CN103613845A - Flame retardant polypropylene composite compounded by layered thermometal hydroxide and intumescent flame retardant and preparation method of flame retardant polypropylene composite - Google Patents
Flame retardant polypropylene composite compounded by layered thermometal hydroxide and intumescent flame retardant and preparation method of flame retardant polypropylene composite Download PDFInfo
- Publication number
- CN103613845A CN103613845A CN201310593819.9A CN201310593819A CN103613845A CN 103613845 A CN103613845 A CN 103613845A CN 201310593819 A CN201310593819 A CN 201310593819A CN 103613845 A CN103613845 A CN 103613845A
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- CN
- China
- Prior art keywords
- flame retardant
- layered double
- polypropylene composite
- retardant
- double hydroxide
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92514—Pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a flame retardant polypropylene composite compounded by layered thermometal hydroxide and an intumescent flame retardant and a preparation method of the flame retardant polypropylene composite. The flame retardant polypropylene composite comprises the following components in percentage by weight: 60-73 percent of polypropylene, 23-33 percent of intumescent flame retardant, 1-2 percent of layered thermometal hydroxide and 3-7 percent of bulking agent. The flame retardant polypropylene composite compounded by the layered thermometal hydroxide and the intumescent flame retardant is excellent in heat stability, does not contain harmful substances such as lead, mercury, cadmium, hexavalent chromium, polybrominated biphenyl and polyborminated diphenyl ethers, is low in calorific value and fuming value in the combustion process, is harmless to the environment and a human body and also has good physical and mechanical properties and processability.
Description
Technical field
The blend, the Flame Retardancy energy technical field of measurement and test that the present invention relates to organic synthesis, polymer composite, be specifically related to a kind of layered double hydroxide and expanding fire retardant compositional flame-retardant polypropylene composite material and preparation method thereof.
Technical background
Layered double hydroxide (LDHs) is a kind of nano material with two-dimensional layered structure.The chemical general formula of layered double hydroxide can be expressed as: [M
2+ 1-Xm
3+ x(OH)
2]
x+a
n- x/nmH
2o.Wherein, M
2+for divalent-metal ion, as Mg
2+, Ni
2+, Zn
2+deng; M
3+for trivalent metal ion, as Al
3+, Fe
3+deng.A
n-for interlayer anion, mainly comprise that inorganic anion is (as Cl
-, NO
3-, CO
3 2-deng), organic anion (as phthalic acid root, dodecyl sodium sulfonate root etc.) etc.
Due to this mutability in component and formation aspect of layered double hydroxide, its kind presents diversity, and the classification of divalence, trivalent metal ion and interlayer anion kind and organic molecule chain degree all play conclusive impact to the character of layered double hydroxide and matrix material thereof.
Peculiar property based on layered double hydroxide, it has obtained and has studied widely and apply at aspects such as fire-retardant, catalysis, medicine and photoelectrochemistry.While considering due to layered double hydroxide one side decomposes, absorb large calorimetric, and in decomposition course, discharge water and carbonic acid gas, thereby the inflammable gas in polymer degradation products is played to dilution, iris action; On the other hand, the degradation production of layered double hydroxide is generally the alkaline porous mass having compared with bigger serface, to obnoxious flavour particularly sour gas there is certain adsorptive power, thereby layered double hydroxide shows very large application potential aspect flame-retardant smoke inhibition, can be used as fire retardant or fire retarding synergist and be applied to macromolecular material flame retardant area.
But, adopt layered double hydroxide and the composite preparation thermostability of expanding fire retardant is high, good flame retardation effect, flame-retardant polypropylene composite material that the amount of being fuming is low, the current report that also there is no correlation technique.
Summary of the invention
The invention provides that a kind of thermostability is high, good flame retardation effect, layered double hydroxide and expanding fire retardant compositional flame-retardant polypropylene composite material that the amount of being fuming is low.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of layered double hydroxide and expanding fire retardant compositional flame-retardant polypropylene composite material, this material is comprised of each component of following weight percent: polypropylene 60%-73%, expanding fire retardant 23%-33%, layered double hydroxide 1%-2%, expanding material 3%-7%.
The above-mentioned polypropylene of the present invention is homo-polypropylene, is called for short PPH, is the homopolymer polymer of single propylene monomer.
The above-mentioned nitrogen phosphorus flame retardant of the present invention is Melamine Polyphosphate fire retardant, and molecular formula is (C
3h
7n
6)
n(H
2pO
4)
m, be a kind of environment-friendly type non-bittern combustion inhibitor of phosphorous, nitrogen component, nitrogen content is greater than 40%, and phosphorus content is greater than 12%, particle diameter 25-50 μ m.
The pillared layered double-metal hydroxide of octadecyl sulfonic acid that the above-mentioned layered double hydroxide of the present invention is prepared for employing coprecipitation method, its preparation method is as follows: first by the Ni (NO of 0.08mol
3)
26H
2al (the NO of O, 0.04mol
3)
39H
2the octadecyl sodium sulfonate of O and 0.06mol (Octadecane base sulfonate sodium) is dissolved in wiring solution-forming A in 200ml deionized water; Separately get 0.31molNaOH and be dissolved in 80ml deionized water wiring solution-forming B; Then under nitrogen protection and agitation condition; solution B is slowly dripped in solution A; keep system pH in 9.0-10(9.5 left and right); and ageing at 75 ℃ (standing) 12 hours; the light blue slurries of gained obtain solid matter after deionized water repetitive scrubbing filters, and solid matter is drying to obtain the pillared layered double-metal hydroxide of octadecyl sulfonic acid at 80 ℃.
The above-mentioned expanding material of the present invention is maleic anhydride inoculated polypropylene multipolymer, is the Co-polypropylene of modified by maleic acid anhydride graft, and referred to as PP-g-MAH, percentage of grafting 0.8-1.0%, is a kind of high molecular interface coupling agent, tackiness agent and compatilizer.
The present invention also provides the preparation method of a kind of above-mentioned layered double hydroxide and expanding fire retardant compositional flame-retardant polypropylene composite material, and preparation process comprises: (1) first weighs above-mentioned each component according to above-mentioned formula rate; (2) then by 60-90 rev/min, middling speed stirrer for each raw material, stir and mix to each raw material for 10-20 minute, proceed in twin screw extruder and melt extrude; The packing area temperature of twin screw extruder is 150-170 ℃, and mixing zone temperature is 200-220 ℃, and reaction zone temperature is 220-230 ℃, and die head temperature is 200-220 ℃, and head pressure is 3-6MPa, extrudes rear cooling granulation.
Layered double hydroxide of the present invention and expanding fire retardant compositional flame-retardant polypropylene composite material tool have the following advantages and beneficial effect:
(1) layered double hydroxide of the present invention and expanding fire retardant compositional flame-retardant polypropylene composite material, adopt the nontoxic composite flame retardant system of Halogen, the objectionable impuritiess such as not leaded, mercury, cadmium, sexavalent chrome, Polybrominated biphenyl and Poly Brominated Diphenyl Ethers, in combustion processes, can not discharge toxic and harmful, there is good environmental effect;
(2) layered double hydroxide of the present invention can be on surface in material temperature-rise period and interlayer discharge large quantity of moisture, inflammable gas in polypropylene thermal degraded product is played to diluting effect, delay the combustion processes of material, thereby coordinated expanding fire retardant to carry out fire-retardant to polypropylene material the early stage of can burning;
(3) layered double hydroxide of the present invention can change metal oxide into by layered crystal under high-temperature condition, thereby these metal oxides can limit polyacrylic thermal destruction by absorption portion heat, therefore to improving polyacrylic thermostability, there is unique effect;
(4) layered bi-metal oxide compound of the present invention has larger specific surface area, can trap heat transmission in polypropylene combustion processes, more can assist expanding fire retardant to form dense char layer, can also play good adsorption to flue gas, thereby in combustion processes, the heating amount of being fuming is low, less to environment and harm;
(5) the layered bi-metal oxide compound the present invention relates to is the pillared layered double-metal hydroxide of octadecyl sulfonic acid that adopts coprecipitation method to prepare, organic anion in its molecule is octadecyl sulfonate radical, containing the olefin polymer of phenyl ring, there is not good consistency with polypropylene, polyethylene etc., thereby can effectively promote the dispersion of stratiform bimetallic oxide in polypropylene, make it have good bonding interface, do not damage mechanical property and the processing characteristics of material.
Embodiment
Below by specific embodiment, the present invention is described in further detail, but the present invention is not only confined to following examples.The person skilled in the art in this field some nonessential improvement that content is made the present invention according to the present invention and adjustment still belong to protection scope of the present invention.
Every raw material that following examples of the present invention are used, is commercially available prod if no special instructions.
Table 1 is the proportioning raw materials in each embodiment:
Formula in each embodiment of table 1.
After the raw material of each embodiment in table 1 is weighed according to proportioning, with middling speed stirrer, stir 10-20 minute to after mixing, proceed in twin screw extruder and melt extrude, packing area temperature is 150-170 ℃, mixing zone temperature is 200-220 ℃, and reaction zone temperature is 220-230 ℃, and die head temperature is 200-220 ℃, head pressure is 3-6MPa, extrudes rear cooling granulation.
Each embodiment sample is carried out to thermal weight loss test (air atmosphere, temperature rise rate is 10 ℃/min, the scope of heating is 50-650 ℃), the carbon residue amount while obtaining the initial heat decomposition temperature, maximum heat decomposition temperature of material and 600 ℃; (with reference to ISO5660 standard, hot irradiation power is 35kW/m to carry out taper calorimetric test
2), the burning time of acquisition material, maximum heat rate of release and average smoke density.Test result is referring to table 2:
The correlated performance of each embodiment of table 2.
From upper table 2, layered double hydroxide of the present invention prepared by the present invention and expanding fire retardant compositional flame-retardant polypropylene composite material, excellent heat stability, the objectionable impuritiess such as not leaded, mercury, cadmium, sexavalent chrome, Polybrominated biphenyl and Poly Brominated Diphenyl Ethers, in combustion processes, the heating amount of being fuming is low, less to environment and harm; And there is good physical and mechanical properties and processing characteristics.
Claims (6)
1. a layered double hydroxide and expanding fire retardant compositional flame-retardant polypropylene composite material, it is characterized in that: this material is comprised of each component of following weight percent: polypropylene 60%-73%, expanding fire retardant 23%-33%, layered double hydroxide 1%-2%, expanding material 3%-7%.
2. layered double hydroxide according to claim 1 and expanding fire retardant compositional flame-retardant polypropylene composite material, is characterized in that: described polypropylene is homo-polypropylene.
3. layered double hydroxide according to claim 1 and expanding fire retardant compositional flame-retardant polypropylene composite material, it is characterized in that: described nitrogen phosphorus flame retardant is Melamine Polyphosphate fire retardant, nitrogen content is greater than 40%, and phosphorus content is greater than 12%, particle diameter 25-50 μ m.
4. layered double hydroxide according to claim 1 and expanding fire retardant compositional flame-retardant polypropylene composite material, it is characterized in that: the octadecyl sulfonic acid pillared layered double-metal hydroxide of described layered double hydroxide for adopting coprecipitation method to prepare, its preparation method is as follows: first by the Ni (NO of 0.08mol
3)
26H
2al (the NO of O, 0.04mol
3)
39H
2the octadecyl sodium sulfonate of O and 0.06mol is dissolved in wiring solution-forming A in 200ml deionized water; Separately get 0.31molNaOH and be dissolved in 80ml deionized water wiring solution-forming B; Then under nitrogen protection and agitation condition; solution B is dripped in solution A; keep pH value of reaction system at 9.0-10; and ageing 12 hours at 75 ℃; the light blue slurries of gained obtain solid matter after deionized water repetitive scrubbing filters, and solid matter is drying to obtain the pillared layered double-metal hydroxide of octadecyl sulfonic acid at 80 ℃.
5. layered double hydroxide according to claim 1 and expanding fire retardant compositional flame-retardant polypropylene composite material, is characterized in that: described expanding material is maleic anhydride inoculated polypropylene multipolymer, percentage of grafting 0.8-1.0%.
6. a preparation method for layered double hydroxide and expanding fire retardant compositional flame-retardant polypropylene composite material, is characterized in that: preparation process comprises: (1) first weighs each component according to formula rate; (2) then by 60-90 rev/min, middling speed stirrer for each raw material, stir and mix to each raw material for 10-20 minute, proceed in twin screw extruder and melt extrude; The packing area temperature of twin screw extruder is 150-170 ℃, and mixing zone temperature is 200-220 ℃, and reaction zone temperature is 220-230 ℃, and die head temperature is 200-220 ℃, and head pressure is 3-6MPa, extrudes rear cooling granulation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310593819.9A CN103613845A (en) | 2013-11-21 | 2013-11-21 | Flame retardant polypropylene composite compounded by layered thermometal hydroxide and intumescent flame retardant and preparation method of flame retardant polypropylene composite |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310593819.9A CN103613845A (en) | 2013-11-21 | 2013-11-21 | Flame retardant polypropylene composite compounded by layered thermometal hydroxide and intumescent flame retardant and preparation method of flame retardant polypropylene composite |
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|---|---|
| CN103613845A true CN103613845A (en) | 2014-03-05 |
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| CN201310593819.9A Pending CN103613845A (en) | 2013-11-21 | 2013-11-21 | Flame retardant polypropylene composite compounded by layered thermometal hydroxide and intumescent flame retardant and preparation method of flame retardant polypropylene composite |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107163407A (en) * | 2017-05-09 | 2017-09-15 | 浙江省仙居县中兴橡胶密封件有限公司 | Halogen-free flameproof EPDM/PP thermoplastic sulfurized rubbers and preparation method thereof |
| CN108299799A (en) * | 2018-01-27 | 2018-07-20 | 浙江大学 | The layered double hydroxide and its preparation method and application that cagelike silsesquioxane is modified |
| CN109082017A (en) * | 2018-07-11 | 2018-12-25 | 河南科技大学 | A kind of phosphorus doping carbon nanotube/organically-modified layered double hydroxide/polyolefin flame-retardant material and preparation method thereof |
| CN110862575A (en) * | 2019-11-15 | 2020-03-06 | 南京理工大学 | Composite intumescent flame retardant, flame-retardant high impact polystyrene material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492172A (en) * | 2011-12-08 | 2012-06-13 | 山东春潮色母料有限公司 | Preparation method and application of nanometer organic-layered composite metal hydroxide |
| CN102936373A (en) * | 2012-10-30 | 2013-02-20 | 上海金发科技发展有限公司 | Basalt fiber polypropylene composite material enhanced by expansion flame retardants and method for preparing same |
-
2013
- 2013-11-21 CN CN201310593819.9A patent/CN103613845A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492172A (en) * | 2011-12-08 | 2012-06-13 | 山东春潮色母料有限公司 | Preparation method and application of nanometer organic-layered composite metal hydroxide |
| CN102936373A (en) * | 2012-10-30 | 2013-02-20 | 上海金发科技发展有限公司 | Basalt fiber polypropylene composite material enhanced by expansion flame retardants and method for preparing same |
Non-Patent Citations (1)
| Title |
|---|
| 王融冰等: "阻燃剂三聚氰胺聚磷酸盐的合成", 《应用化工》, vol. 38, no. 12, 31 December 2009 (2009-12-31), pages 1826 - 1827 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107163407A (en) * | 2017-05-09 | 2017-09-15 | 浙江省仙居县中兴橡胶密封件有限公司 | Halogen-free flameproof EPDM/PP thermoplastic sulfurized rubbers and preparation method thereof |
| CN108299799A (en) * | 2018-01-27 | 2018-07-20 | 浙江大学 | The layered double hydroxide and its preparation method and application that cagelike silsesquioxane is modified |
| CN108299799B (en) * | 2018-01-27 | 2019-09-20 | 浙江大学 | The modified layered double hydroxide and its preparation method and application of cagelike silsesquioxane |
| CN109082017A (en) * | 2018-07-11 | 2018-12-25 | 河南科技大学 | A kind of phosphorus doping carbon nanotube/organically-modified layered double hydroxide/polyolefin flame-retardant material and preparation method thereof |
| CN109082017B (en) * | 2018-07-11 | 2020-11-20 | 河南科技大学 | Phosphorus-doped carbon nanotube/organic modified layered double hydroxide/polyolefin flame-retardant material and preparation method thereof |
| CN110862575A (en) * | 2019-11-15 | 2020-03-06 | 南京理工大学 | Composite intumescent flame retardant, flame-retardant high impact polystyrene material and preparation method thereof |
| CN110862575B (en) * | 2019-11-15 | 2022-03-18 | 南京理工大学 | Composite intumescent flame retardant, flame-retardant high impact polystyrene material and preparation method thereof |
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Application publication date: 20140305 |