CN104744900A - Flame-retardant butylene succinate/starch composite material and preparation method thereof - Google Patents
Flame-retardant butylene succinate/starch composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a flame-retardant butylene succinate/starch composite material and a preparation method thereof. Raw materials for preparing the composite material comprise the following components in percentage by mass: 12.1-19.3% of glycerinum gelatinized starch, 64.4-72.8% of butylene succinate and 15.0-17.7% of an intumescent flame retardant. The preparation method comprises the following steps: placing the butylene succinate subjected to a drying treatment in an internal mixer, setting the temperature of the internal mixer to 125-145 DEG C, setting a rotational speed to 25-40r/min, and internally mixing for 2-5min, then adding the intumescent flame retardant, and internally mixing for 3-5min, and then carrying out shear melt-blending and blanking in the internal mixer to obtain the flame-retardant butylene succinate/starch composite material. The flame-retardant butylene succinate/starch composite material obtained by the preparation method disclosed by the invention is low in cost, good in flame retardance, good in mechanical property, and wide in application range.
Description
Technical field
The invention belongs to fire retardant material technical field, be specifically related to a kind of flame retardant polybutylene succinate/starch composite material and preparation method thereof.
Background technology
Due to the non-biodegradable of conventional plastic, its goods bring also bring more and more serious problem of environmental pollution easily simultaneously to people's life, industrial production, and degradable plastics is the important channel addressed this problem.Poly butylene succinate (PBS) is a kind of semi-crystalline thermo's resin with completely biodegradable energy, also be develop one of completely degradable plastic faster at present, fusing point 114 DEG C, according to the height of molecular weight and the difference of molecular weight distribution, degree of crystallinity is between 25 ~ 45%.The processing characteristics of poly butylene succinate is good, can carry out forming process, processing temperature scope 130 ~ 180 DEG C on common process molding device.Can process with forming methods such as injection moulding, blowing, blown film, plastic uptake, lamination, foaming, spinning, One-stop Shopping bag, biological medical polymer material, packing bottle etc. can be prepared.Poly butylene succinate products waste can be degraded soon in earth or water, and its degraded product is nontoxic, and raw material succinic acid can be obtained by farm crop biological fermentation, is a kind of ecology high molecular synthetic material capable of circulation.
But compare general-purpose plastics, poly butylene succinate price is more expensive, and price general charged is 60,000/ton.And PBS poor heat stability, inflammable, and easily produce melting drip phenomenon in combustion, may ignite his thing thus cause fire.Therefore, PBS, in some occasion, in particular for the industrial circle such as electronic apparatus, the vehicles or when using as (foam) wrapping material, has very large fire hazard.At present about the report of the rarely seen Patents of technology that PBS is fire-retardant and document.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in prior art, provides that a kind of cost is lower, the poly butylene succinate/starch composite material with flame retardant properties and preparation method thereof.
For solving the problems of the technologies described above, technical scheme provided by the invention is:
There is provided a kind of flame retardant polybutylene succinate/starch composite material, each component of starting material and the quality proportioning thereof of preparing this matrix material are:
Glycerine pasted starch 12.1-19.3%
Poly butylene succinate 64.4-72.8%
Expanding fire retardant 15.0-17.7%.
By such scheme, described glycerine pasted starch preparation method is as follows: starch, glycerine are mixed by mass volume ratio 1g:2 ~ 5mL, in 80 ~ 120 DEG C of reaction 0.5 ~ 2h, obtains glycerine pasted starch.
By such scheme, described starch is Zulkovsky starch.
By such scheme, described poly butylene succinate is that succinic acid and BDO direct condensation obtain, and its molecular weight is 5 ~ 8W.
By such scheme, described expanding fire retardant by acid gas source with add source of the gas in mass ratio 3 ~ 5:1 form, wherein acid gas source is ammonium polyphosphate, and adding source of the gas is trimeric cyanamide, and described poly butylene succinate and glycerine pasted starch are charcoal source.
The present invention also provides the preparation method of above-mentioned flame retardant polybutylene succinate/starch composite material, its step is as follows: the poly butylene succinate after drying treatment is put into Banbury mixer, Banbury mixer temperature is set to 125 ~ 145 DEG C, rotating speed is set to 25 ~ 40r/min, the banburying time is 2 ~ 4min, then glycerine pasted starch is added, the banburying time is 2 ~ 5min, add expanding fire retardant again, the banburying time is 3 ~ 5min, then in Banbury mixer, shear melting is carried out blended, blanking, namely flame retardant polybutylene succinate/starch composite material is obtained, the quality proportioning preparing each component of starting material of matrix material is: glycerine pasted starch 12.1-19.3%, poly butylene succinate 64.4-72.8%, expanding fire retardant 15.0-17.7%.
By such scheme, described glycerine pasted starch preparation method is as follows: starch, glycerine are mixed by mass volume ratio 1g:2 ~ 5mL, in 80 ~ 120 DEG C of reaction 0.5 ~ 2h, obtains glycerine pasted starch.
By such scheme, described starch is Zulkovsky starch.
By such scheme, described poly butylene succinate is that succinic acid and BDO direct condensation obtain, and its molecular weight is 5 ~ 8W.
By such scheme, described expanding fire retardant by acid gas source with add source of the gas in mass ratio 3 ~ 5:1 form, wherein acid gas source is ammonium polyphosphate, and adding source of the gas is trimeric cyanamide, and described poly butylene succinate and glycerine pasted starch are charcoal source.
Beneficial effect of the present invention is: 1, the present invention is owing to selecting the glycerine pasted starch of low cost, the preferably blending ratio of itself and poly butylene succinate, and the method selecting Banbury mixer blended prepares matrix material, significantly reduce the cost of completely degradable plastic PBS, and preparation method's technique is simple, pollution-free; 2, the flame retardant polybutylene succinate/starch composite material adopting the inventive method to prepare is due to acid gas source, charcoal source and the choose reasonable of source of the gas and the adding proportion of optimization, improve the flame retardant resistance of poly butylene succinate, in addition, due to using polyester and starch as charcoal source, reduce cost prepared by material, improve the water tolerance of material, solve general charcoal source and the bad problem of polyester consistency, and in combustion there is anti-dripping melt, improve the fire safety of material; 3, adopt flame retardant polybutylene succinate/starch composite material of preparing of the inventive method to have excellent flame retardant properties and thermostability, can be used for the wrapping material of foam material or household electrical appliances, medicine, food.
Accompanying drawing explanation
The layer of charcoal high-resolution-ration transmission electric-lens photo that the poly butylene succinate/starch composite material that do not add fire retardant of Fig. 1 prepared by comparative example 1 obtains under 600 DEG C of high-temp combustions;
The high-resolution-ration transmission electric-lens photo of the layer of charcoal that the flame retardant polybutylene succinate/starch composite material of Fig. 2 prepared by embodiment 1 obtains under 600 DEG C of high-temp combustions.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, below in conjunction with accompanying drawing, the present invention is described in further detail.
Embodiment of the present invention poly butylene succinate used is that succinic acid and BDO direct condensation obtain, and molecular weight is 5 ~ 8W.
Documents 1
First take 10g Zulkovsky starch and be placed in beaker, add 30mL glycerine, at 80 DEG C, constant temperature stirs gelatinization and obtains glycerine pasted starch in 1 hour.Poly butylene succinate was 70 DEG C of dryings 12 hours, and expansion type flame retardant (ammonium polyphosphate, trimeric cyanamide) was 80 DEG C of dryings 12 hours.
By the 50g poly butylene succinate (drying treatment condition is: dry 8-12h at 60-80 DEG C) after drying treatment, (temperature is set to 135 DEG C in melting in Banbury mixer, rotating speed is set to 30r/min), the banburying time is set to 3min, then 10g glycerine pasted starch is added, the banburying time is set to 3min, then complete Banbury mixer shear melting blended, blanking, namely obtain poly butylene succinate/starch composite material.
Be illustrated in figure 1 poly butylene succinate/starch composite material prepared by this comparative example under the condition of not adding fire retardant, the layer of charcoal high-resolution-ration transmission electric-lens photo obtained under 600 DEG C of high-temp combustions, the scanning electron microscopic picture display layer of charcoal of layer of charcoal is not fine and close, and bubble is loose.Its oxygen index is 22, by vertical combustion testing standard UL-94V2 level.Through Mechanics Performance Testing, the elongation at break of this material is 205.36%, and tensile strength is 80.7MPa, and flexural strength is 24.66MPa.
Embodiment 1
First take 10g Zulkovsky starch and be placed in beaker, add 30mL glycerine, at 80 DEG C, constant temperature stirs gelatinization and obtains glycerine pasted starch in 1 hour.Poly butylene succinate was 70 DEG C of dryings 12 hours, and expansion type flame retardant (ammonium polyphosphate, trimeric cyanamide) was 80 DEG C of dryings 12 hours.
By the 50g poly butylene succinate (drying treatment condition is: dry 8-12h at 60-80 DEG C) after drying treatment, (temperature is set to 135 DEG C in melting in Banbury mixer, rotating speed is set to 30r/min), the banburying time is set to 3min, then 10g glycerine pasted starch is added, the banburying time is set to 3min, add 2.1g trimeric cyanamide, 10.5g ammonium polyphosphate again, the banburying time is set to 4min, complete Banbury mixer shear melting blended, blanking, namely obtains flame retardant polybutylene succinate/starch composite material.
Be illustrated in figure 2 the layer of charcoal high-resolution-ration transmission electric-lens photo that the flame retardant polybutylene succinate/starch composite material prepared by the present embodiment obtains under 600 DEG C of high-temp combustions, the scanning electron microscopic picture display of layer of charcoal defines fine and close foamed char, and has more complete bubbles.Its oxygen index reaches 38, by vertical combustion testing standard UL-94V0 level.Through Mechanics Performance Testing, the elongation at break of this material can reach 228.42%, and tensile strength can reach 100.8MPa, and flexural strength can reach 23.2MPa.
Embodiment 2
First take and can be placed in beaker by 10g starch soluble, add 20mL glycerine, at 120 DEG C, constant temperature stirs gelatinization and obtains glycerine pasted starch in 0.5 hour.Poly butylene succinate was 70 DEG C of dryings 12 hours, and expansion type flame retardant (ammonium polyphosphate, trimeric cyanamide) was 80 DEG C of dryings 12 hours.
By 50g poly butylene succinate melting in Banbury mixer of the process through above-mentioned drying, (temperature is set to 125 DEG C, rotating speed is set to 40r/min), the banburying time is set to 3min, then add 15g glycerine pasted starch, the banburying time is set to 3min, then adds 2.1g trimeric cyanamide, 10.5g ammonium polyphosphate, the banburying time is set to 5min, complete Banbury mixer shear melting blended, blanking, namely obtain flame retardant polybutylene succinate/starch composite material of the present invention.
Adopt the method identical with embodiment one to carry out test to the flame retardant polybutylene succinate/starch composite material prepared in the present embodiment known, the oxygen index of this material, up to 33, can reach the V0 level in UL-94 test; The elongation at break of this material can reach 195.71%, and tensile strength can reach 97.53MPa, and flexural strength can reach 21.4MPa.
Embodiment 3
First take 10g Zulkovsky starch and be placed in beaker, add 40mL glycerine, at 100 DEG C, constant temperature stirs gelatinization and obtains glycerine pasted starch in 1 hour.Poly butylene succinate was 70 DEG C of dryings 12 hours, and expansion type flame retardant (ammonium polyphosphate, trimeric cyanamide) was 80 DEG C of dryings 12 hours.
By 55g poly butylene succinate melting in Banbury mixer of the process through above-mentioned drying, (temperature is set to 135 DEG C, rotating speed is set to 25r/min), the banburying time is set to 3min, then add 15g glycerine pasted starch, the banburying time is set to 3min, then adds 3.1g trimeric cyanamide, 9.3g ammonium polyphosphate, the banburying time is set to 4min, complete Banbury mixer shear melting blended, blanking, namely obtain flame retardant polybutylene succinate/starch composite material of the present invention.
Adopt the method identical with embodiment one to carry out test to the flame retardant polybutylene succinate/starch composite material prepared in the present embodiment known, the oxygen index of this material reaches 32, can reach the V1 level in UL-94 test; The elongation at break of this material can reach 174.46%, and tensile strength can reach 90.3MPa, and flexural strength can reach 19.7MPa.
Embodiment 4
First take 10g Zulkovsky starch and be placed in beaker, add 40mL glycerine, at 110 DEG C, constant temperature stirs gelatinization and obtains glycerine pasted starch in 1 hour.Poly butylene succinate was 70 DEG C of dryings 12 hours, and expansion type flame retardant (ammonium polyphosphate, trimeric cyanamide) was 80 DEG C of dryings 12 hours.
By 60g poly butylene succinate melting in Banbury mixer of the process through above-mentioned drying, (temperature is set to 145 DEG C, rotating speed is set to 40r/min), the banburying time is set to 3min, then add 10g glycerine pasted starch, the banburying time is set to 3min, then adds 3.1g trimeric cyanamide, 9.3g ammonium polyphosphate, the banburying time is set to 3min, complete Banbury mixer shear melting blended, blanking, namely obtain flame retardant polybutylene succinate/starch composite material of the present invention.
Adopt the method identical with embodiment one to carry out test to the flame retardant polybutylene succinate/starch composite material prepared in the present embodiment known, the oxygen index of this material, up to 33, can reach the V1 level in UL-94 test; The elongation at break of this material can reach 211.64%, and tensile strength can reach 94.6MPa, and flexural strength can reach 20.2MPa.
Embodiment 5
First take 10g Zulkovsky starch and be placed in beaker, add 20mL glycerine, at 90 DEG C, constant temperature stirs gelatinization and obtains glycerine pasted starch in 2 hours.Poly butylene succinate was 70 DEG C of dryings 12 hours, and expansion type flame retardant (ammonium polyphosphate, trimeric cyanamide) was 80 DEG C of dryings 12 hours.
By 60g poly butylene succinate melting in Banbury mixer of the process through above-mentioned drying, (temperature is set to 135 DEG C, rotating speed is set to 40r/min), the banburying time is set to 3min, then add 12g glycerine pasted starch, the banburying time is set to 3min, then adds 2.67g trimeric cyanamide, 10.68g ammonium polyphosphate, the banburying time is set to 5min, complete Banbury mixer shear melting blended, blanking, namely obtain flame retardant polybutylene succinate/starch composite material of the present invention.
Adopt the method identical with embodiment one to carry out test to the flame retardant polybutylene succinate/starch composite material prepared in the present embodiment known, the oxygen index of this material, up to 33, can reach the V0 level in UL-94 test; The elongation at break of this material can reach 182.51%, and tensile strength can reach 90.3MPa, and flexural strength can reach 20.1MPa.
Embodiment 6
First take 10g Zulkovsky starch and be placed in beaker, add 50mL glycerine, at 120 DEG C, constant temperature stirs gelatinization and obtains glycerine pasted starch in 1 hour.Poly butylene succinate was 70 DEG C of dryings 12 hours, and expansion type flame retardant (ammonium polyphosphate, trimeric cyanamide) was 80 DEG C of dryings 12 hours.
By 50g poly butylene succinate melting in Banbury mixer of the process through above-mentioned drying, (temperature is set to 135 DEG C, rotating speed is set to 40r/min), the banburying time is set to 3min, then add 12g glycerine pasted starch, the banburying time is set to 3min, then adds 2.67g trimeric cyanamide, 10.68g ammonium polyphosphate, the banburying time is set to 4min, complete Banbury mixer shear melting blended, blanking, namely obtain flame retardant polybutylene succinate/starch composite material of the present invention.
Adopt the method identical with embodiment one to carry out test to the flame retardant polybutylene succinate/starch composite material prepared in the present embodiment known, the oxygen index of this material, up to 33, can reach the V0 level in UL-94 test; The elongation at break of this material can reach 152.89%, and tensile strength can reach 87.5MPa, and flexural strength reaches 19.2MPa.
Claims (10)
1. flame retardant polybutylene succinate/starch composite material, is characterized in that, each component of starting material and the quality proportioning thereof of preparing this matrix material are:
Glycerine pasted starch 12.1-19.3%
Poly butylene succinate 64.4-72.8%
Expanding fire retardant 15.0-17.7%.
2. flame retardant polybutylene succinate/starch composite material according to claim 1, it is characterized in that, described glycerine pasted starch preparation method is as follows: starch, glycerine are mixed by mass volume ratio 1g:2 ~ 5mL, in 80 ~ 120 DEG C of reaction 0.5 ~ 2h, obtain glycerine pasted starch.
3. flame retardant polybutylene succinate/starch composite material according to claim 2, is characterized in that, described starch is Zulkovsky starch.
4. flame retardant polybutylene succinate/starch composite material according to claim 1, is characterized in that, described poly butylene succinate is that succinic acid and BDO direct condensation obtain, and its molecular weight is 5 ~ 8W.
5. flame retardant polybutylene succinate/starch composite material according to claim 1, it is characterized in that, described expanding fire retardant by acid gas source with add source of the gas in mass ratio 3 ~ 5:1 form, wherein acid gas source is ammonium polyphosphate, adding source of the gas is trimeric cyanamide, and described poly butylene succinate and glycerine pasted starch are charcoal source.
6. the preparation method of flame retardant polybutylene succinate/starch composite material, it is characterized in that step is as follows: the poly butylene succinate after drying treatment is put into Banbury mixer, Banbury mixer temperature is set to 125 ~ 145 DEG C, rotating speed is set to 25 ~ 40r/min, the banburying time is 2 ~ 4min, then glycerine pasted starch is added, the banburying time is 2 ~ 5min, add expanding fire retardant again, the banburying time is 3 ~ 5min, then in Banbury mixer, shear melting is carried out blended, blanking, namely flame retardant polybutylene succinate/starch composite material is obtained, the quality proportioning preparing each component of starting material of matrix material is: glycerine pasted starch 12.1-19.3%, poly butylene succinate 64.4-72.8%, expanding fire retardant 15.0-17.7%.
7. the preparation method of flame retardant polybutylene succinate/starch composite material according to claim 6, it is characterized in that, described glycerine pasted starch preparation method is as follows: starch, glycerine are mixed by mass volume ratio 1g:2 ~ 5mL, in 80 ~ 120 DEG C of reaction 0.5 ~ 2h, obtain glycerine pasted starch.
8. the preparation method of flame retardant polybutylene succinate/starch composite material according to claim 6, is characterized in that, described starch is Zulkovsky starch.
9. the preparation method of flame retardant polybutylene succinate/starch composite material according to claim 6, is characterized in that, described poly butylene succinate is that succinic acid and BDO direct condensation obtain, and its molecular weight is 5 ~ 8W.
10. the preparation method of flame retardant polybutylene succinate/starch composite material according to claim 6, it is characterized in that, described expanding fire retardant by acid gas source with add source of the gas in mass ratio 3 ~ 5:1 form, wherein acid gas source is ammonium polyphosphate, adding source of the gas is trimeric cyanamide, and described poly butylene succinate and glycerine pasted starch are charcoal source.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105985535A (en) * | 2015-04-09 | 2016-10-05 | 湖南工业大学 | Corn-starch-and-poly-butylene-succinate-compounded foaming material and preparing method thereof |
| CN106496975A (en) * | 2016-09-29 | 2017-03-15 | 中国科学院宁波材料技术与工程研究所 | A kind of polylactic acid/starch intumescent flame-retardant composite and preparation method thereof |
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| CN101781445A (en) * | 2010-02-05 | 2010-07-21 | 中国科学技术大学 | Intumescent flame retardant polybutylene succinate and preparation method thereof |
| US20120299211A1 (en) * | 2001-05-10 | 2012-11-29 | Eric Bryan Bond | Multicomponent fibers comprising a dissolvable starch component, processes therefor, and fibers therefrom |
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| US20120299211A1 (en) * | 2001-05-10 | 2012-11-29 | Eric Bryan Bond | Multicomponent fibers comprising a dissolvable starch component, processes therefor, and fibers therefrom |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105985535A (en) * | 2015-04-09 | 2016-10-05 | 湖南工业大学 | Corn-starch-and-poly-butylene-succinate-compounded foaming material and preparing method thereof |
| CN106496975A (en) * | 2016-09-29 | 2017-03-15 | 中国科学院宁波材料技术与工程研究所 | A kind of polylactic acid/starch intumescent flame-retardant composite and preparation method thereof |
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