CN104927088A - Graphene/layered double hydroxide halogen-free flame retardant masterbatch and preparation method thereof - Google Patents
Graphene/layered double hydroxide halogen-free flame retardant masterbatch and preparation method thereof Download PDFInfo
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- CN104927088A CN104927088A CN201510317445.7A CN201510317445A CN104927088A CN 104927088 A CN104927088 A CN 104927088A CN 201510317445 A CN201510317445 A CN 201510317445A CN 104927088 A CN104927088 A CN 104927088A
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Abstract
The invention relates to a graphene/layered double hydroxide halogen-free flame retardant masterbatch and a preparation method thereof. The graphene/layered double hydroxide halogen-free flame retardant masterbatch is prepared from the following components in parts by weight: 20-90 parts of a graphene/layered double hydroxide (LDH) compound, 0.5-2 parts of one or more antioxidant and 10-80 parts of one or more carrier, wherein the graphene/layered double hydroxide (LDH) compound is prepared from graphene, LDH, an organic solvent and a surfactant. The graphene/layered double hydroxide halogen-free flame retardant masterbatch has the advantages of no halogen, good flame retardancy, suitability for melting mixing, less organic solvent, simple feeding, good dispersity and the like, as a multi-scale composite masterbatch, the graphene/layered double hydroxide halogen-free flame retardant masterbatch can be better dispersed in a polymer matrix, and meanwhile, the polymer with better comprehensive property is provided.
Description
Technical field
The present invention relates to a kind of halogen-free flame-retardant master batch and preparation method thereof, particularly a kind of Graphene/layered double-hydroxide halogen-free flame-retardant master batch and preparation method thereof.
Background technology
Graphene is the thinnest in the world is at present the hardest nano material also, and it is almost completely transparent, only absorbs the light of 2.3%; Thermal conductivity is up to 5300 W/mK.Have a good application prospect in fields such as aerospace, novel material, new forms of energy, electronics.In the practical application of Graphene, polymer/graphene nano composite material is considered to one of direction of most application prospect.Polymer/graphene composite material main advantage performance is six broad aspect, namely high thermal conductivity coefficient, high insulation, high flame retardant, high mechanical strength, low density, low cost, easily process, these performances all have revolutionary character.
Layered double-hydroxide LDH refers to that ideal consists of [N
2+ 1-xm
3+ x(OH)
2]
x+(A
h-)
x/hmH
2the anionic intercalation nano material of one quasi-representative of O, wherein N
2+for divalent-metal ion, comprising: Mg
2+, Ca
2+, Ba
2+, Fe
2+, Zn
2+, Cu
2+, Cr
2+, Co
2+, Ni
2+; M
3+for trivalent metal ion, comprise Al
3+, Fe
3+, Co
3+, Ni
3+.A is negatively charged ion, comprises NO
3 -, Cl
-, CO
3 2-and SO
4 2-, referred to as N
nm/A-LDH, n are N
2+with M
3+mol ratio.LDH, as a kind of nano modifier, has important application at polymeric material field, can be used as anti-flaming smoke-inhibiting agent, biology/medical material, ultraviolet/infrared absorbing material etc.In recent years, particularly polymkeric substance/LDH matrix material obtains the extensive concern of investigator.
Polymer nanocomposites is obtained by being dispersed in by nanometer additive in polymeric matrix, but because the specific surface of Nano filling is larger, there is intrinsic Van der Waals force, nano material is very easy to reunite, and is therefore the gordian technique of polymer nanocomposites by dispersed in polymeric matrix of the functional stuffing of nano-scale.At present, the method preparing polymer nanocomposites has solution composite approach, situ aggregation method and melt-blending process, wherein first two method is easy to realize dispersed in polymeric matrix of nano material, but be the use of a large amount of organic solvents, cause cost high, pollute large, be unfavorable for suitability for industrialized production.And melt-blending process prepares matrix material, if it is uneven to be easy to cause Nano filling to disperse, thus affect the final performance of matrix material.
Summary of the invention
An object of the present invention is for the deficiencies in the prior art, provides a kind of Graphene/layered double-hydroxide halogen-free flame-retardant master batch and preparation method thereof.
The present invention also aims to the preparation method that above-mentioned Graphene/LDH halogen-free flame-retardant master batch is provided.
Above-mentioned purpose of the present invention is achieved by the following technical solution:
A kind of Graphene/layered double-hydroxide halogen-free flame-retardant master batch, is characterized in that the composition of this master batch and parts by weight are:
Graphene/layered double-hydroxide mixture 20 ~ 90 parts
0.5 ~ 2 part, oxidation inhibitor
10 ~ 80 parts, carrier;
Described carrier is at least one in polycarbonate, polyethylene, polypropylene, acrylonitrile-butadiene-styrene (ABS), polymeric amide.
The concrete preparation method of above-mentioned Graphene/layered double-hydroxide (LDH) mixture is:
A. LDH, organic solvent are added in reactor according to mass ratio 0.05 ~ 0.5, ultrasonic 3 ~ 24 hours, under 1000 ~ 10000r/min centrifugal 10 ~ 120 minutes afterwards, the mixture A obtained is filtered, dry, for subsequent use;
(2) Graphene, organic solvent are added in reactor according to mass ratio 0.05 ~ 0.5, ultrasonic 3 ~ 24 hours, under 1000 ~ 10000r/min centrifugal 10 ~ 120 minutes afterwards, the mixture B obtained is filtered, dry, for subsequent use;
(3) step (1) gained mixture A, step (2) gained mixture B, tensio-active agent are added in reactor according to mass ratio 45 ~ 20:45 ~ 20:40 ~ 10 mix, ultrasonic 0.5 ~ 3 hour, under 1000 ~ 5000r/min centrifugal 10 ~ 60 minutes afterwards, dry, pulverize, obtain Graphene/LDH mixture.
Above-mentioned tensio-active agent is one or both in Silane coupling agent KH550, KH560, KH570; Described organic solvent is dehydrated alcohol or dimethyl formamide (DMF).
Above-mentioned LDH refers to that ideal consists of [N
2+ 1-xm
3+ x(OH)
2]
x+(A
h-)
x/hmH
2the anionic intercalation nano material of one quasi-representative of O, wherein N
2+for divalent-metal ion, comprising: Mg
2+, Ca
2+, Ba
2+, Fe
2+, Zn
2+, Cu
2+, Cr
2+, Co
2+, Ni
2+; M
3+for trivalent metal ion, comprise Al
3+, Fe
3+; A is negatively charged ion, comprises NO
3 -, Cl
-, CO
3 2-, SO
4 2-, referred to as N
nm/A-LDH.
Above-mentioned oxidation inhibitor is one or both in antioxidant 1010, irgasfos 168.
A kind of preparation method of above-mentioned Graphene/layered double-hydroxide halogen-free flame-retardant master batch, it is characterized in that the concrete steps of the method are: by dry 2h at Graphene/layered double-hydroxide mixture 100 DEG C, by dried Graphene/LDH mixture, add together with carrier, oxidation inhibitor in high-speed mixer, high-speed stirring mixing 10 ~ 30min, premix obtains raw mixture; Add in forcing machine by obtained raw mixture, heating and melting mixes, and granulation, obtains halogen-free flame-retardant master batch.
The preparation method of above-mentioned Graphene/layered double-hydroxide halogen-free flame-retardant master batch, is characterized in that described forcing machine is the one in twin screw extruder, reciprocating single-bolt extruder or Banbury mixer-single screw extrusion machine; The processing temperature of described forcing machine is 170 ~ 245 DEG C.
Compared with prior art, outstanding effect of the present invention is: the organic solvent that master batch prepared by the present invention provided by the invention uses is few, reduces the environmental pollution in production process, greatly lowers production cost simultaneously, is conducive to suitability for industrialized production.Meanwhile, this master batch adopts multiple dimensioned compounding technology and master-batch techniques, can solve the problems such as feeding in matrix material preparation process is difficult, the unicity of disperseing uneven and performance to improve.The mechanical property of the matrix material that final realization adopts master batch to prepare and flame retardant properties are improved significantly, and are applicable to large-scale industrial production.
Preparation method provided by the invention, rational technology, easy to operate, control accurately, be easy to industrialization, products production cost is low.
Accompanying drawing explanation
Fig. 1 is the HRR data and curves of matrix material prepared by the halogen-free flame-retardant master batch employing embodiment 1 preparation.
Embodiment
embodiment 1:
The Graphene that the present embodiment provides/layered double-hydroxide halogen-free flame-retardant master batch, it is prepared from by the component of following parts by weight:
Graphene/LDH mixture 90 parts
1 part, oxidation inhibitor
80 parts, carrier;
The preparation method of described Graphene/LDH mixture, concrete steps are as follows:
(1) LDH, organic solvent are added in reactor according to mass ratio 20:80, ultrasonic 3 hours, under 10000r/min centrifugal 60 minutes afterwards, the mixture A obtained is filtered, dry, for subsequent use;
(2) Graphene, organic solvent are added in reactor according to mass ratio 10:90, ultrasonic 3 hours, under 10000r/min centrifugal 60 minutes afterwards, the mixture B obtained is filtered, dry, for subsequent use;
(3) step (1) gained mixture A, step (2) gained mixture B, tensio-active agent are added in reactor according to mass ratio 30:30:40 mix, ultrasonic 3 hours, under 1000r/min centrifugal 60 minutes afterwards, dry, grinding, obtains Graphene/LDH mixture.
Described tensio-active agent is Silane coupling agent KH550; Described organic solvent is dehydrated alcohol.Described LDH is Mg
2al/CO
3-LDH.
Described oxidation inhibitor is antioxidant 1010; Described carrier is polycarbonate.
A method for making for Graphene/layered double-hydroxide halogen-free flame-retardant master batch, it comprises the following steps:
(1) according to following ratio precise raw material:
Graphene/LDH mixture 90 parts
1 part, oxidation inhibitor
80 parts, carrier;
(2) by dry 2h at Graphene/LDH mixture 100 DEG C, by dried Graphene/LDH mixture, add in high-speed mixer together with carrier, oxidation inhibitor, high-speed stirring mixing 10min, premix obtains raw mixture;
(3) mixture that step (2) obtains is added in twin screw extruder, melt extrude, granulation, obtain halogen-free flame-retardant master batch.
embodiment 2:
The Graphene that the present embodiment provides/layered double-hydroxide halogen-free flame-retardant master batch, substantially the same manner as Example 1, its difference is: it is prepared from by the component of following parts by weight:
Graphene/LDH mixture 60 parts
0.5 part, oxidation inhibitor
70 parts, carrier;
The preparation method of described Graphene/LDH mixture, concrete steps are as follows:
(1) LDH, organic solvent are added in reactor according to mass ratio 30:60, ultrasonic 12 hours, under 10000r/min centrifugal 10 minutes afterwards, the mixture A obtained is filtered, dry, for subsequent use;
(2) Graphene, organic solvent are added in reactor according to mass ratio 20:80, ultrasonic 12 hours, under 10000r/min centrifugal 30 minutes afterwards, the mixture B obtained is filtered, dry, for subsequent use;
(3) step (1) gained mixture A, step (2) gained mixture B, tensio-active agent are added in reactor according to mass ratio 50:20:30 mix, ultrasonic 0.5 hour, under 1000r/min centrifugal 10 minutes afterwards, dry, grinding, obtains Graphene/LDH mixture.
Described tensio-active agent is Silane coupling agent KH550; Described organic solvent is dehydrated alcohol.Described LDH is Ni
2al/CO
3-LDH.
Described oxidation inhibitor is antioxidant 1010 and irgasfos 168 mass ratio is the mixture of 1:1; Described carrier is polypropylene.
A method for making for Graphene/layered double-hydroxide halogen-free flame-retardant master batch, it comprises the following steps:
(1) according to following ratio precise raw material:
Graphene/LDH mixture 60 parts
0.5 part, oxidation inhibitor
70 parts, carrier;
(2) by dry 2h at Graphene/LDH mixture 100 DEG C, by dried Graphene/LDH mixture, add in high-speed mixer together with carrier, oxidation inhibitor, high-speed stirring mixing 10min, premix obtains raw mixture;
(3) mixture that step (2) obtains is added in twin screw extruder, melt extrude, granulation, obtain halogen-free flame-retardant master batch.
embodiment 3:
The Graphene that the present embodiment provides/layered double-hydroxide halogen-free flame-retardant master batch, substantially identical with embodiment 1,2, its difference is: it is prepared from by the component of following parts by weight:
Graphene/LDH mixture 50 parts
1 part, oxidation inhibitor
50 parts, carrier;
The preparation method of described Graphene/LDH mixture, concrete steps are as follows:
(1) LDH, organic solvent are added in reactor according to mass ratio 10:90, ultrasonic 6 hours, under 1000r/min centrifugal 20 minutes afterwards, the mixture A obtained is filtered, dry, for subsequent use;
(2) Graphene, organic solvent are added in reactor according to mass ratio 20:80, ultrasonic 6 hours, under 1000r/min centrifugal 20 minutes afterwards, the mixture B obtained is filtered, dry, for subsequent use;
(3) step (1) gained mixture A, step (2) gained mixture B, tensio-active agent are added in reactor according to mass ratio 30:30:40 mix, ultrasonic 3 hours, under 1000r/min centrifugal 10 minutes afterwards, dry, grinding, obtains Graphene/LDH mixture.
Described tensio-active agent is silane coupling agent KH570; Described organic solvent is DMF.Described layered double-hydroxide (LDH) is Zn
2al/NO
3-LDH.
Described oxidation inhibitor is antioxidant 1010; Described carrier is acrylonitrile-butadiene-styrene (ABS).
A method for making for multiple dimensioned composite graphite alkene/layered double-hydroxide halogen-free flame-retardant master batch, it comprises the following steps:
(1) according to following ratio precise raw material:
Graphene/LDH mixture 50 parts
1 part, oxidation inhibitor
50 parts, carrier;
(2) by dry 2h at Graphene/LDH mixture 100 DEG C, by dried Graphene/LDH mixture, add in high-speed mixer together with carrier, oxidation inhibitor, high-speed stirring mixing 30min, premix obtains raw mixture;
(3) mixture that step (2) obtains is added in twin screw extruder, melt extrude, granulation, obtain halogen-free flame-retardant master batch.
The present invention is not limited to above-mentioned embodiment; adopt the raw material identical or approximate with the above embodiment of the present invention and preparation method; and other similar Graphenes/layered double-hydroxide halogen-free flame-retardant master batch obtained and preparation method thereof, all within protection scope of the present invention.
Claims (7)
1. Graphene/layered double-hydroxide halogen-free flame-retardant master batch, is characterized in that the composition of this master batch and parts by weight are:
Graphene/layered double-hydroxide mixture 20 ~ 90 parts
0.5 ~ 2 part, oxidation inhibitor
10 ~ 80 parts, carrier;
Described carrier is at least one in polycarbonate, polyethylene, polypropylene, acrylonitrile-butadiene-styrene (ABS), polymeric amide.
2. Graphene according to claim 1/layered double-hydroxide halogen-free flame-retardant master batch, is characterized in that, described layered double-hydroxide refers to that ideal consists of [N
2+ 1-xm
3+ x(OH)
2]
x+(A
h-)
x/hmH
2the anionic intercalation nano material of one quasi-representative of O, wherein N
2+for divalent-metal ion, comprising: Mg
2+, Ca
2+, Ba
2+, Fe
2+, Zn
2+, Cu
2+, Cr
2+, Co
2+, Ni
2+; M
3+for trivalent metal ion, comprise Al
3+, Fe
3+; A is negatively charged ion, comprises NO
3 -, Cl
-, CO
3 2-, SO
4 2-, referred to as N
nm/A-LDH.
3. Graphene according to claim 1/layered double-hydroxide halogen-free flame-retardant master batch, is characterized in that, described oxidation inhibitor is one or both in antioxidant 1010, irgasfos 168; .
4. prepare the method for the Graphene/layered double-hydroxide halogen-free flame-retardant master batch according to any one of claims 1 to 3 for one kind, it is characterized in that the concrete steps of the method are: by dry 2h at Graphene/layered double-hydroxide mixture 100 DEG C, by dried Graphene/LDH mixture, add together with carrier, oxidation inhibitor in high-speed mixer, high-speed stirring mixing 10 ~ 30min, premix obtains raw mixture; Add in forcing machine by obtained raw mixture, heating and melting mixes, and granulation, obtains Graphene/layered double-hydroxide halogen-free flame-retardant master batch.
5. the preparation method of Graphene according to claim 4/layered double-hydroxide halogen-free flame-retardant master batch, is characterized in that the preparation method of described Graphene/layered double-hydroxide mixture is:
A. layered double-hydroxide and organic solvent are added in reactor according to mass ratio 0.05 ~ 0.5:1, ultrasonic 3 ~ 24 hours, under 1000 ~ 10000r/min centrifugal 10 ~ 120 minutes afterwards, filter, dry, obtain mixture A;
B. Graphene and organic solvent are added in reactor according to mass ratio 0.05 ~ 0.5:1, ultrasonic 3 ~ 24 hours, under 1000 ~ 10000r/min centrifugal 10 ~ 120 minutes afterwards, filter, dry, obtain mixture B;
C. by step a gained mixture A, step b gained mixture B, tensio-active agent according to mass ratio (45 ~ 20): (45 ~ 20): (40 ~ 10) add in reactor to mix, ultrasonic 0.5 ~ 3 hour, under 1000 ~ 5000r/min centrifugal 10 ~ 60 minutes afterwards, dry, pulverize, obtain Graphene/layered double-hydroxide mixture.
6. Graphene according to claim 5/layered double-hydroxide halogen-free flame-retardant master batch, is characterized in that described tensio-active agent is one or both in Silane coupling agent KH550, KH560, KH570; Described organic solvent is dehydrated alcohol or dimethyl formamide (DMF).
7. the preparation method of Graphene according to claim 4/layered double-hydroxide halogen-free flame-retardant master batch, is characterized in that described forcing machine is the one in twin screw extruder, reciprocating single-bolt extruder or Banbury mixer-single screw extrusion machine; The processing temperature of described forcing machine is 170 ~ 245 DEG C.
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| CN106674875A (en) * | 2017-01-12 | 2017-05-17 | 中广核高新核材集团（东莞）祈富新材料有限公司 | High-gloss easy-cleaning and flame-retarding PC/ABS composite material and preparation method thereof |
| CN107163289A (en) * | 2017-06-20 | 2017-09-15 | 安徽建筑大学 | Graphene anti-flaming smoke-inhibiting agent that layered double-hydroxide molybdenum acid ion is modified and preparation method thereof |
| CN107312298A (en) * | 2017-06-29 | 2017-11-03 | 江南石墨烯研究院 | A kind of flame retardant type polycarbonate composite material and preparation method thereof |
| CN107936357A (en) * | 2017-11-30 | 2018-04-20 | 广西景康商贸有限公司 | A kind of footwear 3D printing flame-retardant foam material and preparation method thereof |
| CN108715753A (en) * | 2018-06-28 | 2018-10-30 | 芜湖市棠华建材科技有限公司 | Hollow glass fluid sealant |
| CN108795313A (en) * | 2018-06-28 | 2018-11-13 | 芜湖市棠华建材科技有限公司 | High temperature resistant vacuum bag sealing adhesive tape |
| CN108795357A (en) * | 2018-06-28 | 2018-11-13 | 芜湖市棠华建材科技有限公司 | The refractory seals glue of metal product |
| CN108822751A (en) * | 2018-06-28 | 2018-11-16 | 芜湖市棠华建材科技有限公司 | Refractory seals adhesive tape |
| CN114957963A (en) * | 2022-06-11 | 2022-08-30 | 彭宗健 | Preparation method of modified thermoplastic polyurethane resin |
| CN115651307A (en) * | 2022-09-07 | 2023-01-31 | 深圳力越新材料有限公司 | Polypropylene composite material and preparation method thereof |
| US11753509B2 (en) | 2018-03-15 | 2023-09-12 | King Fahd University Of Petroleum And Minerals | In-situ polymerization method for producing a polyethylene nanocomposite |
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| CN107163289A (en) * | 2017-06-20 | 2017-09-15 | 安徽建筑大学 | Graphene anti-flaming smoke-inhibiting agent that layered double-hydroxide molybdenum acid ion is modified and preparation method thereof |
| CN107163289B (en) * | 2017-06-20 | 2020-04-07 | 安徽建筑大学 | Layered double hydroxide-molybdate ion modified graphene flame-retardant smoke suppressant and preparation method thereof |
| CN107312298A (en) * | 2017-06-29 | 2017-11-03 | 江南石墨烯研究院 | A kind of flame retardant type polycarbonate composite material and preparation method thereof |
| CN107936357A (en) * | 2017-11-30 | 2018-04-20 | 广西景康商贸有限公司 | A kind of footwear 3D printing flame-retardant foam material and preparation method thereof |
| US11753509B2 (en) | 2018-03-15 | 2023-09-12 | King Fahd University Of Petroleum And Minerals | In-situ polymerization method for producing a polyethylene nanocomposite |
| CN108715753A (en) * | 2018-06-28 | 2018-10-30 | 芜湖市棠华建材科技有限公司 | Hollow glass fluid sealant |
| CN108795313A (en) * | 2018-06-28 | 2018-11-13 | 芜湖市棠华建材科技有限公司 | High temperature resistant vacuum bag sealing adhesive tape |
| CN108795357A (en) * | 2018-06-28 | 2018-11-13 | 芜湖市棠华建材科技有限公司 | The refractory seals glue of metal product |
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| CN114957963A (en) * | 2022-06-11 | 2022-08-30 | 彭宗健 | Preparation method of modified thermoplastic polyurethane resin |
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