CN105176032A - Halogen-free flame retardant polylactic acid nanocomposite and preparation method thereof - Google Patents
Halogen-free flame retardant polylactic acid nanocomposite and preparation method thereof Download PDFInfo
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- CN105176032A CN105176032A CN201510483462.8A CN201510483462A CN105176032A CN 105176032 A CN105176032 A CN 105176032A CN 201510483462 A CN201510483462 A CN 201510483462A CN 105176032 A CN105176032 A CN 105176032A
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Abstract
The invention relates to a halogen-free flame retardant polylactic acid nanocomposite and a preparation method thereof. Per 100 parts by weight of the flame retardant polylactic acid material contains 70-90 parts of a polylactic acid resin, 10-30 parts of a phosphorus-containing flame retardant agent, 1-10 parts of nano organic modified montmorillonite, 0.01-1 part of an antioxidant and 0.5-5 parts of liquid paraffin. The specific preparation method comprises the following steps: mixing the flame retardant, montmorillonite, antioxidant and liquid paraffin according to a certain proportion, conducting melt blending, and subjecting the materials to cooling, granulation and drying to obtain the flame retardant polylactic acid. The invention adopts nano organic modified montmorillonite as the flame retardant synergist; on the one hand, the nano organic modified montmorillonite generates synergistic flame retardant effect with the phosphorus-containing flame retardant to improve the flame retardancy of the composite; and on the other hand, due to the small addition amount of the nano flame retardant synergist, the nano flame retardant synergist can uniformly disperse in the polymer matrix during processing, and has little influence on the material processing performance, so that the polylactic acid composite material has excellent flame retardance and well maintained mechanical properties.
Description
Technical field
The invention belongs to the flame-retardant modified technical field of poly(lactic acid), be specifically related to a kind of Halogen-free flame-retardant polylactic acid nanocomposite and preparation method thereof.
Background technology
Poly(lactic acid) is the family macromolecule material that monomer obtains through chemosynthesis or biosynthesizing by lactic acid, not based on oil, good consistency is had with biological substrate, the nontoxic nonirritant of its goods, also can being decomposed by the microorganisms and then absorbing after waste and old, is therefore the environment-friendly materials in absolute sense.Because poly(lactic acid) has remarkable mechanical property, biocompatibility, optical property, processing characteristics and thermostability, it is acknowledged as the biodegradable polymer that can replace conventional petroleum based polyalcohol at present to a certain extent.And the various fields such as household electrical appliances, automobile, fitment material for family may be widely used in.But, because poly(lactic acid) is as a kind of aliphatic polyester, its flame retardant properties is poor, and in combustion processes, have obvious drip phenomenon, above deficiency seriously constrains its application in fields such as household electrical appliances, automobile, electronics, therefore, be necessary to carry out modification to poly-lactic acid material, to improve its flame retardant properties.
The fire retardant of poly(lactic acid) can be divided into addition type and the large class of response type two, and the fire retardant of addition type is due to easy to use, and suitability is strong, by a large amount of application in the flame-retardant modified research of poly(lactic acid).Traditional additive flame retardant comprises halogen system, phosphorus system, nitrogen system and metallic compound, and addition type polylactic acid fire retardant the most frequently used is at present expansion type flame retardant, is secondly inorganic nano fire retardant.And halogenated flame retardant is due to excellent fireproof performance, be used in the earliest poly(lactic acid) flame-retardant modified in, but its amount of being fuming is large, and burning produces hydrogen halide poisonous in a large number, is prohibited in a lot of country.Poly(lactic acid), as a kind of green material, more should be avoided using halogenated flame retardant.Therefore, be necessary to explore the more efficient and simple poly(lactic acid) fire retardant material of preparation technology, with make material reach certain flame retardant grade else while also can reduce the impact of additive on material mechanical performance.
Summary of the invention
The object of the invention is to overcome the halogen containing flame-retardant harm environment existed in existing poly-lactic acid material flame-retarded technology, the shortcoming that inorganic combustion inhibitor addition is high, provide that a kind of flame retarding efficiency is high, material mechanical performance obtains Halogen-free flame-retardant polylactic acid nanocomposite better kept and preparation method thereof.
For solving above technical problem, the technical scheme that the present invention takes is: a kind of Halogen-free flame-retardant polylactic acid nanocomposite, can through extrude processing or banburying process, by weight, the composition of raw materials of described Halogen-free flame-retardant polylactic acid nanocomposite comprises: polylactic resin 70 ~ 90 parts, nanometer organic modification montmonrillonite 1 ~ 10 part, 0.01 ~ 1 part, oxidation inhibitor, whiteruss 0.5 ~ 5 part, and all the other are phosphonium flame retardant, its gross weight meets 100%.
In the present invention, described phosphonium flame retardant is one or more in polyphosphoric acid amine, melamine poly-phosphate, pentaerythritol diphosphate or aluminum diethylphosphinate.
In the present invention, described organic modification montmonrillonite is that octadecyltrimethylammonium salt modified montmorillonoid (DK1), 18/hexadecyl double hydroxyethyl methyl ammonium salt modified montmorillonoid (DK2), 18/hexadecyldimethyl benzyl ammonium Benzylmagnesium chloride are by one or more in modified montmorillonoid (DK3), distearyl dimethyl ammonium chloride modified montmorillonoid (DK4) or hexadecyldimethyl benzyl ammonium ammonium chloride polynite (DKIN).
In the present invention, the organic modification montmonrillonite of indication meets following index:
Density=1.8g/cm
3, apparent density <0.35g/cm
3, average wafer thickness <25nm, water capacity <3%.
In the present invention, the intercalator that the organic modification montmonrillonite of indication is selected is that octadecyltrimethylammonium salt, 18/hexadecyl double hydroxyethyl methyl ammonium salt, 18/hexadecyldimethyl benzyl ammonium Benzylmagnesium chloride are by one or more in, distearyl dimethyl ammonium chloride or hexadecyldimethyl benzyl ammonium ammonium chloride.
In the present invention, described oxidation inhibitor is tricresyl phosphite (2,4 one di-tert-butyl-phenyls) ester, phosphorous acid ester three (2,4 one di-tert-butyl phenyl) ester, phosphorous acid benzene two isodecyl ester, three (nonyl is for phenyl) phosphorous acid esters or tricresyl phosphite (nonyl benzene is cruel), pentaerythritol bis-phosphite two (2,4 one di-tert-butyl phenyl) ester, one to multiple kind in the dimer of many alkyl bisphenol A phosphorous acid ester or trimerical mixture.
Halogen-free flame-retardant polylactic acid nanocomposite of the present invention is prepared from by following plastic working method:
First by the drying more than 12 hours in 60 ~ 90 DEG C of baking ovens respectively of polylactic resin, phosphonium flame retardant and nano modification organo montmorillonite, removing moisture, take poly(lactic acid), phosphonium flame retardant, nanometer organic modification montmonrillonite, oxidation inhibitor and whiteruss respectively by composition of raw materials amount again and mix, compound is sent in screw extrusion press or Banbury mixer, melt blending under the processing temperature of 150 ~ 190 DEG C, again through cooling, oven dry, namely obtain described Halogen-free flame-retardant polylactic acid nanocomposite.
The present invention is using organic modification montmonrillonite as fire retarding synergist, itself and phosphonium flame retardant are joined in poly(lactic acid) matrix and forms matrix material, this system can ensure just can reach high flame retarding efficiency when the addition of additive is lower, and matrix material is in use environmentally friendly.Its possible fire retardant mechanism is: phosphonium flame retardant plays fire retardation at condensed phase and gas phase simultaneously on the one hand.Have PO to be formed in the gas phase, it can be caught HO with H in flame region and this kind of high-octane radical conversion is become stable free radical HPO and PO, inhibits free radical chain reactions, thus effectively controls thermolysis; In condensed phase, with O2 effect under high temperature, be heated and progressively resolve into the non-ignitibility viscous liquid film of phosphoric acid, be covered in combustion body surface, isolated air.Meanwhile, phosphoric acid dehydration generates metaphosphoric acid, and metaphosphoric acid polymerization generates vitreous and gathers metaphosphoric acid, can carry out absorbing heat, dewaters, becomes a series of reaction of carbon by catalysis hydroxy-containing compounds.Final phosphorus major part residues in graphite-like coke layer, the combustion of this coke layer difficulty, heat insulation, oxygen barrier, and it is poor to add its heat conductivility, has blocked the further decomposition of bottom.On this basis, then add a small amount of polynite, polylactic acid molecule enters in montmorillonite layer structure, and the laminated structure of silicate prevents heat trnasfer, improves the resistance toheat of poly(lactic acid), effectively can solve the melt drippage problem of poly(lactic acid).Reducing heat release rate further simultaneously, reduce the flaming combustion time, there is good synergistic fire retardation between the two in display.Fire-retardant factor plays a role jointly above, causes poly(lactic acid) formula system of the present invention flame retardant properties while maintenance excellent mechanical performances to be significantly improved.
Due to the enforcement of above technical scheme, the present invention compared with prior art tool has the following advantages:
The organic modification montmonrillonite that the present invention adopts can produce cooperative flame retardant effect with phosphonium flame retardant on the one hand as fire retarding synergist, improve the flame retardant properties of matrix material, nano flame retardant synergist addition on the other hand due to the present invention's employing is few, particle diameter is little and even, therefore can be dispersed in polymeric matrix in material processing, less on the processing characteristics impact of material, lactic acid composite material mechanical property while possessing excellent flame retardant properties also can better be kept.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described in detail, but be not limited to these embodiments.
Embodiment 1
By polylactic resin, ammonium polyphosphate, organic modification montmonrillonite DK1 in 60 DEG C of baking ovens dry 12 hours, to remove moisture.By shared matrix material total mass per-cent by the polylactic resin of 80%, 16% polyphosphoric acid by, octadecyltrimethylammonium salt modified montmorillonoid, the 0.5% oxidation inhibitor tricresyl phosphite (2 of 3%, 4 one di-tert-butyl-phenyls) ester and 0.5% whiteruss (not providing of add-on, should specialize the oxidation inhibitor selected, lower same) mix, 150 ~ 190 DEG C are heated in twin screw extruder, through melt blending, again through extruding, tie rod, cooling, pelletizing and oven dry, obtain the Halogen-free flame-retardant polylactic acid nanocomposite of the present embodiment.The flame retardant properties of this flame-retardant polylactic acid material is: LOI is 29; Tested by UL94V-0 rank.
Embodiment 2
By polylactic resin, ammonium polyphosphate, octadecyltrimethylammonium salt modified montmorillonoid in 60 DEG C of baking ovens dry 12 hours, to remove moisture.By the per-cent of shared matrix material total mass by the polylactic resin of 80%, the ammonium polyphosphate of 15%, octadecyltrimethylammonium salt modified montmorillonoid, the 0.5% oxidation inhibitor tricresyl phosphite (2 of 4%, 4 one di-tert-butyl-phenyls) ester and 0.5% whiteruss mix, 150 ~ 190 DEG C are heated in twin screw extruder, through melt blending, again through extruding, tie rod, cooling, pelletizing and oven dry, obtain the Halogen-free flame-retardant polylactic acid nanocomposite of the present embodiment.The flame retardant properties of this flame-retardant polylactic acid material is: LOI is 31; Tested by UL94V-0 rank.
Embodiment 3
By polylactic resin, ammonium polyphosphate, octadecyltrimethylammonium salt modified montmorillonoid in 60 DEG C of baking ovens dry 12 hours, to remove moisture.By the per-cent of shared matrix material total mass by the polylactic resin of 80%, the ammonium polyphosphate of 18%, octadecyltrimethylammonium salt modified montmorillonoid, the 0.5% oxidation inhibitor tricresyl phosphite (2 of 1%, 4 one di-tert-butyl-phenyls) ester and 0.5% whiteruss mix, 150 ~ 190 DEG C are heated in twin screw extruder, through melt blending, again through extruding, tie rod, cooling, pelletizing and oven dry, obtain the Halogen-free flame-retardant polylactic acid nanocomposite of the present embodiment.The flame retardant properties of this flame-retardant polylactic acid material is: LOI is 30; Tested by UL94V-0 rank.
Embodiment 4
By polylactic resin, aluminum diethylphosphinate, octadecyltrimethylammonium salt modified montmorillonoid in 60 DEG C of baking ovens dry 12 hours, to remove moisture.By the per-cent of shared matrix material total mass by the polylactic resin of 85%, the aluminum diethylphosphinate of 10%, octadecyltrimethylammonium salt modified montmorillonoid, the 0.5% oxidation inhibitor tricresyl phosphite (2 of 4%, 4 one di-tert-butyl-phenyls) ester and 0.5% whiteruss mix, 150 ~ 190 DEG C are heated in twin screw extruder, through melt blending, again through extruding, tie rod, cooling, pelletizing and oven dry, obtain the Halogen-free flame-retardant polylactic acid nanocomposite of the present embodiment.The flame retardant properties of this flame-retardant polylactic acid material is: LOI is 34; Tested by UL94V-0 rank.
Embodiment 5
By polylactic resin, aluminum diethylphosphinate, 18/hexadecyl double hydroxyethyl methyl ammonium salt modified montmorillonoid in 60 DEG C of baking ovens dry 12 hours, to remove moisture.By the per-cent of shared matrix material total mass by the polylactic resin of 85%, the aluminum diethylphosphinate of 11%, 18/hexadecyl double hydroxyethyl methyl ammonium salt modified montmorillonoid, the 0.5% oxidation inhibitor tricresyl phosphite (2 of 3%, 4 one di-tert-butyl-phenyls) ester and 0.5% whiteruss mix, 150 ~ 190 DEG C are heated in twin screw extruder, through melt blending, again through extruding, tie rod, cooling, pelletizing and oven dry, obtain the Halogen-free flame-retardant polylactic acid nanocomposite of the present embodiment.The flame retardant properties of this flame-retardant polylactic acid material is: LOI is 33; Tested by UL94V-0 rank.
Claims (5)
1. a Halogen-free flame-retardant polylactic acid nanocomposite, is characterized in that this flame-retardant polylactic acid material is the blended mixture of polylactic resin, nanometer organic modification montmonrillonite, phosphonium flame retardant, oxidation inhibitor and whiteruss; Wherein: polylactic resin 70 ~ 90 parts, organic modification montmonrillonite 1 ~ 10 part, 0.01 ~ 1 part, oxidation inhibitor, whiteruss 0.5 ~ 5 part, all the other are phosphonium flame retardant, and its gross weight meets 100%.
2. a kind of Halogen-free flame-retardant polylactic acid nanocomposite according to claim 1, is characterized in that: described phosphonium flame retardant is one or more in polyphosphoric acid amine, melamine poly-phosphate, pentaerythritol diphosphate or aluminum diethylphosphinate.
3. a kind of Halogen-free flame-retardant polylactic acid nanocomposite according to claim 1, is characterized in that: described nanometer organic modification montmonrillonite is that octadecyltrimethylammonium salt modified montmorillonoid, 18/hexadecyl double hydroxyethyl methyl ammonium salt modified montmorillonoid, 18/hexadecyldimethyl benzyl ammonium Benzylmagnesium chloride are by one or more in modified montmorillonoid, distearyl dimethyl ammonium chloride modified montmorillonoid (DK4) and the polynite of hexadecyldimethyl benzyl ammonium ammonium chloride.
4. a kind of Halogen-free flame-retardant polylactic acid nanocomposite according to claim 1, it is characterized in that: described oxidation inhibitor is tricresyl phosphite (2,4 one di-tert-butyl-phenyls) ester, phosphorous acid ester three (2,4 one di-tert-butyl phenyl) ester, phosphorous acid benzene two isodecyl ester, three (nonyl is for phenyl) phosphorous acid esters or tricresyl phosphite (nonyl benzene is cruel), pentaerythritol bis-phosphite two (2,4 one di-tert-butyl phenyl) ester, one to multiple kind in the dimer of many alkyl bisphenol A phosphorous acid ester or trimerical mixture.
5. a preparation method for Halogen-free flame-retardant polylactic acid nanocomposite as claimed in claim 1, is characterized in that concrete steps are as follows:
First by the drying more than 12 hours in 60 ~ 90 DEG C of baking ovens respectively of polylactic resin, nanometer organic modification montmonrillonite and phosphonium flame retardant, removing moisture, take polylactic resin, phosphonium flame retardant, nanometer organic modification montmonrillonite, oxidation inhibitor and whiteruss respectively by composition of raw materials amount again and mix, compound is sent in screw extrusion press or Banbury mixer, melt blending under the processing temperature of 150 ~ 190 DEG C, again through cooling, oven dry, namely obtain described Halogen-free flame-retardant polylactic acid nanocomposite.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112759905A (en) * | 2019-11-01 | 2021-05-07 | 南通林格橡塑制品有限公司 | Halogen-free flame-retardant polylactic acid mixture |
| CN113321861A (en) * | 2021-05-20 | 2021-08-31 | 苏州赛荣建筑装饰工程有限公司 | Antifouling flame-retardant high-density resin and preparation method thereof |
| CN117087283A (en) * | 2023-08-21 | 2023-11-21 | 湖北龙辰科技股份有限公司 | Ultrathin polypropylene film and preparation method and application thereof |
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| CN102382433A (en) * | 2011-10-12 | 2012-03-21 | 中国科学院宁波材料技术与工程研究所 | Flame-retardant polylactic acid material |
| CN103374213A (en) * | 2012-04-26 | 2013-10-30 | 苏州达同新材料有限公司 | Preparation method of polylactic acid/montmorillonite nano composite material |
| CN104371291A (en) * | 2014-12-01 | 2015-02-25 | 贵州凯科特材料有限公司 | High-performance halogen-free flame-retardant long fiber reinforced polylactic acid composite material and preparation method thereof |
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2015
- 2015-08-08 CN CN201510483462.8A patent/CN105176032A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102382433A (en) * | 2011-10-12 | 2012-03-21 | 中国科学院宁波材料技术与工程研究所 | Flame-retardant polylactic acid material |
| CN103374213A (en) * | 2012-04-26 | 2013-10-30 | 苏州达同新材料有限公司 | Preparation method of polylactic acid/montmorillonite nano composite material |
| CN104371291A (en) * | 2014-12-01 | 2015-02-25 | 贵州凯科特材料有限公司 | High-performance halogen-free flame-retardant long fiber reinforced polylactic acid composite material and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112759905A (en) * | 2019-11-01 | 2021-05-07 | 南通林格橡塑制品有限公司 | Halogen-free flame-retardant polylactic acid mixture |
| CN112759905B (en) * | 2019-11-01 | 2023-08-08 | 南通林格橡塑制品有限公司 | Halogen-free flame-retardant polylactic acid mixture |
| CN113321861A (en) * | 2021-05-20 | 2021-08-31 | 苏州赛荣建筑装饰工程有限公司 | Antifouling flame-retardant high-density resin and preparation method thereof |
| CN113321861B (en) * | 2021-05-20 | 2023-09-08 | 贵州联创管业有限公司 | Antifouling flame-retardant high-density resin and preparation method thereof |
| CN117087283A (en) * | 2023-08-21 | 2023-11-21 | 湖北龙辰科技股份有限公司 | Ultrathin polypropylene film and preparation method and application thereof |
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