CN104045985B - A kind of RDP clad nano attapulgite prepares flame-proof polylactic acid matrix material - Google Patents
A kind of RDP clad nano attapulgite prepares flame-proof polylactic acid matrix material Download PDFInfo
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- CN104045985B CN104045985B CN201410291025.1A CN201410291025A CN104045985B CN 104045985 B CN104045985 B CN 104045985B CN 201410291025 A CN201410291025 A CN 201410291025A CN 104045985 B CN104045985 B CN 104045985B
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Abstract
The invention discloses a kind of RDP clad nano attapulgite and prepare flame-proof polylactic acid matrix material.This RDP clad nano attapulgite for raw material, prepares RDP clad nano attapulgite with two (diphenyl phosphoester) (RDP) of Resorcinol and nano-attapulgite under ultrasound condition.This flame-proof polylactic acid matrix material be by poly(lactic acid) and RDP clad nano attapulgite by (60 ~ 95): the mass percent high-speed mixing of (40 ~ 5) and extruded by forcing machine, cool, granulation obtains.This flame-proof polylactic acid composite-material formula is simple, and mechanical property improves significantly, and flame retarding efficiency is good, Heat stability is good, can generate stable fine and close carbon-coating during burning, and without molten drop, and raw smoke which is low.
Description
Technical field
The present invention relates to the field of fire-proof technology of poly-lactic acid material, be specifically related to a kind of RDP clad nano attapulgite and prepare flame-proof polylactic acid matrix material.
Background technology
Poly(lactic acid) (PLA) be a kind of with natural reproducible resources such as corn, wheat, straws for raw material, can be degradable, environment amenable aliphatic polyester series macromolecular material, can meet the requirement of Sustainable development.But poly(lactic acid) barrier properties for gases is poor, easy firing, and with molten drop phenomenon, seriously limit its application in multiple field such as electronic apparatus and automobile, this impels people to carry out flame-retardant modified research to poly(lactic acid).
In reality is flame-retardant modified, the fire retardant that poly(lactic acid) is commonly used has expansion type flame retardant, nano-meter flame retardants, reactive flame retardant etc., and in order to improve flame retardant efficacy further, organic and inorganic fire retardant is carried out compound use by people, utilize its synergy, reach the high and effect that addition is low of flame retarding efficiency.(the LiSM such as the Ren Jie of Tongji University, YuanH, YuT, YuanWZ, RenJ.PolymAdvTechol, 2009,20:1114) with phosphorus flame retardant with organic modification montmonrillonite (O-MMT) is composite joins in poly(lactic acid), the LOI value of matrix material reaches 28.7, without molten drop phenomenon.
With polynite similar, nano-attapulgite be a kind of have distinct layer chain-like structure containing Shuifu County's alumina magnesia silicate, wide material sources, cheap at China's rich reserves.In recent years, much research is added to prepare matrix material in some polymkeric substance used as inorganic fill type toughener, and has made some progress gradually.But, its research in flame retarded polymeric material is less, mainly fire retardant and the composite use of attapulgite in existing bibliographical information, will after both simple mixing and polymeric matrix blended, though can solve conventional flame retardant addition increase and cause the defect that mechanical property and processing characteristics significantly decline, but in Blending Processes, there will be fire retardant and attapulgite interacts the problem such as incomplete.And; nano-attapulgite is because of its nanostructure; deployment conditions is in the polymer poor; easily coacervate is formed when addition is larger; be unfavorable for the raising of system performance; so usually also will carry out surface treatment to attapulgite before interpolation, surface treatment method conventional in existing report has the modification of silane coupling agent and acid treatment etc.Though but the traditional surface treatment method of attapulgite can improve the mechanical property DeGrain of polymer materials to a certain extent, and other performances of material particularly flame retardant properties be not significantly improved.
Therefore, before attapulgite adds poly(lactic acid) to, find a kind of compound that not only can play fire retardant effect but also play surface-modifying agent effect and surface modification is carried out to it become the key improving poly-lactic acid material over-all properties.
Summary of the invention
The object of this invention is to provide a kind of RDP clad nano attapulgite and prepare flame-proof polylactic acid matrix material.Be intended to overcome the deficiencies in the prior art, the flame-proof polylactic acid matrix material prepared can not only meet flame retardant properties needed for material and mechanical property simultaneously, and Heat stability is good, can generate stable fine and close carbon-coating during burning, and without molten drop, and raw smoke which is low.
Realizing the object of the invention technical solution is:
A kind of flame-proof polylactic acid matrix material, described flame-proof polylactic acid matrix material is mixed by poly(lactic acid) and the coated nano-attapulgite of RDP, and extruded by forcing machine, cool, granulation and obtaining; The mass percent of described poly(lactic acid) and the coated nano-attapulgite of RDP is (60 ~ 95): (40 ~ 5); The coated nano-attapulgite of described RDP refer to by RDP and nano-attapulgite in a solvent ultrasonic disperse prepare and obtain.
In the nano-attapulgite that described RDP is coated, the content of RDP is 25wt%.
The nano-attapulgite that described RDP is coated is prepared by the following method: be dissolved in by RDP in chloroform, add attapulgite wherein, under the condition of ultrasonic disperse, reaction is not less than 1.5h, and reaction terminates the unnecessary RDP of rear removing and solvent chloroform, namely obtains the nano-attapulgite that RDP is coated.
RDP clad nano attapulgite prepares a method for flame-proof polylactic acid matrix material, comprises the following steps:
The first step, by RDP and nano-attapulgite in a solvent ultrasonic disperse prepare and obtain the coated nano-attapulgite of RDP;
Second step, in proportion by poly(lactic acid) and the coated nano-attapulgite mixing of RDP, and extruded by forcing machine, cool, granulation and obtaining.
In the first step, in the nano-attapulgite that RDP is coated, the content of RDP is 25wt%.
In second step, the mass percent of poly(lactic acid) and the coated nano-attapulgite of RDP is (60 ~ 95): (40 ~ 5).
In second step, solvent is chloroform, and under the condition of ultrasonic disperse, reaction is not less than 1.5h.
The present invention compared with prior art, has obvious progress: the clay class Nano filling that (1) the present invention interpolation fire retardant in system is coated, improving the flame retardant properties of system simultaneously, also effectively improves the mechanical property of matrix material.(2) fire retardant is RDP, good flame retardation effect, high temperature resistant, and P=O is wherein good Hydrogen Bond Acceptors, hydrogen bond action is formed with the O-H in clay class Nano filling, make RDP can be adsorbed on its surface, form the tectum of stable homogeneous, it is nano-attapulgite that existing flame retardant efficiency also can carry out surface modification (3) clay class Nano filling to filler, nano-attapulgite belongs to silicates, can catalysis carbon-forming, the thermal degradation products of the layer of charcoal that PLA is decomposed to form and Attapulgite soil layer chain-like particle can form a kind of cortex-cellular rock steady structure, to heat transmission in combustion processes, burning molecule, the migration of oxygen plays shielding effect, reduce thermolysis speed, thus play fire retardation.(4) nano-attapulgite surface is after the coated process of RDP, its dispersion state in PLA matrix and consistency are improved greatly, there is physics or the increase of chemically combined possibility between the two, thus add bonded area, mechanical property is highly improved.(5) cation exchange capacity (CEC) value of nano-attapulgite is less, and the aggregation force between excellent crystalline substance is a kind of fainter physical adsorption power, and the method by ultrasonic disperse prepares coating layer on its surface, and preparation technology is simple, nontoxic.
Below in conjunction with accompanying drawing, the invention will be further described.
Accompanying drawing explanation
Accompanying drawing is RDP clad nano attapulgite scanning electron microscope (SEM) photograph (a) of the present invention pure attapulgite (b) RDP clad nano attapulgite.
Embodiment
RDP clad nano attapulgite prepares flame-proof polylactic acid matrix material, is mixed by poly-lactic acid material and RDP clad nano attapulgite.Wherein in RDP clad nano attapulgite, the content of RDP is 25wt%, and preparation method is as follows:
The RDP of 2g is added in the chloroformic solution of 100ml, magnetic agitation 20min, after RDP is dissolved completely in chloroform, adds the attapulgite of 3g wherein, and 1.5h is reacted under ultrasound condition, reaction terminates the unnecessary solvent of rear removing and not coated successful RDP.
It is be (60 ~ 95) by mass percentage that RDP clad nano attapulgite of the present invention prepares flame-proof polylactic acid matrix material: poly(lactic acid) pellet, RDP clad nano attapulgite are mixed that merga pass forcing machine is extruded, cooled by (40 ~ 5), granulation and obtaining.
In order to Comprehension and Implementation better, describe below in conjunction with comparative example and embodiment the preparation process that RDP clad nano attapulgite prepares flame-proof polylactic acid matrix material in detail.
Comparative example:
Take poly(lactic acid) pellet 1000g, by good for above-mentioned pellet combination treatment in high-speed mixer, under the condition of the feed rate of routine, temperature and screw speed, add forcing machine, through extruding, cooling, granulation, obtained poly-lactic acid material.Limiting oxygen index(LOI) 20.5%, has molten drop phenomenon, 600 DEG C of carbon yields 1.19%, tensile strength 66.23MPa.
Embodiment 1:
Take poly(lactic acid) pellet 950g, RDP clad nano attapulgite 50g, by good for above-mentioned pellet combination treatment in high-speed mixer, under the condition of the feed rate of routine, temperature and screw speed, add forcing machine, through extruding, cooling, granulation, obtained RDP clad nano attapulgite flame-proof polylactic acid matrix material of the present invention.Limiting oxygen index(LOI) 23.5%, has molten drop phenomenon, 600 DEG C of carbon yields 3.83%, tensile strength 91.76MPa.
Embodiment 2:
Take poly(lactic acid) pellet 900g, RDP clad nano attapulgite 100g, by good for above-mentioned pellet combination treatment in high-speed mixer, under the condition of the feed rate of routine, temperature and screw speed, add forcing machine, through extruding, cooling, granulation, obtained RDP clad nano attapulgite flame-proof polylactic acid matrix material of the present invention.Limiting oxygen index(LOI) 22.0%, without molten drop phenomenon, 600 DEG C of carbon yields 5.24%, tensile strength 93.05MPa.
Embodiment 3:
Take poly(lactic acid) pellet 850g, RDP clad nano attapulgite 150g, by good for above-mentioned pellet combination treatment in high-speed mixer, under the condition of the feed rate of routine, temperature and screw speed, add forcing machine, through extruding, cooling, granulation, obtained RDP clad nano attapulgite flame-proof polylactic acid matrix material of the present invention.Limiting oxygen index(LOI) 22.5%, without molten drop phenomenon, 600 DEG C of carbon yields 9.33%, tensile strength 82.85MPa.
Embodiment 4:
Take poly(lactic acid) pellet 800g, RDP clad nano attapulgite 200g, by good for above-mentioned pellet combination treatment in high-speed mixer, under the condition of the feed rate of routine, temperature and screw speed, add forcing machine, through extruding, cooling, granulation, obtained RDP clad nano attapulgite flame-proof polylactic acid matrix material of the present invention.Limiting oxygen index(LOI) 23.5%, without molten drop phenomenon, 600 DEG C of carbon yields 12.59%, tensile strength 80.30MPa.
Embodiment 5:
Take poly(lactic acid) pellet 700g, RDP clad nano attapulgite 300g, by good for above-mentioned pellet combination treatment in high-speed mixer, under the condition of the feed rate of routine, temperature and screw speed, add forcing machine, through extruding, cooling, granulation, obtained RDP clad nano attapulgite flame-proof polylactic acid matrix material of the present invention.Limiting oxygen index(LOI) 24.5%, without molten drop phenomenon, 600 DEG C of carbon yields 14.56%, tensile strength 76.84MPa.
Embodiment 6:
Take poly(lactic acid) pellet 600g, RDP clad nano attapulgite 400g, by good for above-mentioned pellet combination treatment in high-speed mixer, under the condition of the feed rate of routine, temperature and screw speed, add forcing machine, through extruding, cooling, granulation, obtained RDP clad nano attapulgite flame-proof polylactic acid matrix material of the present invention.Limiting oxygen index(LOI) 26.5%, without molten drop phenomenon, 600 DEG C of carbon yields 23.67%, tensile strength 68.16MPa.
Claims (2)
1. a flame-proof polylactic acid matrix material, is characterized in that, described flame-proof polylactic acid matrix material is mixed by poly(lactic acid) and the coated nano-attapulgite of RDP, and extruded by forcing machine, cool, granulation and obtaining; The mass percent of described poly(lactic acid) and the coated nano-attapulgite of RDP is (60 ~ 95): (40 ~ 5); The coated nano-attapulgite of described RDP refer to by RDP and nano-attapulgite in a solvent ultrasonic disperse prepare and obtain, wherein, in the nano-attapulgite that RDP is coated, the content of RDP is 25wt%; The nano-attapulgite that described RDP is coated is prepared by the following method: be dissolved in by RDP in chloroform, add attapulgite wherein, under the condition of ultrasonic disperse, reaction is not less than 1.5h, and reaction terminates the unnecessary RDP of rear removing and solvent chloroform, namely obtains the nano-attapulgite that RDP is coated.
2. RDP clad nano attapulgite prepares a method for flame-proof polylactic acid matrix material as claimed in claim 1, it is characterized in that comprising the following steps:
The first step, the nano-attapulgite that preparation RDP is coated;
Second step, in proportion by poly(lactic acid) and the coated nano-attapulgite mixing of RDP, and extruded by forcing machine, cool, granulation and obtaining.
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