CN106366627A - Halogen-free flame-retardant long glass fiber reinforced TPU composite material and preparation method thereof - Google Patents
Halogen-free flame-retardant long glass fiber reinforced TPU composite material and preparation method thereof Download PDFInfo
- Publication number
- CN106366627A CN106366627A CN201610779441.5A CN201610779441A CN106366627A CN 106366627 A CN106366627 A CN 106366627A CN 201610779441 A CN201610779441 A CN 201610779441A CN 106366627 A CN106366627 A CN 106366627A
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- Prior art keywords
- halogen
- glass fiber
- fiber reinforced
- long glass
- tpu composite
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- 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
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/14—Homopolymers or copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Abstract
The invention discloses a halogen-free flame-retardant long glass fiber reinforced TPU composite material and a preparation method thereof. According to the invention, TPU serves as a matrix resin, quaternary phosphate intercalation modified montmorillonite is added to serve as a synergist and is capable of producing a positive synergistic effect on the flame-retardant property and mechanical property of the halogen-free flame-retardant long glass fiber reinforced TPU composite material, and a compatilizer in the invention is capable of enhancing the binding force between the matrix resin and fibers and improving the compatibility between the matrix resin and a flexibilizer; a flame retardant DIDIPO is low in melting temperature, high in decomposition temperature, wide in processing temperature area selection range and excellent in melting flowing index; and moreover, a preparation method comprising the following steps can be achieved: directly and uniformly mixing the flame retardant, the matrix resin and the like, extruding the mixed melt, performing continuous glass fiber impregnation in the mixed melt, cooling, drawing and grain-sized dicing.
Description
Technical field
The present invention relates to material science, especially a kind of halogen-free flameproof long glass fiber reinforced tpu composite and its system
Preparation Method.
Background technology
The entitled Polyurethane Thermoplastic Elastomer rubber of tpu (thermoplastic polyurethanes).Its hardness model
Enclose wide (60ha-85hd), wear-resisting, oil resistant, transparent, elasticity is good, in automobile engineering part, soft or hard composite article；Gear lever ball handle,
Roller bearing, shaft joint, grommet and sealing member；Cable plastic sleeve, transmission belt, mine screen cloth, thin film and extrusion profile, gear, protective eye lens
It is used widely in the field such as frame, buffer, Sports shoe sole and castor, article of everyday use, sports goods, toy, ornament materials.Due to
The requirement more and more higher to product quality for the people, the performance that common short glass fiber strengthens tpu material can not meet requirement, roving glass fiber
Enhancing tpu has the excellent performance such as high intensity, high-moduluss, high thermal stability and can meet people to high-performance pursuit；Now
Society, the safety consciousness with people improves, and the environmental protection concept of country is constantly strengthened, therefore, using halogen-free flame retardants system
Standby fire proofing is very important problem.Because halogen-free flame retardants easily decomposes, and directly fire retardant is added to matrix tree
Melt viscosity can be led in fat to increase, make fire retardant and mixed with resin melt cannot complete the dipping to glass fibre.At present, pass
The halogen-free flame-retardant long glass fibre reinforced composite material method of system has two kinds, and one kind is that two-step method (that is: prepares fire-retardant master granule first respectively
With long fiber reinforcement master batch, then mix homogeneously be molded), another kind be a step cladding process (that is: prepare first roving glass fiber increase
Then fire retardant and matrix resin blend melt are coated on long glass fiber reinforced thermoplastic resin material by heat-flash plastic resin material strip again
On bar, thus obtaining halogen-free flameproof long glass fiber reinforced thermoplastic composite).
Content of the invention
The purpose of the present invention is: a kind of halogen-free flameproof long glass fiber reinforced tpu composite and preparation method thereof is provided, it
Preparation method process is simple, fire retardant is uniformly dispersed, and flame retardant effect is excellent, prepares less energy consumption, and the feature of environmental protection is good, combination property
Excellent, to overcome the deficiencies in the prior art.
The present invention is achieved in that halogen-free flameproof long glass fiber reinforced tpu composite, calculates by weight, including
30～60 parts of Polyurethane Thermoplastic Elastomer, 20～40 parts of glass fibre, 9.5～13.6 parts of didopo, 0.5 part of antioxidant, 3～
5 parts of compatilizers, 3～5 parts of triazine carbon forming agents and 1～5 portions of synergist are preparing raw material.
Described fire retardant didopo is phenethyl bridge chain 9 ' 10- dihydro-9-oxy miscellaneous -10- phospho hetero phenanthrene -10- oxide；
The melt temperature of didopo is 180 DEG C, and decomposition temperature is 360 DEG C, and melt fluidity is excellent；Didopo structural formula is:
Described antioxidant is high-efficiency anti-oxidant 245.
Described compatilizer is sag-008.
Described synergist is quaternary alkylphosphonium salt intercalation modifying montmorillonite.
The preparation method of halogen-free flameproof long glass fiber reinforced tpu composite, by above-mentioned parts by weight, takes thermoplastic poly respectively
Urethane elastomer, didopo, triazine carbon forming agent and synergist drying for standby；Take dried each component and antioxidant and compatible
Agent mix homogeneously, carries out blending extrusion, and processing temperature is: 185-205 DEG C, by impregnating runner, glass fibre is impregnated,
Dipping temperature is 240-250 DEG C, cooled, traction, after pelletizing, makes the halogen-free flameproof long glass fiber reinforced that particle diameter is 8～12mm
Tpu composite.
Compared with prior art, the present invention adopts tpu as matrix resin, adds quaternary alkylphosphonium salt intercalation modifying montmorillonite conduct
Synergist, quaternary alkylphosphonium salt intercalation modifying montmorillonite not only can be produced to the anti-flammability of halogen-free flameproof long glass fiber reinforced tpu composite
Raw positive synergistic, but also positive synergistic is produced to the mechanical property of halogen-free flameproof long glass fiber reinforced tpu composite；With styrene-
The ternary atactic copolymer of acrylonitrile-methacylate ethylene oxidic ester as compatilizer, this compatilizer strengthen matrix resin with
Adhesion between fiber；The melt temperature of fire retardant didopo is low (180 DEG C), and decomposition temperature height (360 DEG C), can carry out
Processing temperature regional choice scope is wide, and the melt fluidity of didopo is fabulous, enables directly by fire retardant and matrix tree
Fat etc. carries out mix homogeneously extrusion mixing melt, and continuous glass fibre impregnated in blend melt, cooled, traction, after pelletizing, that is,
Product can be obtained.The method process is simple, fire retardant is uniformly dispersed, and flame retardant effect is excellent, and preparation energy consumption reduces, and be obtained
Product mechanical property is excellent.
Specific embodiment
Embodiments of the invention 1: halogen-free flameproof long glass fiber reinforced tpu composite, calculate by weight, including 45 parts
Polyurethane Thermoplastic Elastomer, 30 parts of glass fibre, 9.5 parts of didopo, 0.5 part of antioxidant, 4 parts of compatilizers, 4 parts of triazines become charcoal
Agent and 1 portions of synergist are preparing raw material；Described antioxidant is high-efficiency anti-oxidant 245；Described compatilizer is sag-008；
Described synergist is quaternary alkylphosphonium salt intercalation modifying montmorillonite.
The preparation method of halogen-free flameproof long glass fiber reinforced tpu composite, specific solution is to take thermoplastic poly respectively
Urethane elastomer, didopo, triazine carbon forming agent and synergist drying for standby；Take dried Polyurethane Thermoplastic Elastomer,
Didopo, triazine carbon forming agent and synergist are mixed homogeneously with antioxidant and compatilizer, carry out blending extrusion, and processing temperature is:
185-205 DEG C, by impregnate runner glass fibre is impregnated, dipping temperature be 245 DEG C, after cooling, traction, pelletizing become 8
The granule of～12mm, obtains halogen-free flameproof long glass fiber reinforced tpu composite.
Embodiment 2: halogen-free flameproof long glass fiber reinforced tpu composite, calculate by weight, including 30 parts of thermoplastic polies
Urethane elastomer, 40 parts of glass fibre, 11 parts of didopo, 0.5 part of antioxidant, 3 parts of compatilizers, 5 parts of triazine carbon forming agents and 1 part
Synergist is preparing raw material；Described antioxidant is high-efficiency anti-oxidant 245；Described compatilizer is sag-008；Described synergistic
Agent is quaternary alkylphosphonium salt intercalation modifying montmorillonite.
Preparation method is with enforcement 1.
Embodiment 3: halogen-free flameproof long glass fiber reinforced tpu composite, calculate by weight, including 60 parts of thermoplastic polies
Urethane elastomer, 20 parts of glass fibre, 8 parts of didopo, 0.5 part of antioxidant, 5 parts of compatilizers, 3 parts of triazine carbon forming agents and 1 part
Synergist is preparing raw material；Described antioxidant is high-efficiency anti-oxidant 245；Described compatilizer is sag-008；Described synergistic
Agent is quaternary alkylphosphonium salt intercalation modifying montmorillonite.
Preparation method is with enforcement 1.
Comparative example 1: halogen-free flameproof long glass fiber reinforced tpu composite, calculate by weight, including 60 parts of thermoplastic polies
Urethane elastomer, 20 parts of glass fibre, 8 parts of didopo, 0.5 part of antioxidant, 5 parts of compatilizers, 3 parts of triazine carbon forming agents are former for preparing
Material；Described antioxidant is high-efficiency anti-oxidant 245；Described compatilizer is sag-008.
The preparation method (dipping cladding process) of halogen-free flameproof long fiber reinforcement tpu composite: take 30 parts of tpu and 5 respectively
Part compatilizer drying for standby, above-mentioned dried tpu, compatilizer are mixed homogeneously with 0.5 part of antioxidant, then carry out blending and squeeze
Go out, processing temperature is 185-215 DEG C, 245 DEG C of dipping temperature, the melt of extrusion is soaked to 20 parts of fibers by impregnating runner
Stain, obtains fiber impregnation material strip；Take again 30 parts of tpu, 8 parts of halogen-free flame retardants, 3 parts of triazine carbon forming agents, by above-mentioned dried thing
Material is mixed with 0.5 part of antioxidant, will add after material mix homogeneously in extruder, in extrusion by the mixed material of melting
It is coated in fiber impregnation material strip, pelletizing after cooling becomes the granule of 8～12mm, obtains halogen-free flameproof long fiber reinforcement tpu
Composite.
Comparative example 2: halogen-free flameproof long glass fiber reinforced tpu composite, calculate by weight, including 45 parts of tpu, 30 parts
Glass fibre, 9.5 parts of didopo, 0.5 part of antioxidant, 4 parts of compatilizers, 4 parts of triazine carbon forming agents are preparing raw material；Described antioxygen
Agent is high-efficiency anti-oxidant 245；Described compatilizer is sag-008.
Preparation method is with enforcement 1.
Main performance is tested: the product produced makes standard testing batten according to standard, carries out every test, its performance
Test result is as shown in table 1.
Table 1
According to table 1 it is known that adopting the preparation-obtained sample of technical scheme, its comprehensive mechanical property is all
Higher, and fire resistance is all v0 level.The prepared Flame Retardancy that obtains can reach v0 rank.The embodiment of the present invention three
The dipping cladding legal system being adopted with comparative example 1 using the halogen-free flameproof long glass fiber reinforced tpu composite of a step infusion process preparation
Standby halogen-free flameproof long glass fiber reinforced tpu composite is compared, the halogen-free flame-retardant long glass of a step infusion process preparation of embodiment three
The fine tensile strength strengthening tpu composite, Izod notched impact strength, bending strength etc. are all than the performance in comparative example 1
Height, and the fire resistance of the halogen-free flameproof long glass fiber reinforced tpu composite of a step infusion process preparation of embodiment three is v0 level,
Comparative example 1 dipping cladding process preparation halogen-free flameproof long glass fiber reinforced tpu composite fire resistance be v1 level, this be by
Directly the fire retardant of halogen-free flameproof long glass fiber reinforced tpu composite is prepared in matrix melt using a step infusion process in the present invention
In be uniformly dispersed, make the excellent fireproof performance of composite.The embodiment of the present invention one adopts the Halogen resistance of a step infusion process preparation
Combustion long glass fiber reinforced tpu composite and comparative example 2 are all the halogen-free flameproof long glass fiber reinforced tpu using a step infusion process preparation
Composite is compared, and does not add synergist in comparative example 2, and the halogen-free flameproof long glass fiber reinforced tpu composite of comparative example 2 draws
Stretching intensity, bending, impact property and anti-flammability performance does not all have the good of embodiment one, and this shows, adds synergistic in embodiment one
Agent not only produces positive synergistic to the mechanical property of halogen-free flameproof long glass fiber reinforced tpu composite, and to halogen-free flame-retardant long glass
The fine fire resistance strengthening tpu composite produces positive synergistic.
Claims (6)
1. a kind of halogen-free flameproof long glass fiber reinforced tpu composite it is characterised in that: calculate by weight, including 30～60
Part Polyurethane Thermoplastic Elastomer, 20～40 parts of glass fibre, 9.5～13.6 parts of didopo, 0.5 part of antioxidant, 3～5 parts of phases
Holding agent, 3～5 parts of triazine carbon forming agents and 1～5 portions of synergist is preparing raw material.
2. halogen-free flameproof long glass fiber reinforced tpu composite according to claim 1 it is characterised in that: described is fire-retardant
Agent didopo is phenethyl bridge chain 9 ' 10- dihydro-9-oxy miscellaneous -10- phospho hetero phenanthrene -10- oxide；The melt temperature of didopo is
180 DEG C, decomposition temperature is 360 DEG C, and melt fluidity is excellent；Didopo structural formula is:
3. halogen-free flameproof long glass fiber reinforced tpu composite according to claim 1 it is characterised in that: described antioxygen
Agent is high-efficiency anti-oxidant 245.
4. halogen-free flameproof long glass fiber reinforced tpu composite according to claim 1 it is characterised in that: described is compatible
Agent is sag-008.
5. halogen-free flameproof long glass fiber reinforced tpu composite according to claim 1 it is characterised in that: described synergistic
Agent is quaternary alkylphosphonium salt intercalation modifying montmorillonite.
6. a kind of preparation method of halogen-free flameproof long glass fiber reinforced tpu composite as claimed in claim 1, its feature exists
In: by above-mentioned parts by weight, take Polyurethane Thermoplastic Elastomer, didopo, triazine carbon forming agent and synergist drying standby respectively
With；Take dried each component to mix homogeneously with antioxidant and compatilizer, carry out blending extrusion, processing temperature is: 185-205
DEG C, by impregnating runner, glass fibre is impregnated, dipping temperature is 240-250 DEG C, cooled, traction, after pelletizing, make
Particle diameter is the halogen-free flameproof long glass fiber reinforced tpu composite of 8～12mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610779441.5A CN106366627A (en) | 2016-08-31 | 2016-08-31 | Halogen-free flame-retardant long glass fiber reinforced TPU composite material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610779441.5A CN106366627A (en) | 2016-08-31 | 2016-08-31 | Halogen-free flame-retardant long glass fiber reinforced TPU composite material and preparation method thereof |
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Cited By (2)
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| CN107201023A (en) * | 2017-06-05 | 2017-09-26 | 江林（贵州）高科发展股份有限公司 | Anti-dripping melt transparent flame-retarding TPU materials and preparation method thereof |
| CN114031930A (en) * | 2021-11-25 | 2022-02-11 | 广州敬信高聚物科技有限公司 | High-strength high-flame-retardance polyurethane cable sheath material and preparation method thereof |
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