CN104194291A - Halogen-free intumescent flame-retardant polylactic acid composite material and preparation method thereof - Google Patents
Halogen-free intumescent flame-retardant polylactic acid composite material and preparation method thereof Download PDFInfo
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- CN104194291A CN104194291A CN201410426124.6A CN201410426124A CN104194291A CN 104194291 A CN104194291 A CN 104194291A CN 201410426124 A CN201410426124 A CN 201410426124A CN 104194291 A CN104194291 A CN 104194291A
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Abstract
The invention relates to the field of halogen-free intumescent flame-retardant material preparation, relates to a halogen-free intumescent flame-retardant polylactic acid composite material and a preparation method thereof. The halogen-free intumescent flame-retardant polylactic acid composite material is composed of the following components in percentage by weight: 60-97% of polylactic acid, 2-25% of ammonium polyphosphate and 1-15% of hyperbranched ethylenediamine triazine carbonizing agent. The hyperbranched ethylenediamine triazine carbonizing agent has high nitrogen element content, thereby overcoming the defects of high deliquescence tendency, poor heat stability, poor migration resistance and the like when the carbonizing agent is prepared from polyol in the prior art. The hyperbranched ethylenediamine triazine carbonizing agent is compounded with the polylactic acid and ammonium polyphosphate according to certain percentage to obtain the halogen-free intumescent flame-retardant polylactic acid composite material with excellent flame-retardant effect.
Description
Technical field
The present invention relates to halogen-free expanded flame-retardant field of material preparation, in particular to a kind of halogen-free expanded flame-retardant lactic acid composite material and preparation method thereof.
Background technology
Poly(lactic acid) (PLA) has high strength, high transparent and the advantage such as good biological degradation and biocompatibility, thereby is identified as " can replace to a certain extent traditional petroleum base polymkeric substance "; 2004, Japanese Sony, NECDeng company be the shell material as DVD and notebook computer by PLA respectively, and PLA starts to show up prominently in field of electronics.Yet PLA produces serious molten drop when very easily burning (the low oxygen index value of 19%-20%) and burning, thus serious restriction its application in fields such as electronic apparatus, automotive industrys.
Easily know ground, as environmentally friendly flame-retardant system, P-N expanding fire retardant is the advantage such as non-corrosiveness gas generation because its flame retarding efficiency is high, during burning, finds application gradually in fire-retardant PLA.In correlation technique, many use polyvalent alcohols in Intumscent Flame Retardant System (as, tetramethylolmethane) as char-forming agent.But, polyvalent alcohol has the shortcomings such as easy moisture absorption deliquescence, thermostability and anti-transport property be poor, using it as char-forming agent and be applied to after the preparation of lactic acid composite material, its flame retardant properties of PLA matrix that can run down, and then make the flame retardant effect of whole matrix material undesirable.
Summary of the invention
The object of the present invention is to provide a kind of halogen-free expanded flame-retardant lactic acid composite material, to solve above-mentioned technical problem.Another object of the present invention is to provide a kind of preparation method of above-mentioned halogen-free expanded flame-retardant lactic acid composite material.
A kind of halogen-free expanded flame-retardant lactic acid composite material is provided in an embodiment of the present invention, and according to weight percent meter, it is comprised of following component: poly(lactic acid) 60%-97%, ammonium polyphosphate 2%-25%, hyperbranched quadrol triazine char-forming agent 1%-15%.
This halogen-free expanded flame-retardant lactic acid composite material provided by the invention, is major ingredient by take poly(lactic acid), ammonium polyphosphate, is aided with hyperbranched quadrol triazine char-forming agent, has determined the percentage composition of each component and then has obtained halogen-free expanded flame-retardant lactic acid composite material.Because hyperbranched its nitrogen element content of quadrol triazine char-forming agent is high, overcome in prior art when polyvalent alcohol is as char-forming agent, the shortcomings such as its easily wet deliquescence, thermostability and anti-transport property are poor, hyperbranched quadrol triazine char-forming agent and poly(lactic acid), ammonium polyphosphate are worked in coordination with so that set percentage composition is composite, and then are obtained the halogen-free expanded flame-retardant lactic acid composite material of flame retardant effect excellence.
Optionally, the chemical structural formula of described hyperbranched quadrol triazine char-forming agent is:
It is a kind of according to the preparation method of above-mentioned halogen-free expanded flame-retardant lactic acid composite material that the embodiment of the present invention also provides, and comprises the following steps:
1), poly(lactic acid), ammonium polyphosphate, hyperbranched triazine char-forming agent are mixed according to set weight percent, obtain mixing raw material;
2), described mixing raw material is carried out to melt blending, obtain halogen-free expanded flame-retardant lactic acid composite material.
Optionally, in step 2) in:
In the process of described melt blending, mixing raw material is stirred
Optionally, in step 2) in:
In the process of described melt blending, temperature is 180-200 ℃; Time is 5-7 minute;
The rotating speed of described stirring is 50-70 rev/min.
Accompanying drawing explanation
In order to be illustrated more clearly in the specific embodiment of the invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, accompanying drawing in the following describes is some embodiments of the present invention, for those of ordinary skills, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is halogen-free expanded flame-retardant lactic acid composite material preparation flow figure provided by the invention.
Embodiment
For making the object, technical solutions and advantages of the present invention clearer; to technical scheme of the present invention be carried out to clear, complete description below; embodiment based in the present invention; those of ordinary skills are resulting all other embodiments under the prerequisite of not making creative work, all belong to the scope that the present invention protects.
This halogen-free expanded flame-retardant lactic acid composite material provided by the invention, it is comprised of following component: poly(lactic acid) 60%-97%, ammonium polyphosphate 2%-25%, hyperbranched quadrol triazine char-forming agent 1%-15%.In addition, can be by kind and then the better halogen-free expanded flame-retardant lactic acid composite material of acquisition flame retardant effect of preferred hyperbranched quadrol triazine char-forming agent, on above-mentioned content, preferred, the chemical structural formula of described hyperbranched quadrol triazine char-forming agent is:
This kind of halogen-free expanded flame-retardant lactic acid composite material provided by the invention, this halogen-free expanded flame-retardant lactic acid composite material provided by the invention, by take poly(lactic acid), ammonium polyphosphate, it is major ingredient, be aided with hyperbranched quadrol triazine char-forming agent, determined the percentage composition of each component and then obtained halogen-free expanded flame-retardant lactic acid composite material.Because hyperbranched its nitrogen element content of quadrol triazine char-forming agent is high, overcome in prior art when polyvalent alcohol is as char-forming agent, the shortcomings such as its easily wet deliquescence, thermostability and anti-transport property are poor, hyperbranched quadrol triazine char-forming agent and poly(lactic acid), ammonium polyphosphate are worked in coordination with so that set percentage composition is composite, and then are obtained the halogen-free expanded flame-retardant lactic acid composite material of flame retardant effect excellence.
Hyperbranched quadrol triazine char-forming agent, it is neutral state hyperbranched macromolecular structure when poly(lactic acid) is combined, therefore, there is good stability to hydrolysis, and it has higher thermostability, therefore, in the process of high temperature process, there is high processing stability, compare with conventional linear char-forming agent, it has overcome poor heat stability and defect that the poly(lactic acid) that causes is easily hydrolyzed.
In addition, the preparation method of this halogen-free expanded flame-retardant lactic acid composite material provided by the invention, comprises the following steps, and please refer to Fig. 1:
Step 101: poly(lactic acid), ammonium polyphosphate, hyperbranched triazine char-forming agent are mixed according to set weight percent, obtain mixing raw material;
Step 102: described mixing raw material is carried out to melt blending, obtain halogen-free expanded flame-retardant lactic acid composite material.
In step 102, in order to make mixing raw material blend abundant, preferred, in the process of described melt blending, mixing raw material is stirred; In addition, preferred, in the process of melt blending, its temperature is controlled at 180-200 ℃; Time is 5-7 minute; The rotating speed of described stirring is 50-70 rev/min.
Next, the present invention, also in conjunction with above-mentioned content, provides following specific embodiment to its composition of halogen-free expanded flame-retardant lactic acid composite material and preparation method:
Embodiment mono-
The halogen-free expanded flame-retardant lactic acid composite material of the present embodiment, according to weight percent meter, it is comprised of following component: poly(lactic acid) 80%, ammonium polyphosphate 10%, hyperbranched quadrol triazine char-forming agent 10%.
Its preparation method comprises: take PLA, 19.5 (0.1) g APP and 19.5g EA after 156g is dried, artificial premix is even; 190 ℃ and 60 revs/min of lower melt blendings 6 minutes; Obtain expandable flame retardant lactic acid composite material; The oxygen index of matrix material is 33.2%.
Embodiment bis-
The halogen-free expanded flame-retardant lactic acid composite material of the present embodiment, according to weight percent meter, it is comprised of following component: poly(lactic acid) 80%, ammonium polyphosphate 12%, hyperbranched quadrol triazine char-forming agent 8%.
Its preparation method comprises: take PLA, 23.4g APP and 15.6g EA after 156g is dried, artificial premix is even; 190 ℃ and 60 revs/min of lower melt blendings 6 minutes, obtain expandable flame retardant lactic acid composite material; The oxygen index of matrix material is 33.6%.
Embodiment tri-
The halogen-free expanded flame-retardant lactic acid composite material of the present embodiment, according to weight percent meter, it is comprised of following component: poly(lactic acid) 80%, ammonium polyphosphate 14%, hyperbranched quadrol triazine char-forming agent 6%.
Its preparation method comprises: take PLA, 27.3g APP and 11.7g EA after 156g is dried, artificial premix is even; 190 ℃ and 60 revs/min of lower melt blendings 6 minutes; Obtain expandable flame retardant lactic acid composite material; The oxygen index of matrix material is 35.6%, and fire-retardant rank is UL 94V-2 level.
Embodiment tetra-
The halogen-free expanded flame-retardant lactic acid composite material of the present embodiment, according to weight percent meter, it is comprised of following component: poly(lactic acid) 80%, ammonium polyphosphate 15%, hyperbranched quadrol triazine char-forming agent 5%.
Its preparation method comprises: take PLA, 29.25g APP and 9.75g EA after 156g is dried, artificial premix is even; 190 ℃ and 60 revs/min of lower melt blendings 6 minutes; Obtain expandable flame retardant lactic acid composite material; The oxygen index of matrix material is 41.2%, and fire-retardant rank is UL 94V-0 level.
Embodiment five
The halogen-free expanded flame-retardant lactic acid composite material of the present embodiment, according to weight percent meter, it is comprised of following component: poly(lactic acid) 80%, ammonium polyphosphate 18%, hyperbranched quadrol triazine char-forming agent 2%.
Its preparation method comprises: take PLA, 35.1g APP and 3.9g EA after 156g is dried, artificial premix is even; 190 ℃ and 60 revs/min of lower melt blendings 6 minutes; Obtain expandable flame retardant lactic acid composite material; The oxygen index of matrix material is 34.0%, and fire-retardant rank is UL 94V-2 level.
Embodiment six
The halogen-free expanded flame-retardant lactic acid composite material of the present embodiment, according to weight percent meter, it is comprised of following component: poly(lactic acid) 60%, ammonium polyphosphate 25%, hyperbranched quadrol triazine char-forming agent 15%.
Its preparation method comprises: take PLA, 48.75g APP and 29.25EA after 117g is dried, artificial premix is even; 180 ℃ and 70 revs/min of lower melt blendings 7 minutes; Obtain expandable flame retardant lactic acid composite material.
Embodiment seven
The halogen-free expanded flame-retardant lactic acid composite material of the present embodiment, according to weight percent meter, it is comprised of following component: poly(lactic acid) 97%, ammonium polyphosphate 2%, hyperbranched quadrol triazine char-forming agent 1%.
Take PLA, 3.9g APP and 1.95g EA after 189.15 oven dry, artificial premix is even; 200 ℃ and 50 revs/min of lower melt blendings 5 minutes; Obtain expandable flame retardant lactic acid composite material.
By melt blending, prepare halogen-free expanded flame-retardant poly(lactic acid) and meet material, its method is simple; APP and EA with certain proportioning and PLA blend after, flame-proof composite material not only shows good thermostability, but also shows excellent flame retardant properties; The flame retardant properties of matrix material and the correlation data of comparative example please refer to as table 1:
The flame retardant properties of the PLA matrix material of the different proportionings of table 1
It is to be noted: for ammonium polyphosphate, itself and poly(lactic acid) and hyperbranched triazine char-forming agent are composite, as a kind of requisite component, its reason with, ammonium polyphosphate is not only a kind of nonpoisonous and tasteless, do not produce etchant gas, water absorbability is little, the good non-halogen fire retardant that thermostability is high, the more important thing is, the lactic acid composite material that itself and hyperbranched quadrol triazine char-forming agent form according to set percentage composition, between two components, pass through collaborative proportioning, can make the flame retardant properties of lactic acid composite material significantly increase, for example, when by poly(lactic acid) and ammonium polyphosphate during with the composite composition lactic acid composite material of 5:1 material, its LOI (%) is only 28.1, and after the hyperbranched quadrol triazine of its 2% use char-forming agent is substituted, i.e. the technical scheme of the embodiment of the present invention 5, its LOI (%) has directly brought up to 34.0, therefore,, in lactic acid composite material field, ammonium polyphosphate and hyperbranched triazine char-forming agent is composite, and it has obtained unexpected technique effect.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (5)
1. halogen-free expanded flame-retardant lactic acid composite material, is characterized in that, in described matrix material, according to weight percent meter, it is comprised of following component:
Poly(lactic acid) 60%-97%, ammonium polyphosphate 2%-25%, hyperbranched quadrol triazine char-forming agent 1%-15%.
2. halogen-free expanded flame-retardant lactic acid composite material according to claim 1, is characterized in that, the chemical structural formula of described hyperbranched quadrol triazine char-forming agent is:
3. according to a preparation method for the halogen-free expanded flame-retardant lactic acid composite material described in claim 1-2 any one, it is characterized in that, comprise the following steps:
1), poly(lactic acid), ammonium polyphosphate, hyperbranched triazine char-forming agent are mixed according to set weight percent, obtain mixing raw material;
2), described mixing raw material is carried out to melt blending, obtain halogen-free expanded flame-retardant lactic acid composite material.
4. the preparation method of halogen-free expanded flame-retardant lactic acid composite material according to claim 3, is characterized in that, in step 2) in:
In the process of described melt blending, mixing raw material is stirred.
5. the preparation method of halogen-free expanded flame-retardant lactic acid composite material according to claim 4, is characterized in that, in step 2) in:
In the process of described melt blending, temperature is 180-200 ℃; Time is 5-7 minute; The rotating speed of described stirring is 50-70 rev/min.
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| CN105968753A (en) * | 2016-05-04 | 2016-09-28 | 北京工商大学 | Phosphonitrile/triazine double-group molecular synergistic flame retardation polylactic acid composite material and preparation method thereof |
| CN110204877A (en) * | 2019-07-12 | 2019-09-06 | 顺德职业技术学院 | Expansion type flame-retarding lactic acid composite material and preparation method thereof |
| CN110226001A (en) * | 2016-10-14 | 2019-09-10 | 奥克兰联合服务有限公司 | Fire-retardant keratin fiber |
| CN110218425A (en) * | 2019-06-10 | 2019-09-10 | 北京工商大学 | A kind of flame-retardant polyester material and preparation method thereof having both high flame resistance and strong mechanical performance |
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| CN103044868A (en) * | 2013-01-09 | 2013-04-17 | 四川大学 | Halogen-free flame-retardant polybutylece terephthalate/glass fiber composite and preparation method thereof |
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| CN101792602A (en) * | 2010-03-11 | 2010-08-04 | 四川大学 | Halogen-free expansible flame-retardant thermoplastic resin composition |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105968753A (en) * | 2016-05-04 | 2016-09-28 | 北京工商大学 | Phosphonitrile/triazine double-group molecular synergistic flame retardation polylactic acid composite material and preparation method thereof |
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| CN110218425A (en) * | 2019-06-10 | 2019-09-10 | 北京工商大学 | A kind of flame-retardant polyester material and preparation method thereof having both high flame resistance and strong mechanical performance |
| CN110218425B (en) * | 2019-06-10 | 2021-10-01 | 北京工商大学 | Flame-retardant polyester material with high flame-retardant performance and high mechanical performance and preparation method thereof |
| CN110204877A (en) * | 2019-07-12 | 2019-09-06 | 顺德职业技术学院 | Expansion type flame-retarding lactic acid composite material and preparation method thereof |
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Application publication date: 20141210 |