CN106496975A - A kind of polylactic acid/starch intumescent flame-retardant composite and preparation method thereof - Google Patents
A kind of polylactic acid/starch intumescent flame-retardant composite and preparation method thereof Download PDFInfo
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- CN106496975A CN106496975A CN201610864002.4A CN201610864002A CN106496975A CN 106496975 A CN106496975 A CN 106496975A CN 201610864002 A CN201610864002 A CN 201610864002A CN 106496975 A CN106496975 A CN 106496975A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/02—Esters
- C08B31/04—Esters of organic acids, e.g. alkenyl-succinated starch
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- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses polylactic acid/starch intumescent flame-retardant composite of a kind of excellent fireproof performance and preparation method thereof, the composite is comprised the following raw materials by weight percent：Polylactic acid 60～89%；Acid source 5～30%；Modified starch 5～30%；Source of the gas 1～15%.In a preferred approach, modified starch is phosphatization modified by maleic acid anhydride graft starch (i.e. the phosphorous starch of bio-based).In the present invention, polylactic acid has the good compatibility with modified starch, by the mutual synergism of acid source, carbon source (modified starch) and source of the gas between, effectively facilitates the char forming ability of polylactic acid matrix, its high high-temp stability is improved, the fire resistance of polylactic acid is greatly improved.The preparation method of polylactic acid/starch intumescent flame-retardant composite of the present invention, can achieve using existing equipment double screw extruder, prepare simple, it is easy to implement, it is easy to industrialized production.
Description
Technical field
The present invention relates to technical field, and in particular to a kind of polylactic acid/starch intumescent flame-retardant composite and its preparation side
Method.
Background technology
As environmental problem is increasingly serious with oil crisis, people gradually increase to the research of sustainability material, biological
Sill complies fully with growth requirement now as the green material of fully biodegradable, gets the attention.Wherein,
Polylactic acid (PLA) as wherein most potential biological plasticss, with excellent mechanical performance, good processing characteristics,
It is widely used in fields such as auto industry, electric utilities.But its inflammability causes its popularization in these areas
It is extremely restricted.At present, as have the advantages that low toxicity, environmental protection and suppression cigarette, expansion type flame-retarding instead of biography in PLA is fire-retardant
The halide-containing of system is fire-retardant, becomes the fire-retardant developing direction of PLA.But, compared with halogen flame retardant, expansion type flame-retarding efficiency
Low, amount of flame-retardant agent is larger, and with PLA matrix resin poor compatibilities, the serious mechanical performance for reducing composite, especially to material
Tensile strength, impact strength affect very big.Therefore, the boundary of the flame retarding efficiency and improvement and PLA of expanding fire retardant is improved
The face compatibility becomes the key of polylactic acid flame-proof composite material practical application.Wherein, traditional carbon source such as tetramethylolmethane, Sorbitol
Deng, polyhydroxy micromolecular compound is, hygroscopic, easily migrate, with PLA matrix poor compatibilities, the mechanicalness to composite
Can affect especially pronounced.Therefore, being modified or seek new carbon source to carbon source becomes its inexorable trend for developing.
Native starch as a kind of common biological material, in food processing, water process, biological medicine, modifying plastics
It is widely used in field, excellent with wide material sources, cheap, fully biodegradable and good reactable etc.
Point.Particularly there is important application in preparation degradable polymeric material field, the degradability of polymeric material can be significantly improved
Can, improve hot property, improve polymeric material toughness.At present, application report of the native starch in the plastics such as polylactic acid, polypropylene
Road has a lot, but there is obvious defect：First, the heat stability of starch is bad, degradable in process, occurs yellow
Change phenomenon, cause product unsightly；Secondly, the compatibility between starch and matrix plastic is very poor, limits the loading of starch, material
Material poor mechanical properties, it is impossible to meet application request.
The present invention not only has more preferable heat stability using modified starch as carbon source, and higher phosphorus content is more excellent
Different carbon-forming performance, is also significantly improved with the interface compatibility of PLA, improves the mechanical performance of flame-proof composite material, with acid source, gas
The lower content polylactic acid/starch intumescent flame-retardant composite of excellent fireproof performance is prepared for after the interworking of source.
Content of the invention
Present invention aim to address defect of the starch in polymer-filled modification, the invention provides a kind of anti-flammability
The excellent polylactic acid/starch intumescent flame-retardant composite extremely preparation method of energy.
A kind of polylactic acid/starch intumescent flame-retardant composite, comprises the following raw materials by weight percent：
The present invention, polylactic acid have the good compatibility with modified starch, by acid source, carbon source (modified starch) and source of the gas
Between mutual synergism, effectively facilitate the char forming ability of polylactic acid matrix, improve its high high-temp stability, greatly improve poly-
The fire resistance of lactic acid.
Following as the preferred technical solution of the present invention：
Described polylactic acid can adopt the commercially available general trade mark, preferably, described polylactic acid is transparent extrusion grade
Or injection grade, fusing point is 145～170 DEG C, and melt index is 2～30g/10min.More preferably U.S. Natureworks
4032D, relative to the polylactic acid of other trades mark, the 4032D type polylactic acid of Natureworks enables to Compound Material Engineering
Performance is more excellent.
Described acid source is in phosphoric acid, boric acid, sulphuric acid, phosphate ester, polyphosphoric acids, polyphosphate, sulfate etc.
Plant or two or more (including two kinds), be further used as preferably, described acid source is polyphosphoric acids, polyphosphate.More enter
One step is preferably ammonium polyphosphate, and relative to other acid sources, ammonium polyphosphate not only catalysis carbon-forming excellent performance, while can make
Play an important role in expandable flame retardant process for a kind of source of the gas.
In described modified starch, starch is corn starch, wheat and barley starch, sweet potato starch, potato starch, tapioca
One kind in Deng modified starch, preferably maize modified starch, relative to the native starch of other species, corn starch is originated more
Extensively, relative low price.
Described modified starch is maleic anhydride modified starch, phosphate ester starch, hydroxypropyl PASELLI EASYGEL, acetylation
One kind in the modified starches such as starch, propionic andydride modified starch, phosphatization modified by maleic acid anhydride graft starch, further preferably, be
Phosphatization modified by maleic acid anhydride graft starch (the phosphorous starch of bio-based i.e. in the present invention), relative to other modified starches, phosphatization
Modified by maleic acid anhydride graft starch not only has excellent heat stability, and phosphorus content is high, itself has certain fire resistance, Er Qieyu
Matrix has good interface compatibility, has certain promotion to the mechanical performance of composite.
Described source of the gas is nitrogen-containing compound or its modified compound such as urea, tripolycyanamide, carbamide, polyamide, biuret
In one or two kinds of more than (including two kinds), preferred tripolycyanamide, compared to other sources of the gas, tripolycyanamide is thermally-stabilised relative
Well, with excellent gas generated and speed, there is remarkable effect to forming porous carbon layer.
Further preferably, described polylactic acid/starch intumescent flame-retardant composite, by the raw material group of following percetage by weight
Into：
Described acid source is ammonium polyphosphate；
Described modified starch is the phosphorous starch of bio-based；
Described source of the gas is tripolycyanamide.
The present invention, polylactic acid have the good compatibility with modified starch, by acid source, carbon source (modified starch) and source of the gas
Between mutual synergism, effectively facilitate the char forming ability of polylactic acid matrix, improve its high high-temp stability, greatly improve poly-
The fire resistance of lactic acid.
Most preferably, described polylactic acid/starch intumescent flame-retardant composite, is made up of the raw material of following percetage by weight：
Described acid source is ammonium polyphosphate；
Described modified starch is the phosphorous starch of bio-based；
Described source of the gas is tripolycyanamide.
The polylactic acid/starch intumescent flame-retardant composite has very excellent fire resistance, and maintains good power
Learn performance.
A kind of preparation method of polylactic acid/starch intumescent flame-retardant composite, comprises the following steps：
After polylactic acid, modified starch, acid source, source of the gas are dried, mix homogeneously is added in double screw extruder, through melting
Extrusion, cooling, after pelletize, obtain polylactic acid/starch intumescent flame-retardant composite.
Preferably, polylactic acid and modified starch baking temperature are 105 DEG C, the baking temperature of acid source and source of the gas is 85 DEG C,
Drying time is 8h.
Preferably, in described double screw extruder, the draw ratio of screw rod is 35:1～45:1, the temperature of melting extrusion
For 170～190 DEG C.
Phosphorous starch of a kind of bio-based and its preparation method and application, the phosphorous starch of the bio-based are high thermal stability, excellent
The hydrophobized starch of out-phase capacitive.
The technical scheme for solving the above problems is：With native starch, DOPO, MA as raw material, two step under inert gas shielding
Method is prepared for phosphorous starch, significantly improves the heat stability of starch, while improving the interface compatibility of starch and matrix resin.
Its reaction equation is as follows：
A kind of preparation method of the phosphorous starch of bio-based, comprises the following steps：
1) will be organic with first to miscellaneous for 9,10- dihydro-9-oxies -10- phospho hetero phenanthrenes -10- oxides (DOPO), maleic anhydride (MA)
Solvent mixes, and back flow reaction 12h～36h reactions under 40 DEG C～100 DEG C and protective gas, vacuum distillation are dried, obtain product
1；
2) starch, catalyst and the second organic solvent are mixed, heat-activated 2h under 60 DEG C～120 DEG C and protective gas
～24h, obtains activated Starch solution；
3) product 1 is added in the activated Starch solution after cooling, is continued under 30 DEG C～90 DEG C and protective gas anti-
12h～64h is answered, is washed, dried, obtain the phosphorous starch of bio-based.
Following as the preferred technical solution of the present invention：
Step 1) in, back flow reaction 12h～36h reactions under 40 DEG C～80 DEG C and protective gas.
Miscellaneous -10- phospho hetero phenanthrenes -10- the oxides (DOPO) of described 9,10- dihydro-9-oxies and the quality of maleic anhydride (MA)
Than=1:0.5～1.5, more preferably 1:0.9～1.25.
The first described organic solvent is preferably at least one in toluene, dimethylbenzene, tetrahydrofuran, dioxane, enters
It is 2～5 that one step is preferably the volume ratio of the mixed solvent of dimethylbenzene and tetrahydrofuran, dimethylbenzene and tetrahydrofuran：1.
Step 2) in, heat-activated 2h～24h under 65 DEG C～95 DEG C and protective gas.
Described starch be sweet potato starch, corn starch, potato starch, wheaten starch, the one kind in soybean starch or
Two or more (including two kinds).
Described catalyst is pyridine, PA, 4-aminopyridine, 2- dimethyl aminopyridines, 4- dimethylaminos
More than the one or two kinds of in yl pyridines, ethylenediamine, aniline, triethylamine, ethanolamine.The catalyst also serves as activator, enters
One step is preferably PA, 4-aminopyridine, 2- dimethyl aminopyridines, 4-dimethylaminopyridine, compared to other
Activator, used as activator, its activation efficiency is higher for aminopyridine, dimethylaminopyridine class compound.
The second described organic solvent be water, methanol, ethanol, acetone, tetrahydrofuran, dimethyl sulfoxide, N, N- dimethyl
One or more (including two kinds) in Methanamide, DMAC N,N' dimethyl acetamide.Further preferably, described second is organic
Solvent is preferably dimethyl sulfoxide, DMF, the one kind in N,N-dimethylacetamide, still more preferably for
Dimethyl sulfoxide.
Step 3) in, continue reaction 12h～64h under 50 DEG C～75 DEG C and protective gas.
Step 3) in the product 1 that adds and step 2) mass ratio=1.0～2.5 of starch that adopt：1, further preferably
For 1.0～2.25：1, each material is weighed by above-mentioned mass ratio, obtain the phosphorous starch of final product.
Step 1), 2) and 3) in, described protective gas is noble gases or nitrogen.
The phosphorous starch of bio-based of the present invention, with high percent grafting and high content of phosphorus, the warm of the phosphorous starch of the bio-based for obtaining
Stability and it is significantly increased with matrix resin interface compatibility, application request can be met.
The phosphorous starch of described bio-based can be used to prepare PLA/Starch Blends, with polylactic acid based resin circle
Preferably, heat stability also improves a lot for the face compatibility.Described PLA/Starch Blends are by mass ratio 75～85：
15～25 polylactic acid and the phosphorous starch composition of bio-based.Further preferably, described PLA/Starch Blends are by quality
Than 80：20 polylactic acid and the phosphorous starch composition of bio-based.
Compared with prior art, the invention has the advantages that：
The present invention has obtained the phosphorous starch of bio-based of environmental protection, through 1HNMR with native starch, DOPO, MA as raw material
The checking synthesis such as (proton nmr spectra), FT-IR (fourier transform infrared spectroscopy), XPS (X-ray photoelectron spectroscopic analysis)
Phosphorous starch through having high percent grafting and high content of phosphorus, prove through TGA (thermogravimetric analysiss), SEM (scanning electron microscope) etc.
The phosphorous starch heat stability that obtains and it is significantly increased with matrix resin interface compatibility, application request can be met.This
With the starch of cheap, wide material sources as raw material, each step reaction side reaction is few, yield is high, has prepared bio-based for invention
The phosphorus content of phosphorous starch is high, and heat stability is good, and carbon-forming performance is excellent, can be used as the carbon in a kind of excellent Intumescent Retardant System
Source component, the functionalized application for starch provide an effective way.
The present invention not only solves its heat stability difference and adds by the use of phosphorous modified by maleic acid anhydride graft starch as carbon source
Work degradation-labile defect, while giving carbon source high phosphorus content, reduces fire retardant addition, to the fire resistance of composite and
The mechanical property effect of improving a lot.
Polylactic acid/starch intumescent flame-retardant composite of the present invention, by acid source, carbon source (modified starch) and source of the gas between
Mutually synergism, effectively facilitates the char forming ability of polylactic acid matrix, improves its high high-temp stability, greatly improve polylactic acid
Fire resistance.Due to applying the Hydrophobic Modified Starch of new green environment protection as carbon source in the present invention, resistance can not only be effectively improved
The flame retarding efficiency of combustion agent, simultaneously because the modification on starch surface can significantly improve the interface compatibility of fire retardant and polylactic acid, right
The mechanical performance of polylactic acid flame-proof composite material has very big facilitation.Present invention achieves the resistance of the polylactic acid under few additive
Combustion, have very big protective effect to the mechanical property of polylactic acid, to polylactic acid the fields such as electronic device, automobile case application
Effect is remarkably promoted.
The preparation method of polylactic acid/starch intumescent flame-retardant composite of the present invention, using existing equipment double screw extruder
Can achieve, prepare simple, it is easy to implement, it is easy to industrialized production.
Description of the drawings
Fig. 1 is the infrared spectrum of phosphorous starch prepared by embodiment 1；
Fig. 2 is the thermogravimetric analysis figure of phosphorous starch prepared by common starch and embodiment 1；
In Fig. 3, (a) is mass ratio 80：The section SEM figures of 20 PLA/ starch composite materials, in Fig. 3, (b) is mass ratio
80：The section SEM figures of phosphorous starch composite material prepared by 20 PLA/ embodiments 1.
Specific embodiment
With reference to specific embodiment, the invention will be further described.
Embodiment 1：
In 250mL three-necked bottles, 20g 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxides (DOPO) and 15g horses
Carry out anhydride (MA) to be dissolved in 50mL toluene and 20mL dioxane respectively, be heated to 40 DEG C, nitrogen is protected, back flow reaction 12h.
After reaction terminates, rotary evaporation removes solvent, obtains product 1 after vacuum drying, standby.
In 250mL three-necked bottles, 20g starch (corn starch) and 40mL pyridines are heated to 65 DEG C, under nitrogen protection, return
Stream 2h.After temperature is down to 50 DEG C, 20g products 1 (being dissolved in DMSO) add catalyst DMAP, nitrogen to protect,
50 DEG C of back flow reaction 12h.After reaction terminates, through washing purification, vacuum drying obtains the phosphorous starch of bio-based, i.e., modified shallow lake
Powder.
Embodiment 2：
In 250mL three-necked bottles, 20g DOPO and 18g maleic anhydrides (MA) is dissolved in 50mL dimethylbenzene and 20mL respectively
In THF (tetrahydrofuran), 50 DEG C are heated to, nitrogen is protected, back flow reaction 24h.After reaction terminates, rotary evaporation removes solvent,
Product 1 is obtained after vacuum drying, standby.
In 250mL three-necked bottles, 20g starch (corn starch) and 60mL pyridines are heated to 75 DEG C, under nitrogen protection, return
Stream 4h.After temperature is down to 50 DEG C, 25g products 1 (being dissolved in DMSO) add catalyst DMAP, nitrogen to protect,
Back flow reaction 24h.After reaction terminates, through washing purification, vacuum drying obtains the phosphorous starch of bio-based, i.e. modified starch.
Embodiment 3：
In 250mL three-necked bottles, 20g DOPO and 21g maleic anhydrides (MA) is dissolved in 70mL dimethylbenzene, is heated to 60
DEG C, nitrogen is protected, back flow reaction 24h.After reaction terminates, rotary evaporation removes solvent, obtains product 1 after vacuum drying, standby.
In 250mL three-necked bottles, 20g starch (corn starch) and 80mL pyridines are heated to 85 DEG C, under nitrogen protection, return
Stream 8h.After temperature is down to 65 DEG C, 35g products 1 (being dissolved in DMSO) add catalyst DMAP, nitrogen to protect,
Back flow reaction 24h.After reaction terminates, through washing purification, vacuum drying obtains the phosphorous starch of bio-based, i.e. modified starch.
Embodiment 4：
In 250mL three-necked bottles, 20g DOPO and 25g maleic anhydrides (MA) is dissolved in 50mL dimethylbenzene and 20mL respectively
In THF (tetrahydrofuran), 70 DEG C are heated to, nitrogen is protected, back flow reaction 36h.After reaction terminates, rotary evaporation removes solvent,
Product 1 is obtained after vacuum drying, standby.
In 250mL three-necked bottles, 20g starch (corn starch) and 100mL pyridines are heated to 85 DEG C, under nitrogen protection, return
Stream 16h.After temperature is down to 75 DEG C, 40g products 1 (being dissolved in DMSO) add proper catalyst DMAP, nitrogen
Protection, back flow reaction 36h.After reaction terminates, through washing purification, vacuum drying obtains the phosphorous starch of bio-based, i.e., modified shallow lake
Powder.
Embodiment 5：
In 250mL three-necked bottles, 20g DOPO and 25g maleic anhydrides (MA) is dissolved in 70mLTHF (tetrahydrofuran) respectively
In, 80 DEG C are heated to, nitrogen is protected, back flow reaction 36h.After reaction terminates, rotary evaporation removes solvent, obtains after vacuum drying
Product 1, standby.
In 250mL three-necked bottles, 20g starch (corn starch) and 100mL pyridines are heated to 95 DEG C, under nitrogen protection, return
Stream 24h.After temperature is down to 75 DEG C, 45g products 1 (being dissolved in DMSO) add proper catalyst DMAP, nitrogen
Protection, back flow reaction 64h.After reaction terminates, through washing purification, vacuum drying obtains the phosphorous starch of bio-based, i.e., modified shallow lake
Powder.
As shown in figure 1, Fig. 1 mid-infrareds spectrogram effectively proves the successful preparation of phosphorous starch, phosphorous starch in spectrogram
(DOPOMASt) several groups of new peaks are substantially occurred in that compared to pure starch (pure starch), respectively：1731cm-1, 1624cm-1
And 1202cm-1、1024cm-1、930cm-1, the appearance of these characteristic peaks effectively can prove the phosphatization of starch modified into
Work(, DOPOMA are product 1.
Table 1 is starch and phosphorous starch data display under nitrogen atmosphere.Number under the nitrogen atmosphere of Fig. 2 and Biao 1
According to display, the phosphorous starch initial decomposition temperature of synthesis is improved to 266 DEG C, and heat stability is greatly improved；And maximum decomposition temperature
About 20 DEG C have dropped on the contrary, and final remaining carbon is significantly improved to 33.8%.It is based entirely on bio-based materials, the phosphorous starch of synthesis
This characteristic meet very much requirement in expanding fire retardant to carbon source, before there is wide application in polymer expandable flame retardant
Scape.
Table 1
| T5%(℃) | T10%(℃) | TMax(℃) | Remaining carbon (%) | |
| Starch virgin starch | 237 | 284 | 323 | 16.0 |
| Phosphorous starch DOPOMASt | 266 | 275 | 288 | 33.8 |
Fig. 3 is schemed for the section SEM of PLA/Starch Blends, and wherein, in Fig. 3, (a) is mass ratio 80：20 PLA/
The section SEM figures of starch composite material, in Fig. 3, (b) is mass ratio 80：The section SEM of the 20 phosphorous starch composite materials of PLA/
Figure.Can be apparent from from figure, compared to the interface mistake of pure starch and polylactic acid, modified phosphorous starch and polylactic acid
The compatibility is greatly improved, and the synthetic method effect is significant of described phosphorous starch is described.
Embodiment 6
Weigh the raw material of following weight：
Polylactic acid (U.S. Natureworks 4032D) 79Kg, modified starch 10Kg prepared by embodiment 1, polyphosphoric acids
Ammonium 10Kg, tripolycyanamide 1Kg；
The preparation method of polylactic acid/starch intumescent flame-retardant composite：
Polylactic acid, the modified starch of the preparation of embodiment 1 and ammonium polyphosphate, tripolycyanamide are respectively at 105 DEG C and 85 DEG C
Lower drying, is 8h drying time.After mixing in high speed blender, melt blending (screw rod in adding to double screw extruder
Temperature is 170～190 DEG C), polylactic acid/starch intumescent flame-retardant composite is obtained after cooling, pelletize.From twin screw squeeze
The screw slenderness ratio for going out machine is 40:1.
Embodiment 7
Weigh the raw material of following weight：
Polylactic acid (U.S. Natureworks 4032D) 79Kg, modified starch 15Kg prepared by embodiment 1, polyphosphoric acids
Ammonium 5Kg, tripolycyanamide 1Kg；
Preparation method is as described in Example 1.
Embodiment 8
Weigh the raw material of following weight：
Polylactic acid (U.S. Natureworks 4032D) 89Kg, modified starch 5Kg prepared by embodiment 1, ammonium polyphosphate
5Kg, tripolycyanamide 1Kg；
Preparation method is as described in Example 1.
Embodiment 9
Weigh the raw material of following weight：
Polylactic acid (U.S. Natureworks 4032D) 85Kg, modified starch 5Kg prepared by embodiment 1, ammonium polyphosphate
5Kg, tripolycyanamide 5Kg；
Preparation method is as described in Example 1.
Comparative example 1
Weigh the raw material of following weight：
Polylactic acid (U.S. Natureworks 4032D) 80Kg, modified starch 20Kg prepared by embodiment 1；
Preparation method is as described in Example 1.
Comparative example 2
Weigh the raw material of following weight：
Polylactic acid (U.S. Natureworks 4032D) 80Kg, ammonium polyphosphate 20Kg；
Preparation method is as described in Example 1.
Comparative example 3
Weigh the raw material of following weight：
Polylactic acid (U.S. Natureworks 4032D) 80Kg, corn starch 20Kg；
Preparation method is as described in Example 1.
The polylactic acid/starch intumescent flame-retardant composite injection mo(u)lding that embodiment 6～9 and comparative example 1～3 are obtained is mark
Quasi- vertical combustion (UL-94) batten, limited oxygen index (LOI) batten and bending batten, wherein, injection temperature is 175～185
DEG C, injection pressure is 70～90MPa, and dwell pressure is 45MPa.According to ASTM D3801, ASTM D 2863-97 and GB/T
1040.1-2006 carries out combustibility, bending property test, and as shown in table 2, NC represents nonrated to its test result.
Table 2
As shown in Table 1, by embodiment 6～9 compared with comparative example 1～3, modified starch, ammonium polyphosphate and melamine
Amine, the fire resistance of lactic acid composite material are significantly improved, and vertical combustion grade reaches V0 grades, and oxygen index (OI) also has and significantly carries
High.Further, since modified starch phosphorus content is high, surface-hydrophobicized degree is big, not only realizes the relatively low fire retardant addition of polylactic acid
Under fire-retardant, additionally it is possible to significantly improve the interface compatibility between fire retardant and polylactic acid, greatly improve the machinery of composite
Performance, to realizing that application of the polylactic acid in fields such as auto industry, electronic devices plays an important role.
Claims (10)
1. a kind of polylactic acid/starch intumescent flame-retardant composite, it is characterised in that comprise the following raw materials by weight percent：
2. polylactic acid/starch intumescent flame-retardant composite according to claim 1, it is characterised in that described acid source is
More than the one or two kinds of in phosphoric acid, boric acid, sulphuric acid, phosphate ester, polyphosphoric acids, polyphosphate, sulfate.
3. polylactic acid/starch intumescent flame-retardant composite according to claim 1, it is characterised in that described modified shallow lake
In powder, starch is corn starch, wheat and barley starch, sweet potato starch, potato starch, the one kind in tapioca；
Described modified starch is maleic anhydride modified starch, phosphate ester starch, hydroxypropyl PASELLI EASYGEL, acetylation shallow lake
One kind in powder, propionic andydride modified starch, phosphatization modified by maleic acid anhydride graft starch.
4. polylactic acid/starch intumescent flame-retardant composite according to claim 1, it is characterised in that described source of the gas is
More than the one or two kinds of in urea, tripolycyanamide, carbamide, polyamide, biuret.It is preferred that tripolycyanamide.
5. polylactic acid/starch intumescent flame-retardant composite according to claim 1, it is characterised in that described polylactic acid/
Starch intumescent flame-retardant composite, is made up of the raw material of following percetage by weight：
Described acid source is ammonium polyphosphate；
Described modified starch is the phosphorous starch of bio-based；
Described source of the gas is tripolycyanamide.
6. the preparation method of the polylactic acid/starch intumescent flame-retardant composite according to any one of Claims 1 to 5, its are special
Levy and be, comprise the following steps：
Polylactic acid, modified starch, acid source, source of the gas dry after, mix homogeneously is added in double screw extruder, through melting extrusion,
After cooling, pelletize, polylactic acid/starch intumescent flame-retardant composite is obtained.
7. preparation method according to claim 6, it is characterised in that in described double screw extruder, the major diameter of screw rod
Than for 35:1～45:1, the temperature of melting extrusion is 170～190 DEG C.
8. preparation method according to claim 6, it is characterised in that described modified starch is the phosphorous starch of bio-based,
The preparation method of the phosphorous starch of described bio-based, comprises the following steps：
1) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, maleic anhydride are mixed with the first organic solvent, 40
DEG C～100 DEG C and protective gas under back flow reaction 12h～36h reactions, vacuum distillation dries, obtains product 1；
2) starch, catalyst and the second organic solvent are mixed, under 60 DEG C～120 DEG C and protective gas heat-activated 2h～
24h, obtains activated Starch solution；
3) product 1 is added in the activated Starch solution after cooling, continues reaction 12h under 30 DEG C～90 DEG C and protective gas
～64h, washing are dried, are obtained the phosphorous starch of bio-based.
9. preparation method according to claim 7, it is characterised in that step 1) in, described 9,10- dihydro-9-oxies are miscellaneous-
10- phospho hetero phenanthrene -10- oxides and mass ratio=1 of maleic anhydride:0.5～1.5；
Step 3) in the product 1 that adds and step 2) mass ratio=1.0～2.5 of starch that adopt：1.
10. preparation method according to claim 7, it is characterised in that step 1) in, the first described organic solvent is first
At least one in benzene, dimethylbenzene, tetrahydrofuran, dioxane；
Step 2) in, described starch be sweet potato starch, corn starch, potato starch, wheaten starch, in soybean starch one
Plant or two or more；
Step 2) in, described catalyst is pyridine, PA, 4-aminopyridine, 2- dimethyl aminopyridines, 4- diformazans
More than the one or two kinds of in base aminopyridine, ethylenediamine, aniline, triethylamine, ethanolamine；
Step 2) in, described the second organic solvent is water, methanol, ethanol, acetone, tetrahydrofuran, dimethyl sulfoxide, N, N- bis-
One or more in methylformamide, DMAC N,N' dimethyl acetamide.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109315861A (en) * | 2018-11-23 | 2019-02-12 | 福泉市筑梦服装有限公司 | A kind of flame-retardant garment plus material and preparation method thereof |
| CN109627452A (en) * | 2018-12-12 | 2019-04-16 | 怀化学院 | For the fire retardant of poly butylene succinate, flame retardant polybutylene succinate material and preparation method thereof |
| CN109627453A (en) * | 2018-12-12 | 2019-04-16 | 怀化学院 | For the fire retardant of polylactic acid, flame-retardant polylactic acid material and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014060004A1 (en) * | 2012-10-16 | 2014-04-24 | Wolfgang Wehner | Method for producing metal-2-hydroxydiphenyl-2'-(thio)phosphinates and metal-diphenylene-(thio)phosphonates, compositions containing same and use thereof as flame-proofing agents |
| CN103772926A (en) * | 2013-12-18 | 2014-05-07 | 江苏悦达新材料科技有限公司 | High-performance flame-retardant PLA (polylactic acid)/graphene nano-sheet composite material and preparation method thereof |
| CN104744900A (en) * | 2015-03-27 | 2015-07-01 | 武汉理工大学 | Flame-retardant butylene succinate/starch composite material and preparation method thereof |
| CN105885660A (en) * | 2016-05-30 | 2016-08-24 | 福建盈浩工艺制品有限公司 | Flame-retardant environment-friendly paint and preparation method thereof |
-
2016
- 2016-09-29 CN CN201610864002.4A patent/CN106496975B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014060004A1 (en) * | 2012-10-16 | 2014-04-24 | Wolfgang Wehner | Method for producing metal-2-hydroxydiphenyl-2'-(thio)phosphinates and metal-diphenylene-(thio)phosphonates, compositions containing same and use thereof as flame-proofing agents |
| CN103772926A (en) * | 2013-12-18 | 2014-05-07 | 江苏悦达新材料科技有限公司 | High-performance flame-retardant PLA (polylactic acid)/graphene nano-sheet composite material and preparation method thereof |
| CN104744900A (en) * | 2015-03-27 | 2015-07-01 | 武汉理工大学 | Flame-retardant butylene succinate/starch composite material and preparation method thereof |
| CN105885660A (en) * | 2016-05-30 | 2016-08-24 | 福建盈浩工艺制品有限公司 | Flame-retardant environment-friendly paint and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 谭登峰: "木薯淀粉反应共混改性及马来酸淀粉酯/聚乳酸复合材料的研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN109627452B (en) * | 2018-12-12 | 2021-05-04 | 怀化学院 | Flame retardant for poly (butylene succinate), flame-retardant poly (butylene succinate) material and preparation method thereof |
| CN109627452A (en) * | 2018-12-12 | 2019-04-16 | 怀化学院 | For the fire retardant of poly butylene succinate, flame retardant polybutylene succinate material and preparation method thereof |
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