CN106496975B - 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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Abstract
The invention discloses polylactic acid/starch intumescent flame-retardant composites of a kind of excellent fireproof performance and preparation method thereof, which comprises the following raw materials by weight percent: polylactic acid 60~89%；Acid source 5~30%；Modified starch 5~30%；Gas source 1~15%.In a preferred approach, modified starch is phosphatization modified by maleic acid anhydride graft starch (i.e. the phosphorous starch of biology base).In the present invention, there is good compatibility to effectively facilitate the char forming ability of polylactic acid matrix by the mutual synergistic effect between acid source, carbon source (modified starch) and gas source for polylactic acid and modified starch, its high high-temp stability is improved, the flame retardant property of polylactic acid is greatly improved.The preparation method of polylactic acid/starch intumescent flame-retardant composite of the present invention, can be realized using existing equipment double screw extruder, and preparation is simple, easy to implement, easy to industrialized production.
Description
Technical field
The present invention relates to technical fields, and in particular to a kind of polylactic acid/starch intumescent flame-retardant composite and its preparation side
Method.
Background technique
As environmental problem is increasingly serious with oil crisis, people gradually increase the research of sustainability material, biology
Sill complies fully with growth requirement now as the green material of fully biodegradable, gets the attention.Wherein,
Polylactic acid (PLA) has an excellent mechanical performance as wherein most potential biological plastics, good processing performance,
It is widely used in fields such as auto industry, electric utilities.But its inflammability leads to its popularization in these areas
It is extremely restricted.Currently, expansion type flame-retarding is in PLA is fire-retardant instead of biography due to having many advantages, such as low toxicity, environmental protection and suppression cigarette
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, with PLA matrix resin poor compatibility, the serious mechanical performance for reducing composite material, especially to material
Tensile strength, impact strength influence it is very big.Therefore, it improves the flame retarding efficiency of expanding fire retardant and improves the boundary with PLA
Face compatibility becomes the key of polylactic acid flame retardant composite material practical application.Wherein, traditional carbon source such as pentaerythrite, sorbierite
Deng, it is polyhydroxy small molecule compound, hygroscopic, easy to migrate, and PLA matrix poor compatibility, to the mechanicalness of composite material
It can influence especially pronounced.Therefore, being modified to carbon source or seeking novel carbon source becomes the inexorable trend of its development.
Native starch is as a kind of common biological material, in food processing, water process, biological medicine, modifying plastics
Equal fields are widely used, and have from a wealth of sources, cheap, fully biodegradable and good reactable etc. excellent
Point.Especially there is important application in preparation degradable polymeric material field, the degradability of polymer material can be significantly improved
Can, improve hot property, improves polymer material toughness.Currently, application report of the native starch in the plastics such as polylactic acid, polypropylene
Road has very much, but there are apparent defects: firstly, the thermal stability of starch is bad, it is degradable in process, occur yellow
Change phenomenon, leads to product unsightly；Secondly, the compatibility between starch and matrix plastic is very poor, the loading of starch, material are limited
Expect poor mechanical properties, is unable to satisfy application request.
The present invention, as carbon source, not only has better thermal stability using modified starch, and higher phosphorus content is more excellent
Different carbon-forming performance also significantly improves with the interface compatibility of PLA, improves the mechanical performance of flame retardant 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.
Summary of the invention
It is the defects of modified in polymer-filled that present invention aim to address starch, and the present invention provides a kind of anti-flammabilitys
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 and modified starch have good compatibility, pass through acid source, carbon source (modified starch) and gas source
Between mutual synergistic effect, effectively facilitate the char forming ability of polylactic acid matrix, improve its high high-temp stability, greatly improve poly-
The flame retardant property of lactic acid.
It is used as the preferred technical solution of the present invention below:
The polylactic acid can use the commercially available general trade mark, preferably, the polylactic acid is transparent extrusion grade
Or injection grade, fusing point are 145~170 DEG C, melt index is 2~30g/10min.Further 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.
The acid source is one in phosphoric acid, boric acid, sulfuric acid, phosphate, polyphosphoric acids, polyphosphate, sulfate etc.
Kind is two or more (including two kinds), is further used as preferably, and the acid source is polyphosphoric acids, polyphosphate.More into
One step is preferably ammonium polyphosphate, and relative to other acid sources, not only catalysis carbon-forming is had excellent performance ammonium polyphosphate, while can be made
It plays an important role for a kind of gas source in expandable flame retardant process.
Starch is cornstarch, wheat starch, starch from sweet potato, potato starch, tapioca in the modified starch
One of equal modified starches, preferably maize modified starch, relative to the native starch of other types, cornstarch source is more
Extensively, relative low price.
The modified starch is maleic anhydride modified starch, phosphate ester starch, hydroxypropyl PASELLI EASYGEL, acetylation
One of modified starches such as starch, propionic andydride modified starch, phosphatization modified by maleic acid anhydride graft starch further preferably, are
Phosphatization modified by maleic acid anhydride graft starch (the phosphorous starch of biology base i.e. in the present invention), relative to other modified starches, phosphatization
Modified by maleic acid anhydride graft starch not only has excellent thermal stability, and phosphorus content is high, itself there is certain flame retardant property, Er Qieyu
Matrix has good interface compatibility, has certain promotion to the mechanical performance of composite material.
The gas source is nitrogenous compounds or its modified compound such as urea, melamine, urea, polyamide, biuret
One of or two or more (including two kinds), preferred melamine, compared to other gas sources, melamine thermostabilization is opposite
Well, there is excellent gas generated and rate, have remarkable effect to porous carbon layer is formed.
Further preferably, the polylactic acid/starch intumescent flame-retardant composite, by the raw material group of following weight percent
At:
The acid source is ammonium polyphosphate；
The modified starch is the phosphorous starch of biology base；
The gas source is melamine.
The present invention, polylactic acid and modified starch have good compatibility, pass through acid source, carbon source (modified starch) and gas source
Between mutual synergistic effect, effectively facilitate the char forming ability of polylactic acid matrix, improve its high high-temp stability, greatly improve poly-
The flame retardant property of lactic acid.
Most preferably, the polylactic acid/starch intumescent flame-retardant composite, is made of the raw material of following weight percent:
The acid source is ammonium polyphosphate；
The modified starch is the phosphorous starch of biology base；
The gas source is melamine.
The polylactic acid/starch intumescent flame-retardant composite has very excellent flame retardant property, and maintains good power
Learn performance.
A kind of preparation method of polylactic acid/starch intumescent flame-retardant composite, comprising the following steps:
After polylactic acid, modified starch, acid source, gas source are dry, it is uniformly mixed, is added in double screw extruder, through melting
After squeezing out, is cooling, being granulated, polylactic acid/starch intumescent flame-retardant composite is obtained.
Preferably, polylactic acid and modified starch drying temperature are 105 DEG C, the drying temperature of acid source and gas source is 85 DEG C,
Drying time is 8h.
Preferably, the draw ratio of screw rod is 35:1~45:1, the temperature of melting extrusion in the double screw extruder
It is 170~190 DEG C.
A kind of phosphorous starch of biology base and its preparation method and application, the phosphorous starch of the biology base is high thermal stability, excellent
The hydrophobized starch of out-phase capacitive.
The technical solution to solve the above problems is: using native starch, DOPO, MA as raw material, two step under inert gas shielding
Method is prepared for phosphorous starch, significantly improves the thermal 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 biology base, comprising the following steps:
1) miscellaneous -10- phospho hetero phenanthrene -10- oxide (DOPO) of 9,10- dihydro-9-oxy, maleic anhydride (MA) and first is organic
Solvent mixing, back flow reaction 12h~36h reacts under 40 DEG C~100 DEG C and protective gas, is evaporated under reduced pressure, dry, obtains product
1；
2) starch, catalyst and the second organic solvent are mixed, the heat-activated 2h under 60 DEG C~120 DEG C and protective gas
~for 24 hours, obtain activated Starch solution；
3) product 1 is added in activated Starch solution after cooling, is continued under 30 DEG C~90 DEG C and protective gas anti-
12h~64h is answered, is washed, it is dry, obtain the phosphorous starch of biology base.
It is used as the preferred technical solution of the present invention below:
In step 1), back flow reaction 12h~36h reacts under 40 DEG C~80 DEG C and protective gas.
The quality of the 9,10- dihydro-9-oxy miscellaneous -10- phospho hetero phenanthrene -10- oxide (DOPO) and maleic anhydride (MA)
Than=1:0.5~1.5, further preferably 1:0.9~1.25.
First organic solvent is preferably at least one of toluene, dimethylbenzene, tetrahydrofuran, dioxane, into
One step is preferably the mixed solvent of dimethylbenzene and tetrahydrofuran, and the volume ratio of dimethylbenzene and tetrahydrofuran is 2~5:1.
In step 2), the heat-activated 2h~for 24 hours under 65 DEG C~95 DEG C and protective gas.
The starch be one of sweet potato starch, cornstarch, potato starch, wheaten starch, soybean starch or
Two or more (including two kinds).
The catalyst is pyridine, 2-aminopyridine, 4-aminopyridine, 2- dimethyl aminopyridine, 4- dimethylamino
One of yl pyridines, ethylenediamine, aniline, triethylamine, ethanol amine are two or more.The catalyst is also used as activator, into
One step is preferably 2-aminopyridine, 4-aminopyridine, 2- dimethyl aminopyridine, 4-dimethylaminopyridine, compared to other
Activator, as activator, activation efficiency is higher for aminopyridine, dimethylaminopyridine class compound.
Second organic solvent is water, methanol, ethyl alcohol, acetone, tetrahydrofuran, dimethyl sulfoxide, N, N- dimethyl
One or more of formamide, DMAC N,N' dimethyl acetamide (including two kinds).Further preferably, described second is organic
Solvent is preferably one of dimethyl sulfoxide, n,N-Dimethylformamide, n,N-dimethylacetamide, still more preferably for
Dimethyl sulfoxide.
In step 3), the reaction was continued under 50 DEG C~75 DEG C and protective gas 12h~64h.
Mass ratio=1.0~the 2.5:1 for the starch that the product 1 and step 2) being added in step 3) use, further preferably
For 1.0~2.25:1, each substance is weighed by above-mentioned mass ratio, obtains the phosphorous starch of final product.
Step 1), 2) and 3) in, the protective gas is inert gas or nitrogen.
The phosphorous starch of biology base of the present invention has high grafting rate and high content of phosphorus, the heat of the phosphorous starch of obtained biology base
It stability and is significantly increased with matrix resin interface compatibility, is able to satisfy application request.
The phosphorous starch of the biology base can be used for preparing PLA/Starch Blends, with polylactic acid based resin circle
Face compatibility is preferable, and thermal stability also improves a lot.The PLA/Starch Blends are by mass ratio 75~85:
The phosphorous starch composition of 15~25 polylactic acid and biology base.Further preferably, the PLA/Starch Blends are by quality
Starch composition more phosphorous than the polylactic acid of 80:20 and biology base.
Compared with prior art, the present invention has the advantage that
The present invention has obtained the phosphorous starch of environmentally protective biology base, through 1HNMR using native starch, DOPO, MA as raw material
The verifyings such as (nuclear magnetic resonance spectroscopy), FT-IR (fourier transform infrared spectroscopy), XPS (X-ray photoelectron spectroscopic analysis) synthesis
Phosphorous starch pass through have high grafting rate and high content of phosphorus, through TGA (thermogravimetric analysis), SEM (scanning electron microscope) etc. prove
It obtained phosphorous starch thermal stability and is significantly increased with matrix resin interface compatibility, is able to satisfy application request.This
Invention is using starch cheap, from a wealth of sources as raw material, and each step reaction side reaction is few, yield is high, and biology base has been prepared
The phosphorus content of phosphorous starch is high, and thermal stability is good, and carbon-forming performance is excellent, can be as the carbon in a kind of excellent Intumescent Retardant System
Source component provides an effective way for the functionalized application of starch.
The present invention not only solves its thermal stability difference and adds using phosphorous modified by maleic acid anhydride graft starch as carbon source
Work degradation-labile defect, while assigning carbon source high phosphorus content reduces fire retardant additive amount, flame retardant property to composite material and
The mechanical property effect of improving a lot.
Polylactic acid/starch intumescent flame-retardant composite of the present invention, by between acid source, carbon source (modified starch) and gas source
Mutually synergistic effect, effectively facilitates the char forming ability of polylactic acid matrix, improves its high high-temp stability, greatly improve polylactic acid
Flame retardant property.Since the Hydrophobic Modified Starch of application new green environment protection is as carbon source in the present invention, resistance can not only be effectively improved
The flame retarding efficiency of agent is fired, simultaneously because the modification on starch surface can significantly improve the interface compatibility of fire retardant and polylactic acid, it is right
The mechanical performance of polylactic acid flame retardant composite material has very big facilitation.The present invention realizes the resistance of the polylactic acid under few additive
Combustion, has very big protective effect to the mechanical property of polylactic acid, the application to polylactic acid in fields such as electronic device, automobile cases
Remarkably promote effect.
The preparation method of polylactic acid/starch intumescent flame-retardant composite of the present invention, using existing equipment double screw extruder
It can be realized, preparation is simple, and it is easy to implement, it is easy to industrialized production.
Detailed description of the invention
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；
(a) is the section SEM figure of the PLA/ starch composite material of mass ratio 80:20 in Fig. 3, and (b) is mass ratio in Fig. 3
The section SEM figure of phosphorous starch composite material prepared by the PLA/ embodiment 1 of 80:20.
Specific embodiment
The present invention is further explained in the light of specific embodiments.
Embodiment 1:
In 250mL three-necked bottle, 20g 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and 15g horse
Carry out acid anhydrides (MA) to be dissolved in respectively in 50mL toluene and 20mL dioxane, is heated to 40 DEG C, nitrogen protection, back flow reaction 12h.
After reaction, rotary evaporation removes solvent, and product 1 is obtained after vacuum drying, spare.
In 250mL three-necked bottle, 20g starch (cornstarch) and 40mL pyridine are heated to 65 DEG C, under nitrogen protection, return
Flow 2h.After temperature is down to 50 DEG C, 20g product 1 (is dissolved in DMSO), addition catalyst 4-dimethylaminopyridine, nitrogen protection,
50 DEG C of back flow reaction 12h.After reaction, it is purified by washing, vacuum drying obtains the phosphorous starch of biology base, i.e., modified to form sediment
Powder.
Embodiment 2:
In 250mL three-necked bottle, 20g DOPO and 18g maleic anhydride (MA) are dissolved in 50mL dimethylbenzene and 20mL respectively
In THF (tetrahydrofuran), 50 DEG C are heated to, nitrogen protection, back flow reaction is for 24 hours.After reaction, rotary evaporation removes solvent,
Product 1 is obtained after vacuum drying, it is spare.
In 250mL three-necked bottle, 20g starch (cornstarch) and 60mL pyridine are heated to 75 DEG C, under nitrogen protection, return
Flow 4h.After temperature is down to 50 DEG C, 25g product 1 (is dissolved in DMSO), addition catalyst 4-dimethylaminopyridine, nitrogen protection,
Back flow reaction is for 24 hours.After reaction, it is purified by washing, vacuum drying obtains the phosphorous starch of biology base, i.e. modified starch.
Embodiment 3:
In 250mL three-necked bottle, 20g DOPO and 21g maleic anhydride (MA) are dissolved in 70mL dimethylbenzene, are heated to 60
DEG C, nitrogen protection, back flow reaction is for 24 hours.After reaction, rotary evaporation removes solvent, and product 1 is obtained after vacuum drying, spare.
In 250mL three-necked bottle, 20g starch (cornstarch) and 80mL pyridine are heated to 85 DEG C, under nitrogen protection, return
Flow 8h.After temperature is down to 65 DEG C, 35g product 1 (is dissolved in DMSO), addition catalyst 4-dimethylaminopyridine, nitrogen protection,
Back flow reaction is for 24 hours.After reaction, it is purified by washing, vacuum drying obtains the phosphorous starch of biology base, i.e. modified starch.
Embodiment 4:
In 250mL three-necked bottle, 20g DOPO and 25g maleic anhydride (MA) are dissolved in 50mL dimethylbenzene and 20mL respectively
In THF (tetrahydrofuran), it is heated to 70 DEG C, nitrogen protection, back flow reaction 36h.After reaction, rotary evaporation removes solvent,
Product 1 is obtained after vacuum drying, it is spare.
In 250mL three-necked bottle, 20g starch (cornstarch) and 100mL pyridine are heated to 85 DEG C, under nitrogen protection, return
Flow 16h.After temperature is down to 75 DEG C, 40g product 1 (is dissolved in DMSO), and proper catalyst 4-dimethylaminopyridine, nitrogen is added
Protection, back flow reaction 36h.After reaction, it is purified by washing, vacuum drying obtains the phosphorous starch of biology base, i.e., modified to form sediment
Powder.
Embodiment 5:
In 250mL three-necked bottle, 20g DOPO and 25g maleic anhydride (MA) are dissolved in 70mLTHF (tetrahydrofuran) respectively
In, it is heated to 80 DEG C, nitrogen protection, back flow reaction 36h.After reaction, rotary evaporation removes solvent, obtains after vacuum drying
Product 1, it is spare.
In 250mL three-necked bottle, 20g starch (cornstarch) and 100mL pyridine are heated to 95 DEG C, under nitrogen protection, return
Stream is for 24 hours.After temperature is down to 75 DEG C, 45g product 1 (is dissolved in DMSO), and proper catalyst 4-dimethylaminopyridine, nitrogen is added
Protection, back flow reaction 64h.After reaction, it is purified by washing, vacuum drying obtains the phosphorous starch of biology base, i.e., modified to form sediment
Powder.
As shown in Figure 1, infrared spectrum effectively proves the successful preparation of phosphorous starch, phosphorous starch in spectrogram in Fig. 1
(DOPOMASt) obviously there are several groups of new peaks compared to pure starch (pure starch), be respectively as follows: 1731cm-1, 1624cm-1
And 1202cm-1、1024cm-1、930cm-1, the appearance of these characteristic peaks can effectively prove the phosphatization of starch it is modified at
Function, DOPOMA are product 1.
Table 1 is that the data of starch and phosphorous starch under nitrogen atmosphere are shown.Number under from the nitrogen atmosphere of Fig. 2 and table 1
According to display, the phosphorous starch initial decomposition temperature of synthesis is improved to 266 DEG C, and thermal stability greatly improves；And maximum decomposition temperature
About 20 DEG C are had dropped instead, and final remaining carbon is significantly improved to 33.8%.Based entirely on bio-based materials, the phosphorous starch of synthesis
This characteristic meet very much the requirement in expanding fire retardant to carbon source, in polymer expandable flame retardant with wide application before
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 that the section SEM of PLA/Starch Blends schemes, wherein (a) is the PLA/ of mass ratio 80:20 in Fig. 3
The section SEM of starch composite material schemes, and (b) is the section SEM of the phosphorous starch composite material of PLA/ of mass ratio 80:20 in Fig. 3
Figure.It can be apparent from from figure, compared to pure starch and polylactic acid, the interface mistake of modified phosphorous starch and polylactic acid
Compatibility greatly improves, and illustrates the synthetic method significant effect of the phosphorous starch.
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, melamine 1Kg；
The preparation method of polylactic acid/starch intumescent flame-retardant composite:
Modified starch and ammonium polyphosphate, melamine prepared by polylactic acid, embodiment 1 is respectively in 105 DEG C and 85 DEG C
Lower drying, drying time are 8h.After mixing in high speed blender, the melt blending (screw rod into double screw extruder is added
Temperature is 170~190 DEG C), polylactic acid/starch intumescent flame-retardant composite is obtained after cooling, granulation.The twin-screw of selection squeezes
The screw slenderness ratio of machine is 40:1 out.
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, melamine 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, melamine 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, melamine 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, cornstarch 20Kg；
Preparation method is as described in Example 1.
The polylactic acid/starch intumescent flame-retardant composite injection molding that embodiment 6~9 and comparative example 1~3 are obtained is mark
Quasi- vertical combustion (UL-94) batten, limit oxygen index (LOI) batten and bending batten, wherein injection temperature is 175~185
DEG C, injection pressure is 70~90MPa, dwell pressure 45MPa.According to ASTM D3801, ASTM D 2863-97 and GB/T
1040.1-2006 carries out combustibility, bending property test, and test result is as shown in table 2, and NC indicates nonrated.
Table 2
As shown in Table 1, through embodiment 6~9 compared with comparative example 1~3, modified starch, ammonium polyphosphate and melamine
The flame retardant property of amine, lactic acid composite material significantly improves, and vertical combustion grade reaches V0 grade, and oxygen index (OI), which also has, significantly to be mentioned
It is high.In addition, surface-hydrophobicized degree is big since modified starch phosphorus content is high, the lower fire retardant additive amount of polylactic acid is not only realized
Under it is fire-retardant, additionally it is possible to significantly improve the interface compatibility between fire retardant and polylactic acid, greatly improve the machinery of composite material
Performance, the application to realization polylactic acid in fields such as auto industry, electronic devices play an important role.
Claims (8)
1. a kind of polylactic acid/starch intumescent flame-retardant composite, which is characterized in that comprise the following raw materials by weight percent:
Polylactic acid 60%~89%；
Acid source 5%~30%；
Modified starch 5%~30%；
Gas source 1%~15%；
The modified starch is phosphatization modified by maleic acid anhydride graft starch；
The preparation method of the phosphatization modified by maleic acid anhydride graft starch, comprising 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 react, be evaporated under reduced pressure, it is dry, obtain 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~
For 24 hours, activated Starch solution is obtained；
3) product 1 is added in activated Starch solution after cooling, the reaction was continued under 30 DEG C~90 DEG C and protective gas 12h
~64h is washed, dry, obtains phosphatization modified by maleic acid anhydride graft starch.
2. polylactic acid/starch intumescent flame-retardant composite according to claim 1, which is characterized in that the acid source is
One of phosphoric acid, boric acid, sulfuric acid, phosphate, polyphosphoric acids, polyphosphate, sulfate are two or more.
3. polylactic acid/starch intumescent flame-retardant composite according to claim 1, which is characterized in that the gas source is
One of melamine, urea, polyamide, biuret are two or more.
4. polylactic acid/starch intumescent flame-retardant composite according to claim 1, which is characterized in that the polylactic acid/
Starch intumescent flame-retardant composite is made of the raw material of following weight percent:
Polylactic acid 79%~89%；
Acid source 5%~10%；
Modified starch 10%~15%；
Gas source 1%~5%；
The acid source is ammonium polyphosphate；
The modified starch is phosphatization modified by maleic acid anhydride graft starch；
The gas source is melamine.
5. polylactic acid/starch intumescent flame-retardant composite according to claim 1, which is characterized in that described in step 1)
9,10- dihydro-9-oxy miscellaneous -10- phospho hetero phenanthrene -10- oxide and maleic anhydride mass ratio=1:0.5~1.5；
Mass ratio=1.0~the 2.5:1 for the starch that the product 1 and step 2) being added in step 3) use.
6. polylactic acid/starch intumescent flame-retardant composite according to claim 5, which is characterized in that described in step 1)
The first organic solvent be at least one of toluene, dimethylbenzene, tetrahydrofuran, dioxane；
In step 2), the starch is sweet potato starch, cornstarch, potato starch, wheaten starch, one in soybean starch
Kind is two or more；
In step 2), the catalyst is pyridine, 2-aminopyridine, 4-aminopyridine, 2- dimethyl aminopyridine, 4- diformazan
One of base aminopyridine, ethylenediamine, aniline, triethylamine, ethanol amine are two or more；
In step 2), second organic solvent is methanol, ethyl alcohol, acetone, tetrahydrofuran, dimethyl sulfoxide, N, N- diformazan
One or more of base formamide, DMAC N,N' dimethyl acetamide.
7. the preparation method of described in any item polylactic acid/starch intumescent flame-retardant composites according to claim 1~6, special
Sign is, comprising the following steps:
After polylactic acid, modified starch, acid source, gas source are dry, are uniformly mixed, are added in double screw extruder, through melting extrusion,
After cooling, granulation, polylactic acid/starch intumescent flame-retardant composite is obtained.
8. preparation method according to claim 7, which is characterized in that in the double screw extruder, the major diameter of screw rod
Than being 170~190 DEG C for the temperature of 35:1~45:1, melting extrusion.
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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 |
| CN109627453B (en) * | 2018-12-12 | 2021-05-04 | 怀化学院 | Flame retardant for polylactic acid, flame-retardant polylactic acid material and preparation method thereof |
| CN111171539B (en) * | 2020-02-27 | 2022-05-31 | 中国科学院宁波材料技术与工程研究所 | Flame-retardant biodegradable polylactic acid/starch composite material and preparation method thereof |
| CN112625409A (en) * | 2020-10-23 | 2021-04-09 | 威骏(上海)环保包装有限公司 | Biodegradable plastic bottle cap and preparation method thereof |
| CN112500600B (en) * | 2020-11-23 | 2023-01-24 | 威骏(上海)环保包装有限公司 | Self-cleaning antibacterial degradable daily chemical bottle and preparation method thereof |
| CN112724524B (en) * | 2020-12-28 | 2022-04-01 | 会通新材料股份有限公司 | Biodegradable flame-retardant polypropylene composite material and preparation method thereof |
| CN114426764A (en) * | 2022-03-07 | 2022-05-03 | 安徽海铭塑业有限公司 | Flame-retardant environment-friendly packaging film and preparation method thereof |
| CN115216129B (en) * | 2022-09-19 | 2023-01-10 | 河北百展科技发展有限公司 | Heat-resistant bio-based degradable composite material and preparation method thereof |
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