CN102643464A - Nano halogen-free flame retardant polyolefin material and preparation method thereof - Google Patents
Nano halogen-free flame retardant polyolefin material and preparation method thereof Download PDFInfo
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- CN102643464A CN102643464A CN2012101428633A CN201210142863A CN102643464A CN 102643464 A CN102643464 A CN 102643464A CN 2012101428633 A CN2012101428633 A CN 2012101428633A CN 201210142863 A CN201210142863 A CN 201210142863A CN 102643464 A CN102643464 A CN 102643464A
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- 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
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Abstract
The invention relates to a nano halogen-free flame retardant polyolefin material and a preparation method thereof. The nano halogen-free flame retardant polyolefin material is prepared by melting and mixing 50-90 parts of polyolefin, 1-10 parts of nano particles, 10-65 parts of expansion type flame retardant and 0.5-5 parts of dispersing agent according to reasonable proportion. According to the nano halogen-free flame retardant polyolefin material and the preparation method thereof, the nano particles are added based on the expansion type halogen-free flame retardant polyolefin, the cooperation flame retardant effect is achieved, the negative influence on the mechanical property of the polyolefin caused by the heavy addition of the flame retardant can be overcome, and compared with the polyolefin material with pure expansion type flame retardant, the nano halogen-free flame retardant polyolefin material has the advantages of good flame retarding effect and excellent mechanical property. The material can be applied to fields of electric wires and cables, automobiles, sports goods and the like.
Description
[technical field]
The present invention relates to nanometer halogen-free anti-flaming composite polyolefine material technical field, specifically, is a kind of nanometer halogen-free anti-flaming polyolefine material and preparation method thereof.
[background technology]
Polyolefine is to be the general name of main all homopolymer, multipolymer and composition thereof with alkene.Polyolefine is owing to light weight, nontoxic, cheap, and processibility is good, is widely used in industries such as electrical equipment, chemical industry, food, machinery, traffic, becomes one of indispensable Chemicals in the national economy.But because polyolefine is an inflammable material, oxygen index is less than 18, and the burning fuming amount is big, produces a large amount of molten drops, and very easily propagating flame makes its application receive very big restriction.Flame-retardant modified to polyolefine is the important means of widening its field.The fire retardant of traditional fire retardant polyolefin is a halogen flame, and is used with Antimony Trioxide: 99.5Min, also has inorganic aquo compound and phosphorus flame retardant in addition, like white lake, Marinco H, red phosphorus etc.As everyone knows, halogenated flame retardant can be emitted poisonous gas when burning, and some bromide fire retardant can form poisonous carcinogenic PBDD and PBDF, and this harm to human body and environment is far longer than fire itself; The loading level of inorganic aquo compound (like white lake) usually just can reach flame retardant effect greater than 50%, but high loading level has destroyed the mechanical property of material; The fire retardant of phosphorus system is mainly used in and contains the fire-retardant of oxygen superpolymer, and the red phosphorus in the phosphorus flame retardant is not suitable in the demanding product of color because color is heavy.
Expansion type flame retardant is a kind of green fire retardant of environmental protection, and is not halogen-containing, and also not adopting weisspiessglanz is synergist, and its system self has collaborative effect.The material that contains expansion type flame retardant generates the carbonaceous foam layer in the surface when burning; Play heat insulation, oxygen barrier, press down cigarette, the effect of anti-molten drop; Have good flame retardant property, and low cigarette, low toxicity, non-corrosiveness gas produce, meet following Study of Flame Retardant exploitation direction.Expansion type flame retardant has become one of the most active in recent years fire retardant research field both at home and abroad.Chinese patent publication number CN101508809A discloses a kind of halogen-free expansion type flame-proof polyolefin composite material, adds under the situation of 15～25% fire retardant again, and oxygen index reaches about 33.But; Because the fire retardant addition is big, to fire-retardant polyolefine material can cause the decline of mechanical property, Chinese patent CN100365051C discloses a kind of toughness reinforcing flame retardant polyolefine material preparation method that strengthens; Use organo montmorillonite and bromide fire retardant; Its mechanical property and flame retardant properties all reach better effects, but the halogen-containing fire retardant that uses is prone to produce deleterious flue gas.
[summary of the invention]
The objective of the invention is to overcome the deficiency of prior art, a kind of nanometer halogen-free anti-flaming polyolefine material and preparation method thereof is provided.
The objective of the invention is to realize through following technical scheme:
A kind of nanometer halogen-free anti-flaming polyolefine material is made up of polyolefine, nanoparticle, expansibility flame-proof agent, dispersion agent, and its composition weight mark is:
Described expansion type flame retardant is the multi-component expansion type flame retardant or the expansion type flame retardant of single-component.Multi-component expansion type flame retardant is by containing acid source, source of the gas, carbon source material two kinds and two or more the composition.Wherein acid source is the material that mineral acid or heating condition produce mineral acid down, like phosphoric acid, sulfuric acid, boric acid, ammonium phosphate, ammonium polyphosphate, urea phosphoric acid salt, triphenylphosphate, aryl phosphate ester etc.; Carbon source is the polyhydroxy substance of rich carbon, like starch, sorbyl alcohol, tetramethylolmethane and double focusing polymer, resol etc.; Source of the gas is some materials that add the thermogenesis non-flammable gases, as, urea, urea-formaldehyde resin, Dyhard RU 100, trimeric cyanamide, ammonium polyphosphate etc.The fire retardant of single-component is to be the macromole expansion type flame retardant of one with acid source, source of the gas, carbon source.
Described nanoparticle is meant nano silicon, nano aluminium oxide, nano zine oxide, nano-calcium carbonate, organically-modified stratiform polynite, nano-manganese dioxide, nano titanium oxide, layered double-hydroxide, carbon nanotube, nano molecular sieve etc.
Described dispersion agent is meant whiteruss, polyethylene wax, microcrystalline wax, Injecatable EVA Copolymer, Triple Pressed Stearic Acid and its esters.
A kind of preparation method of nanometer halogen-free anti-flaming polyolefine material may further comprise the steps:
After polyolefine, expansion type flame retardant, nanoparticle vacuum-drying; Polyolefine, expansion type flame retardant, nanoparticle, dispersion agent are mixed in high-speed mixer; Mix plasticizing and granulation through screw extrusion press, extruding melting temperature is 120～300 ℃; At last under 100～300 ℃ through extruding or injection moulding or compression molding, obtain the nanometer halogen-free anti-flaming polyolefine material.
Expansion type flame retardant is made up of acid source, carbon source, source of the gas three components.Expansion charcoal layer has following steps formation: 1. acid source decomposes generation ability esterification polyol and the mineral acid that can be used as dewatering agent when temperature is low; 2. under the temperature of high slightly release mineral acid, mineral acid and carbon source are carried out esterification, and the amine in the system makes the esterification acceleration as the catalyzer of esterification; 3. system melts before esterification or in the esterification process; 4. the rare gas element of the water vapour of reaction process generation and source of the gas decomposition generation makes the system that is in molten state expanded foamed, and meanwhile, polyvalent alcohol and ester dehydration carbonization form inorganics and charcoal resistates, and system are further expanded foamed; When 5. reaction was near completion, system gel and curing formed porous foam charcoal layer at last.This Carbon foam layer has intercepted the transmission of heat and the diffusion of oxygen, stops the behavior of polymer melt drippage effectively, has prevented the generation of volatile combustible composition, thereby has played the purpose of interrupting polymer combustion.
Nanoparticle added in the intumescent system can produce very big synergistic effect.Under flame or thermal radiation, nanoparticle has changed the physical behavior (like rate of expansion, charcoal layer intensity and heat physical properties) and the chemical conduct (like the reaction between nanoparticle and expansion component) of expansion charcoal layer, thereby plays collaborative effect with expansion type flame retardant.The mechanism of action of nanoparticle and expansion type flame retardant is not unified.The nanoparticle that has is as the catalyzer of expansion system, can catalytic specie deposits with stable structure more, can promote the formation of active substance, carries out selection chemical reaction at condensed phase, forms the resist with certain dynamics.The nanoparticle that has is moved to material surface and is formed resist when material combustion.
Simultaneously, adding nanoparticle is improved the mechanical property of material.When nano particle is evenly dispersed in the matrix resin, can cause stress concentration, wrap in circumgranular matrix and also can surrender, produce crazing, absorb a certain amount of deformation work, matrix is produced stronger toughening effect thereby cause matrix resin in matrix inside.Because the nano particle specific surface area is bigger, surface energy is high, and the bonding strength that produces with matrix resin is high; Under external force; Particle be prone to cause produces more tiny crack (crazing) and unsticking not, thereby absorbs more energy, so the over-all properties of matrix material can significantly improve.
Compared with prior art, positively effect of the present invention is:
Have good mechanical performance and flame retardant properties by polyolefine, expansion type flame retardant, nanoparticle, dispersion agent through the nanometer halogen-free anti-flaming composite polyolefine material of melt blending preparation.Compare with the expansion type flame retardant fire retardant polyolefin, have the mechanical property of intensity height, good springiness.Compare with halogenous fire retardant polyolefin, have the characteristics of low cigarette, low toxicity, no molten drop during burning, reduce injury environment and human body.
[embodiment]
The embodiment of a kind of nanometer halogen-free anti-flaming polyolefine material of the present invention and preparation method thereof below is provided.
Embodiment 1
After 70 parts of polyolefine, 20 parts of ammonium polyphosphates, 6,1 part of urea vacuum-drying of 9 parts of nylon; Adding 1 part of polyolefin-wax mixed 10 minutes in 80 ℃ of following high-speed mixers; With said mixture in length-to-diameter ratio 32; Carry out extruding pelletization in the twin screw extruder of branch six district's temperature controls, the processing temperature in one to six district is followed successively by: 190 ℃, 190 ℃, 195 ℃, 195 ℃, 200 ℃, 190 ℃.With pellet compression molding on 165～170 ℃ of vulcanizing presses, on universal testing machine, cut into the standard batten on request, be used for the test of combustionproperty and mechanical property.
Embodiment 2
After 70 parts of polyolefine, 20 parts of ammonium polyphosphates, 6,1 part of urea of 9 parts of nylon, 2 parts the sodium-based montmorillonite vacuum-drying of cetyl trimethylammonium bromide modification; Adding 1 part of polyolefin-wax mixed 10 minutes in 80 ℃ of following high-speed mixers; With said mixture in length-to-diameter ratio 32; Carry out extruding pelletization in the twin screw extruder of branch six district's temperature controls, the processing temperature in one to six district is followed successively by: 190 ℃, 190 ℃, 195 ℃, 195 ℃, 200 ℃, 190 ℃.With pellet compression molding on 165～170 ℃ of vulcanizing presses, on universal testing machine, cut into the standard batten on request, be used for the test of combustionproperty and mechanical property.
Embodiment 3
After 70 parts of polyolefine, 20 parts of ammonium polyphosphates, 6,1 part of urea of 9 parts of nylon, 2 parts nanometer A12O3 vacuum-drying; Adding 1 part of polyolefin-wax mixed 10 minutes in 80 ℃ of following high-speed mixers; With said mixture in length-to-diameter ratio 32; Carry out extruding pelletization in the twin screw extruder of branch six district's temperature controls, the processing temperature in one to six district is followed successively by: 190 ℃, 190 ℃, 195 ℃, 195 ℃, 200 ℃, 190 ℃.With pellet compression molding on 165～170 ℃ of vulcanizing presses, on universal testing machine, cut into the standard batten on request, be used for the test of combustionproperty and mechanical property.
The concrete data of each instance are as shown in the table:
The test data of each embodiment of table 1
| Limiting oxygen index(LOI) (%) | Tensile strength MPa | Elongation at break % | |
| Pure LDPE | 17.5±0.1 | 10.3±0.1 | 116.0 |
| Embodiment 1 | 27±0.1 | 8.5±0.1 | 49.2 |
| Embodiment 2 | 33±0.1 | 9.7±0.1 | 100.5 |
| Embodiment 3 | 34±0.1 | 10.1±0.1 | 95.8 |
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the present invention's design; Can also make some improvement and retouching, these improvement and retouching also should be regarded as in protection scope of the present invention.
Claims (8)
1. a nanometer halogen-free anti-flaming polyolefine material is characterized in that, is made up of polyolefine, nanoparticle, expansibility flame-proof agent, dispersion agent, and its composition weight mark is:
2. a kind of nanometer halogen-free anti-flaming polyolefine material as claimed in claim 1 is characterized in that, described expansion type flame retardant is the multi-component expansion type flame retardant or the expansion type flame retardant of single-component.
3. a kind of nanometer halogen-free anti-flaming polyolefine material as claimed in claim 2 is characterized in that, described multi-component expansion type flame retardant is by containing acid source, source of the gas, carbon source material two kinds and two or more the composition.
4. a kind of nanometer halogen-free anti-flaming polyolefine material as claimed in claim 3 is characterized in that, described acid source is the material that mineral acid or heating condition produce mineral acid down; Carbon source is the polyhydroxy substance of rich carbon; Source of the gas is the material that adds the thermogenesis non-flammable gases.
5. a kind of nanometer halogen-free anti-flaming polyolefine material as claimed in claim 2 is characterized in that, the fire retardant of described single-component is to be the macromole expansion type flame retardant of one with acid source, source of the gas, carbon source.
6. a kind of nanometer halogen-free anti-flaming polyolefine material as claimed in claim 2; It is characterized in that described nanoparticle is meant one or several mixing in nano silicon, nano aluminium oxide, nano zine oxide, nano-calcium carbonate, organically-modified stratiform polynite, nano-manganese dioxide, nano titanium oxide, layered double-hydroxide, carbon nanotube, the nano molecular sieve.
7. a kind of nanometer halogen-free anti-flaming polyolefine material as claimed in claim 2; It is characterized in that described dispersion agent is meant one or several mixing in whiteruss, polyethylene wax, microcrystalline wax, Injecatable EVA Copolymer, Triple Pressed Stearic Acid and its esters.
8. the preparation method of a nanometer halogen-free anti-flaming polyolefine material; It is characterized in that; May further comprise the steps: after polyolefine, expansion type flame retardant, nanoparticle vacuum-drying; Polyolefine, expansion type flame retardant, nanoparticle, dispersion agent are mixed in high-speed mixer, mix plasticizing and granulation through screw extrusion press, extruding melting temperature is 120～300 ℃; At last under 100～300 ℃ through extruding or injection moulding or compression molding, obtain the nanometer halogen-free anti-flaming polyolefine material.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107286437A (en) * | 2017-07-24 | 2017-10-24 | 谢泳江 | A kind of preparation method for colloidal sol polytene corrugated tube of preventing fires |
| CN109880232A (en) * | 2019-03-01 | 2019-06-14 | 苏州华盖信息科技有限公司 | A kind of function additive compounds cooperative flame retardant polypropylene material with nano-oxide |
| CN111607219A (en) * | 2020-07-01 | 2020-09-01 | 福州大学 | Low-smoke thermoplastic polyurethane elastomer composite material and preparation method thereof |
| CN112159549A (en) * | 2020-08-31 | 2021-01-01 | 浙江工业大学 | Flame retardant and application thereof |
| CN114075791A (en) * | 2021-12-06 | 2022-02-22 | 浙江圆融科技有限公司 | Production method of novel fireproof fabric |
| CN114685848A (en) * | 2020-12-29 | 2022-07-01 | 洛阳尖端技术研究院 | Intumescent flame retardant, plastic and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1446844A (en) * | 2003-04-01 | 2003-10-08 | 华东理工大学 | Expansion type fire retardant material |
| CN101012324A (en) * | 2007-01-25 | 2007-08-08 | 宝鸡市云鹏塑料科技有限公司 | Nano modified plastic composite material, preparing method thereof and special-purpose apparatus |
| CN101899183A (en) * | 2010-09-02 | 2010-12-01 | 中国科学技术大学 | Radiation cross-linking waterproof flame retardant polyolefin nano-composite material and preparation method thereof |
-
2012
- 2012-05-09 CN CN2012101428633A patent/CN102643464A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1446844A (en) * | 2003-04-01 | 2003-10-08 | 华东理工大学 | Expansion type fire retardant material |
| CN101012324A (en) * | 2007-01-25 | 2007-08-08 | 宝鸡市云鹏塑料科技有限公司 | Nano modified plastic composite material, preparing method thereof and special-purpose apparatus |
| CN101899183A (en) * | 2010-09-02 | 2010-12-01 | 中国科学技术大学 | Radiation cross-linking waterproof flame retardant polyolefin nano-composite material and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107286437A (en) * | 2017-07-24 | 2017-10-24 | 谢泳江 | A kind of preparation method for colloidal sol polytene corrugated tube of preventing fires |
| CN109880232A (en) * | 2019-03-01 | 2019-06-14 | 苏州华盖信息科技有限公司 | A kind of function additive compounds cooperative flame retardant polypropylene material with nano-oxide |
| CN111607219A (en) * | 2020-07-01 | 2020-09-01 | 福州大学 | Low-smoke thermoplastic polyurethane elastomer composite material and preparation method thereof |
| CN112159549A (en) * | 2020-08-31 | 2021-01-01 | 浙江工业大学 | Flame retardant and application thereof |
| CN114685848A (en) * | 2020-12-29 | 2022-07-01 | 洛阳尖端技术研究院 | Intumescent flame retardant, plastic and preparation method and application thereof |
| CN114075791A (en) * | 2021-12-06 | 2022-02-22 | 浙江圆融科技有限公司 | Production method of novel fireproof fabric |
| CN114075791B (en) * | 2021-12-06 | 2023-11-21 | 浙江圆融科技有限公司 | Novel production method of fireproof fabric |
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Application publication date: 20120822 |