CN105968753B - A kind of biradical molecule synergistic flame-proof polylactic acid composite of phosphonitrile/triazine and preparation method thereof - Google Patents
A kind of biradical molecule synergistic flame-proof polylactic acid composite of phosphonitrile/triazine and preparation method thereof Download PDFInfo
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- CN105968753B CN105968753B CN201610289629.1A CN201610289629A CN105968753B CN 105968753 B CN105968753 B CN 105968753B CN 201610289629 A CN201610289629 A CN 201610289629A CN 105968753 B CN105968753 B CN 105968753B
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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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
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- C—CHEMISTRY; METALLURGY
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/5205—Salts of P-acids with N-bases
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/329—Phosphorus containing acids
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract
The invention discloses a kind of biradical molecule synergistic flame-proof polylactic acid composite of phosphonitrile/triazine, the flame-proof polylactic acid composite is in parts by weight, contain 75~90 parts of polylactic resin, phosphorus flame retardant and the biradical molecule synergist total amount of phosphonitrile/triazine are 25~10 parts, the weight ratio of the biradical molecule synergist of 0.03~0.1 part of antioxidant, wherein phosphorus flame retardant and phosphonitrile/triazine is 1~3：3~1.After mentioned component is premixed in proportion, the melt blending at 170 DEG C~230 DEG C, that is, the biradical molecule synergistic flame-proof polylactic acid composite of phosphonitrile/triazine is obtained.The flame-proof polylactic acid composite has the characteristics of anti-dropping effect is good, and oxygen index (OI) is high, and at fire retardant addition relatively low (10%), oxygen index (OI) can still maintain more than 30%, while can pass through vertical combustion UL94 V0 ranks.
Description
Technical field
The present invention relates to technical field of polymer materials, and in particular to a kind of biradical molecule synergistic of phosphonitrile/triazine is fire-retardant poly-
Lactic acid composite and preparation method thereof.
Background technology
With enhancing of the people to environmental consciousness and the aggravation of energy crisis, bio-based materials and Biodegradable material
Research, exploitation and application receive the pay attention to day by day of people.PLA (PLA) derives from reproducible cornstarch, in nature
It can turn into water and carbon dioxide with degradable in boundary, while also there is higher rigidity and intensity, easy processing shaping, plasticity
By force, the advantages that good biocompatibility, it is referred to as most promising " green plastic ".At present, PLA has been able to carry out various
Processing and forming, increasingly extensive application is achieved in the field such as weaving, packaging, agricultural, health care, daily living article.So
And the fire resistances of PLA in itself only have UL94HB levels, limited oxygen index (LOI) is 21%, and only forming one layer during burning just may be used
The carburization zone seen, then liquefies quickly, with serious drippage and burning.In order to overcome these defects, it is widened in aviation, electricity
The application in the fields such as sub- electrical equipment, automobile, the flame-retardant modified research to PLA have turned into the focus of concern.
Having been used for the fire retardant of PLA at present includes halogen system, phosphorus system, nitrogen system, silicon systems, Intumscent Flame Retardant System, inorganic resistance
Fire agent, nano-powder and the synergistic system containing two or more fire retardants.Wherein, halogen containing flame-retardant can be produced fire-retardant while
Raw dense smoke and poisonous, aggressive gas, are gradually abandoned by people.Inorganic combustion inhibitor addition is big, generally connects
Nearly 50%, the processing characteristics and mechanical property all high degrees for causing material deteriorate, document Carbohydrate Polymers
When aluminium hydroxide addition is 50wt% in 87,1119-1123,2012, fire-retardant PLA LOI is 36%, although can pass through
UL94V0 ranks, but have molten drop phenomenon.Silicon-series five-retardant has that addition is small, while can improve material processing characteristics and fire-retardant
The advantages that effect, but generally only as auxiliary addition agent and other fire retardant compounding uses.
Phosphorus flame retardant aboundresources, purposes be wide and good flame retardation effect, is most important one kind in environment friendly flame retardant, but
It is that its resistance to elevated temperatures is poor.Nitrogenated flame retardant is free of halogen, corrosion-free effect, and ultraviolet resistance shines, good electrical property, but its is fire-retardant
Efficiency is not high enough, and the physical property of material is had a certain impact.Therefore nitrogenated flame retardant and phosphonium flame retardant are used in combination by people
Phosphorus, nitrogen synergistic system are formed, to obtain higher flame retarding efficiency.Expansion type flame retardant (IFR) just belongs to phosphorus-nitrogen containing flame retardant, grinds
Study carefully and show that IFR is added to the fire-retardant rank that PLA can be effectively improved in PLA.But there is addition in most of expansion type flame retardants
Greatly, the physical property of base material is impacted and the problem of flame retarding efficiency has much room for improvement.Expansion type phosphor nitrogen synergistic flame retardant is poly-
The general flame retardant effect and more than 30% oxygen index (OI) that all need addition more than 25% to reach UL-94V0 ranks simultaneously in lactic acid
Value.
Patent CN101434843 and document Polymer Degradation and Stability 95,763-770,
A kind of superelevation degree of branching polyamine carbon forming agent (HPCA) is reported in 2010.When adding single HPCA in PLA, material
Fire resistance is not improved well, and HPCA and APP is added and then shown to act synergistically well simultaneously.But the two
Total addition level could reach 28% when being 30wt% by UL94V-0 levels and oxygen index (OI), and material can be made by reducing the dosage of the two
Oxygen index (OI) reduces.In recent years, researchers are directed to how research reduces the dosage of expansion type flame retardant, improve expansion type flame-retarding
The flame retarding efficiency of agent.It is an effective approach to add fire retarding synergist.
Document Polymer Degradation and Stability, 95,1063-1076,2010 and Polymer
Advanced Technology, 22,30-37,2011 report organic modification montmonrillonite, oligomeric silsesquioxane, CNT,
The nanometer synergistic flame retardant synergistic flame-proof polylactic acid such as expanded graphite, although there is no molten drop phenomenon during burning, it can not pass through
UL94V-0 ranks.In patent CN 101260227B, the flame-retardant mixture of phosphonium flame retardant and other flame retardants, hydrogen have been used
Magnesia is 5 parts, APP is 12 parts, pentaerythrite is 6 parts, and antioxidant is 1 part.When flame-retardant mixture is 24 parts, sample
The limited oxygen index of product is more than 31, can pass through UL-94V-0 level combustion testings.In the patent 2134379B of CN 10, use is organic
Phosphate and poly- penta tetrol, when flame retardant agent content is more than 20%, could keep material as fire retardant PLA
Oxygen index (OI) is more than 30%.Patent CN 103073862A, using expansible graphite, phosphonium flame retardant, nano flame retardant synergist is answered
With flame-proof polylactic acid, when total amount of adding is more than 13%, the flame retardant effect and more than 30% of UL-94V0 ranks can be reached simultaneously
Oxygen index value.Patent CN 102382433B be reported in PLA compound between graphite layers of the addition less than 10 parts, fire retardant,
Antioxidant, synergist, the mixture that forms of carbon forming agent blending, material can be made and meanwhile reach the flame retardant effects of UL-94V0 ranks with
More than 30% oxygen index value.But the problem of existing, which is the addition of compound between graphite layers, can make the mechanical property of PLA matrix
It can substantially reduce, while the graphite for adding black can greatly limit the application field of material, in addition, the catalyst component of graphite layers
It can cause the fast degradation during PLA use with strong acid.Patent CN 102002222B, with the addition of 7.5 parts of polyphosphoric acid
Ammonium and 2.5 parts of pentaerythrite, and 1 part of catalyst can reach vertical combustion UL-94V0 ranks flame retardant effect and
More than 30% oxygen index value.Although the amount of flame-retardant agent of the system is also fewer, the addition that catalyst be present easily is drawn
Play the problem of PLA degraded makes PLA degrade with the easy moisture absorption of pentaerythrite.
In summary, the addition of expansion type flame retardant can be reduced by adding synergist, improves flame retarding efficiency.But
In general synergistic flame-retardant system, it is desirable to while reach oxygen index value more than 30% and vertical combustion rank UL-94V0 levels still need
The total addition level of fire retardant is wanted 15%~20%.The synergist that minority has catalytic effect can reduce the addition of fire retardant
It is that catalyst easily causes PLA to be degraded to 10%, but the problem of exist.And in the research of existing flame-proof polylactic acid also not
See the relevant report on the biradical molecule synergist of phosphonitrile/triazine.
The content of the invention
The purpose of the present invention is in view of the shortcomings of the prior art, there is provided a kind of biradical molecule synergistic of phosphonitrile/triazine is fire-retardant poly-
Lactic acid composite and preparation method thereof, the flame-proof polylactic acid composite have the characteristics of anti-dropping effect is good, and oxygen index (OI) is high,
At fire retardant addition relatively low (10%), oxygen index (OI) can still maintain more than 30%, while can pass through vertical combustion
UL94V0 ranks.
The biradical molecule synergistic flame-proof polylactic acid composite of a kind of phosphonitrile/triazine provided by the invention, the flame-proof polylactic acid
Composite in parts by weight, containing 75~90 parts of polylactic resin, phosphorus flame retardant and the biradical molecule synergist of phosphonitrile/triazine
Total amount is 25~10 parts, the weight of the biradical molecule synergist of 0.03~0.1 part of antioxidant, wherein phosphorus flame retardant and phosphonitrile/triazine
Amount is than being 1~3：3~1.
Described phosphorus flame retardant, preferably phosphate flame-retardant compound, for example, APP, poly aluminium phosphate, polyphosphoric acid,
Phosphoric acid ester, polyphosphoric acid melamine, melamine pyrophosphate or aromatic series polycondensation phosphoric acid.
The biradical molecule synergist of described phosphonitrile/triazine, its chemical structural formula are：
Wherein, R is diamino compounds.
The preferred p-phenylenediamine of described diamino compounds, hexamethylene diamine, butanediamine, 4,4- diaminodiphenyl ethers, 4,4- bis-
Aminodiphenyl sulfone, 4,4- MDAs, adjacent biphenyl methylamine, o-phenylenediamine, 1,2- propane diamine, 1,3- propane diamine, 2,4-
Double [4- (the 4- aminobenzene oxygen of diaminotoluene, 3- diethyl amino propylamines, 1,2- cyclohexanediamine, 4,5- dichloros o-phenylenediamine, 2,2-
Base phenyl)] propane, 4,4- diaminodiphenyl sulfides or 4,4- diaminourea diphenyl disulfide.
The preparation of the above-mentioned biradical molecule synergistic flame-proof polylactic acid composite of phosphonitrile/triazine is in parts by weight, will first to gather
75~90 parts of lactic acid resin, phosphorus flame retardant and the biradical molecule synergist of phosphonitrile/triazine amount to 25~10 parts, antioxidant 0.03~
0.1 part of premix, wherein the weight ratio of the biradical molecule synergist of phosphorus flame retardant and phosphonitrile/triazine are 1~3：3~1；Then exist
Melt blending obtains the biradical molecule synergistic flame-proof polylactic acid composite of phosphonitrile/triazine at 170 DEG C~230 DEG C.
The flame-proof polylactic acid composite of the present invention has the characteristics of anti-dropping effect is good, and oxygen index (OI) is high, adds in fire retardant
Oxygen index (OI) can still maintain more than 30% during dosage relatively low (10%), while can pass through vertical combustion UL94V0 ranks.
Brief description of the drawings
Fig. 1 is the molecular formula of the biradical molecule synergist A1~A4 of phosphonitrile/triazine described in the embodiment of the present invention.
Fig. 2 is the heat release rate curve of flame-proof polylactic acid composite provided by the invention and pure PLA.
Embodiment
The present invention is explained in detail with reference to preferred embodiment (described part is parts by weight).
Embodiment 1.
By 75 parts of the poly-lactic acid in high molecular weight of viscosity average molecular weigh more than 100,000, the biradical molecule synergist A1 (A1 of phosphonitrile/triazine
R in structural formula is hexamethylene diamine base) 12.5 parts, APP (ammonium polyphosphate, initialism APP) 12.5
Part, 170 DEG C are placed in torque rheometer after 0.03 part of antioxidant premix and is kneaded, obtains flame-proof polylactic acid composite PLA-
1.The fire resistance of the composite is：LOI is 40.8%；Tested by UL94V-0 ranks.
Embodiment 2.
By 75 parts of the poly-lactic acid in high molecular weight of viscosity average molecular weigh more than 100,000, the biradical molecule synergist A1 (A1 of phosphonitrile/triazine
R in structural formula is hexamethylene diamine base) 18.75 parts, 6.25 parts of polyphosphoric acid melamine, torque is placed in after 0.04 part of premix of antioxidant
230 DEG C are kneaded in rheometer, obtain flame-proof polylactic acid composite PLA-2.The fire resistance of the composite is：LOI
For 41.3%；Tested by UL94V-0 ranks.
Embodiment 3.
By 80 parts of the poly-lactic acid in high molecular weight of viscosity average molecular weigh more than 100,000, the biradical molecule synergist A2 (A2 of phosphonitrile/triazine
R in structural formula is p-phenylenediamine base) 15 parts, 5 parts of APP (APP), torque rheology is placed in after 0.03 part of premix of antioxidant
220 DEG C are kneaded in instrument, obtain flame-proof polylactic acid composite PLA-3.The fire resistance of the composite is：LOI is
39.5%；Tested by UL94V-0 ranks.Embodiment 4.
By 80 parts of the poly-lactic acid in high molecular weight of viscosity average molecular weigh more than 100,000, the biradical molecule synergist A2 (A2 of phosphonitrile/triazine
R in structural formula is p-phenylenediamine base) 10 parts, 10 parts of melamine pyrophosphate, torque is placed in after 0.06 part of premix of antioxidant
200 DEG C are kneaded in rheometer, obtain flame-proof polylactic acid composite PLA-4.The fire resistance of the composite is：LOI
For 38.5%；Tested by UL94V-0 ranks.
Embodiment 5.
By 90 parts of the poly-lactic acid in high molecular weight of viscosity average molecular weigh more than 100,000, the biradical molecule synergist A3 (A3 of phosphonitrile/triazine
R in structural formula is 4,4- MDAs base) 2.5 parts, 7.5 parts of polyphosphoric acid, it is placed in after 0.05 part of premix of antioxidant and turns
190 DEG C are kneaded in square rheometer, obtain flame-proof polylactic acid composite PLA-5.The fire resistance of the composite is：
LOI is 35.1%；Tested by UL94V-0 ranks.
Embodiment 6.
By 90 parts of the poly-lactic acid in high molecular weight of viscosity average molecular weigh more than 100,000, the biradical molecule synergist A3 (A3 of phosphonitrile/triazine
R in structural formula is 4,4- MDAs base) 5 parts, 5 parts of polyphosphoric acid, torque flow is placed in after 0.04 part of premix of antioxidant
230 DEG C are kneaded in change instrument, obtain flame-proof polylactic acid composite PLA-6.The fire resistance of the composite is：LOI is
36.4%；Tested by UL94V-0 ranks.
Embodiment 7.
By 85 parts of the poly-lactic acid in high molecular weight of viscosity average molecular weigh more than 100,000, the biradical molecule synergist A4 (A4 of phosphonitrile/triazine
R in structural formula is 4,4- diaminodiphenyl sulfides base) 10 parts, 5 parts of APP (APP), 0.07 part of premix of antioxidant is rearmounted
200 DEG C are kneaded in torque rheometer, obtain flame-proof polylactic acid composite PLA-7.The fire resistance of the composite
For：LOI is 37.0%；Tested by UL94V-0 ranks.
Embodiment 8.
By 85 parts of the poly-lactic acid in high molecular weight of viscosity average molecular weigh more than 100,000, the biradical molecule synergist A4 (A4 of phosphonitrile/triazine
R in structural formula is 4,4- diaminodiphenyl sulfides base) 5 parts, 10 parts of polyphosphoric acid melamine, 0.1 part of premix of antioxidant is rearmounted
170 DEG C are kneaded in torque rheometer, obtain flame-proof polylactic acid composite PLA-8.The fire resistance of the composite
For：LOI is 34.6%；Tested by UL94V-1 ranks.
The biradical molecule synergist A1-A4 of phosphonitrile/triazine structural formula is as shown in Figure 1 in described embodiment 1-8.
Taper calorimetric test result closer to the true condition of a fire due to can be widely used, with pure PLA and embodiment 5,6
Taper calorimetric test is carried out exemplified by the flame-proof polylactic acid composite of gained, specific test data is shown in Table 1 and accompanying drawing 2.It is as follows：
The taper calorimetric test data of the flame-proof polylactic acid composite of table 1
Above content is to combine specific preferred embodiment further description made for the present invention, it is impossible to is assert
The specific implementation of the present invention is confined to these explanations.For general technical staff of the technical field of the invention,
On the premise of not departing from present inventive concept, some equivalent substitutes or obvious modification are made, and performance or purposes are identical, all should
It is considered as belonging to protection scope of the present invention.
Claims (3)
1. a kind of biradical molecule synergistic flame-proof polylactic acid composite of phosphonitrile/triazine, it is characterised in that the flame-proof polylactic acid is compound
Material in parts by weight, containing 75~90 parts of polylactic resin, phosphorus flame retardant and the biradical molecule synergist total amount of phosphonitrile/triazine
For 25~10 parts, the weight ratio of the biradical molecule synergist of 0.03~0.1 part of antioxidant, wherein phosphorus flame retardant and phosphonitrile/triazine
For 1~3：3~1, described phosphorus flame retardant is phosphate flame-retardant compound, the biradical molecule synergist of described phosphonitrile/triazine,
Its chemical structural formula is：
Wherein, R is the group containing diaminourea, from diamino compounds, described diamino compounds be p-phenylenediamine, oneself two
Amine, butanediamine, 4,4- diaminodiphenyl ethers, 4,4- diaminodiphenylsulfones, 4,4- MDAs, adjacent biphenyl methylamine, neighbour
Phenylenediamine, 1,2- propane diamine, 1,3- propane diamine, 2,4- diaminotoluenes, 3- diethyl amino propylamines, 1,2- cyclohexanediamine, 4,5-
Double [4- (4- aminophenoxy phenyls)] propane, 4,4- diaminodiphenyl sulfides or 4, the 4- diaminourea of dichloro o-phenylenediamine, 2,2-
Diphenyl disulfide.
2. the biradical molecule synergistic flame-proof polylactic acid composite of phosphonitrile/triazine according to claim 1, it is characterised in that
Described phosphorus flame retardant is APP, poly aluminium phosphate, polyphosphoric acid, phosphoric acid ester, polyphosphoric acid melamine, melamine Jiao
Phosphate or aromatic series polycondensation phosphoric acid.
3. the preparation of the biradical molecule synergistic flame-proof polylactic acid composite of phosphonitrile/triazine as described in claim any one of 1-2
Method, it is characterised in that in parts by weight, first by 75~90 parts of polylactic resin, phosphorus flame retardant and biradical point of phosphonitrile/triazine
Sub- synergist amounts to 25~10 parts, wherein 0.03~0.1 part of premix of antioxidant, phosphorus flame retardant and the biradical molecule of phosphonitrile/triazine
The weight ratio of synergist is 1~3：3~1；Then the melt blending at 170 DEG C~230 DEG C, obtains the biradical molecule of phosphonitrile/triazine
Synergistic flame-proof polylactic acid composite.
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| CN106543473B (en) * | 2016-10-14 | 2018-02-09 | 北京工商大学 | Biradical molecule fire retardant of a kind of phosphonitrile/triazine based on dopen Nano level metallic compound in situ and preparation method thereof |
| CN106854222A (en) * | 2016-12-06 | 2017-06-16 | 沈阳化工大学 | A kind of phosphorus, nitrogen type flame retardant and preparation method thereof |
| CN106928489B (en) * | 2017-03-07 | 2018-12-25 | 北京工商大学 | A kind of ammonium polyphosphate, preparation method and its resistance combustion polyurethane foam of phosphonitrile/triazine retardant surfaces inorganic agent processing |
| CN108530682B (en) * | 2018-04-02 | 2020-07-03 | 北京工商大学 | Phosphazene/triazine double-base molecule micro-crosslinking flame-retardant system and flame-retardant thermoplastic resin thereof |
| CN111363322B (en) * | 2018-12-26 | 2022-05-31 | 浙江海正生物材料股份有限公司 | Flame-retardant polylactic resin composition and preparation method thereof |
| CN112759905B (en) * | 2019-11-01 | 2023-08-08 | 南通林格橡塑制品有限公司 | Halogen-free flame-retardant polylactic acid mixture |
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| CN104250434B (en) * | 2014-10-24 | 2016-04-06 | 北京工商大学 | A kind of phosphorous-nitrogen system bittern-free flame-retardant polylactic acid material |
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