organo montmorillonite OMMT) is prepared by the prior art method in common, specifically comprises the following steps:
(1), the chain alkyl ammonium salt aqueous solution is added in the aqueous dispersions of sodium-based montmorillonite, 60-80 ℃ of following the stirring 10-24 hour;
(2), leave standstill and be cooled to discharging after the room temperature, washing and filtering 3-5 time up to filtrate with the no white precipitate material of Silver Nitrate check;
(3), grind refinement after being dried to constant weight, obtain the organically-modified sodium-based montmorillonite (being called for short organo montmorillonite OMMT) of white powder at 80 ℃;
The parts by weight of above-mentioned raw materials are as follows:
Sodium-based montmorillonite 70-100
Chain alkyl ammonium salt 40-60
Water 1500-3000.
The interlamellar spacing of unmodified sodium-based montmorillonite is about 1.23nm, and organically-modified sodium-based montmorillonite (OMMT) interlamellar spacing of method for preparing can reach 2.14nm.
More specifically, the preparation method of nano composite fire retardant parent material of the present invention comprises: novolac epoxy is warming up to 60-80 ℃, adding is through chain alkyl ammonium salt organically-modified sodium-based montmorillonite and silane coupling agent, stirred 1-6 hour, and obtained novolac epoxy/organic montmorillonite nano composite flame-proof masterbatch;
The parts by weight of above-mentioned raw materials are as follows:
Through the organically-modified sodium-based montmorillonite 1-20 of chain alkyl ammonium salt
Novolac epoxy 80-100
Silane coupling agent 0.1-2.0
The interlamellar spacing of the novolac epoxy/organic montmorillonite nano composite flame-proof masterbatch for preparing reaches 3.77nm.
After described nano composite fire retardant parent material and organophosphate are composite, join in the plastics such as polypropylene, ABS, can prepare polypropylene flame redardant and ABS plastic that oxygen index reaches more than 36.5, has good mechanical property.
Particularly, the application of described nano composite fire retardant parent material in the preparation flame retardant plastics comprises the steps:
(1) described nano composite fire retardant parent material mixes with organophosphate, forms fire-retardant mixture;
(2) under 160-170 ℃ of temperature, make polypropylene or ABS fusion bag roller, add the fire-retardant mixture that oxidation inhibitor and step (1) obtain then;
(3) mixing even back compressing tablet makes flame retardant plastics;
The parts by weight of above-mentioned raw materials are as follows:
Novolac epoxy/organic montmorillonite nano composite flame-proof masterbatch 5-30
Organophosphate 5-10
Oxidation inhibitor 0.002
Polypropylene or ABS 90-60.
Described organophosphate the best is selected triphenylphosphate (TPP), triphenyl phosphite (TPPI) or triethyl phosphate (TEP) for use.
Described oxidation inhibitor is the general oxidation inhibitor in this area, as 1010, B215 etc.
The present invention has following advantage compared with prior art:
(1) the present invention is earlier with organo montmorillonite and novolac epoxy blend, make novolac epoxy (NER) enter organo montmorillonite (OMMT) interlayer, obtain novolac epoxy/organic montmorillonite nano composite flame-proof masterbatch, this flame-retardant master batch is very easy to use, can be dispersed in the plastics such as polypropylene, ABS at an easy rate by common plastics melt blending working method, technology is simple, and control has good application and promotion prospect easily.
(2) novolac epoxy/organic montmorillonite nano composite flame-proof masterbatch of the present invention and organophosphate have good synergistic fire retardation to plastics such as polypropylene, ABS.As add the triphenylphosphate of this novolac epoxy/organic montmorillonite nano composite flame-proof masterbatch of 13.3wt% and 6.7wt%, just polyacrylic oxygen index can be brought up to 36.5 from 1 8.5; Add the triphenylphosphate of this novolac epoxy/organic montmorillonite nano composite flame-proof masterbatch of 7.5wt% and 7.5wt%, just the oxygen index of ABS can be brought up to 41.0 from 18.0.
(3) novolac epoxy of the present invention/organic montmorillonite nano composite flame-proof masterbatch decapacitation significantly improves outside the flame retardant of plastic performances such as polypropylene, ABS, and is less to the comprehensive mechanical property infringement of plastic basis material, even some performance can also improve.As the polyacrylic notched Izod impact strength of adding the triphenylphosphate of the nano composite fire retardant parent material of 13.3wt% and 6.7wt% reaches 6.93KJ/m
2, than the shock strength 3.24KJ/m of virgin pp
2Be significantly improved.
(4) preparation process of novolac epoxy/organic montmorillonite nano composite flame-proof masterbatch of the present invention does not have " three wastes " discharging, 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 the X-ray diffractogram of sodium-based montmorillonite (MMT), octadecyl trimethyl ammonium chloride modified montmorillonoid (OMMT) and NER/OMMT nano composite fire retardant parent material;
Fig. 2 is the X-ray diffractogram by the fire-retardant PP of the organo montmorillonite novolac epoxy different with the novolac epoxy mass ratio/organic montmorillonite nano composite master batch preparation.
Embodiment
The preparation of embodiment 1 organo montmorillonite
Earlier the 10.0g sodium-based montmorillonite is joined in the 300ml water, stirring is warmed up to 70 ℃, forms aqueous dispersions, 100ml is contained 5.4g octadecyl trimethyl ammonium chloride (OTAC again, many industrial and trading companies are found in Guangzhou) the aqueous solution join in the aqueous dispersions of sodium-based montmorillonite, stir down 20h at 70 ℃.Leave standstill and be cooled to discharging after the room temperature, filter and washing impurity-removing 3-5 time,, after being dried to constant weight under 80 ℃, grind refinement again, obtain the organo montmorillonite (OMMT) of white powder up to checking filtrate not have chlorion with Silver Nitrate.
The preparation of novolac epoxy/organic montmorillonite nano composite flame-proof masterbatch
The 100g novolac epoxy is warming up to 70 ℃, adds 5g organo montmorillonite (OMM) and 0.5g silane coupling agent KH560, stir 2h, obtain novolac epoxy/organic illiteracy and take off interior rice composite fire retardant parent material (NER/OMMT).
Fig. 1 is respectively the X-ray diffractogram of sodium-based montmorillonite (MMT), octadecyl trimethyl ammonium chloride modified montmorillonoid (OMMT) and NER/OMMT nano composite fire retardant parent material.(a) MMT among the figure, (b) OMMT, (c) NER/OMMT;
Not having the modified MMT interlamellar spacing as can be seen is 1.23nm, and the interlamellar spacing of OMMT is increased to 2.14nm, and the interlamellar spacing of NER/OMMT has reached 3.77nm.
The application of NER/OMMT nano composite fire retardant parent material
Earlier the NER/OMMT nano composite fire retardant parent material of 13.3wt% and the triphenylphosphate of 6.7wt% (TPP, Shanghai chemical reagents corporation of Chinese Medicine group) are mixed stirring under 70 ℃, be uniformly dispersed, form fire-retardant mixture.Open warm-up mill is warming up to 170 ℃, make polypropylene (T30S, West Pacific Petro chemical Co. Ltd. Dalian) fusion bag roller, the oxidation inhibitor B215 and the above-mentioned fire-retardant mixture that add 0.2wt% then, mixing even back slice, test according to carry out oxygen index by GB/T2406-93 after the pressed sizing, carry out the test of socle girder notched Izod impact strength according to GB/T 1843-1996, carry out the tensile strength test according to GB/T1040-1992, the fire-retardant PP combustionproperty and the mechanical property comparing result of PP and the preparation of NER/OMMT nano composite fire retardant parent material are as shown in table 1.Can see that all be improved significantly with oxygen index and the shock strength of the fire-retardant PP of method of the present invention preparation, tensile strength keeps substantially, has obtained better comprehensive performance.
Table 1
| Sample | Oxygen index (%) | Shock strength (KJ/m 2) | Tensile strength (MPa) |
| PP | 18.5 | 3.24 | 33.64 |
| Fire-retardant PP | 36.5 | 6.93 | 30.56 |
The preparation method of NER/OMMT nano composite fire retardant parent material of the present invention and reaction conditions such as embodiment 1, keep mass ratio (2: 1) and the total consumption (20wt%) of NER/OMMT nano composite fire retardant parent material and TPP constant, the mass ratio of organo montmorillonite and novolac epoxy in the change flame-retardant master batch, gained organo montmorillonite and novolac epoxy mass ratio are as shown in table 2 to the influence of fire-retardant PP oxygen index and mechanical property.As can be seen, when OMMT and novolac epoxy mass ratio were 5: 100, the oxygen index of fire-retardant PP was the highest, and comprehensive mechanical property is best; After OMMT and novolac epoxy mass ratio surpassed 5: 100, oxygen index and mechanical property descended on the contrary.When the OMMT consumption is suitable, help novolac epoxy and enter the OMMT interlayer, and when flame-retardant master batch that obtains and PP melt blending, more help OMMT and in the PP matrix, be uniformly dispersed, when PP burns, form fine and close barrier layer and play fire retardation.When the OMMT consumption was too much, not only bad for the homodisperse of OMMT, excessive on the contrary OMMT had played the effect that " wick " ignites, and made material be more prone to burning, had reduced the flame retardant properties of material.Take all factors into consideration flame retardant properties and mechanical property and in conjunction with the embodiments 1, the suitable mass ratio of organo montmorillonite and novolac epoxy is 5: 100.
Table 2
| The mass ratio of organo montmorillonite and novolac epoxy | Oxygen index (%) | Shock strength (KJ/m 2) | Tensile strength (MPa) |
| 0∶100 | 29.0 | 5.59 | 25.27 |
| 5∶100 | 36.5 | 6.93 | 30.56 |
| 10∶100 | 29.0 | 5.17 | 25.68 |
| 20∶100 | 27.0 | 5.98 | 26.09 |
Fig. 2 is the X-ray diffractogram by the fire-retardant PP of the organo montmorillonite novolac epoxy different with the novolac epoxy mass ratio/organic montmorillonite nano composite flame-proof masterbatch preparation.Among the figure, a.OMMT: NER=5: 100, b.0MMT: NER=10: 100, c.OMMT: NER=20: 100.As can be seen, organo montmorillonite and novolac epoxy mass ratio are lower than at 10: 100 o'clock, can't see the obvious diffraction peak, and it is more even to show that polynite disperses in PP, and have the part montmorillonite layer to have produced to peel off; When organic polynite and novolac epoxy mass ratio reach 20: 100, can see tangible polynite diffraction peak, illustrated that the part montmorillonite layer reaches the nano level homodisperse in PP.
Embodiment 3
The preparation method of NER/OMMT nano composite fire retardant parent material of the present invention and reaction conditions such as embodiment 1, the mass ratio (100: 5) of maintenance novolac epoxy and organo montmorillonite and total consumption (20wt%) of NER/OMMT nano composite fire retardant parent material and TPP are constant, change the mass ratio of NER/OMMT nano composite fire retardant parent material and PP, the mass ratio of gained NER/OMMT nano composite fire retardant parent material and TPP is as shown in table 3 to the influence of the oxygen index of fire-retardant PP and mechanical property.As can be seen, use NER/OMMT nano composite fire retardant parent material or TPP all can not reach good flame-retardant effect separately, along with the rising of NER/OMMT proportion, fire-retardant PP oxygen index presents elder generation and increases the trend that afterwards reduces.Take all factors into consideration flame retardant properties and mechanical property and in conjunction with the embodiments 1 result as can be known, the optimum quality ratio of NER/OMMT nano composite fire retardant parent material and TPP is 2: 1.
Table 3
| The mass ratio of NER/OMMT nano composite fire retardant parent material and TPP | Oxygen index (%) | Shock strength (KJ/m 2) | Tensile strength (MPa) |
| 0∶1 | 22.0 | 7.21 | 25.86 |
| 1∶2 | 26.0 | 6.60 | 27.44 |
| 1∶1 | 30.5 | 5.68 | 31.00 |
| 2∶1 | 36.5 | 6.93 | 30.56 |
| 1∶0 | 24.0 | 3.72 | 25.63 |
The preparation method of NER/OMMT nano composite fire retardant parent material of the present invention and reaction conditions such as embodiment 1, the mass ratio (100: 5) of maintenance novolac epoxy and organo montmorillonite and the mass ratio (2: 1) of NER/OMMT and TPP are constant, change NER/OMMT and the total consumption of TPP, the total consumption of gained NER/OMMT and TPP is as shown in table 4 to the influence of fire-retardant PP oxygen index and mechanical property.Along with the increase of NER/OMMT and the total consumption of TPP, the oxygen index of fire-retardant PP improves gradually, but the difference of total consumption 20wt% and 30wt% and not obvious, and also when total consumption was 30wt%, the shock strength of fire-retardant PP and tensile strength were all lower.Take all factors into consideration flame retardant properties and mechanical property and in conjunction with the embodiments 1, suitable total consumption of NER/OMMT and TPP is 20wt% as can be known.
Table 4
| NER/OMMT+TPP(wt％) | Oxygen index (%) | Shock strength (KJ/m 2) | Tensile strength (MPa) |
| 0.0 | 18.5 | 3.24 | 33.64 |
| 10.0 | 26.0 | 4.83 | 30.85 |
| 20.0 | 36.5 | 6.93 | 30.56 |
| 30.0 | 37.0 | 4.95 | 23.47 |
Embodiment 5
Method and reaction conditions according to embodiment 1 make the NER/OMMT nano composite fire retardant parent material, and wherein the mass ratio of novolac epoxy and organo montmorillonite changes 100: 6.7 into.The TPP of the NER/OMMT nano composite fire retardant parent material of 7.5wt% and 7.5wt% is mixed stirring in 70 ℃, be uniformly dispersed, form fire-retardant mixture.Open warm-up mill is warming up to 160 ℃, make ABS fusion bag roller, add 0.2% oxidation inhibitor B215 and above-mentioned composite flame-proof thing then, mixing even back slice, carry out performance test according to every standard among the embodiment 1, compare with the flame-proof ABS of the ABS that does not add any fire retardant and adding novolac epoxy and each 7.5wt% of TPP, ABS and flame-proof ABS combustionproperty and mechanical property comparative result are as shown in table 5.As can be seen, the oxygen index of directly using the flame-proof ABS of NER and the composite preparation of TPP has only 33.0, and the oxygen index of the flame-proof ABS plastics of application NER/OMMT nano composite fire retardant parent material and the composite preparation of TPP is up to 41.0.As seen, adopt method of the present invention, a spot of polynite can significantly improve the flame retardant properties of ABS.
Table 5
| Sample | Oxygen index (%) | Shock strength (KJ/m 2) | Tensile strength (MPa) |
| ABS | 18.0 | 17.32 | 47.12 |
| ABS+NER+TPP | 33.0 | 7.67 | 34.43 |
| ABS+NER/OMMT+TPP | 41.0 | 6.05 | 35.79 |
Claims (4)
1, a kind of preparation method of nano composite fire retardant parent material is characterized in that novolac epoxy is warming up to 60-80 ℃, adds through chain alkyl ammonium salt organically-modified sodium-based montmorillonite and silane coupling agent, stirs 1-6 hour; Novolac epoxy is entered through the organically-modified sodium-based montmorillonite interlayer of chain alkyl ammonium salt; Described chain alkyl ammonium salt comprises octadecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride or dodecyl dimethyl Bian ammonium chloride, and silane coupling agent comprises KH550, KH560 or KH570, and the parts by weight of above-mentioned raw materials are as follows:
Organically-modified sodium-based montmorillonite 1-20
Novolac epoxy 80-100
Silane coupling agent 0.1-2.0.
2, the nano composite fire retardant parent material for preparing of the described method of claim 1.
3, the application of the described nano composite fire retardant parent material of claim 2 in the preparation flame retardant plastics is characterized in that comprising the steps:
(1) described nano composite fire retardant parent material is mixed with organophosphate, form fire-retardant mixture;
(2) under 160-170 ℃ of temperature, make polypropylene or ABS fusion bag roller, add the fire-retardant mixture that oxidation inhibitor and step (1) obtain then;
(3) mixing even back compressing tablet makes flame retardant plastics;
The parts by weight of above-mentioned raw materials are as follows:
Novolac epoxy/organic montmorillonite nano composite flame-proof masterbatch 5-30
Organophosphate 5-10
Oxidation inhibitor 0.002
Polypropylene or ABS 90-60.
4, application according to claim 3 is characterized in that described organophosphate comprises triphenylphosphate, triphenyl phosphite or triethyl phosphate.
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| CN105713352B (en) * | 2016-03-01 | 2018-03-16 | 北京理工大学 | A kind of phosphorous small molecule/montmorillonite nano composite flame-proof agent fire retarded epoxy resin composition and preparation method thereof |
| CN106867109A (en) * | 2017-03-09 | 2017-06-20 | 常州塑金高分子科技有限公司 | A kind of low VOC PP composite materials and preparation method thereof |
| CN107201005A (en) * | 2017-07-14 | 2017-09-26 | 芜湖市三山区绿色食品产业协会 | High polymer material based on modified montmorillonoid and preparation method thereof |
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| CN1250790A (en) * | 1998-10-13 | 2000-04-19 | 中国科学院化学研究所 | Antiflowing epoxy resin/mentmorillonite compound and its preparing process |
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| Title |
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| 有机蒙脱土改性环氧树脂的研究 傅万里，刘竞超.工程塑料应用，第30卷第05期 2002 * |
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