CN106280341B - Halogen-free flameproof long glass fiber reinforced lactic acid composite material and preparation method thereof - Google Patents

Halogen-free flameproof long glass fiber reinforced lactic acid composite material and preparation method thereof Download PDF

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Publication number
CN106280341B
CN106280341B CN201610779341.2A CN201610779341A CN106280341B CN 106280341 B CN106280341 B CN 106280341B CN 201610779341 A CN201610779341 A CN 201610779341A CN 106280341 B CN106280341 B CN 106280341B
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halogen
parts
glass fiber
fiber reinforced
lactic acid
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CN106280341A (en
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张道海
何敏
于杰
秦舒浩
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Jiang Lin (guizhou) Hi Tech Development Ltd By Share Ltd
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Jiang Lin (guizhou) Hi Tech Development Ltd By Share Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/02Making granules by dividing preformed material
    • B29B9/06Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/22Halogen free composition
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/08Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers

Abstract

The invention discloses a kind of halogen-free flameproof long glass fiber reinforced lactic acid composite materials and preparation method thereof.The present invention, as matrix resin, adds the montmorillonite of quaternary alkylphosphonium salt intercalation modifying as synergist, it generates positive synergistic to the anti-flammability and mechanical property of halogen-free flameproof long glass fiber reinforced lactic acid composite material using polylactic acid;Compatilizer of the present invention not only enhances the binding force between matrix resin and fiber, but also also improves the compatibility between matrix resin and toughener;Fire retardant DIDOPO melting temperature is low, and decomposition temperature is high, it is wide can to carry out processing temperature regional choice range, and the melt fluidity of DIDOPO is fabulous;It is able to achieve and directly carries out fire retardant and matrix resin etc. to be uniformly mixed extrusion mixing melt, continuous glass fibre is impregnated in blend melt, through cooling, traction, pelletizing.

Description

Halogen-free flameproof long glass fiber reinforced lactic acid composite material and preparation method thereof
Technical field
The present invention relates to materials science field, especially a kind of halogen-free flameproof long glass fiber reinforced lactic acid composite material and its Preparation method.
Background technique
Polylactic acid (PLA) is a kind of biodegradable polymer, cheap due to polylactic acid abundance, and is had There is good mechanical property, more and more experts and scholars are very interested in the research and application of polylactic acid.But polylactic acid Material thermal stability is poor, easy firing, and molten drop phenomenon is serious when burning, limits polylactic acid in electronic product, automotive upholstery, electricity Sub- power equipment, traffic etc. have the application in flame-retardancy requirements field, it is therefore desirable to carry out to it flame-retardant modified;Since people are to product The requirement of quality is higher and higher, and the performance of common short glass fiber enhancing poly-lactic acid material cannot be met the requirements, and long glass fiber reinforced is poly- There is lactic acid the excellent performances such as high intensity, high-modulus, high thermal stability can satisfy people to high-performance pursuit;Current society Meeting, as the awareness of safety of people improves, and the environmental protection concept of country is constantly reinforced, and therefore, is prepared using halogen-free flame retardants Fire proofing is very important project.Since halogen-free flame retardants easily decomposes, and fire retardant is directly added to matrix resin In will lead to melt viscosity increase, make fire retardant and resin blend melt be unable to complete dipping to glass fibre.Currently, traditional Halogen-free flame-retardant long glass fibre reinforced composite material method there are two types of, one is two-step method (that is: prepare respectively first fire-retardant master granule and Then long fiber reinforcement master batch is uniformly mixed and is molded), another kind is that a step cladding process (that is: prepares long glass fiber reinforced first Then fire retardant and matrix resin blend melt are coated on long glass fiber reinforced thermoplastic resin material strip again by thermoplastic resin material strip On, to obtain halogen-free flameproof long glass fiber reinforced thermoplastic composite).
Summary of the invention
The object of the present invention is to provide a kind of halogen-free flameproof long glass fiber reinforced lactic acid composite material and preparation method thereof, What it was realized has the technical effect that a step infusion process prepares halogen-free flameproof long glass fiber reinforced lactic acid composite material, preparation method technique Simply, fire retardant is uniformly dispersed, and less energy consumption is prepared, and the feature of environmental protection is good, with overcome the deficiencies in the prior art.
The present invention is implemented as follows: halogen-free flameproof long glass fiber reinforced lactic acid composite material, in parts by weight, packet Include 30~60 parts of polylactic acid, 20~40 parts of glass fibres, 8~10 parts of DIDOPO, 0.5 part of antioxidant, 3~5 parts of compatilizers, 5~ 10 parts of toughener, 3~5 parts of triazine carbon forming agents, 1~5 portions of synergist and 0.02~0.1 part of cumyl peroxide are that preparation is former Material.
The fire retardant DIDOPO is the miscellaneous -10- phospho hetero phenanthrene -10- oxide of 9 ' 10- dihydro-9-oxy of phenethyl bridge chain; The melting temperature of DIDOPO is 180 DEG C, and decomposition temperature is 360 DEG C, and melt fluidity is excellent;DIDOPO structural formula are as follows:
The antioxidant is antioxidant AS4500.
The compatilizer is SAG-008.
The toughener is POE-g-GMA or TPU.
The synergist is the montmorillonite of quaternary alkylphosphonium salt intercalation modifying.
The preparation method of halogen-free flameproof long glass fiber reinforced lactic acid composite material takes poly- cream by above-mentioned parts by weight respectively Acid, DIDOPO, triazine carbon forming agent, toughener and synergist drying for standby;Each component and antioxidant, compatilizer after taking drying And cumyl peroxide is uniformly mixed, and carries out blending extrusion, processing temperature are as follows: 185-205 DEG C, by dipping runner to glass Fiber is impregnated, and dipping temperature is 220-240 DEG C, and after supercooling, traction, pelletizing, the Halogen that partial size is 8~12mm is made Fire-retardant long-fiberglass-reinforced polylactic acid composite material.
Compared with prior art, the present invention adds the montmorillonite of quaternary alkylphosphonium salt intercalation modifying using polylactic acid as matrix resin As synergist, the montmorillonite of quaternary alkylphosphonium salt intercalation modifying not only can be to the resistance of halogen-free flameproof long glass fiber reinforced lactic acid composite material Combustion property generates positive synergistic, but also generates positive synergistic to the mechanical property of halogen-free flameproof long glass fiber reinforced lactic acid composite material; Using styrene-acrylonitrile-glycidyl methacrylate ternary atactic copolymer as compatilizer, which enhances base Binding force between body resin and fiber;Fire retardant DIDOPO melting temperature is low (180 DEG C), and decomposition temperature is high (360 DEG C), It is wide can to carry out processing temperature regional choice range, and the melt fluidity of DIDOPO is fabulous;And it is prepared using a step infusion process Halogen-free flameproof long glass fiber reinforced lactic acid composite material directly carries out fire retardant and matrix resin etc. to be uniformly mixed extrusion mixed Melt is closed, continuous glass fibre is impregnated in blend melt, obtains finished product, this method simple process, resistance through cooling, traction, pelletizing Combustion agent is uniformly dispersed, and flame retardant effect is excellent, and preparation energy consumption is reduced, and product mechanical property obtained is excellent.
Specific embodiment
The embodiment of the present invention 1: halogen-free flameproof long glass fiber reinforced lactic acid composite material, in parts by weight, including 45 parts of polylactic acid, 30 parts of glass fibres, 8 parts of DIDOPO, 0.5 part of antioxidant, 4 parts of compatilizers, 8 parts of toughener, 4 parts of triazines are at charcoal Agent, 1 portions of synergist and 0.08 cumyl peroxide are to prepare raw material;The fire retardant is DIDOPO (phenethyl bridge chain 9 ' Miscellaneous -10- phospho hetero phenanthrene -10- the oxide of 10- dihydro-9-oxy).The antioxidant is antioxidant AS4500;The compatilizer is SAG-008;The toughener is POE-g-GMA;The synergist is the montmorillonite of quaternary alkylphosphonium salt intercalation modifying.
The preparation method of halogen-free flameproof long glass fiber reinforced lactic acid composite material, specific solution are by above-mentioned parts by weight Number, takes polylactic acid, DIDOPO, triazine carbon forming agent, toughener and synergist drying for standby respectively;Take it is dry after polylactic acid, DIDOPO, triazine carbon forming agent, toughener and synergist are uniformly mixed with antioxidant, compatilizer and cumyl peroxide, are carried out Blending extrusion, processing temperature are as follows: 185-205 DEG C, glass fibre is impregnated by impregnating runner, dipping temperature 230 DEG C, after cooling, draw, particle of the pelletizing at 8~12mm, acquisition halogen-free flameproof long glass fiber reinforced lactic acid composite material.
Embodiment 2: halogen-free flameproof long glass fiber reinforced lactic acid composite material, in parts by weight, including 30 parts of poly- creams Acid, 40 parts of glass fibres, 10 parts of DIDOPO, 0.5 part of antioxidant, 3 parts of compatilizers, 10 parts of toughener, 5 parts of triazine carbon forming agents, 1 part Synergist and 0.02 part of cumyl peroxide are to prepare raw material;The fire retardant is DIDOPO;The antioxidant is anti- Oxygen agent AS4500;The compatilizer is SAG-008;The toughener is TPU;The synergist is that quaternary alkylphosphonium salt intercalation changes Property montmorillonite.
Preparation method is the same as implementation 1.
Embodiment 3: halogen-free flameproof long glass fiber reinforced lactic acid composite material, in parts by weight, including 60 parts of poly- creams Acid, 20 parts of glass fibres, 7.5 parts of DIDOPO, 0.5 part of antioxidant, 5 parts of compatilizers, 5 parts of toughener, 3 parts of triazine carbon forming agents, 1 part Synergist and 0.1 part of cumyl peroxide are to prepare raw material;The fire retardant is DIDOPO;The antioxidant is antioxygen Agent AS4500;The compatilizer is SAG-008;The toughener is POE-g-GMA;The synergist is inserted for quaternary alkylphosphonium salt Layer modified montmorillonoid.
Preparation method is the same as implementation 1.
Comparative example 1: halogen-free flameproof long glass fiber reinforced lactic acid composite material, in parts by weight, including 60 parts of poly- creams Acid, 20 parts of glass fibres, 7.5 parts of DIDOPO, 0.5 part of antioxidant, 5 parts of compatilizers, 5 parts of toughener, 3 parts of triazine carbon forming agents, 1 part Synergist and 0.1 part of cumyl peroxide are to prepare raw material;The fire retardant is DIDOPO (9 ' 10- bis- of phenethyl bridge chain Hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxide).The antioxidant is antioxidant AS4500;The compatilizer is SAG- 008;The toughener is POE-g-GMA;The synergist is the montmorillonite of quaternary alkylphosphonium salt intercalation modifying.
The preparation method (dipping cladding process) of halogen-free flame-retardant long fiber reinforced polylactic acid composite material: 30 parts of poly- creams are taken respectively Polylactic acid after above-mentioned drying, compatilizer are uniformly mixed with 0.5 part of antioxidant by acid and 5 parts of compatilizer drying for standby, then into Row blending extrusion, processing temperature are 185-215 DEG C, and 230 DEG C of dipping temperature, the melt of extrusion is passed through dipping runner to 20 parts of fibres Dimension is impregnated, and fiber impregnation material strip is obtained;Take again 30 parts of polylactic acid, 8 parts of halogen-free flame retardants, 3 parts of triazine carbon forming agents, will be above-mentioned Material after drying is mixed with 0.5 part of antioxidant, and material is added in extruder after mixing, will melting when squeezing out Mixed material be coated in fiber impregnation material strip, it is cooling after pelletizing at the particle of 8~12mm, it is fine to obtain halogen-free flame-retardant long Dimension enhancing lactic acid composite material.
Comparative example 2: halogen-free flameproof long glass fiber reinforced lactic acid composite material, in parts by weight, including 45 parts of poly- creams Acid, 30 parts of glass fibres, 8 parts of DIDOPO, 0.5 part of antioxidant, 4 parts of compatilizers, 8 parts of toughener, 4 parts of triazine carbon forming agents and 0.08 Cumyl peroxide is to prepare raw material;The fire retardant is the DIDOPO (9 ' miscellaneous -10- of 10- dihydro-9-oxy of phenethyl bridge chain Phospho hetero phenanthrene -10- oxide).The antioxidant is antioxidant AS4500;The compatilizer is SAG-008;The toughening Agent is POE-g-GMA.
Preparation method is the same as implementation 1.
Main performance test: standard testing batten is made according to standard in the product produced, and carries out every test, performance Test result is as shown in table 1.
Table 1
According to table 1 it is known that comprehensive mechanical property is all using technical solution of the present invention preparation-obtained sample It is higher, and flame retardant property is all V0 grades.The prepared Flame Retardancy that obtains can achieve V0 rank.The embodiment of the present invention three The dipping cladding process used using step halogen-free flameproof long glass fiber reinforced lactic acid composite material prepared by infusion process and comparative example 1 The halogen-free flameproof long glass fiber reinforced lactic acid composite material of preparation is compared, the step halogen-free flameproof prepared by infusion process of embodiment three Tensile strength, Izod notched impact strength, bending strength of long-fiberglass-reinforced polylactic acid composite material etc. are all than in comparative example 1 Performance it is high, and the anti-flammability of the step halogen-free flameproof long glass fiber reinforced lactic acid composite material prepared by infusion process of embodiment three It can be V0 grades, the flame retardant property of the halogen-free flameproof long glass fiber reinforced lactic acid composite material of the dipping cladding process preparation of comparative example 1 It is V1 grades, this is because the present invention, which directlys adopt a step infusion process, prepares halogen-free flameproof long glass fiber reinforced lactic acid composite material Fire retardant is uniformly dispersed in matrix melt, makes the excellent fireproof performance of composite material.The embodiment of the present invention one is soaked using a step The halogen-free flameproof long glass fiber reinforced lactic acid composite material and comparative example 2 of stain method preparation are all using step nothing prepared by infusion process The fire-retardant long-fiberglass-reinforced polylactic acid composite material of halogen is compared, that synergist, the halogen-free flameproof of comparative example 2 is not added in comparative example 2 Long-fiberglass-reinforced polylactic acid composite material tensile strength, bending, impact property and anti-flammability performance all without the good of embodiment one, This shows that synergist is added in embodiment one not only produces the mechanical property of halogen-free flameproof long glass fiber reinforced lactic acid composite material Raw positive synergistic, and positive synergistic is generated to the flame retardant property of halogen-free flameproof long glass fiber reinforced lactic acid composite material.

Claims (6)

1. a kind of halogen-free flameproof long glass fiber reinforced lactic acid composite material, it is characterised in that: in parts by weight, including 30~ 60 parts of polylactic acid, 20~40 parts of glass fibres, 8~10 parts of DIDOPO, 0.5 part of antioxidant, 3~5 parts of compatilizers, 5~10 parts of increasings Tough dose, 3~5 parts of triazine carbon forming agents, 1~5 portions of synergist and 0.02~0.1 part of cumyl peroxide are to prepare raw material;By upper Parts by weight are stated, take polylactic acid, DIDOPO, triazine carbon forming agent, toughener and synergist drying for standby respectively;After taking drying Polylactic acid, DIDOPO, triazine carbon forming agent, toughener and synergist are mixed with antioxidant, compatilizer and cumyl peroxide Uniformly, blending extrusion, processing temperature are carried out are as follows: 185-205 DEG C, impregnate by impregnating runner to glass fibre, dipping temperature Degree is 220-240 DEG C, and after supercooling, traction, pelletizing, the poly- cream of halogen-free flameproof long glass fiber reinforced that partial size is 8~12mm is made Sour composite material;Wherein, the synergist is the montmorillonite of quaternary alkylphosphonium salt intercalation modifying.
2. halogen-free flameproof long glass fiber reinforced lactic acid composite material according to claim 1, it is characterised in that: described DIDOPO is phenethyl bridge chain 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide;The melting temperature of DIDOPO is 180 DEG C, decomposition temperature is 360 DEG C, and melt fluidity is excellent;DIDOPO structural formula are as follows:
3. halogen-free flameproof long glass fiber reinforced lactic acid composite material according to claim 1, it is characterised in that: described is anti- Oxygen agent is antioxidant AS4500.
4. halogen-free flameproof long glass fiber reinforced lactic acid composite material according to claim 1, it is characterised in that: the phase Appearance agent is SAG-008.
5. halogen-free flameproof long glass fiber reinforced lactic acid composite material according to claim 1, it is characterised in that: the increasing Tough dose is POE-g-GMA or TPU.
6. a kind of preparation method of halogen-free flameproof long glass fiber reinforced lactic acid composite material as described in claim 1, feature It is: by above-mentioned parts by weight, takes polylactic acid, DIDOPO, triazine carbon forming agent, toughener and synergist drying for standby respectively; Polylactic acid, DIDOPO, triazine carbon forming agent, toughener and synergist and antioxidant, compatilizer and peroxidating two after taking drying Isopropylbenzene is uniformly mixed, and carries out blending extrusion, processing temperature are as follows: 185-205 DEG C, is soaked by impregnating runner to glass fibre Stain, dipping temperature is 220-240 DEG C, and after supercooling, traction, pelletizing, the halogen-free flameproof roving glass fiber that partial size is 8~12mm is made Enhance lactic acid composite material.
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CN108929524A (en) * 2018-09-05 2018-12-04 贵州省材料产业技术研究院 A kind of increasing reaction flame-retardant polyester material and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104371291A (en) * 2014-12-01 2015-02-25 贵州凯科特材料有限公司 High-performance halogen-free flame-retardant long fiber reinforced polylactic acid composite material and preparation method thereof
CN105385122A (en) * 2015-10-18 2016-03-09 贵州省材料产业技术研究院 Application of bridged DOPO-based compound, product thereof and preparation method of product

Family Cites Families (2)

* Cited by examiner, † Cited by third party
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KR20070007068A (en) * 2004-01-30 2007-01-12 디에스엠 아이피 어셋츠 비.브이. Halogen-free flame-retarded polyester composition
KR100653601B1 (en) * 2004-07-08 2006-12-04 삼박엘에프티 (주) Long fiber reinforced polyolefin composition, and method for producing long fiber reinforced and colored article with the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104371291A (en) * 2014-12-01 2015-02-25 贵州凯科特材料有限公司 High-performance halogen-free flame-retardant long fiber reinforced polylactic acid composite material and preparation method thereof
CN105385122A (en) * 2015-10-18 2016-03-09 贵州省材料产业技术研究院 Application of bridged DOPO-based compound, product thereof and preparation method of product

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