CN105131543A - Halogen-free expansive-type flame-retardant system flame-retardant polylactic acid material and preparation method thereof - Google Patents
Halogen-free expansive-type flame-retardant system flame-retardant polylactic acid material and preparation method thereof Download PDFInfo
- Publication number
- CN105131543A CN105131543A CN201510614110.1A CN201510614110A CN105131543A CN 105131543 A CN105131543 A CN 105131543A CN 201510614110 A CN201510614110 A CN 201510614110A CN 105131543 A CN105131543 A CN 105131543A
- Authority
- CN
- China
- Prior art keywords
- flame
- ammonium polyphosphate
- acid material
- halogen
- retardant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a halogen-free expansive-type flame-retardant system flame-retardant polylactic acid material and a preparation method thereof. A system comprises polylactic particles, modified ammonium polyphosphate and carbonific. Surface pretreatment on the carbonific is carried out by virtue of a drying, crushing and washing method, and organic macromolecule phosphorus-containing flame-retardant agent is used for respectively modifying the surface pretreated carbonific and the ammonium polyphosphate, so that not only can the compatibility of the carbonific and the ammonium polyphosphate with a polylactic acid basal body be improved, the mechanical performance is improved, but also the flame-retardant performance of the material can be improved by virtue of the synergistic effect of various components; moreover, a compact and stable carbon layer is generated in combustion, an anti-melt dripping effect is realized, and the secondary combustion caused by the melt dripping can be effectively avoided.
Description
Technical field
The present invention relates to the fire-retardant of poly-lactic acid material and enhancement techniques field, be specifically related to a kind of halogen-free expansion type flame-proof system flame-retardant polylactic acid material and preparation method thereof
Background technology
Poly(lactic acid) (PLA), the starch material proposed primarily of the plant resources of the natural reproducibles such as corn is made, not only reduce the dependence to resources such as oil, also indirectly reduce the discharge of the dusty gas such as oxynitride and oxysulfide in the processes such as crude oil refinery.In addition, after a procedure, PLA and products thereof can be degradable by microorganism, very little to the pollution of environment.Moreover, the excellent in mechanical performance of poly(lactic acid) itself, but its flame retardant effect is poor, during burning, molten drop is serious, can cause secondary combustion, limits his application in the high field of fire protection requirement.Therefore, in poly(lactic acid) is flame-retardant modified, flame retardant properties is improved on the basis of mechanical property keeping original excellence and has become key, wherein conventional in enhancing modified method adds Mierocrystalline cellulose, nanoclay etc. wherein.
In fire retardant, phosphorus flame retardant in these years develops rapidly, is the Green Flammability agent of applying widely, but is applied in poly(lactic acid) that to there is efficiency not high yet, and the defect such as affect the mechanical properties.In the research of phosphorus flame retardant polydactyl acid, researcher's application response type flame-retarded technology, introduces in poly(lactic acid) main chain by chain extension by phosphoric, increases the molecular weight of poly(lactic acid) thus keeps its original mechanical property, the advantage such as to have efficiently, do not move.But this polymerization technique is complicated, cost is high, range of application is narrow.Except this method, phosphorus nitrogen synergistic intumescent flame retardant can improve the thermostability of polymkeric substance because of it, reduces the study hotspot that the advantages such as raw smoke which have become flame retardant area.The most frequently used expansion type flame retardant system is ammonium polyphosphate and tetramethylolmethane, but the people such as Rita study discovery, and ammonium polyphosphate/tetramethylolmethane system is added in poly(lactic acid), and addition is 40% flame retardant effect that just can reach UL-94V-2 rank.In addition, tetramethylolmethane lifeless matter degradability, limits its use in the bio-based materials such as poly(lactic acid) more.Vinasse are by-product industry of wine brewing, and the Mierocrystalline cellulose be wherein rich in is the addition type strongthener commonly used in recent years.China is wine brewing big country, has the abandoned vinasse more than 2,000 ten thousand tons to produce every year, and wherein contained material has high acidity, is easy to putrid and deteriorated, causes very large harm to environment.
In the research of the efficient halogen-free anti-inflaming poly(lactic acid) openly reported at present, also do not occur using Chinese liquor distiller grains as additive application in flame-proof polylactic acid, therefore this system can be very helpful to the research of low-cost high-efficiency flame-proof polylactic acid aspect.
Summary of the invention
The object of this invention is to provide a kind of halogen-free expansion type flame-proof system flame-retardant polylactic acid material and preparation method thereof, be intended to overcome the deficiencies in the prior art, the flame retardant properties needed for material and mechanical property can not only be met simultaneously, and Heat stability is good, the carbon-coating generated during burning is stable fine and close, effectively can suppress molten drop.
Realizing the object of the invention technical solution is:
A kind of halogen-free expansion type flame-proof system flame-retardant polylactic acid material, described poly-lactic acid material is formed by poly(lactic acid), ammonium polyphosphate modifying and char-forming agent melt blending; Wherein, the mass percent of described poly(lactic acid), ammonium polyphosphate modifying and char-forming agent is 70:(25 ~ 5): (5 ~ 25).
Described ammonium polyphosphate modifying is the ammonium polyphosphate of Resorcinol two (diphenyl phosphoester) (being called for short RDP) modification, by Resorcinol two (diphenyl phosphoester) is dissolved in chloroform, add ammonium polyphosphate wherein, ultrasonic lower reaction is no less than 1h, after reaction terminates, product is dried at not higher than 60 DEG C, obtained after removing unnecessary solvent chloroform.
Described char-forming agent is modification Chinese liquor distiller grains, by drying to constant weight by Chinese liquor distiller grains at not higher than 60 DEG C, pulverize, the Chinese liquor distiller grains after sieving is placed in deionized water again, stirring, suction filtration, washing, dry, sieve, obtain the Chinese liquor distiller grains through surface preparation; Finally Resorcinol two (diphenyl phosphoester) is dissolved in chloroform, add the Chinese liquor distiller grains through surface preparation wherein, under the condition of ultrasonic disperse, reaction is no less than 1.5h, is dried by product after reaction terminates at not higher than 60 DEG C, obtained after removing unnecessary solvent chloroform.
In ammonium polyphosphate modifying, the molecular formula of ammonium polyphosphate is (NH
4pO
3) n, the value >1500 of polymerization degree n, the content >14% of N element, its particle diameter <15um.
In modification Chinese liquor distiller grains, described sieving is the accurate sub-sieve of 60 target, and churning time is no less than 30min, and the Chinese liquor distiller grains after sieving and the mass ratio of deionized water are 1:100.
Above-mentioned halogen-free expansion type flame-proof system flame-retardant polylactic acid material, comprises the following steps:
Poly(lactic acid), ammonium polyphosphate modifying and modification Chinese liquor distiller grains are mixed in proportion, and obtains described poly-lactic acid material through melt blending.
The temperature of described melt blending is 170 ~ 190 DEG C, and the blended time is 5 ~ 10min.
The present invention compared with prior art, has obvious progress:
(1) Chinese liquor distiller grains itself is containing more water soluble acid etc., and resistance toheat is poor, and decomposition temperature is only about 177 DEG C, does not reach the processing temperature of poly(lactic acid).The treatment process that the present invention adopts is washing, simple to operation, improves the resistance toheat of Chinese liquor distiller grains and its dispersiveness in poly-lactic acid material to a great extent.And Chinese liquor distiller grains replaces traditional char-forming agent to play the effect of carbon source in Intumscent Flame Retardant System.
(2) surface-modifying agent used in the present invention is RDP, effectively can improve the consistency of Chinese liquor distiller grains, ammonium polyphosphate and poly(lactic acid) matrix, thus improves the mechanical property of material.
(3) RDP belongs to efficient organic fire-retardant, and a small amount of RDP not only plays the effect of surface-modifying agent and can work in coordination with other components, and improve the flame retardant properties of material, its fire-retardant rank reaches V-0 level, and oxygen index is up to more than 40%.
Embodiment
Bio-based degradable anti-flaming poly(lactic acid) engineering materials of the present invention is formed by poly(lactic acid), ammonium polyphosphate modifying and modification Chinese liquor distiller grains melt blending, and wherein the preparation method of ammonium polyphosphate modifying and modification Chinese liquor distiller grains is as follows:
The Chinese liquor distiller grains of humidity is dried to constant weight at 60 DEG C, the accurate sub-sieve of 60 target is crossed after pulverizing, vinasse after sieving are placed in a certain amount of deionized water, wherein the ratio of Chinese liquor distiller grains and water is 1:100, stirring is no less than 30min, suction filtration, washing, oven dry, the excessively accurate sub-sieve of 60 target, the obtained Chinese liquor distiller grains through surface preparation.Be dissolved in by RDP in chloroform, add the Chinese liquor distiller grains through surface preparation wherein, ultrasonic lower reaction is no less than 1.5h, is dried by product, remove unnecessary solvent chloroform after reaction terminates at not higher than 60 DEG C.
Be dissolved in by RDP in chloroform, add a certain amount of ammonium polyphosphate wherein, under the condition of ultrasonic disperse, reaction is no less than 1h, is dried by product, remove unnecessary solvent chloroform after reaction terminates at not higher than 60 DEG C.
Halogen-free expansion fire retardant flame-retardant polylactic acid material of the present invention is by mass percentage for 70:(30 ~ 5 by poly(lactic acid), ammonium polyphosphate modifying and modification Chinese liquor distiller grains): (0 ~ 25) melting mixing forms.
In order to Comprehension and Implementation better, describe the preparation process of halogen-free expansion fire retardant flame-retardant polylactic acid material in detail below in conjunction with comparative example and embodiment.
Embodiment 1:
Take poly(lactic acid) pellet 700g, modification Chinese liquor distiller grains 50g, ammonium polyphosphate modifying 250g, by good for above-mentioned pellet combination treatment in high-speed mixer, at the temperature of routine and the condition of screw speed, be added to melt blending in torque rheometer, obtained poly-lactic acid material of the present invention.Limiting oxygen index(LOI) 24.5%, without molten drop phenomenon, UL-94 tests V-0 level, the carbon yield 10.2%, tensile strength 37.30MPa when 600 DEG C.
Embodiment 2:
Take poly(lactic acid) pellet 700g, modification Chinese liquor distiller grains 100g, ammonium polyphosphate modifying 200g, by good for above-mentioned pellet combination treatment in high-speed mixer, at the temperature of routine and the condition of screw speed, be added to melt blending in torque rheometer, obtained poly-lactic acid material of the present invention.Limiting oxygen index(LOI) 26.5%, without molten drop phenomenon, UL-94 tests V-0 level, the carbon yield 12.4%, tensile strength 40.57MPa when 600 DEG C.
Embodiment 3:
Take poly(lactic acid) pellet 700g, modification Chinese liquor distiller grains 150g, ammonium polyphosphate modifying 150g, by good for above-mentioned pellet combination treatment in high-speed mixer, at the temperature of routine and the condition of screw speed, be added to melt blending in torque rheometer, obtained poly-lactic acid material of the present invention.Limiting oxygen index(LOI) 32%, without molten drop phenomenon, UL-94 tests V-0 level, the carbon yield 15.8%, tensile strength 43.11MPa when 600 DEG C.
Embodiment 4:
Take poly(lactic acid) pellet 700g, modification Chinese liquor distiller grains 200g, ammonium polyphosphate modifying 100g, by good for above-mentioned pellet combination treatment in high-speed mixer, at the temperature of routine and the condition of screw speed, be added to melt blending in torque rheometer, obtained poly-lactic acid material of the present invention.Limiting oxygen index(LOI) 37.5%, without molten drop phenomenon, UL-94 tests V-0 level, the carbon yield 16.9%, tensile strength 41.38MPa when 600 DEG C.
Embodiment 5:
Take poly(lactic acid) pellet 700g, modification Chinese liquor distiller grains 250g, ammonium polyphosphate modifying 50g, by good for above-mentioned pellet combination treatment in high-speed mixer, at the temperature of routine and the condition of screw speed, be added to melt blending in torque rheometer, obtained poly-lactic acid material of the present invention.Limiting oxygen index(LOI) 41.5%, without molten drop phenomenon, UL-94 tests V-0 level, the carbon yield 17.9%, tensile strength 40.98MPa when 600 DEG C.
Comparative example 1:
Take poly(lactic acid) pellet 700g, modification Chinese liquor distiller grains 300g, by good for above-mentioned pellet combination treatment in high-speed mixer, at the temperature of routine and the condition of screw speed, be added to melt blending in torque rheometer, obtained poly-lactic acid material of the present invention.Limiting oxygen index(LOI) 18.5%, without molten drop phenomenon, cannot be tested by UL-94, the carbon yield 14.9%, tensile strength 40.63MPa when 600 DEG C.
Comparative example 2:
Take poly(lactic acid) pellet 700g, washing Chinese liquor distiller grains 150g, ammonium polyphosphate 150g, by good for above-mentioned pellet combination treatment in high-speed mixer, at the temperature of routine and the condition of screw speed, be added to melt blending in torque rheometer, obtained poly-lactic acid material of the present invention.Limiting oxygen index(LOI) 30.0%, without molten drop phenomenon, UL-94 tests V-0 level, the carbon yield 14.6%, tensile strength 38.5MPa when 600 DEG C.
Can be obtained by above comparative example and embodiment: the Intumscent Flame Retardant System be made up of Chinese liquor distiller grains and the ammonium polyphosphate of RDP modification can effective flame-retardant polylactic acid material, described poly-lactic acid material has excellent flame retardant properties and mechanical property in the component formula of embodiment, and the over-all properties of material is good.
Claims (7)
1. a halogen-free expansion type flame-proof system flame-retardant polylactic acid material, is characterized in that, described poly-lactic acid material is formed by poly(lactic acid), ammonium polyphosphate modifying and char-forming agent melt blending; Wherein, the mass percent of described poly(lactic acid), ammonium polyphosphate modifying and char-forming agent is 70:(25 ~ 5): (5 ~ 25).
2. halogen-free expansion type flame-proof system flame-retardant polylactic acid material as claimed in claim 1, it is characterized in that, described ammonium polyphosphate modifying is the ammonium polyphosphate of two (diphenyl phosphoester) modification of Resorcinol, by Resorcinol two (diphenyl phosphoester) is dissolved in chloroform, add ammonium polyphosphate wherein, ultrasonic lower reaction is no less than 1h, is dried by product after reaction terminates at not higher than 60 DEG C, obtained after removing unnecessary solvent chloroform.
3. halogen-free expansion type flame-proof system flame-retardant polylactic acid material as claimed in claim 1, it is characterized in that, described char-forming agent is modification Chinese liquor distiller grains, by Chinese liquor distiller grains is dried to constant weight at not higher than 60 DEG C, pulverize, Chinese liquor distiller grains after sieving is placed in deionized water again, stirring, suction filtration, washing, dries, sieves, and obtains the Chinese liquor distiller grains through surface preparation; Finally Resorcinol two (diphenyl phosphoester) is dissolved in chloroform, add the Chinese liquor distiller grains through surface preparation wherein, under the condition of ultrasonic disperse, reaction is no less than 1.5h, is dried by product after reaction terminates at not higher than 60 DEG C, obtained after removing unnecessary solvent chloroform.
4. halogen-free expansion type flame-proof system flame-retardant polylactic acid material as claimed in claim 1 or 2, it is characterized in that, in ammonium polyphosphate modifying, the molecular formula of ammonium polyphosphate is (NH
4pO
3) n, the value >1500 of polymerization degree n, the content >14% of N element, its particle diameter <15um.
5. halogen-free expansion type flame-proof system flame-retardant polylactic acid material as claimed in claim 3, it is characterized in that, in modification Chinese liquor distiller grains, described sieving is the accurate sub-sieve of 60 target, churning time is no less than 30min, and the Chinese liquor distiller grains after sieving and the mass ratio of deionized water are 1:100.
6. the preparation method of the halogen-free expansion type flame-proof system flame-retardant polylactic acid material as described in as arbitrary in claim 1-3, is characterized in that, comprise the following steps:
Poly(lactic acid), ammonium polyphosphate modifying and modification Chinese liquor distiller grains are mixed in proportion, and obtains described poly-lactic acid material through melt blending.
7. the preparation method of halogen-free expansion type flame-proof system flame-retardant polylactic acid material as claimed in claim 6, it is characterized in that, the temperature of described melt blending is 170 ~ 190 DEG C, and the blended time is 5 ~ 10min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510614110.1A CN105131543B (en) | 2015-09-23 | 2015-09-23 | Halogen-free expansive-type flame-retardant system flame-retardant polylactic acid material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510614110.1A CN105131543B (en) | 2015-09-23 | 2015-09-23 | Halogen-free expansive-type flame-retardant system flame-retardant polylactic acid material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105131543A true CN105131543A (en) | 2015-12-09 |
| CN105131543B CN105131543B (en) | 2017-01-18 |
Family
ID=54717140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510614110.1A Active CN105131543B (en) | 2015-09-23 | 2015-09-23 | Halogen-free expansive-type flame-retardant system flame-retardant polylactic acid material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105131543B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107974127A (en) * | 2018-01-11 | 2018-05-01 | 长春顺风新材料有限公司 | A kind of bio-based is except methanal paint and preparation method thereof |
| CN112852133A (en) * | 2021-03-22 | 2021-05-28 | 合肥工业大学 | Anti-droplet PLA/PVA composite material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5041493A (en) * | 1989-11-16 | 1991-08-20 | Enichem Americas, Inc. | Moldable polyblends |
| CN102002222A (en) * | 2010-10-21 | 2011-04-06 | 中国科学院宁波材料技术与工程研究所 | Halogen-free flame retardant polylactic acid composite material |
| JP2013007043A (en) * | 2012-08-15 | 2013-01-10 | Mitsubishi Plastics Inc | Resin composition and injection-molded article |
-
2015
- 2015-09-23 CN CN201510614110.1A patent/CN105131543B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5041493A (en) * | 1989-11-16 | 1991-08-20 | Enichem Americas, Inc. | Moldable polyblends |
| CN102002222A (en) * | 2010-10-21 | 2011-04-06 | 中国科学院宁波材料技术与工程研究所 | Halogen-free flame retardant polylactic acid composite material |
| JP2013007043A (en) * | 2012-08-15 | 2013-01-10 | Mitsubishi Plastics Inc | Resin composition and injection-molded article |
Non-Patent Citations (1)
| Title |
|---|
| SHANSHAN YUAN: "Synergistic Effect of THEIC-based Charring Agent on Flame Retardant Properties of Polylactide", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107974127A (en) * | 2018-01-11 | 2018-05-01 | 长春顺风新材料有限公司 | A kind of bio-based is except methanal paint and preparation method thereof |
| CN112852133A (en) * | 2021-03-22 | 2021-05-28 | 合肥工业大学 | Anti-droplet PLA/PVA composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105131543B (en) | 2017-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Laoutid et al. | Novel bio-based flame retardant systems derived from tannic acid | |
| Subasinghe et al. | Effects of wool fibre and other additives on the flammability and mechanical performance of polypropylene/kenaf composites | |
| Kurt et al. | The effects of boron compounds synergists with ammonium polyphosphate on mechanical properties and burning rates of wood-HDPE polymer composites | |
| CN103522447B (en) | The preparation method of halogen-free composite flame retardant polypropylene/thermopolyurethane polyurethane elastomer composite material | |
| Das et al. | Naturally-occurring bromophenol to develop fire retardant gluten biopolymers | |
| CN105440652A (en) | Flame retardant thermoplastic polyurethane elastomer (TPU) and preparation method thereof | |
| CN112692945A (en) | Water-based bio-based intumescent flame-retardant coating and preparation method and application thereof | |
| Zdanowicz et al. | Thermoplastic starch/ternary deep eutectic solvent/lignin materials: study of physicochemical properties and fire behavior | |
| CN105348635A (en) | Nano cooperative intumescent flame retardant and toughening polypropylene blend composite material and preparation method thereof | |
| CN105131543A (en) | Halogen-free expansive-type flame-retardant system flame-retardant polylactic acid material and preparation method thereof | |
| CN114015115B (en) | Preparation method of intumescent flame retardant based on piperazine pyrophosphate/melamine cyanurate/ammonium polyphosphate | |
| CN105524301B (en) | A kind of preparation method of microencapsulation basic zirconium phosphate and the halogen-free flame retardant PC being made from it | |
| Sun et al. | Improving flame retardant and smoke suppression function of ethylene vinyl acetate by combining the piperazine pyrophosphate, expandable graphite and melamine phosphate | |
| CN114507406A (en) | Flame-retardant biodegradable PVA film | |
| CN106317809B (en) | A kind of bio-based degradable anti-flaming polylactic acid engineering material and preparation method thereof | |
| Xia et al. | Fire retardants from renewable resources | |
| CN104017356A (en) | Preparation method of flame retardant nylon material | |
| CN111793338B (en) | Compound halogen-free flame-retardant plant fiber reinforced polylactic acid material and preparation method thereof | |
| CN107189396B (en) | Hydrolysis PC-ABS alloy | |
| CN108822396A (en) | A kind of regenerated plastics computer desk material and preparation method thereof | |
| AT511015A1 (en) | COMPOSITION FOR PREPARING FLAME-REDUCING SURFACES OR OBJECTS | |
| CN106700523B (en) | Preparation method of nano hydrotalcite composite material | |
| CN103709589A (en) | Mica-ABS (Acrylonitrile Butadiene Styrene) flame-retardant insulation material and preparation method thereof | |
| CN103773393A (en) | Composite type flame retardant containing modified zeolite powder | |
| CN105295091A (en) | Calcium-zinc flame-retarding smoke-suppressing material, preparation method thereof, composite flame-retarding smoke-suppressing material, and preparation method of composite flame-retarding smoke-suppressing material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |