CN104031364B - A kind of enhancing flame-retardant polylactic acid material and preparation method thereof - Google Patents
A kind of enhancing flame-retardant polylactic acid material and preparation method thereof Download PDFInfo
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- CN104031364B CN104031364B CN201410267381.XA CN201410267381A CN104031364B CN 104031364 B CN104031364 B CN 104031364B CN 201410267381 A CN201410267381 A CN 201410267381A CN 104031364 B CN104031364 B CN 104031364B
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Abstract
A kind of enhancing flame-retardant polylactic acid material and preparation method thereof.This poly-lactic acid material comprises poly(lactic acid) particle, modification bluish dogbane, boron bakelite resin and polymer polycondenseng phosphate.This enhancing flame-retardant polylactic acid material preparation method is: after bluish dogbane is first carried out alkaline purification by (1), then uses vinyltrimethoxy silane modification bluish dogbane, pulverizes for subsequent use; (2) a certain proportion of poly(lactic acid) particle and modification bluish dogbane, boron bakelite resin, polymer polycondenseng phosphate are joined in torque rheometer, obtain and strengthen fire-retardant poly-lactic acid material by bluish dogbane, boron bakelite resin, polymer polycondenseng phosphate.This enhancing flame-retardant polylactic acid material formula is simple, halogen-free environmental, and become charcoal remarkable after burning, effectively inhibit the further propagation of flame, tensile strength increases simultaneously.
Description
Technical field
The invention belongs to the enhancing field of fire-proof technology of poly-lactic acid material, be specifically related to a kind of enhancing flame-retardant polylactic acid material and preparation method thereof.
Background technology
Poly(lactic acid) (PLA) is a kind of biodegradable polymer, in recent years due to its abundance, cheap, and good mechanical properties and receive the concern of more and more experts and scholars.Poly(lactic acid) can be made into sheet material, foam, pressing, fiber etc.In order to better cater to the demand in the fields such as electron electric power equipment, traffic, fire-retardant, the enhancing modified of poly(lactic acid) become an important topic.
Natural fiber, such as flax, coconut husk, flax, sisal hemp etc., because their mechanical strengths own are large, abundance, density is little, cheap and by as strongthener enhancing modified polymkeric substance.Bluish dogbane, abounds with in China, and mechanical property is particularly outstanding, is widely used in enhancement engineering plastics.Miriam
deng (Miriam
, IzaskunGarmendia, Javier
journalofAppliedPolymerScience, 2008,107,2994-3004) have studied the reinforced effects of bluish dogbane to poly(lactic acid), result shows, the mechanical property of bluish dogbane/lactic acid composite material is excellent, is even better than the enhancing modified effect of mineral filler to polymkeric substance, but, the interpolation of the bluish dogbane of ecosystem can reduce the tensile strength of matrix material, therefore must carry out necessary modification to improve the consistency between bluish dogbane and polymeric matrix to bluish dogbane.
Phosphonium flame retardant is fire-retardant with condensed phase mechanism, and be the very fast a kind of fire retardant of development in recent years, efficiently, consumption is few.SeongchanPack etc. (SeongchanPack, EzraBobo, NeilMuir, etal.Polymer, 2012,53:4787-4799) have studied the modified effect of RDP to poly-lactic acid material, and result shows, the UL94 of flame-retardant polylactic acid material reaches V0 level.But common polymer phosphonium flame retardant mostly is liquid, thermotolerance, poor compatibility, and have serious molten drop phenomenon during burning.In order to avoid these problems, polymer polycondenseng phosphate such as PX-220 becomes the focus of research.(the Liu Yuan such as Liu Yuan, Han Yi, Wang Qi, engineering plastics are applied, and 2012,40,5-9) have studied the burning of boron modified phenolic resin in polymer composites and charring, result shows, boron modified phenolic resin significantly can increase neat coal amout and improve layer of charcoal stability, improves the condensed phase flame retardant effect of phosphor-containing flame-proof system.But use single fire retardant poor effect, and addition is large, cost is high, the composite use of suitable fire retardant is therefore selected to be the wise move of polymer modification.
Summary of the invention
The object of the present invention is to provide and a kind of strengthen flame-retardant polylactic acid material and preparation method thereof, described enhancing flame-retardant polylactic acid material consist of poly(lactic acid), modification bluish dogbane, boron bakelite resin, polymer polycondenseng phosphate.Be intended to overcome the deficiencies in the prior art, the flame retardant properties needed for material and mechanical property can not only be met, and the molten drop that burning produces reduces, promote the increase of neat coal amout, stop the further propagation of flame, system Halogen, nontoxicity, to the harm of human body and environment and pollution level low.
The technical solution realizing the object of the invention is: a kind of enhancing flame-retardant polylactic acid material, described enhancing flame-retardant polylactic acid material is mixed by poly(lactic acid), modification bluish dogbane, boron bakelite resin, polymer polycondenseng phosphate, and the mass ratio of poly(lactic acid), modification bluish dogbane, boron bakelite resin, polymer polycondenseng phosphate is 70:10:(2.5 ~ 10): (10 ~ 17.5); Described modification bluish dogbane is that bluish dogbane is carried out alkaline purification, is washed to neutral post-drying; Bluish dogbane after oven dry is placed in the aqueous ethanolic solution magnetic agitation of vinyltrimethoxy silane, suction filtration, alcohol wash, obtains after oven dry.
In described enhancing flame-retardant polylactic acid material, boron bakelite resin is a buff powder, and structure is as follows:
m＝2～3。
In described enhancing flame-retardant polylactic acid material, in boron bakelite resin, the massfraction of boron is 2% ~ 4%.
In described enhancing flame-retardant polylactic acid material, polymer polycondenseng phosphate is poly aryl phosphate ester PX-220, white solid.
The preparation method of above-mentioned enhancing flame-retardant polylactic acid material, is prepared by following steps:
(1) preparation of modification bluish dogbane: bluish dogbane is carried out alkaline purification, is washed to neutral post-drying; Bluish dogbane after oven dry is placed in the aqueous ethanolic solution magnetic agitation of vinyltrimethoxy silane, suction filtration, alcohol wash, dries, be crushed to 5 ~ 10mm;
(2) in proportion by poly(lactic acid), modification bluish dogbane, boron bakelite resin, polymer polycondenseng phosphate, fully after mixing, torque rheometer is placed in, obtained enhancing flame-retardant polylactic acid material.
In step (1), bluish dogbane is through alkaline purification and vinyltrimethoxy silane process, and during alkaline purification, the concentration of NaOH is 20wt%, and the concentration of vinyltrimethoxy silane is 10wt%.
In step (2), the mass ratio of poly(lactic acid), modification bluish dogbane, boron bakelite resin, polymer polycondenseng phosphate is 70:10:(2.5 ~ 10): (10 ~ 17.5).
In step (2), the structural formula of boron bakelite resin is as follows:
m＝2～3。
In step (2), in boron bakelite resin, the massfraction of boron is 2% ~ 4%.
In step (2), polymer polycondenseng phosphate is poly aryl phosphate ester PX-220.
Compared with prior art, its remarkable advantage is in the present invention:
(1) there is abundant polar group on ecosystem bluish dogbane surface, poor with the consistency of poly(lactic acid), thus affects the mechanical property of matrix material.The present invention has carried out alkaline purification and silane coupler modified to bluish dogbane, the polarity on its surface is reduced, substantially improves the dispersion effect of bluish dogbane in poly(lactic acid) matrix, can play the effect promoting into charcoal, can improve again the mechanical property of material.
(2) use polymer polycondenseng phosphate, overcome that common polymer phosphonium flame retardant poor heat resistance, volatility are large, poor compatibility, and mostly be liquid, not easily the shortcoming such as processing, flame retardant effect is remarkable.
(3) boron bakelite resin is the phenolic hydroxyl group in boron part substituted phenolic resin, and-B-O-is flexible large, and resin matrix toughness is large, thus improves the physical strength of matrix material.In combustion processes, boron bakelite resin generates fine and close and abundant vitreous state layer of charcoal at composite material surface, serves good isolation action, inhibits generation and the flame transmission of inflammable gas.
(4) combustion processes and product halogen-free environmental.
Accompanying drawing explanation
The tensile strength of flame-retardant polylactic acid material is strengthened in Fig. 1 the present invention.
The combustion phenomena of flame-retardant polylactic acid material is strengthened in Fig. 2 the present invention.
Embodiment
Of the present inventionly strengthening fire-retardant poly-lactic acid material by modification bluish dogbane, boron bakelite resin, polymer polycondenseng phosphate, is that modification bluish dogbane, 2.5 ~ 10 boron bakelite resins, 10 ~ 17.5 polymer polycondenseng phosphates and 70 poly(lactic acid) being 10 by mass percent become through torque rheometer stream.Bluish dogbane is through alkaline purification and vinyltrimethoxy silane process, and during alkaline purification, the concentration of NaOH is 20wt%, and the concentration of vinyltrimethoxy silane is 10wt%.
In order to Comprehension and Implementation better, describe below in conjunction with comparative example and embodiment the present invention to be strengthened fire-retardant poly-lactic acid material preparation process by modification bluish dogbane, boron bakelite resin, polymer polycondenseng phosphate in detail.
The preparation of modification bluish dogbane: bluish dogbane is carried out alkaline purification, is washed to neutral post-drying; Bluish dogbane after oven dry is placed in aqueous ethanolic solution (6:4v/v) the magnetic agitation 2h of 10wt% vinyltrimethoxy silane, suction filtration, alcohol wash, dries, be crushed to 5 ~ 10mm;
Comparative example:
Take 50g poly(lactic acid) pellet, join in torque rheometer, rheological temperature is 175 DEG C, and output speed is 30rpm, obtained poly-lactic acid material, and measure by GB/T2406.2-2009 standard test methods, limiting oxygen index(LOI) is 20.0%, 600 DEG C of charring rates is 0.28%; Measuring tensile strength by GB/T1040-2006 standard test methods is 55.4MPa.
The mass ratio of embodiment 1:(poly(lactic acid), modification bluish dogbane, boron bakelite resin, polymer polycondenseng phosphate is 70:10:2.5:17.5)
Take 35g poly(lactic acid) pellet, 5g modification bluish dogbane, 1.25g boron bakelite resin, join after 8.75gPX-220 fully mixes in torque rheometer, rheological temperature is 175 DEG C, and output speed is 30rpm, obtained poly-lactic acid material, measure by GB/T2406.2-2009 standard test methods, limiting oxygen index(LOI) is 25.0%, 600 DEG C of charring rates is 3.29%; Measuring tensile strength by GB/T1040-2006 standard test methods is 53.6MPa.
The mass ratio of embodiment 2:(poly(lactic acid), modification bluish dogbane, boron bakelite resin, polymer polycondenseng phosphate is 70:10:5:15)
Take 35g poly(lactic acid) pellet, 5g modification bluish dogbane, 2.5g boron bakelite resin, join after 7.5gPX-220 fully mixes in torque rheometer, rheological temperature is 175 DEG C, and output speed is 30rpm, obtained poly-lactic acid material, measure by GB/T2406.2-2009 standard test methods, limiting oxygen index(LOI) is 25.0%, 600 DEG C of charring rates is 6.78%; Measuring tensile strength by GB/T1040-2006 standard test methods is 54.1MPa.
The mass ratio of embodiment 3:(poly(lactic acid), modification bluish dogbane, boron bakelite resin, polymer polycondenseng phosphate is 70:10:10:10)
Take 35g poly(lactic acid) pellet, 5g modification bluish dogbane, 5g boron bakelite resin, join after 5gPX-220 fully mixes in torque rheometer, rheological temperature is 175 DEG C, and output speed is 30rpm, obtained poly-lactic acid material, measure by GB/T2406.2-2009 standard test methods, limiting oxygen index(LOI) is 24.5%, 600 DEG C of charring rates is 7.49%; Measuring tensile strength by GB/T1040-2006 standard test methods is 55.8MPa.
As shown in Figure 1, adding of boron bakelite resin makes the tensile strength of poly-lactic acid material increase, and along with the increase of addition, mechanical property is in rising trend, compensate for the impact of PX-220 on material mechanical performance to a certain extent.As shown in Figure 2, a small amount of boron bakelite resin add the molten drop phenomenon obviously improving poly-lactic acid material, when the interpolation of boron bakelite resin reaches 5%, poly-lactic acid material (embodiment 2) generates fine and close abundant layer of charcoal, addition is larger, becomes charcoal more obvious.As can be seen here, boron bakelite resin is not only a kind of fire retardant of excellence, and the kindliness of-B-O-makes mechanical property improve, and the existence of a large amount of phenyl ring determines boron bakelite resin is simultaneously a kind of good char-forming agent.
Fire retardant (PX-220, boron bakelite resin) composite use can reduce the add-on of fire retardant, makes up deficiency each other simultaneously, thus improves flame retarding efficiency, reduces costs.Adding of natural fiber, play significant enhancement, the impact of other fillers on Polymer Mechanical performance can be made up.The research of fire-retardant enhancing poly-lactic acid material should towards environmental protection, efficient, energy-conservation future development.
Claims (8)
1. one kind strengthens flame-retardant polylactic acid material, it is characterized in that, described enhancing flame-retardant polylactic acid material is mixed by poly(lactic acid), modification bluish dogbane, boron bakelite resin, polymer polycondenseng phosphate, the mass ratio of described poly(lactic acid), modification bluish dogbane, boron bakelite resin, polymer polycondenseng phosphate is 70:10:(2.5 ~ 10): (10 ~ 17.5), described modification bluish dogbane is that bluish dogbane is carried out alkaline purification, is washed to neutral post-drying; Bluish dogbane after oven dry is placed in the aqueous ethanolic solution magnetic agitation of vinyltrimethoxy silane, suction filtration, alcohol wash, obtains after oven dry; The structural formula of described boron bakelite resin is as follows:
m＝2～3。
2. enhancing flame-retardant polylactic acid material according to claim 1, is characterized in that, in described boron bakelite resin, the massfraction of boron is 2% ~ 4%.
3. enhancing flame-retardant polylactic acid material according to claim 1, is characterized in that, described polymer polycondenseng phosphate is poly aryl phosphate ester PX-220.
4. strengthen a preparation method for flame-retardant polylactic acid material, it is characterized in that, prepared by following steps:
(1) preparation of modification bluish dogbane: bluish dogbane is carried out alkaline purification, is washed to neutral post-drying; Bluish dogbane after oven dry is placed in the aqueous ethanolic solution magnetic agitation of vinyltrimethoxy silane, suction filtration, alcohol wash, dries, be crushed to 5 ~ 10mm;
(2) in proportion by poly(lactic acid), modification bluish dogbane, boron bakelite resin, polymer polycondenseng phosphate, fully after mixing, torque rheometer is placed in, obtained enhancing flame-retardant polylactic acid material; Wherein, the structural formula of boron bakelite resin is as follows:
m＝2～3。
5. the preparation method of enhancing flame-retardant polylactic acid material according to claim 4, it is characterized in that, in step (1), bluish dogbane is through alkaline purification and vinyltrimethoxy silane process, and during alkaline purification, the concentration of NaOH is 20wt%, and the concentration of vinyltrimethoxy silane is 10wt%.
6. the preparation method of enhancing flame-retardant polylactic acid material according to claim 4, it is characterized in that, in step (2), the mass ratio of poly(lactic acid), modification bluish dogbane, boron bakelite resin, polymer polycondenseng phosphate is (60 ~ 70): 10:(2.5 ~ 10): (10 ~ 22.5).
7. the preparation method of enhancing flame-retardant polylactic acid material according to claim 4, is characterized in that, in step (2), in boron bakelite resin, the massfraction of boron is 2% ~ 4%.
8. the preparation method of enhancing flame-retardant polylactic acid material according to claim 4, is characterized in that, in step (2), polymer polycondenseng phosphate is poly aryl phosphate ester PX-220.
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Citations (3)
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|---|---|---|---|---|
| CN101538401A (en) * | 2009-03-13 | 2009-09-23 | 上海大学 | High temperature resistance binary fiber/polylactic acid based composite material and preparation method thereof |
| CN103467945A (en) * | 2013-09-04 | 2013-12-25 | 上海悦萌环保科技有限公司 | Kenaf fiber reinforced polylactic acid degradable plastic |
| CN103694657A (en) * | 2013-12-24 | 2014-04-02 | 南京理工大学 | Flame-retardant polylactic acid material of ternary composite flame-retardant system and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538401A (en) * | 2009-03-13 | 2009-09-23 | 上海大学 | High temperature resistance binary fiber/polylactic acid based composite material and preparation method thereof |
| CN103467945A (en) * | 2013-09-04 | 2013-12-25 | 上海悦萌环保科技有限公司 | Kenaf fiber reinforced polylactic acid degradable plastic |
| CN103694657A (en) * | 2013-12-24 | 2014-04-02 | 南京理工大学 | Flame-retardant polylactic acid material of ternary composite flame-retardant system and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 三聚氰胺聚磷酸盐／硼酚醛协效体系阻燃PA66／GF复合材料的研究;刘渊等;《工程塑料应用》;20120831;第40卷(第8期);第5-9页 * |
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