CN103013098A - Halogen-free flame-retardant continuous long glass fiber reinforced polyamide 6 composite material and preparation method thereof - Google Patents
Halogen-free flame-retardant continuous long glass fiber reinforced polyamide 6 composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a halogen-free flame-retardant continuous long glass fiber reinforced polyamide 6 composite material, which consists of the following components in percentage by weight: 42-72.5 percent of polyamide 6, 2-6 percent of flexibilizer, 10-20 percent of halogen-free flame retardant, 0.5-2.0 percent of heat stabilizer and 15-30 percent of long glass fiber, wherein the relative viscosity of polyamide 6 is 2.0-3.0; and the long glass fiber is an LFT alkali-free continuous long glass fiber special for polyamide 6. The material prepared by the preparation method has high liquidity, excellent heat resistance, high rigidity, high impact, high dimensional stability, excellent flame retardant property and high CTI value; and due to the detection, the tensile strength is more than or equal to 120MPa, the flexural modulus is more than or equal to 6,500MPa, the notch impact strength is more than or equal to 20KJ/M<2>, the distortion temperature (1.80MPa) is more than or equal to 200 DEG C, the flame-retardant level reaches UL94 1.6mmV-0, and the CTI value is more than or equal to 500V; and moreover, by adoption of the high/low-temperature dual-melt infiltration tank series technology, the defect that the halogen-free flame retardant is decomposed at a high temperature is overcome.
Description
Technical field
The present invention relates to a kind of halogen-free flame-retardant polymer matrix material, relate in particular to a kind of halogen-free flame-retardant long fiber glass reinforced polyamide 6 matrix materials and preparation method thereof.
Background technology
Fiber glass reinforced polyamide 6 products have good integrated application performance, are widely used in the fields such as electric.Along with the day by day raising of entire society's Environmental awareness, halogen-free flameproof becomes the main flow of fiber glass reinforced polyamide 6 technical developments.Need to add a lot of halogen-free flame retardantss but fiber glass reinforced polyamide 6 will reach the V-0 grade non-halogen flame-retardant, this can the serious mechanical property, particularly notched Izod impact strength that reduces the material of fiber glass reinforced polyamide 6.If the enhancing glass of halogen-free flame-retardant polyamide 6 adopts continuous long glass fiber to improve to get roving glass fiber reinforced polyamide 6(LFTPA6), just then the mechanical property of halogen-free flame-retardant polyamide 6 can General Promotion, just can realize the high performance of halogen-free flame-retardant polyamide 6.But owing to be the effect of impregnation may of assurance polyamide 6 to continuous long glass fiber in the LFTPA6 production process, very high (〉=300 ℃) that the melt temperature of polyamide 6 arranges usually, and halogen-free flame retardants can serious decomposition under the high temperature.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the invention provides continuous roving glass fiber reinforced polyamide 6 matrix materials of a kind of halogen-free flameproof and preparation method thereof, this matrix material is by adopting continuous roving glass fiber to strengthen, make halogen-free flame-retardant polyamide 6 high performances, and improved existing preparation technology, solved the shortcoming of halogen-free flame retardants pyrolytic decomposition in the impregnation process.
The present invention for the technical scheme that solves its technical problem and adopt is:
Continuous roving glass fiber reinforced polyamide 6 matrix materials of a kind of halogen-free flameproof are comprised of following each component by total weight percent:
The relative viscosity of wherein said polyamide 6 is 2.0 ~ 3.0; Described long glass fibres is the special-purpose LFT alkali-free of polyamide 6 continuous long glass fiber.
Its further technical scheme is:
Described thermo-stabilizer is at least a in mixture class, phosphorous acid esters, half Hinered phenols, amine and the calixarene of phenols, acryl functional group and monothioester.
Described toughner is the polar monomer graft polymkeric substance, and wherein polymkeric substance is at least a in multipolymer, polyethylene-polystyrene-polypropylene terpolymer, ethylene-propylene-butadiene terpolymer, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer and the ethylene-acrylate-glycidyl methacrylate copolymer of polyethylene, polypropylene, ethene-α-ethylene-octene copolymer, vinylbenzene and divinyl; But described polar monomer is at least a in anhydrides monomer, acrylic monomer and the acrylic ester monomer of double-bond polymerization.
But the anhydrides monomer of described double-bond polymerization is at least a in maleic anhydride, fumaric acid, methylene-succinic acid, citraconic acid, citraconic anhydride and the vinyl Succinic anhydried; Described acrylic monomer is at least a in vinylformic acid and the methacrylic acid; Described acrylic ester monomer is at least a in methyl acrylate, ethyl propenoate, methyl methacrylate and the glytidyl methacrylate.
Described halogen-free flame retardants is at least a in organic hypophosphite, melamine polyphosphate and the melamine cyanurate.
The present invention also provides a kind of halogen-free flameproof continuous roving glass fiber reinforced polyamide 6 composite manufacture methods, may further comprise the steps:
(1) 20 ~ 50wt.% with described polyamide 6 total amount is transported to the high-temperature fusant immersion slot by the single screw extrusion machine plasticizing is rear by the mouth mould, and temperature is 300 ~ 360 ℃ in the described high-temperature fusant immersion slot, and described high-temperature fusant immersion slot length is 2 ~ 2.5m;
(2) be transported to low-temperature melt immersion slot by the single screw extrusion machine plasticizing is rear by the mouth mould with remaining polyamide 6,0.5 ~ 2.0wt.% thermo-stabilizer, 2 ~ 6 wt.% toughner and 10 ~ 20 wt.% halogen-free flame retardantss described in (1), temperature is 230 ~ 250 ℃ in the groove of described low-temperature melt immersion slot, and described low-temperature melt immersion slot length is 1 ~ 1.5m;
(3) 15 ~ 30 wt.% long glass fibress are entered high-temperature fusant immersion slot in (1) and the low-temperature melt immersion slot in (2) successively with the speed drawing of 25 ~ 70m/min; after traction infiltration and cooling, adopt the special-purpose dicing machine of LFT to cut into the long particle of 12mm.
Useful technique effect of the present invention is: the present invention strengthens by continuous long glass fiber makes the halogen-free flame-retardant polyamide high performance, adopt simultaneously high, the production technique of low-temperature melt immersion slot series connection, in the high-temperature fusant immersion slot, realize realizing that at first the part polyamide 6 is to the infiltration of long glass fibres, then in low-temperature melt, coat the skin that one deck polyamide 6 adds halogen-free flame retardants in the immersion slot, final product is that internal layer is that polyamide 6 infiltrates the long glass fibres master batch, skin is the mixture of polyamide 6 and halogen-free flame retardants, ectonexine can be realized abundant dispersion in later stage product injection moulding process, this technology can effectively solve the serious defective of polyamide 6 halogen-free flame retardants decomposition under the condition of high temperature, products obtained therefrom tensile strength 〉=120MPa, modulus in flexure 〉=6500MPa, notched Izod impact strength 〉=20KJ/m
2, heat-drawn wire (1.80MPa) 〉=200 ℃, flame retardant rating reaches UL94 1.6mmV-0, CTI value 〉=500V.
Embodiment
The present invention is described in further detail below in conjunction with specific embodiment, but the present invention is not limited to following embodiment.
Embodiment one:
The first step: 15 kilograms of polyamide 6 Volgamid24 are transported to the high-temperature fusant immersion slot by the plasticizing of length-to-diameter ratio 20:1 single screw extrusion machine is rear by the mouth mould, temperature is 300 ℃ in the groove of described high-temperature fusant immersion slot, and described high-temperature fusant immersion slot length is 2m;
Second step: 57.5 kilograms of polyamide 6 Volgamid24,2 kilograms of toughner 493D, 0.2 kilogram of phenols thermo-stabilizer 1010,0.3 kilogram of phosphite antioxidant 168,10 kilograms of Ke Laien fire retardant OP 1312 are transported to the low-temperature melt immersion slot by the plasticizing of length-to-diameter ratio 20:1 single screw extrusion machine is rear by the mouth mould, temperature is 230 ℃ in the groove of described low-temperature melt immersion slot, and described low-temperature melt immersion slot length is 1m;
The 3rd step: 15 kilograms of PPG companies are produced continuous long glass fiber Tufrov 4510 pass through successively high-temperature fusant groove in the first step and the low-temperature melt groove in the second step with 25mm/min speed; after long glass fibres draws from melt tank and infiltrates; be cut into the particle of the long homogeneous of 12mm with the special-purpose dicing machine of LFT; get composite A, its performance is as shown in table 1:
The performance of table 1 composite A
| Performance | Unit | Testing standard | Test result |
| Density (23 ℃) | g/cm 3 | ISO?1183 | 1.32 |
| Glass fiber content (750 ℃, 30min) | % | ISO?3451/1 | 15 |
| HDT（1.80MPa） | ℃ | ISO75/1-93 | 208 |
| Tensile strength | MPa | ISO527/2-93 | 140 |
| Modulus in flexure | MPa | ISO178/2-93 | 6800 |
| Notched Izod impact strength | KJ/m 2 | ISO179/2-93 | 25.5 |
| Flame retardant resistance | -- | UL94 | 1.6mmV-0 |
| The CTI value | V | IEC?60112 | 600 |
Embodiment two:
The first step: 20 kilograms of polyamide 6 Volgamid25 are transported to the high-temperature fusant immersion slot by the plasticizing of length-to-diameter ratio 20:1 single screw extrusion machine is rear by the mouth mould, temperature is arranged on 320 ℃ in the groove of described high-temperature fusant immersion slot, and described high-temperature fusant immersion slot length is 2m;
Second step: 40 kilograms of polyamide 6 Volgamid25,4 kilograms of toughner 560D, 0.5 kilogram of phenols thermo-stabilizer 1010,0.5 kilogram of phosphite antioxidant 627A, 15 kilograms of Ke Laien fire retardant OP 1311 are transported to the low-temperature melt immersion slot by the plasticizing of length-to-diameter ratio 20:1 single screw extrusion machine is rear by the mouth mould, temperature is 240 ℃ in the groove of described low-temperature melt immersion slot, and described low-temperature melt immersion slot length is 1m;
The 3rd step: 20 kilograms of PPG companies are produced continuous long glass fiber Tufrov 4510 pass through successively high-temperature fusant groove in the first step and the low-temperature melt groove in the second step with 50mm/min speed; after long glass fibres draws from melt tank and infiltrates; be cut into the particle of the long homogeneous of 12mm with dicing machine; get matrix material B, its performance is such as table
Shown in 2:
The performance of table 2 matrix material B
| Performance | Unit | Testing standard | Test result |
| Density (23 ℃) | g/cm 3 | ISO?1183 | 1.39 |
| Glass fiber content (750 ℃, 30min) | % | ISO?3451/1 | 20 |
| HDT（1.80MPa） | ℃ | ISO75/1-93 | 210 |
| Tensile strength | MPa | ISO527/2-93 | 170 |
| Modulus in flexure | MPa | ISO178/2-93 | 7500 |
| Notched Izod impact strength | KJ/m 2 | ISO179/2-93 | 29.0 |
| Flame retardant resistance | -- | UL94 | 1.6mmV-0 |
| The CTI value | V | IEC?60112 | 600 |
Embodiment three:
The first step: 20 kilograms of polyamide 6 Volgamid27 are transported to the high-temperature fusant immersion slot by the plasticizing of length-to-diameter ratio 20:1 single screw extrusion machine is rear by the mouth mould, temperature is 340 ℃ in the groove of described high-temperature fusant immersion slot, and described high-temperature fusant immersion slot length is 2.5m;
Second step: 33.5 kilograms of polyamide 6 Volgamid27,5 kilograms of toughner Bondyram 7003,0.8 kilogram of phenols thermo-stabilizer 1010,0.7 kilogram of phosphite antioxidant 627A, 10 kilograms of Ke Laien fire retardant OP 1230 and 5 kilograms of fire-retartant agent MP P are transported to the low-temperature melt immersion slot by the plasticizing of length-to-diameter ratio 20:1 single screw extrusion machine is rear by the mouth mould, temperature is arranged on 245 ℃ in the groove of described low-temperature melt immersion slot, and described low-temperature melt immersion slot length is 1.5m;
The 3rd step: 25 kilograms of PPG companies are produced continuous long glass fiber Tufrov 4588 pass through successively high-temperature fusant groove in the first step and the low-temperature melt groove in the second step with 70mm/min speed; after long glass fibres draws from melt tank and infiltrates; be cut into the particle of the long homogeneous of 12mm with dicing machine; get matrix material C, its performance is as shown in table 3:
The performance of table 3 matrix material C
| Performance | Unit | Testing standard | Test result |
| Density (23 ℃) | g/cm 3 | ISO?1183 | 1.43 |
| Glass fiber content (750 ℃, 30min) | % | ISO?3451/1 | 25 |
| HDT（1.80MPa） | ℃ | ISO75/1-93 | 212 |
| Tensile strength | MPa | ISO527/2-93 | 185 |
| Modulus in flexure | MPa | ISO178/2-93 | 8200 |
| Notched Izod impact strength | KJ/m 2 | ISO179/2-93 | 33 |
| Flame retardant resistance | -- | UL94 | 1.6mmV-0 |
| The CTI value | V | IEC?60112 | 550 |
Embodiment four:
The first step: 20 kilograms of polyamide 6 Volgamid27 are transported to the high-temperature fusant immersion slot by the plasticizing of length-to-diameter ratio 20:1 single screw extrusion machine is rear by the mouth mould, temperature is arranged on 360 ℃ in the groove of described high-temperature fusant immersion slot, and described high-temperature fusant immersion slot length is 2.3m;
Second step: 22 kilograms of polyamide 6 Volgamid27,6 kilograms of toughner 560D, 1 kilogram of phenols thermo-stabilizer 1010,1 kilogram of monothioester oxidation inhibitor 412S, 15 kilograms of Ke Laien fire retardant OP 1312 and 5 kilograms of fire retardant MCA are transported to the low-temperature melt immersion slot by the plasticizing of length-to-diameter ratio 20:1 single screw extrusion machine is rear by the mouth mould, temperature is arranged on 250 ℃ in the groove of described low-temperature melt immersion slot, and described low-temperature melt immersion slot length is 1.3m;
The 3rd step: 30 kilograms of PPG companies are produced continuous long glass fiber Tufrov 4588 pass through successively high-temperature fusant groove in the first step and the low-temperature melt groove in the second step with 70mm/min speed; after long glass fibres draws from melt tank and infiltrates; be cut into the particle of the long homogeneous of 12mm with dicing machine; get matrix material D, its performance is as shown in table 4:
The performance of table 4 matrix material D
| Performance | Unit | Testing standard | Test result |
| Density (23 ℃) | g/cm 3 | ISO?1183 | 1.47 |
| Glass fiber content (750 ℃, 30min) | % | ISO?3451/1 | 30 |
| HDT（1.80MPa） | ℃ | ISO75/1-93 | 215 |
| Tensile strength | MPa | ISO527/2-93 | 200 |
| Modulus in flexure | MPa | ISO178/2-93 | 9000 |
| Notched Izod impact strength | KJ/m 2 | ISO179/2-93 | 38.5 |
| Flame retardant resistance | -- | UL94 | 1.6mmV-0 |
| The CTI value | V | IEC?60112 | 500 |
Can be found out by above-described embodiment, the material that the present invention prepares gained has high workability, excellent thermotolerance, high rigidity, HI high impact, high-dimensional stability, excellent flame retardant properties and high CTI value, its tensile strength 〉=120MPa after testing, modulus in flexure 〉=6500MPa, notched Izod impact strength 〉=20KJ/m
2, heat-drawn wire (1.80MPa) 〉=200 ℃, flame retardant rating reaches UL94 1.6mmV-0, CTI value 〉=500V, and the present invention adopts the technology of the two melt immersion slots series connection of high low temperature to solve the shortcoming of halogen-free flame retardants pyrolytic decomposition.
Above embodiment is exemplary embodiment of the present invention only, is not used in restriction the present invention.Those skilled in the art can make various modifications or be equal to replacement the present invention in essence of the present invention and protection domain, this modification or be equal to replacement and also should be considered as dropping in protection scope of the present invention.
Claims (6)
1. continuous roving glass fiber reinforced polyamide 6 matrix materials of halogen-free flameproof is characterized in that: be comprised of following each component by total weight percent:
The relative viscosity of wherein said polyamide 6 is 2.0 ~ 3.0; Described long glass fibres is the special-purpose LFT alkali-free of polyamide 6 continuous long glass fiber.
2. continuous roving glass fiber reinforced polyamide 6 matrix materials of halogen-free flameproof according to claim 1 is characterized in that: described thermo-stabilizer is at least a in mixture class, phosphorous acid esters, half Hinered phenols, amine and the calixarene of phenols, acryl functional group and monothioester.
3. continuous roving glass fiber reinforced polyamide 6 matrix materials of halogen-free flameproof according to claim 1, it is characterized in that: described toughner is the polar monomer graft polymkeric substance, and wherein polymkeric substance is at least a in multipolymer, polyethylene-polystyrene-polypropylene terpolymer, ethylene-propylene-butadiene terpolymer, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer and the ethylene-acrylate-glycidyl methacrylate copolymer of polyethylene, polypropylene, ethene-α-ethylene-octene copolymer, vinylbenzene and divinyl; But described polar monomer is at least a in anhydrides monomer, acrylic monomer and the acrylic ester monomer of double-bond polymerization.
4. continuous roving glass fiber reinforced polyamide 6 matrix materials of halogen-free flameproof according to claim 3 is characterized in that: but the anhydrides monomer of described double-bond polymerization is at least a in maleic anhydride, fumaric acid, methylene-succinic acid, citraconic acid, citraconic anhydride and the vinyl Succinic anhydried; Described acrylic monomer is at least a in vinylformic acid and the methacrylic acid; Described acrylic ester monomer is at least a in methyl acrylate, ethyl propenoate, methyl methacrylate and the glytidyl methacrylate.
5. continuous roving glass fiber reinforced polyamide 6 matrix materials of halogen-free flameproof according to claim 1 is characterized in that: described halogen-free flame retardants is at least a in organic hypophosphite, melamine polyphosphate and the melamine cyanurate.
6. continuous roving glass fiber reinforced polyamide 6 composite manufacture methods of the described halogen-free flameproof of arbitrary claim in 5 according to claim 1 is characterized in that: may further comprise the steps:
(1) 20 ~ 50wt.% with described polyamide 6 total amount is transported to the high-temperature fusant immersion slot by the single screw extrusion machine plasticizing is rear by the mouth mould, and temperature is 300 ~ 360 ℃ in the described high-temperature fusant immersion slot, and described high-temperature fusant immersion slot length is 2 ~ 2.5m;
(2) be transported to low-temperature melt immersion slot by the single screw extrusion machine plasticizing is rear by the mouth mould with remaining polyamide 6,0.5 ~ 2.0wt.% thermo-stabilizer, 2 ~ 6 wt.% toughner and 10 ~ 20 wt.% halogen-free flame retardantss described in (1), temperature is 230 ~ 250 ℃ in the groove of described low-temperature melt immersion slot, and described low-temperature melt immersion slot length is 1 ~ 1.5m;
(3) 15 ~ 30 wt.% long glass fibress are entered high-temperature fusant immersion slot in (1) and the low-temperature melt immersion slot in (2) successively with the speed drawing of 25 ~ 70m/min; after traction infiltration and cooling, adopt the special-purpose dicing machine of LFT to cut into the long particle of 12mm.
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