CN109401232A - Flame-proof polylactic acid composition and its expanded bead - Google Patents

Flame-proof polylactic acid composition and its expanded bead Download PDF

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Publication number
CN109401232A
CN109401232A CN201710705948.0A CN201710705948A CN109401232A CN 109401232 A CN109401232 A CN 109401232A CN 201710705948 A CN201710705948 A CN 201710705948A CN 109401232 A CN109401232 A CN 109401232A
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polylactic acid
flame
weight
parts
proof
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CN109401232B (en
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郭鹏
吕明福
张师军
徐耀辉
权慧
宋文波
白弈青
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract

The present invention provides a kind of flame-proof polylactic acid compositions comprising: polylactic acid base resin, fire retardant, Nucleating Agent and optionally antioxidant, wherein the fire retardant includes the complex that phosphine oxide and transition metal salt are formed.Expanded bead abscess dense uniform made of the polylactic acid base resin that the present invention uses, and the compressive strength of manufactured expanded bead formed body is very high；Meanwhile when being used cooperatively flame-proof polylactic acid composition provided by the invention and specific fire retardant and specific antistatic agent, it can act synergistically between fire retardant and antistatic agent, while improving flame retardant property and antistatic property.Have the characteristics that good high temperature shock resistance, antistatic, fire-retardant, simple process, rate of closed hole is high, density is controllable by expanded bead prepared by flame-proof polylactic acid composition of the invention.

Description

Flame-proof polylactic acid composition and its expanded bead
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of fire-retardant lactic acid composition and its expanded bead.
Background technique
As a kind of thermoplastic aliphatic polyester of fully biodegradable, polylactic acid (PLA) have it is non-stimulated, nontoxic, The features such as good bioresorbable and compatibility, mechanical strength also with higher and good processability.PLA is mainly by can The starch raw material that regenerated plant resources (such as high-celluloses such as corn, palm, stalks) are extracted is made.These starch via Hydrolysis obtains glucose, then the lactic acid that high-purity is made is obtained under the fermentation of certain strain, then obtain by chemical synthesis The polylactic acid of certain molecular weight.So PLA has resource and environment double dominant, also there is two aspect of function and structure material Feature.The research and development and application of PLA are to the dependence for reducing petroleum resources and improve the white pollutions objects such as waste high polymer to ring The pollution in border is of great significance.Since the 1990s, as biodegradated polymer materal, PLA is used for one Secondary property consumer article development is very rapid, but lacks certain competitiveness compared with traditional polyolefin plastics in cost performance. From the point of view of long-time service, the application field of PLA has been extended to electric equipment products and automobile and other industries.For example, day This Fuji Tsu has obtained computor-keyboard and shell using polycarbonate (PC)/PLA blend by injection molding.But PLA poor flame retardant properties, limit oxygen index (LOI) only have 20 or so, and melt quickly after burning and drip and burn, therefore the drippage that burns Soften fairly obvious.Therefore, PLA will be realized is applied in the fields such as electronic apparatus and automobile, it is necessary to improve its anti-flammability, make Its limit oxygen index > 28, burning rank reach UL94-V0 grades.
The fire-retardant approach for solving the problems, such as polylactic acid is that fire retardant is added, and two class of fire retardant classification: one is additions Type fire retardant；Another kind is reactive flame retardant.Additive flame retardant refers to that same high molecular material carries out physical blending and plays resistance The fire retardant of combustion effect.Reactive flame retardant is to make to polymerize by the way that some monomers containing ignition-proof element are participated in polymerization reaction Ignition-proof element is had in the main chain or side chain of object, plays fire-retardant effect, therefore its flame retardant effect is lasting, and to the object of material It is smaller to manage Effect on Mechanical Properties, but because is greatly limited its promotion and application the problem of technology and price.With it is anti- The type fire retardant of answering is compared, and additive flame retardant is easy to use, cheap, thus is the current common side for realizing that polylactic acid is fire-retardant Method, being usually used in the flame-retardant modified additive flame retardant of polylactic acid has halogenated flame retardant, halogen-free flame retardants and composite flame retardant system etc..
In the production, processing and application process of polylactic acid, electrostatic generation is very universal.However, the body of polylactic acid Product resistivity is generally 1016-1020In the range of Ω cm, electrostatic charge is difficult to eliminate after generating.These charge buildups are easy to lead Cause the generation of the perils such as fire, explosion and electric shock in processing and use process.
There are two main classes for the method for the electrostatic problem of solution polylactic acid: one kind is that addition has the antistatic of surface-active Agent makes hydrophilic radical enhancing surface hygroscopicity therein, the conductive film of one layer of monolayer is formed, to accelerate the leakage of electrostatic charge It lets out；Another kind of is the additive or electroconductive resin that addition has certain electric conductivity, is formed in plastic blend system using it Conductive channel play antistatic effect, this blend is known as conductive polymeric composite or conducting polymer alloy.It is right For polylactic acid, volume resistivity drops to 1012Ω cm has reached antistatic requirement.
However, there are fire-retardant and antistatic property for existing polylactic acid and expanded polylactic acid bead prepared therefrom (EPLA) Difference, and after flame-proof antistatic modified, abscess pattern and the expansion ratio control of EPLA expanded bead go wrong, and influence subsequent Molded application.Therefore, presently, there are the problem of be to be badly in need of researching and developing one kind having both good flame retardant property and antistatic The flame-proof polylactic acid composition and its expanded bead of performance.
Summary of the invention
The technical problem to be solved by the present invention is to solve the above shortcomings of the prior art and to provide a kind of flame-proof polylactic acid groups Close object and its expanded bead.Meanwhile it is by flame-proof polylactic acid composition provided by the invention and specific fire retardant and specifically anti- It when electrostatic agent is used cooperatively, can act synergistically between fire retardant and antistatic agent, while improve flame retardant property and resisting quiet Electrical property.The expanded bead prepared by flame-proof polylactic acid composition of the invention is good, antistatic with high temperature shock resistance, hinders Combustion, simple process, the feature that rate of closed hole is high, density is controllable.
For this purpose, first aspect present invention provides a kind of flame-proof polylactic acid composition comprising: polylactic acid base resin, Fire retardant and optionally antioxidant, wherein the fire retardant includes the complex that phosphine oxide and transition metal salt are formed.
According to the present invention, the polylactic acid base resin includes the mixture of polylactic acid or polylactic acid and other resins.It is excellent Selecting the polylactic acid includes homopolymerization polylactic acid and/or copolymerization polylactic acid.It is preferred that the copolymerization polylactic acid includes lactic acid and aliphatic Copolymer, lactic acid and the aliphatic polybasic of the copolymer of hydroxycarboxylic acid, lactic acid and the pure and mild aliphatic polycarboxylic acid of aliphatic polybasic One of copolymer of the copolymer and lactic acid and aliphatic polyol that contract sour is a variety of.The copolymerization polylactic acid further includes standing Structure composite polylactic acid (stereocomplexpolylactic acid) and stereoblock polylactic acid (stereoblock polylactic acid)。
In certain embodiments of the present invention, the lactic acid includes Pfansteihl, D-ALPHA-Hydroxypropionic acid, DL-LACTIC ACID, their ring-type Dimer (i.e. L- lactide, D- lactide, DL- lactide) and its mixture.
According to the present invention, the example of the aliphatic hydroxyl carboxylic acid includes but is not limited to glycolic, hydroxybutyric acid, hydroxyl penta Acid, hydroxycaproic acid, hydroxyheptanoic acid, Hydroxyoctanoic acid, hydroxynonanoic acid and hydroxydecanoic acid.
According to the present invention, the example of the aliphatic polyol include but is not limited to ethylene glycol, 1,4-butanediol, 1,6- oneself Glycol, 1,4 cyclohexane dimethanol, neopentyl glycol, decanediol, glycerol, trimethylolpropane and pentaerythrite.
According to the present invention, the example of the aliphatic polycarboxylic acid include but is not limited to succinic acid, adipic acid, suberic acid, Decanedioic acid, dodecanedioic acid, succinic anhydride, adipic anhydride, trimesic acid, the third three acid, Pyromellitic Acid and Pyromellitic Acid Acid anhydride.
Conventional method in that art can be used in the preparation method of polylactic acid base resin of the present invention, for example including but not It is limited to following method:
(1) method that Direct Dehydration polycondensation is imposed to the mixture of lactic acid or lactic acid and aliphatic hydroxyl carboxylic acid；
(2) method that ring-opening polymerisation is imposed to the cyclic dimer of lactic acid (i.e. lactide)；
(3) in the presence of a catalyst to the cyclic dimer of lactic acid and aliphatic hydroxyl carboxylic acid, such as lactide and glycolide The method for imposing ring-opening polymerisation with 6-caprolactone；
(4) method that Direct Dehydration polycondensation is imposed to the mixture of lactic acid, the pure and mild aliphatic dibasic acid of binary aliphatic；
(5) method that polycondensation is imposed to lactic acid, the pure and mild aliphatic dibasic acid of binary aliphatic in organic solvent；
(6) dehydrating polycondensation is imposed to lactic acid polymer in the presence of a catalyst to generate polyester and wrap in polycondensation process The method for including at least one solid phase polymerization step.
The above method can be in a small amount of aliphatic polyol (such as glycerol), aliphatic polybasic acids (such as butane tetramethyl Acid) or polyalcohol (such as polysaccharide) in the presence of carry out to obtain copolymer.Also can be used adhesive (polymer chain extender, Such as polyisocyanates, epoxide) Lai Tigao molecular weight.Branching agent can also be used, usually aliphatic polyol (such as season Penta tetrol) make the polylactic acid branching.
Preferably, heretofore described polylactic acid is blocked in its molecular chain-end, and polylactic acid base resin can be inhibited to send out The hydrolysis in bead preparation process is steeped, the progress of kettle foam process is conducive to.That is, easily prepared high foamability institute The poly- cream of hydrolysis that need to be poor compared with the physical qualitative change of resin caused by high-foaming temperature and the hydrolysis being resistant to during mould internal shaping Sour expanded bead.In addition, there is more preferably weatherability by the expanded polylactic acid bead mechanograph that mould internal shaping obtains.
The end-capping reagent of the present invention for blocking polylactic acid in its molecular chain-end includes carbodiimide compound, oxazoline Compound, isocyanate compound and epoxide, particularly preferred carbodiimide compound.Carbodiimide compound it is specific Example includes aromatics single carbon diimine (such as bis- (dipropyl phenyl) carbodiimides), the poly- carbodiimide of aromatics and aliphatic poly carbon two One of imines (such as poly- 4,4 '-dicyclohexyl methyl hydride carbodiimide) is a variety of.
It is 0.1 to 5 parts by weight, preferably 0.5 to 3 weight that the dosage of the end-capping reagent, which is based on every 100 parts by weight polylactic acid, Part.Polylactic acid of the present invention is preferably selected from carbodiimide compound, epoxide and isocyanation esterification at least one Close the polydactyl acid of the modifier modification of object, polydactyl acid more preferably modified using carbodiimide compound.
According to the present invention, when polylactic acid base resin is the hybrid resin of polylactic acid and other resins, in hybrid resin The content of polylactic acid is at least 40wt%, more preferably at least 60wt%, more preferably at least 80wt%.It can be with the polylactic acid Other resins that mixing constitutes hybrid resin include polyvinyl resin, acrylic resin, polystyrene resin and polyester resin.It is excellent Choosing uses the biodegradable aliphatic polyester resin containing at least 35mol% aliphatic ester component.Aliphatic polyester tree Rouge includes the ring opening polymerization product and rouge of the polycondensation product of the carboxylic acid in addition to polylactic resin, lactone (such as polycaprolactone) The polycondensation product of fat race polyalcohol and aliphatic polycarboxylic acid, such as poly butylene succinate, poly adipate succinic acid ester, polybutadiene Sour tetramethylene adipate and poly- (adipic acid-mutual-phenenyl two acid bromide two alcohol ester).
In some preferred embodiments of the invention, the polylactic acid base resin includes by PDLA/PLLA moles Than the polylactic acid blend formed for 1:1, or the copolymerization polylactic acid of 0.5wt%TDI+0.5wt%MDI end-capping reagent is added, or The copolymerization polylactic acid of person's addition epoxies polyfunctional monomer.
The epoxies polyfunctional monomer is selected from three glycidyl isocyanuric acids, glycerin triglycidyl ether, three hydroxyl first Base propane triglycidyl ether, triglycidyl group para-aminophenol, N, N, N ', N '-four glycidyl group -4,4 ' diamino two Phenylmethane, 1,3,5-trihydroxybenzene triglycidyl ether, four glycidol of Pyromellitic Acid be cruel, 1,1 ', 2,2 '-four (p-hydroxybenzenes) Four glycidol ether of ethane, four glycidol ether of resorcinol formal, double four glycidol ethers of resorcinol formal and first One of base glycidyl acrylate oligomer is a variety of.
According to the present invention, the phosphine oxide has the structure as shown in following formula I:
In Formulas I, R1、R2And R3It is identical or different, it is each independently selected from C1-C18Straight chained alkyl, C3-C18Branched alkyl, C1-C18Unbranched alkoxy, C3-C18Branched alkoxy, C6-C20Aromatic radical and C substituted or unsubstituted6-C20It is substituted or unsubstituted Aryloxy group.
Preferred embodiment in accordance with the present invention, R1、R2And R3It is each independently selected from methyl, ethyl, propyl, C4-C18 Linear or branched alkyl group and C6-C20Aromatic radical substituted or unsubstituted；It is more preferably selected from C4-C18Linear or branched alkyl group and C6-C18 Aromatic radical substituted or unsubstituted.
Preferred embodiment according to the present invention, R1、R2And R3It is each independently selected from C4-C18Linear chain or branched chain alkane The C that base and carbocyclic ring number are 1 or 26-C18Aromatic radical.
Further preferred embodiment according to the present invention, R1、R2And R3Main carbochain is each independently selected from 6 The C of above carbon atom6-C12Linear or branched alkyl group and phenyl substituted or unsubstituted.
According to the present invention, the aromatic radical can be with substituent groups such as hydroxyl, carboxyls.
Further preferred embodiment according to the present invention, R1、R2And R3For identical substituent group.Oxygen with the structure Changing phosphine and transition metal has stronger mating capability.
According to the preferred embodiment of the present invention, the phosphine oxide is selected from triphenylphosphine oxide, bis- (4- hydroxy phenyl) benzene Base phosphine oxide, bis- (4- carboxyl phenyl) phenyl phosphine oxides, tributylphosphine oxide, three hexyl phosphine oxides, trioctylphosphine oxide and three At least one of decyl phosphine oxide is more preferably selected from triphenylphosphine oxide, trioctyl phosphine oxide, three hexyl phosphine oxides and three last of the ten Heavenly stems At least one of base phosphine oxide.
According to the present invention, the transition metal salt includes transition metal organic salt and/or transition metal inorganic salts, preferably mistake Cross at least one of chloride, nitrate, sulfate, formates, acetate and the oxalates of metal, more preferable nitrate. The transition metal is preferably group VIII metal element, more preferably cobalt and/or nickel.Specifically, the transition metal salt is for example Selected from least one of nickel chloride, cobalt chloride, cobalt acetate, nickel acetate, cobalt nitrate, nickel nitrate, nickel sulfate and cobaltous sulfate.
A preferred embodiment according to the present invention, the transition metal salt are cobalt nitrate and/or nickel nitrate.Both Salt is easier to form complex with phosphine oxide, obtains higher yield.
According to the preferred embodiment of the present invention, the complex that the phosphine oxide and transition metal salt are formed has following knot Structure Formula II:
In Formula II, M is transition metal.R1、R2With R3With the R in Formulas I1、R2With R3It is identical.
R4And R5It is identical or not identical, it is each independently selected from formate ion (HCOO-), acetate ion (CH3COO-)、 Oxalate denominationby (C2O4H-), halide ion (Cl-, Br-, I-), nitrate ion (NO3 -) and thiocyanate ion (SCN-) in It is at least one；It is preferred that halide ion, nitrate ion and thiocyanate ion；More preferable nitrate ion.
According to the present invention, the preparation step of the complex includes: by the oxidation of 1-10 parts by weight, preferably 2-5 parts by weight Phosphine and the transition metal salt of 3-15 parts by weight, preferably 5-10 parts by weight are stirred in organic solvent, then microwave heating, are surpassed Critical drying obtains the complex；The organic solvent be preferably in ethyl alcohol, acetone, pyridine, tetrahydrofuran and DMF extremely Few one kind.
Wherein, the speed of stirring can be, for example, 90-120rpm, and the power of microwave is 35-55W, the temperature of microwave heating It is 35-50 DEG C, heating time is 3-4.5 hour.
In a preferred embodiment of the invention, the complex obtained after supercritical drying is represented by M (CHO2)2 (OPR3)2, wherein M can be Ni or Co, and R can be phenyl, hexyl, octyl or decyl.
Flame-proof polylactic acid composition according to the present invention, the polylactic acid base resin based on 100 parts by weight, the resistance The amount for firing agent is 5-50 parts by weight, preferably 10-20 parts by weight；Optionally, the amount of the antioxidant is 0.1-0.5 parts by weight, excellent Select 0.15-0.25 parts by weight.
According to the present invention, the fire retardant further comprises inorganic fire retardants component, the preferably described inorganic fire retardants group It is selected from IIA and Group IIIA metal hydroxides, is more preferably selected from magnesium hydroxide and/or aluminium hydroxide.By increasing inorganic resistance Agent component is fired, flame retardant effect can be further enhanced.
According to the preferred embodiment of the present invention, the weight of the complex in the fire retardant and the inorganic fire retardants component Amount is than being (1-5): 1, preferably (2.5-3.5): 1.
In some preferred embodiments of the invention, the fire retardant includes: 1-10 parts by weight, preferably 2-5 weight The phosphine oxide and 3-15 parts by weight of part, the complex of the transition metal salt formation of preferably 5-10 parts by weight and 1-10 parts by weight, It is preferred that the inorganic fire retardants component of 3-6 parts by weight.
When comprising inorganic fire retardants group timesharing, fire retardant of the present invention can be by first preparing the complex, then The complex is subjected to physical mixed with inorganic fire retardants component to be prepared.Here physical mixed can be ball milling, Mechanical stirring.It is preferred that mechanical stirring homogenizes, mixing speed is 10rpm or so.
Flame-proof polylactic acid composition of the present invention is particularly suitable for thermoplastic foamed material or the preparation of its formed body In, it can be formed and be cooperateed with used in promotion with antistatic agent, thermoplastic article is made to reach the requirement of Environmental Safety, improve flame retarding efficiency.
According to the present invention, carbon nano-fiber antistatic agent is further included in the flame-proof polylactic acid composition (conduction is filled out Material).It is preferably based on the polylactic acid base resin of 100 parts by weight, the amount of the carbon nano-fiber antistatic agent is 0.1-10 weight Measure part, preferably 1-3 parts by weight.
In some preferred embodiments of the invention, the weight of the fire retardant and the carbon nano-fiber antistatic agent Amount is than being (3-20): 1, more preferable (6-15): 1.
In accordance with the present invention it is preferred that containing transition metal (such as nickel or cobalt) 1- in the flame-proof polylactic acid composition 5wt%, such as 2-4wt%.This section transitions metal can come from being made in the carbon nano-fiber antistatic agent preparation process Catalyst.As it is one of the advantages of the invention that the carbon nano-fiber used is not required to remove transition gold therein Metal catalyst, and be directly used in and prepare the flame retardant thermoplastic material.Presence and other potential originals due to transition metal Cause, carbon nano-fiber that the present invention uses can occur synergistic effect with fire retardant, help to generate barrier flame and material Fine and close carbon-coating, so as to reduce the additive amount of fire retardant, and with fire retardant it is compound after negative effect does not lead to property each other mutually It can lower, not influence subsequent foaming process and foaming structure and physical property.
According to the present invention, there is no particular/special requirements for the purity, draw ratio of the carbon nano-fiber, diameter and pattern.
The preparation method for being suitable for the invention carbon nano-fiber includes: that carbon source is carried out sour processing, then golden with transition Metal catalyst forms compound, and the compound is carried out charing process.
The following are the illustrative preparation methods of carbon nano-fiber.
1) carbon source is carried out in advance with phosphoric acid nitric acid hydrochloric acid (volume ratio 1:1:1) mixed acid processing method or grinding processing method Processing obtains pretreatment object.
Wherein, carbon source is condensed state carbon source, can be anthraxolite, asphalt, coal tar pitch, coal tar, natural graphite, people Make at least one of graphite, bamboo charcoal, carbon black, active carbon and graphene；Here preferred carbon content is the carbon source of 80wt% or more, example If carbon content is at least one of selected from coal tar pitch and petroleum asphalt of 80wt% or more and bamboo charcoal.
2) compound: will pretreatment object with metallic catalyst is compound obtains compound.
Metallic catalyst is preferably sulfate, nitrate, acetate or the cyclopentadienyl compound of transition metal, the transition gold Belonging to is preferably group VIII metal element, such as Fe, Co or Ni, is also possible to Cr.
The mass percent of transition metal atoms and carbon source is (35-70) in metallic catalyst: 100.
It can be conducive to synergistic effect promotion flame retardant effect in view of containing nitrogen in catalyst, metallic catalyst is excellent here Select cobalt nitrate and/or nickel nitrate.
3) charing process: by compound 800-1200 DEG C temperature, high pure nitrogen protection under carry out carbonization reaction, constant temperature It 0.5-5 hours, cools to room temperature and obtains self assembly carbon fiber.Here preferred 950-1150 DEG C of the temperature of charing process, constant temperature is anti- It answers 1.5-2.5 hours.Metal impurities are removed without post-processing.
Compared to short-acting antistatic agent commonly used in the prior art, such as high molecular polymer antistatic agent, the present invention uses Carbon nano-fiber be a kind of long-acting antistatic agent, be capable of providing long-acting antistatic property.
The flame-proof polylactic acid composition can be prepared according to existing various methods, for example, directly by polylactic acid Composition and the fire retardant compound, antistatic agent and the lubricant selectively contained and other auxiliary agents are according to the proportion in machine Mechanical mixture is carried out in tool mixing apparatus, is then added in melt blending equipment and is carried out melt blending under the conditions of 140-210 DEG C It is granulated.First a small amount of polylactic acid can also be blended with fire retardant or conductive filler concentration respectively, be made under the conditions of 140-210 DEG C Fire-retardant master granule and antistatic master granule, then two kinds of master batches are blended in proportion with polylactic acid, it is made under the conditions of 140-210 DEG C Grain.Wherein, the mechanical mixing equipment can be for example high-speed mixer, kneader etc..The melt blending equipment for example may be used Think double screw extruder, single screw extrusion machine, open mill, mixer, buss kneader etc..Particularly, polylactic acid in order to prevent Resin is by hydrolytic degradation, the dry polylactic acid base resin preferably before kneading.In addition, in order to inhibit polylactic resin to pass through water Solution degradation, can also be using the extruder for having exhaust apparatus be used, to remove the humid air in polylactic acid.From polylactic acid tree Moisture is removed in rouge can inhibit resin microparticle to hydrolyze, and prevent from wherein generating bubble and can improve the stability of extrusion step.
Second aspect of the present invention provides a kind of flame-proof polylactic acid expanded bead, by that will include such as first party of the present invention Flame-proof polylactic acid composition described in face, 0.001-5 parts by weight, the preferably Nucleating Agent of 0.05-1.5 parts by weight and 0.2 The material of the antioxidant of parts by weight, is prepared by impregnated foaming process.
In order to control the apparent density and cell diameter of gained expanded bead, Nucleating Agent can be mixed into polylactic acid in advance In base resin particle.The blowing promotor is selected from hydrophobic substance.The blowing promotor includes inorganic powder, such as talcum powder, carbon Sour calcium, borax, zinc borate, aluminium hydroxide and silica, polytetrafluoroethylene (PTFE), polyethylene wax, polycarbonate, poly terephthalic acid Glycol ester, polypropylene terephthalate, polybutylene terephthalate (PBT), two methylene of polycyclohexylene Ester, poly- last of the ten Heavenly stems naphthalate, poly- last of the ten Heavenly stems dioctyl phthalate butanediol ester, silicone, methylmethacrylate copolymer and crosslinking polyphenyl Ethylene.Preferably polytetrafluoroethylene, polyethylene wax and crosslinked polystyrene, more preferable hydrophobic polytetrafluorethylepowder powder.
In addition, this method includes will be above-mentioned the present invention also provides the preparation method of above-mentioned flame-proof polylactic acid expanded bead Flame-proof polylactic acid composition is granulated, and obtained particles of polylactic acid is foamed.
The granulation can be carried out using existing various modes, for example, can be by flame-proof polylactic acid composition via double One or more extrusions of screw rod or single screw extrusion machine are at wire rod and cut and obtain flame-proof polylactic acid bead, can also be with Using underwater microparticle pelletizing system, specific operation process is known to the skilled person.
Some specific embodiments according to the present invention, the granulation are carried out as follows: by above-mentioned fire-retardant poly- cream After acid composition is blended using high-speed mixer, squeezed out by double screw extruder, it is earnestly rear to import 75 DEG C or less, preferably 70 DEG C Below, microparticle cutting is carried out more preferably in 55-65 DEG C of water, makes the length/diameter ratio 0.5-2.0, preferably of each particle For 0.8-1.3, it is more preferably 0.9-1.1, and average weight is 0.1-20mg, preferably 0.2-10mg, more preferably 1-3mg. Length/diameter ratio described herein is the average value of 200 optional particles of polylactic acid.
The foaming can also be carried out using existing various modes, for example, can be carried out using extrusion foaming process, it can also To be carried out using reaction kettle dipping foaming, it is preferred to use the expanded polylactic acid pearl that reaction kettle dipping foaming is obtained in this way Grain does not cause secondary pollution for non-crosslinking structure so as to recycle according to modified polylactic acid material, meets circular economy Requirement.
Some specific embodiments according to the present invention, the foaming are carried out using reaction kettle dipping foaming, specific mistake Journey is as follows:
(1) in autoclave, by particles of polylactic acid and decentralized medium, surfactant, dispersing agent and dispersion intensifier etc. Auxiliary agent is uniformly mixed；
(2) kettle cover is first covered tightly, uses foaming agent that residual air in autoclave is discharged with air-discharging method, it later will foaming Agent continues to feed in the autoclave, begins to warm up and just successive step pressure is subsequently agitated for the autoclave, stirring speed until its stabilization Degree is 50-150rmp, preferably 90-110rmp, stablizes low 0.1-5 DEG C, preferably low 0.5-1 than expansion to be at the uniform velocity heated to DEG C temperature；
(3) it adjusts pressure in autoclave and reaches the required pressure of foaming, which is 1-10MPa, is preferably 3-5MPa, with Temperature is increased to blowing temperature by 0.1 DEG C/min of average heating rate, and blowing temperature is 0.1-5 lower than microparticle melting temperature DEG C, it is 0.5-1 DEG C preferably low, under blowing temperature and pressure condition, persistently stir 0.1-2 hours, preferably 0.25-0.5 hours；
(4) discharge port of autoclave is opened, is excreted to the material in autoclave in collecting tank, to obtain polylactic acid hair Bead is steeped, carbon dioxide gas is fed while being discharged, so that before all particles foam completely and enter collecting tank, Pressure in autoclave is maintained near blow pressure.
In the present invention, the pressure refers both to gauge pressure.
The decentralized medium various can be such that particles of polylactic acid is dispersed therein and not dissolve the poly- cream to be existing The component of granulates, for example, can be at least one of water, ethylene glycol, glycerol, methanol, ethyl alcohol etc., particularly preferably water. In addition, the particles of polylactic acid relative to 100 parts by weight, the dosage of the decentralized medium can be 1000-5000 parts by weight, preferably For 2500-3500 parts by weight.
The surfactant various can promote particles of polylactic acid dispersion group in a dispersion medium to be existing Point, for example, can be sweet for stearic acid, neopelex, quaternary ammonium compound, lecithin, amino acid, glycine betaine, fatty acid At least one of grease, fatty acid sorbitan, polysorbate etc., particularly preferably neopelex.In addition, opposite In the particles of polylactic acid of 100 parts by weight, the dosage of the surfactant can be 0.001-10 parts by weight, preferably 0.01-5 Parts by weight, more preferably 0.1-0.5 parts by weight.
The purpose of the dispersing agent addition is that particles of polylactic acid is melt bonded each other during foaming in order to prevent.Described point Powder can be organic dispersing agent, or inorganic dispersant, preferably inorganic dispersant.The inorganic dispersant can be Natural or synthesis clay mineral (such as kaolin, mica, pyrope, clay etc.), alumina, titanium dioxide, alkali formula carbon At least one of sour magnesium, basic zinc carbonate, calcium carbonate, silica, zinc borate and iron oxide etc., particularly preferably kaolinite Soil.In addition, the particles of polylactic acid relative to 100 parts by weight, the dosage of the dispersing agent can be 0.01-20 parts by weight, preferably For 0.1-10 parts by weight, more preferably 0.5-5 parts by weight.
The purpose of the dispersion intensifier addition is the dispersion efficiency in order to improve dispersing agent, that is, is reducing dispersant dosage While retain it and prevent melt bonded function between particle.The dispersion intensifier can be existing various in 100mL, 40 Solubility is 1mg and provides the inorganic compound of divalent or trivalent anion or cation in DEG C water.The dispersion intensifier Example include but is not limited to magnesium nitride, magnesium nitrate, aluminum phosphate, magnesium sulfate, aluminium nitride, aluminum nitrate, aluminum sulfate, iron chloride, sulphur At least one of sour iron and ferric nitrate etc., preferably aluminum sulfate.The use of the dispersion intensifier is conducive to obtain apparent close Degree is the expanded polylactic acid bead of 100g/L or more.In addition, the particles of polylactic acid relative to 100 parts by weight, the dispersion enhancing The dosage of agent can be 0.0001-1 parts by weight, preferably 0.01-0.2 parts by weight.
The foaming agent can be organic physical blowing agent, or inorganic physical blowing agent.Wherein, described to have The example of machine class physical blowing agent includes but is not limited to aliphatic hydrocarbon such as propane, butane, pentane, hexane and heptane, alicyclic ring Race's hydro carbons such as cyclobutane and hexamethylene and halogenated hydrocarbon such as chlorofluoromethane, fluoroform, 1,2- Difluoroethane, 1,2, At least one of 2,2- tetrafluoroethane, methyl chloride, ethyl chloride and methylene chloride etc..The example packet of the inorganic physical blowing agent Include but be not limited at least one of air, nitrogen, carbon dioxide, oxygen and water.In view of expanded polylactic acid bead is apparently close Stability (homogeneity), low cost and the environmental-friendly problem of degree, the foaming agent are preferably carbon dioxide and/or nitrogen, spy It You Xuanwei not carbon dioxide.In addition, the dosage of the foaming agent can be according to the specific type of foaming agent, blowing temperature and institute The apparent density of the expanded polylactic acid bead to be produced is determined.For example, when employing nitrogen as foaming agent and using water Pressure (the pressure in closed container inner upper space when as decentralized medium, when foam device pressure release in the closed container Power (gauge pressure)) it controls in 1-12MPa；When using carbon dioxide as foaming agent, then above-mentioned gauge pressure is controlled in 1-7MPa.One As for, desired pressure in the closed container inner upper space is reduced with the apparent density of obtained expanded polylactic acid bead And increase.
Since polylactic acid based resin is easy hydrolysis, the additive to blend with matrix resin is wished selected from hydrophobic substance, It is avoided as far as possible using hydrophilic substance simultaneously.Therefore, when using hydrophobic blowing promotor, polylactic acid base resin can prevented The effect as blowing promotor is obtained while because of hydrolytic degradation.Particularly, polylactic acid base resin water can be substantially prevented from The general formula of solution reduces apparent density (improving foaming ratio) and keeps cell diameter uniform.
Have at low cost, abscess fine and close using the expanded polylactic acid bead of the method for the present invention preparation and even aperture distribution etc. Advantage can be applied to automobile component, food and electronic packaging and building decoration etc. and have higher requirements to plastic products lightweight Occasion.
Preferred embodiment in accordance with the present invention, the antioxygen being added in the preparation process of the expanded polylactic acid bead are Hinered phenols antioxidant.The antioxidant is selected from 1,3,5- trimethyl -2,4,6- three (3,5- di-t-butyl -4- hydroxyphenylmethyl) Benzene, 4,4 '-thiobis (6- tert-butyl -3- methylphenol), four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] Ji Wusi One of alcohol ester and 2,6 di tert butyl 4 methyl phenol are a variety of.
In addition, various can also can lead in expanded polylactic acid bead containing existing in the polylactic acid base resin Other auxiliary agents being often used, for example, ultraviolet absorber, antistatic agent, fire retardant, metal inactivator, pigment, nucleating agent, filler, Stabilizer, reinforcing agent etc..The type and content of above-mentioned auxiliary agent all can be this field conventional selection, to this those skilled in the art Member can know that therefore not to repeat here.
Third aspect present invention provides a kind of flame-proof polylactic acid expanded bead formed body, by second party according to the present invention The molded moulding process of flame-proof polylactic acid expanded bead described in face is prepared.
Flame-proof polylactic acid expanded bead formed body according to the present invention, it is described it is molded can be existing various Carried out in molding forming machine, and molded condition all can be this field conventional selection, to this those skilled in the art Member can know that therefore not to repeat here.
Term " base resin " of the present invention refers to pure resin, i.e., the resin of not formed composition.
Term " Halogen " of the present invention refers to be halogen-free in compound or mixture or composition.
Term " optionally " of the present invention, which refers to, to be contained or not contain, and is also referred to be added or is added without.
Compared with prior art, the invention has the following beneficial effects:
(1) long-acting comprising inorganic fire retardants component and one kind in the fire retardant the present invention provides a kind of halogen-free flame retardants Antistatic agent (carbon nano-fiber) can play synergistic effect between both functionalization auxiliary agents, effectively improve flame retarding efficiency, change Kind flame retardant effect, reduces fire retardant additive amount, while having no adverse effect to antistatic property.
(2) flame-proof polylactic acid expanded bead provided by the invention has anti-impact, lower forming temperature, antistatic, fire-retardant The advantages that function admirable, thus it is suitable for automobile component, medical instrument, electronic packaging, household items, low temperature cold chain packaging, body Educating equipment, building heat preservation and aerospace etc. has the excellent material in field of comprehensive requirement to flame-retardant and anti-static low temperature impact Material.The preparation method of flame-proof polylactic acid composition provided by the invention is simple and effective, easily operated.
(3) present invention is had compared with using organic foaming agent in the prior art using carbon dioxide as foaming agent The advantages that environmental-friendly, safe.
(4) flame-proof polylactic acid expanded bead prepared by the present invention is non-crosslinking structure, can be according to general polylactic acid modified MAT'L recycling does not cause secondary pollution, meets the requirement of circular economy.
Detailed description of the invention
It is next with reference to the accompanying drawing that invention is further described in detail.
Fig. 1 shows the cross-sectional scans electromicroscopic photograph of the flame-proof polylactic acid expanded bead of the embodiment of the present invention 1.
Fig. 2 shows the cross-sectional scans electromicroscopic photograph of traditional flame-proof polylactic acid expanded bead of comparative example 1 of the present invention.
Specific embodiment
The present invention is described in further detail with reference to the following example, but should be illustrated: the present invention is in no way limited to these Embodiment.
Related data in the embodiment of the present invention are obtained by following test method:
(1) Breadth parameter of molecular weight distribution Mw/Mn: the model produced using Polymer Laboratories company, Britain For the measurement of PL-GPC220 type gel permeation chromatograph combination IR5 type infrared detector, wherein the chromatographic column of gel permeation chrommatograph is 3 Root 10 μm of MIXED-B columns of concatenated Plgel, solvent and mobile phase be 1,2,4- trichloro-benzenes (antioxidant containing 0.3g/1000mL 2, 6- di-tert-butyl p-cresol), column temperature is 150 DEG C, flow velocity 1.0mL/min, and the EasiCal PS-1 produced using PL company is narrow Disperse polystyrene standards carry out universal calibration；
(2) it melt index MI: is measured according to method specified in GB/T3682-2000, wherein test temperature is 190 DEG C, load 2.16kg；
(3) it density: is measured according to method specified in GB/T1033.2-2010 and using density gradient column method；
(4) limit oxygen index is tested: being tested according to the method that national standard GB/T 5454-1997 is described；
(5) surface resistivity is tested: being tested according to GB/T 1410-2006；
(6) compressive strength is tested: being tested according to U.S.ASTM standard D3575-08, utilizes the compression speed of 10mm/min Degree carries out compression test, obtains compressive strength of the formed body by compression 50% when；
(7) tensile strength is tested: being tested according to U.S.ASTM standard ASTM D 3575.
Embodiment
Embodiment 1
The raw material proportioning and reaction of the products such as fire retardant, flame-proof polylactic acid composition and expanded bead manufactured in the present embodiment Condition is listed in Tables 1 and 2, and table 2 also lists the performance parameter of expanded bead.In table, flame retardant compositions A is phosphine oxide, resistance Firing agent component B is transition metal salt, and flame retardant compositions C is inorganic fire retardants component.
(1) preparation of fire retardant
The triphenylphosphine oxide of 7 parts by weight and the cobalt nitrate of 3 parts by weight are added in ethyl alcohol, carried out with the rate of 100rpm Then stirring uses microwave heating mixed material, heating power 50W under stiring, temperature is 40 DEG C, reaction time 4h.It will Material after microwave heating reaction carries out supercritical drying, obtains the complex Co of the formation of triphenylphosphine oxide and cobalt nitrate (OPPh3)2(NO3)2。
By the complex Co (OPPh of above-mentioned preparation3)2(NO3)2It is homogenized with magnesium hydroxide mechanical stirring, mixing speed is 10rpm obtains fire retardant.
(2) preparation of carbon nano-fiber antistatic agent
The coal tar pitch for being 80mol% or more using carbon content is mixed as carbon source with phosphoric acid/nitric acid/hydrochloric acid (volume ratio 1:1:1) Acid carries out grinding pretreatment, obtains pretreatment object.
Above-mentioned pretreatment object and catalyst cobalt nitrate are added in ball mill and mixed, compound is obtained.
The compound is subjected to carbonization reaction in the case where 950 DEG C of high pure nitrogens are protected, constant temperature 1.5 hours, is then cooled to Room temperature obtains self-assembled nanometer carbon fiber.Catalyst metals impurity, after measured, 2.0wt% containing cobalt are removed without post-processing.
(3) preparation of polylactic acid base resin PLA101
Polylactic resin (PDLA and PLLA molar ratio=1:1) is 100 parts by weight, the 0.1%TDI+ of 1000ppm (weight) Polylactic resin is prepared as end-capping reagent in 0.1%MDI%.
Lubricant is the PEG lubricant produced by Switzerland's Clariant Corporation, number-average molecular weight 10000.
Above-mentioned 100 parts by weight of polylactic resin are weighed, lubricant is then added (with above-mentioned polylactic resin weight for 100 Parts by weight meter, the additional amount of lubricant are 0.1 parts by weight), it adds mixture in high speed agitator and is uniformly mixed later, then The material mixed is added in the feeder of the double screw extruder of Nanjing Ke Beilong company manufacture, material is via feeder Into in twin-screw, the temperature of screw rod is maintained between 140-210 DEG C in process, is squeezed after screw rod melting mixing is uniform Out, it pelletizing and dries, obtains polylactic acid base resin pellet.
(4) preparation of flame-proof polylactic acid composition
Above-mentioned each component is weighed and mixed according to the ratio, wherein the polylactic acid base resin in step (3) is 100 Parts by weight, flame retardant compositions are 15 parts by weight, and carbon nano-fiber antistatic agent is 1 parts by weight, the hydrophobic polytetrafluoro of Nucleating Agent Ethylene is 0.3 parts by weight.In addition, being also added into processing aid in the preparation process of the composition includes antioxidant 1010 (BASF Company), irgasfos 168 (BASF AG) etc., dosage is conventional amount used, relative to 100 parts by weight of polylactic acid base resin, point It Wei not 0.2 parts by weight and 0.1 parts by weight.It later adds mixture in high speed agitator and is uniformly mixed, then will mix Material is added in the feeder of the double screw extruder of Ke Beilong company manufacture, and material enters in twin-screw via feeder, The temperature of screw rod is maintained between 140-210 DEG C in process, through screw rod melting mixing uniformly, into Lab100 particulate system Standby system, moment of torsion control is 65% or so, revolving speed 300rpm.Obtain flame-proof polylactic acid composition microparticle.
(5) preparation method of flame-proof polylactic acid expanded bead
The flame-proof polylactic acid composition microparticle and decentralized medium deionized water, surfactant ten that step (4) is obtained The auxiliary agents such as dialkyl benzene sulfonic acids sodium, dispersing agent kaolin and dispersion intensifier aluminum sulfate are added at one time in autoclave and mix It is even, and the flame-proof polylactic acid composition relative to 100 parts by weight, the dosage of decentralized medium are 2700 parts by weight, surfactant Dosage be 0.4 parts by weight, the dosage of dispersing agent is 5 parts by weight, and the dosage of dispersion intensifier is 0.2 parts by weight.
Autoclave kettle cover is covered tightly, residual air in autoclave is discharged using carbon dioxide, later continues carbon dioxide It feeds in autoclave, begins to warm up and just pressure is subsequently agitated for the autoclave, mixing speed is until its stabilization in successive step kettle 100rmp, the temperature in autoclave is at the uniform velocity heated to 144.5 DEG C.
Pressure is adjusted in autoclave to 4MPa, and raises the temperature to 145 DEG C with 0.1 DEG C/min of average heating rate, Then it is persistently stirred under above-mentioned pressure and temperature 0.5 hour.
The discharge port of autoclave is opened, is excreted to the material in autoclave in collecting tank, to obtain expanded bead, Carbon dioxide gas is fed while discharging, so that before all particles foam completely and enter collecting tank, by autoclave In pressure be maintained near blow pressure.
Dehydrated after collecting bead, the use of aperture is 3.35mm and the sieve of 2.8mm to screen out partial size be 2.8- The electromicroscopic photograph difference of the expanded polylactic acid bead of 3.35mm, section is as shown in Figure 1.It can be seen that from the result of Fig. 1 by this The abscess dense uniform for the expanded polylactic acid bead that the poly (lactic acid) composition that invention provides obtains.
(6) preparation of flame-proof polylactic acid expanded bead formed body
(German Kurtz Ersa company is raw using molding forming machine for the flame-proof polylactic acid expanded bead that step (5) is obtained It is the Kurtz T-Line of production, similarly hereinafter) molded under the pressure of 0.15MPa, then by obtained formed body temperature be 65 DEG C, Pressure be standard atmospheric pressure under conditions of cure 24 hours to get arrive molded product.Specific expanded bead fusion pressure and The Molding parameters such as water vapour pressure are shown in Table 2.Molded product are used for oxygen index (OI), carbon yield, flame height, smoke condition, surface The test of resistivity, compressive strength, rebound degree, permanent compression set rate.The side described according to national standard GB T 2406.2-2009 Method carries out oxygen index (OI) test, carries out surface resistivity test according to GB/T 1410-2006.It is cut from expanded bead formed body The sample of 50*50*25mm out carries out compressive strength test based on U.S.ASTM standard D3575-08, utilizes the pressure of 10mm/min Contracting speed carries out compression test, obtains compressive strength of the formed body by compression 50% when.According to U.S.ASTM standard ASTM D 3575 carry out tensile strength test.Above-mentioned every test the results are shown in Table 2.
Embodiment 2
(1) the preparation method is the same as that of Example 1 with (two) carbon nano-fiber antistatic agent for the preparation method of fire retardant, different Place is, composition of raw materials and reaction condition shown in Tables 1 and 2.For example, the fire retardant that the embodiment is formed is trioctylphosphine Complex Ni (the OPOt that phosphine oxide and nickel nitrate are formed3)2(NO3)2。
(3) preparation of polylactic acid base resin PLA102
Polylactic resin is prepared by following methods: in the presence of a catalyst to the ring of lactic acid and aliphatic hydroxyl carboxylic acid Shape dimer, as (such as United States Patent (USP) US4 057 is disclosed in 537 for lactide and glycolide and the method for 6-caprolactone ring-opening polymerisation Preparation method).
Lubricant is the PEG lubricant produced by Switzerland's Clariant Corporation, number-average molecular weight 10000.
Above-mentioned 100 parts by weight of polylactic resin are weighed, lubricant is then added (with above-mentioned polylactic resin weight for 100 Parts by weight meter, the additional amount of lubricant are 0.1 parts by weight), it adds mixture in high speed agitator and is uniformly mixed later, then The material mixed is added in the feeder of the double screw extruder of Nanjing Ke Beilong company manufacture, material is via feeder Into in twin-screw, the temperature of screw rod is maintained between 140-210 DEG C in process, is squeezed after screw rod melting mixing is uniform Out, it pelletizing and dries, obtains polylactic acid base resin pellet.
(4) preparation of flame-proof polylactic acid composition
The preparation of flame-proof polylactic acid composition is with embodiment 1, the difference is that the raw material proportioning in table 1.For example, the reality Applying the flame retardant compositions in example is 14 parts by weight, and carbon nano-fiber antistatic agent is 1.5 parts by weight, Nucleating Agent polyethylene wax For 0.06 parts by weight.
(5) preparation of flame-proof polylactic acid expanded bead
The poly (lactic acid) composition microparticle and decentralized medium deionized water, surfactant sodium dodecyl that step (4) is obtained The auxiliary agents such as base benzene sulfonic acid sodium salt, dispersing agent kaolin and dispersion intensifier aluminum sulfate are added at one time in autoclave and are uniformly mixed, and Relative to the poly (lactic acid) composition pellet of 100 parts by weight, the dosage of decentralized medium is 3000 parts by weight, the dosage of surfactant For 0.3 parts by weight, the dosage of dispersing agent is 4.5 parts by weight, and the dosage of dispersion intensifier is 0.15 parts by weight.
Autoclave kettle cover is covered tightly, residual air in autoclave is discharged using carbon dioxide, later continues carbon dioxide It feeds in autoclave, begins to warm up and just pressure is subsequently agitated for the autoclave, mixing speed is until its stabilization in successive step kettle 100rmp, the temperature in autoclave is at the uniform velocity heated to 142 DEG C.
Pressure is adjusted in autoclave to 5MPa, and raises the temperature to 142.5 with 0.1 DEG C/min of average heating rate DEG C, then persistently stirred under above-mentioned pressure and temperature 0.5 hour.
The discharge port of autoclave is opened, is excreted to the material in autoclave in collecting tank, to obtain expanded bead, Carbon dioxide gas is fed while discharging, so that before all particles foam completely and enter collecting tank, by autoclave In pressure be maintained near blow pressure.
Dehydrated after collecting bead, the use of aperture is 3.35mm and the sieve of 2.8mm to screen out partial size be 2.8- The expanded polylactic acid bead of 3.35mm.
(6) preparation of expanded polylactic acid bead molding
The expanded polylactic acid bead that step (5) obtains is molded as under the pressure of 0.18MPa using molding forming machine Obtained formed body is cured 24 hours under conditions of temperature is 65 DEG C, pressure is standard atmospheric pressure then to get molding is arrived by type Molded product.Oxygen index (OI), carbon yield, flame height, smoke condition, surface resistivity, tensile strength and compressive strength are carried out to it Test, the result is shown in tables 2.
Embodiment 3
(1) the preparation method is the same as that of Example 1 with (two) carbon nano-fiber antistatic agent for the preparation method of fire retardant, different Place is, composition of raw materials and reaction condition shown in Tables 1 and 2.For example, the fire retardant that the embodiment is formed is trioctylphosphine Complex Co (the OPOt that phosphine oxide and cobalt nitrate are formed3)2(NO3)2。
(3) preparation of polylactic acid base resin PLA103
Polylactic resin is prepared by following methods: the mixing to lactic acid, the pure and mild aliphatic dibasic acid of binary aliphatic Object imposes the method (preparation method as disclosed in United States Patent (USP) US428126) of Direct Dehydration polycondensation.
Lubricant is the PEG lubricant produced by Switzerland's Clariant Corporation, number-average molecular weight 10000.
Above-mentioned 100 parts by weight of polylactic resin are weighed, lubricant is then added (with above-mentioned polylactic resin weight for 100 Parts by weight meter, the additional amount of lubricant are 0.1 parts by weight), it adds mixture in high speed agitator and is uniformly mixed later, then The material mixed is added in the feeder of the double screw extruder of Nanjing Ke Beilong company manufacture, material is via feeder Into in twin-screw, the temperature of screw rod is maintained between 140-210 DEG C in process, is squeezed after screw rod melting mixing is uniform Out, it pelletizing and dries, obtains polylactic acid base resin pellet.
(4) preparation of flame-proof polylactic acid composition is the same as embodiment 1
The preparation of flame-proof polylactic acid composition is with embodiment 1, the difference is that the raw material proportioning in table 1.For example, the reality Applying the flame retardant compositions in example is 15.4 parts by weight, and carbon nano-fiber antistatic agent is 1.5 parts by weight, and Nucleating Agent is hydrophobic poly- Tetrafluoroethene is 0.12 parts by weight.
(5) preparation of flame-proof polylactic acid expanded bead
The flame-proof polylactic acid composition microparticle and decentralized medium deionized water, surfactant ten that step (4) is obtained The auxiliary agents such as dialkyl benzene sulfonic acids sodium, dispersing agent kaolin and dispersion intensifier aluminum sulfate are added at one time in autoclave and mix It is even, and the poly (lactic acid) composition pellet relative to 100 parts by weight, the dosage of decentralized medium are 3000 parts by weight, surfactant Dosage be 0.35 parts by weight, the dosage of dispersing agent is 4.8 parts by weight, and the dosage of dispersion intensifier is 0.15 parts by weight.
Autoclave kettle cover is covered tightly, is discharged using residual air in the carbon dioxide autoclave, later continues carbon dioxide It feeds in autoclave, begins to warm up and just pressure is subsequently agitated for the autoclave, mixing speed is until its stabilization in successive step kettle 100rmp, the temperature in autoclave is at the uniform velocity heated to 143 DEG C.
Pressure is adjusted in autoclave to 5MPa, and raises the temperature to 143.5 with 0.1 DEG C/min of average heating rate DEG C, then persistently stirred under above-mentioned pressure and temperature 0.5 hour.
The discharge port of autoclave is opened, is excreted to the material in autoclave in collecting tank, to obtain expanded bead, Carbon dioxide gas is fed while discharging, so that before all particles foam completely and enter collecting tank, by autoclave In pressure be maintained near blow pressure.
Dehydrated after collecting bead, the use of aperture is 3.35mm and the sieve of 2.8mm to screen out partial size be 2.8- The expanded polylactic acid bead of 3.35mm.
(6) preparation of flame-proof polylactic acid expanded bead formed body
The expanded polylactic acid bead that step (5) obtains is molded as under the pressure of 0.16MPa using molding forming machine Obtained formed body is cured 24 hours under conditions of temperature is 65 DEG C, pressure is standard atmospheric pressure then to get molding is arrived by type Molded product.Oxygen index (OI), carbon yield, flame height, smoke condition, surface resistivity, tensile strength and compressive strength are carried out to it Test, the result is shown in tables 2.
Embodiment 4
(1) the preparation method is the same as that of Example 1 with (two) carbon nano-fiber antistatic agent for the preparation method of fire retardant.
(3) preparation of polylactic acid base resin PLA104
Polylactic resin is prepared by following methods: in organic solvent to lactic acid, the pure and mild aliphatic of binary aliphatic Binary acid imposes the method (such as preparation method disclosed in European patent 0712880A2) of polycondensation.
Lubricant is the PEG lubricant produced by Switzerland's Clariant Corporation, number-average molecular weight 10000.
Above-mentioned 100 parts by weight of polylactic resin are weighed, lubricant is then added (with above-mentioned polylactic resin weight for 100 Parts by weight meter, the additional amount of lubricant are 0.1 parts by weight), it adds mixture in high speed agitator and is uniformly mixed later, then The material mixed is added in the feeder of the double screw extruder of Nanjing Ke Beilong company manufacture, material is via feeder Into in twin-screw, the temperature of screw rod is maintained between 140-210 DEG C in process, is squeezed after screw rod melting mixing is uniform Out, it pelletizing and dries, obtains polylactic acid base resin pellet.
(4) preparation of flame-proof polylactic acid composition is the same as embodiment 1
The preparation of flame-proof polylactic acid composition is with embodiment 1, the difference is that the raw material proportioning in table 1.For example, the reality Applying the hydrophobic polytetrafluoroethylene (PTFE) of Nucleating Agent in example is 0.2 parts by weight.
(5) preparation of flame-proof polylactic acid expanded bead
The flame-proof polylactic acid composition microparticle and decentralized medium deionized water, surfactant ten that step (4) is obtained The auxiliary agents such as dialkyl benzene sulfonic acids sodium, dispersing agent kaolin and dispersion intensifier aluminum sulfate are added at one time in autoclave and mix It is even, and the poly (lactic acid) composition pellet relative to 100 parts by weight, the dosage of decentralized medium are 3000 parts by weight, surfactant Dosage be 0.35 parts by weight, the dosage of dispersing agent is 4.8 parts by weight, and the dosage of dispersion intensifier is 0.15 parts by weight.
Autoclave kettle cover is covered tightly, is discharged using residual air in the carbon dioxide autoclave, later continues carbon dioxide It feeds in autoclave, begins to warm up and just pressure is subsequently agitated for the autoclave, mixing speed is until its stabilization in successive step kettle 100rmp, the temperature in autoclave is at the uniform velocity heated to 141 DEG C.
Pressure is adjusted in autoclave to 5MPa, and raises the temperature to 141.5 with 0.1 DEG C/min of average heating rate DEG C, then persistently stirred under above-mentioned pressure and temperature 0.5 hour.
The discharge port of autoclave is opened, is excreted to the material in autoclave in collecting tank, to obtain expanded bead, Carbon dioxide gas is fed while discharging, so that before all particles foam completely and enter collecting tank, by autoclave In pressure be maintained near blow pressure.
Dehydrated after collecting bead, the use of aperture is 3.35mm and the sieve of 2.8mm to screen out partial size be 2.8- The expanded polylactic acid bead of 3.35mm.
(6) preparation of flame-proof polylactic acid expanded bead formed body
The expanded polylactic acid bead that step (5) obtains is molded as under the pressure of 0.19MPa using molding forming machine Obtained formed body is cured 24 hours under conditions of temperature is 65 DEG C, pressure is standard atmospheric pressure then to get molding is arrived by type Molded product.Oxygen index (OI), carbon yield, flame height, smoke condition, surface resistivity, tensile strength and compressive strength are carried out to it Test, the result is shown in tables 2.
Embodiment 5
Fire retardant, polylactic acid base resin, flame-proof polylactic acid composition, flame-proof polylactic acid expanded bead and flame-proof polylactic acid The preparation method is the same as that of Example 1 for expanded bead formed body, the difference is that, it is antistatic that carbon nano-fiber is not made and used Agent.Oxygen index (OI), carbon yield, flame height, smoke condition, surface resistivity, tensile strength and the pressure of obtained molded product The test result of contracting intensity is shown in Table 2.
Embodiment 6
Fire retardant, carbon nano-fiber antistatic agent, polylactic acid base resin, flame-proof polylactic acid composition, flame-proof polylactic acid The preparation method of expanded bead and flame-proof polylactic acid expanded bead formed body with embodiment 4, the difference is that, by antistatic agent Carbon black is replaced with, and dosage is the experiment condition in 6 parts by weight and Tables 1 and 2.The oxygen index (OI) of obtained molded product, Carbon yield, flame height, smoke condition, surface resistivity, the test result of tensile strength and compressive strength are shown in Table 2.
Comparative example 1
Fire retardant, carbon nano-fiber antistatic agent, polylactic acid base resin, flame-proof polylactic acid composition, flame-proof polylactic acid The preparation method is the same as that of Example 1 for expanded bead and flame-proof polylactic acid expanded bead formed body, the difference is that, fire retardant is replaced It is changed to red phosphorus, and dosage is the experiment condition in 20 parts by weight and Tables 1 and 2.It is the oxygen index (OI) of obtained molded product, residual Charcoal rate, flame height, smoke condition, surface resistivity, the test result of tensile strength and compressive strength are shown in Table 2.
Comparative example 2
Fire retardant, carbon nano-fiber antistatic agent, polylactic acid base resin, flame-proof polylactic acid composition, flame-proof polylactic acid The preparation method of expanded bead and flame-proof polylactic acid expanded bead formed body with embodiment 2, the difference is that, fire retardant is replaced To only use magnesium hydroxide, and dosage is the experiment condition in 30 parts by weight and Tables 1 and 2.Obtained molded product Oxygen index (OI), carbon yield, flame height, smoke condition, surface resistivity, the test result of tensile strength and compressive strength are shown in Table 2.
Comparative example 3
Fire retardant, carbon nano-fiber antistatic agent, polylactic acid base resin, flame-proof polylactic acid composition, flame-proof polylactic acid The preparation method of expanded bead and flame-proof polylactic acid expanded bead formed body with embodiment 3, the difference is that, fire retardant is replaced It is changed to the composition of hexabromocyclododecane and antimony oxide, and dosage is the experiment item in 30 parts by weight and Tables 1 and 2 Part.Oxygen index (OI), carbon yield, flame height, smoke condition, surface resistivity, tensile strength and the pressure of obtained molded product The test result of contracting intensity is shown in Table 2.
Comparative example 4
Fire retardant, carbon nano-fiber antistatic agent, polylactic acid base resin, flame-proof polylactic acid composition, flame-proof polylactic acid The preparation method is the same as that of Example 1 for expanded bead and flame-proof polylactic acid expanded bead formed body, the difference is that, in fire retardant not Contain the experiment condition in flame retardant compositions B cobalt nitrate and Tables 1 and 2.Oxygen index (OI), the carbon residue of obtained molded product Rate, flame height, smoke condition, surface resistivity, the test result of tensile strength and compressive strength are shown in Table 2.
Comparative example 5
Fire retardant, carbon nano-fiber antistatic agent, polylactic acid base resin, flame-proof polylactic acid composition, flame-proof polylactic acid The preparation method is the same as that of Example 1 for expanded bead and flame-proof polylactic acid expanded bead formed body, the difference is that, in fire retardant not Contain the experiment condition in flame retardant compositions A triphenylphosphine oxide and Tables 1 and 2.The oxygen index (OI) of obtained molded product, Carbon yield, flame height, smoke condition, surface resistivity, the test result of tensile strength and compressive strength are shown in Table 2.
It can be seen that the PLA101-104 prepared through the invention by embodiment 1-4 and all have good foam performance, Using it as basic resin, organophosphorus complexes and inorganic hydroxide compound flame retardant, nickeliferous or cobalt Nano carbon fibers are added Dimension is used as antistatic agent, prepares flame-retardant and anti-static poly (lactic acid) composition.Then, it impregnates and foams according to autoclave provided by the invention Method, the expanded bead for being 0.08-0.20g/L by adjusting the available density of the conditions such as blow pressure and temperature, use are non-super Foaming effect is good when critical carbon dioxide is as foaming agent, and cell density is higher, and abscess dense uniform, abscess-size is smaller, Cell wall is relatively thin, and surface of beads is smooth, and wherein the sectional view of the bead of embodiment 1 is as shown in Fig. 1.Specific molded shape Mechanics, fire-retardant and antistatic property is as shown in table 2.Wherein, good foam structure makes compression performance and the drawing of formed body Stretch function admirable；Formed body oxygen index (OI) and related flame retardant test situation show that fire retardant compound can be played with antistatic agent Synergistic effect, can be effectively reduced fire retardant additive amount, and oxygen index (OI) is higher than 28, can be used for the more demanding neck of flame retardant level Domain, while surface resistivity reaches 109The antistatic rank of Ω.
Can be seen that by embodiment 6 and embodiment 1-4 using traditional antistatic agent carbon black, fire retardant and carbon black it Between can not play synergistic effect, therefore, flame retardant property and antistatic property are low compared with embodiment 1-4.Pass through comparative example 1-3 and table 2 as can be seen that using traditional red phosphorus, bromide fire retardant, be used alone the fire retardants such as magnesium hydroxide and nickeliferous or cobalt nanometer The cooperation such as carbon fiber, the polylactic acid base resin that the flame-retardant and anti-static agent as compounding obtains prepare expanded bead, gained bead The fire retardancy and antistatic property for being formed by formed body are inferior to the obtained expanded bead of composition described in embodiment 1-4, And the addition of fire retardant described in comparative example and antistatic agent plays negative effect for foam performance, abscess is uneven, abscess Wall has breakage.By embodiment 1-4 compared with comparative example 5-6, it can be seen that formed using transition metal such as organic phosphorus and nickel cobalts Complex and magnesium hydroxide or aluminium hydroxide as in the antistatic system of fire retardant and carbon nano-fiber composition, transition metal with Concerted catalysis effect occurs for magnesium hydroxide, improves the flame retarding efficiency of phosphorus flame retardant.Carbon nano-fiber can inside resin structure Effective conductive network is built, to form the long-acting antistatic network system, effectively reduces the table of expanded bead formed body Surface resistivity.Remaining nickel or cobalt series catalyst equally form good synergistic effect with chelate in carbon fiber, improve fire-retardant Efficiency.In addition, in comparative example 1, the obtained composition of system formed using traditional red phosphorus combustion inhibitor and antistatic agent, two Person does not have synergistic effect, and interact reduces fire-retardant and antistatic property instead, and causes negatively to the foam structure of bead It influences, the cell density of obtained expanded bead is lower, and cell diameter is larger, and the phenomenon that cell wall rupture occur is (such as attached Shown in Fig. 2).

Claims (11)

1. a kind of flame-proof polylactic acid composition comprising: polylactic acid base resin, fire retardant and optionally antioxidant, wherein The fire retardant includes the complex that phosphine oxide and transition metal salt are formed.
2. flame-proof polylactic acid composition according to claim 1, which is characterized in that the polylactic acid base resin includes poly- The mixture of lactic acid or polylactic acid and other resins；Other resins include polyvinyl resin, acrylic resin, polystyrene One of resin and polyester resin are a variety of；
It is preferred that the polylactic acid includes homopolymerization polylactic acid and/or copolymerization polylactic acid；It is preferred that the copolymerization polylactic acid include lactic acid with The copolymer of aliphatic hydroxyl carboxylic acid, the copolymer of lactic acid and the pure and mild aliphatic polycarboxylic acid of aliphatic polybasic, lactic acid and fat One of copolymer of the copolymer and lactic acid of race's polybasic carboxylic acid and aliphatic polyol is a variety of.
3. flame-proof polylactic acid composition according to claim 1 or 2, which is characterized in that the phosphine oxide has following knot Structure Formulas I:
Wherein, R1、R2And R3It is identical or different, it is each independently selected from C1-C18Straight chained alkyl, C3-C18Branched alkyl, C1-C18Directly Chain alkoxy, C3-C18Branched alkoxy, C6-C20Aromatic radical and C substituted or unsubstituted6-C20Substituted or unsubstituted virtue oxygen Base；
It is preferred that R1、R2And R3It is each independently selected from C4-C18The C that linear or branched alkyl group and carbocyclic ring number are 1 or 26-C18Fragrance Base；
More preferable R1、R2And R3It is each independently selected from C of the main carbochain with 6 or more carbon atoms6-C12Linear chain or branched chain alkane Base and phenyl substituted or unsubstituted；
The further preferred phosphine oxide is selected from triphenylphosphine oxide, bis- (4- hydroxy phenyl) phenyl phosphine oxides, bis- (4- carboxyl benzene Base) phenyl phosphine oxide, tributylphosphine oxide, three hexyl phosphine oxides, trioctylphosphine oxide, three decyl phosphine oxides, tributyl phosphate At least one of with butyl dibutyl phosphate.
4. flame-proof polylactic acid composition described in any one of -3 according to claim 1, which is characterized in that the transition metal Salt includes transition metal organic salt and/or transition metal inorganic salts, preferably the nitrate of transition metal, rhodanate, formates, At least one of acetate and oxalates；The transition metal is preferably group VIII metal element, more preferably cobalt and/or Nickel.
5. flame-proof polylactic acid composition described in any one of -4 according to claim 1, which is characterized in that the complex Preparation step includes: to stir the phosphine oxide of 1-10 parts by weight and the transition metal salt of 3-15 parts by weight in organic solvent to mix It closes, then microwave heating, supercritical drying obtains the complex；The organic solvent is preferably ethyl alcohol, acetone, pyridine, four At least one of hydrogen furans and DMF.
6. flame-proof polylactic acid composition described in any one of -5 according to claim 1, which is characterized in that be based on 100 weight The polylactic acid base resin of part, the amount of the fire retardant are 5-50 parts by weight, preferably 10-20 parts by weight；Optionally, described anti- The amount of oxygen agent is 0.1-0.5 parts by weight.
7. flame-proof polylactic acid composition described in any one of -6 according to claim 1, which is characterized in that in the fire retardant Inorganic fire retardants component is further included, the preferably described inorganic fire retardants group is selected from IIA and Group IIIA metal hydroxides, more It is preferably selected from magnesium hydroxide and/or aluminium hydroxide；And/or
The weight ratio of complex and the inorganic fire retardants component in the fire retardant is (1-5): 1.
8. flame-proof polylactic acid composition according to any one of claims 1-7, which is characterized in that the fire-retardant poly- cream Carbon nano-fiber antistatic agent is further included in acid composition；It is preferably based on the polylactic acid base resin of 100 parts by weight, it is described The amount of carbon nano-fiber antistatic agent is 0.1-10 parts by weight, preferably 1-3 parts by weight；And/or
The carbon nano-fiber antistatic agent contains transition metal 1-5wt%.
9. flame-proof polylactic acid composition according to claim 8, which is characterized in that the carbon nano-fiber antistatic agent Preparation method includes:
Carbon source is subjected to sour processing, then compound is formed with transition-metal catalyst, by the compound at 800-1200 DEG C Temperature, carry out charing process under inert gas protection；
The carbon source is preferably selected from anthraxolite, asphalt, coal tar pitch, coal tar, natural graphite, artificial graphite, bamboo charcoal, charcoal At least one of black, active carbon and graphene, be more preferably selected from carbon content be 80wt% or more selected from coal tar pitch and petroleum asphalt and At least one of bamboo charcoal；
In chloride, sulfate, nitrate, acetate and cyclopentadienyl compound of the transition-metal catalyst selected from transition metal At least one；The transition metal is preferably selected from least one of iron, cobalt, nickel and chromium；And/or it is described transition metal-catalyzed Agent is with transition metal and the mass ratio of carbon source for (35-70): 100.
10. a kind of flame-proof polylactic acid expanded bead, by that will include fire-retardant poly- as described in any one of claim 1-9 The material of lactic acid composition and the Nucleating Agent of 0.001-5 parts by weight is prepared by impregnated foaming process.
11. a kind of flame-proof polylactic acid formed body, molded by flame-proof polylactic acid expanded bead according to claim 10 Moulding process is prepared.
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