CN103013098B - Continuous roving glass fiber reinforced polyamide 6 composites of halogen-free flameproof and preparation method thereof - Google Patents
Continuous roving glass fiber reinforced polyamide 6 composites of halogen-free flameproof and preparation method thereof Download PDFInfo
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Abstract
The invention discloses continuous roving glass fiber reinforced polyamide 6 composites of a kind of halogen-free flameproof, by forming by each component of total weight percent below: polyamide 6? 42 ~ 72.5%, flexibilizer 2 ~ 6%, halogen-free flame retardants 10 ~ 20%, heat stabilizer 0.5 ~ 2.0% and long glass fibres 15 ~ 30%; The relative viscosity of wherein said polyamide 6 is 2.0 ~ 3.0; Described long glass fibres is the special LFT alkali-free of polyamide 6 continuous long glass fiber. The material that the present invention prepares gained has high fluidity, excellent heat resistance, high rigidity, HI high impact, high-dimensional stability, excellent fire resistance and high CTI value, its hot strength >=120MPa after testing, bending modulus >=6500MPa, notched Izod impact strength >=20KJ/m2, heat distortion temperature (1.80MPa)>=200 DEG C, does flame retardant rating reach UL94? 1.6mmV-0, CTI value>=500V, and the present invention adopts the technology of the two melt immersion slot series connection of high low temperature to solve the shortcoming of halogen-free flame retardants pyrolytic.<!--1-->
Description
Technical field
The present invention relates to a kind of halogen-free flame-retardant polymer composite, relate in particular to oneHalogen-free flame-retardant long fiber glass reinforced polyamide 6 composites and preparation method thereof.
Background technology
Fiber glass reinforced polyamide 6 products have good integrated application performance, extensively shouldBe used for the fields such as electric. Along with the raising day by day of entire society's environmental consciousness, nothingThe fire-retardant main flow that becomes fiber glass reinforced polyamide 6 technical developments of halogen. But glass strengthens poly-Acid amides 6 will reach V-0 grade non-halogen flame-retardant need to add a lot of halogen-free flame retardants, this meetingThe mechanical property of the serious material that reduces fiber glass reinforced polyamide 6, particularly breach punchingHit intensity. If the enhancing glass of halogen-free flame-retardant polyamide 6 adopts continuous long glass fiberImprove to obtain roving glass fiber reinforced polyamide 6 (LFTPA6), halogen-free flame-retardant polyamide 6Mechanical property just can General Promotion, just can realize the height of halogen-free flame-retardant polyamide 6Performance-based. But due in LFTPA6 production process for ensureing that polyamide 6 is to continuouslyThe effect of impregnation of long glass fibres, the melt temperature of polyamide 6 arranges very conventionallyHigh (>=300 DEG C), and under high temperature, halogen-free flame retardants can seriously decompose.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the invention provides oneContinuous roving glass fiber reinforced polyamide 6 composites of halogen-free flameproof and preparation method thereof, shouldComposite, by adopting continuous roving glass fiber to strengthen, makes the high property of halogen-free flame-retardant polyamide 6Energyization, and improved existing preparation technology, solve halogen-free flameproof in impregnation processThe shortcoming of agent pyrolytic.
The present invention for the technical scheme that solves its technical problem and adopt is:
Continuous roving glass fiber reinforced polyamide 6 composites of a kind of halogen-free flameproof, by belowEach component composition by total weight percent:
The relative viscosity of wherein said polyamide 6 is 2.0～3.0; Described long glass fibersDimension is the special LFT alkali-free of polyamide 6 continuous long glass fiber.
Its further technical scheme is:
Described heat stabilizer is the compound of phenols, acryloyl group functional group and monothioesterAt least one in class, phosphorous acid esters, half Hinered phenols, amine and calixarenes.
Described flexibilizer is polar monomer graft polymer, and wherein polymer is poly-secondBeing total to of alkene, polypropylene, ethene-α-ethylene-octene copolymer, styrene and butadienePolymers, polyethylene-polystyrene-polypropylene terpolymer, ethylene-propylene-Ding bis-Alkene terpolymer, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymerizationIn thing and ethylene-acrylate-glycidyl methacrylate copolymer at leastA kind of; Described polar monomer be can double-bond polymerization anhydrides monomer, acrylic compounds listAt least one in body and acrylic ester monomer.
Described anhydrides monomer that can double-bond polymerization is maleic anhydride, citraconic anhydride and secondAt least one in enetutanedioic acid anhydride; Described acrylic monomer is acrylic acid and firstAt least one in base acrylic acid; Described acrylic ester monomer be methyl acrylate,In ethyl acrylate, methyl methacrylate and GMA at leastA kind of.
Described halogen-free flame retardants is organic hypophosphites, melamine polyphosphate and threeAt least one in poly cyanamid cyanurate.
The present invention also provides a kind of halogen-free flameproof continuous roving glass fiber reinforced polyamide 6The preparation method of composite, comprises the following steps:
(1) 20～50wt.% of described polyamide 6 total amount is passed through to single Screw ExtrusionAfter machine plasticizing, be transported to high-temperature fusant immersion slot by mouth mould, described high-temperature fusant infiltratesIn groove, temperature is 300～360 DEG C, and described high-temperature fusant immersion slot length is2～2.5m；
(2) by described in (1), remain polyamide 6,0.5～2.0wt.% heat stabilizer,2～6wt.% flexibilizer and 10～20wt.% halogen-free flame retardants pass through single screw extrusion machineAfter plasticizing, be transported to low-temperature melt immersion slot by mouth mould, described low-temperature melt immersion slotGroove in temperature be 230～250 DEG C, and described low-temperature melt immersion slot length is1～1.5m；
(3) 15～30wt.% long glass fibres is led with the speed of 25～70m/minThe low-temperature melt drawing successively in high-temperature fusant immersion slot and (2) that enter in (1) soaksProfit groove, by traction infiltrates also cooling after, the special pelleter of employing LFT cuts intoThe long particle of 12mm.
Useful technique effect of the present invention is: the present invention increases by continuous long glass fiberForce halogen-free flame-retardant polyamide high performance, adopt high and low temperature melt immersion slot simultaneouslyThe production technology of series connection realizes and first realizes part polyamides in high-temperature fusant immersion slotThe infiltration of amine 6 resins to long glass fibres then wrapped in immersion slot in low-temperature meltCover the skin that one deck polyamide 6 adds halogen-free flame retardants, final product is that internal layer is poly-Acid amides 6 infiltrates long glass fibres master batch, skin is polyamide 6 and halogen-free flame retardantsCompound, ectonexine can be realized abundant dispersion in later stage product injection moulding process, thisOne technology can effectively solve polyamide 6 halogen-free flame retardants under the condition of high temperature and decomposeSerious defect, products obtained therefrom hot strength >=120MPa, bending modulus >=6500MPa, notched Izod impact strength >=20KJ/m2, heat distortion temperature (1.80MPa)>=200 DEG C, flame retardant rating reaches UL941.6mmV-0, CTI value >=500V.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail, but thisInvention is not limited to following embodiment.
Embodiment mono-:
The first step: 15 kilograms of polyamide 6 Volgamid24 are passed through to draw ratio 20:After 1 single screw extrusion machine plasticizing, be transported to high-temperature fusant immersion slot by mouth mould, described inIn the groove of high-temperature fusant immersion slot, temperature is 300 DEG C, and described high-temperature fusant immersion slotLength is 2m;
Second step: by 57.5 kilograms of polyamide 6 Volgamid24,2 kilograms of flexibilizer493D, 1010,0.3 kilogram of phosphite antioxidant of 0.2 kilogram of phenols heat stabilizer168,10 kilograms of Ke Laien fire retardant OP1312 are by the mono-screw rod of draw ratio 20:1After extruder plasticizing, be transported to low-temperature melt immersion slot by mouth mould, described low-temperature meltIn the groove of immersion slot, temperature is 230 DEG C, and described low-temperature melt immersion slot length is1m；
The 3rd step: 15 kilograms of PPG companies are produced to continuous long glass fiber Tufrov4510 pass through the high-temperature fusant groove and in the first step successively with 25mm/min speedLow-temperature melt groove in two steps, long glass fibres is used after drawing from melt tank and infiltratingThe special pelleter of LFT is cut into the particle of the long homogeneous of 12mm, obtains composite A, itsPerformance is as shown in table 1:
The performance of table 1 composite A
| Performance | Unit | Testing standard | Test result |
| Density (23 DEG C) | g/cm3 | ISO 1183 | 1.32 |
| Glass fiber content (750 DEG C, 30min) | ％ | ISO 3451/1 | 15 |
| HDT(1.80MPa) | ℃ | ISO75/1-93 | 208 |
| Hot strength | MPa | ISO527/2-93 | 140 |
| Bending modulus | MPa | ISO178/2-93 | 6800 |
| Notched Izod impact strength | KJ/m2 | ISO179/2-93 | 25.5 |
| Anti-flammability | -- | UL94 | 1.6mmV-0 |
| CTI value | V | IEC 60112 | 600 |
Embodiment bis-:
The first step: 20 kilograms of polyamide 6 Volgamid25 are passed through to draw ratio 20:After 1 single screw extrusion machine plasticizing, be transported to high-temperature fusant immersion slot by mouth mould, described inIn the groove of high-temperature fusant immersion slot, temperature is arranged on 320 DEG C, and described high-temperature fusant soaksProfit slot length is 2m;
Second step: by 40 kilograms of polyamide 6 Volgamid25,4 kilograms of flexibilizer560D, 1010,0.5 kilogram of phosphite antioxidant of 0.5 kilogram of phenols heat stabilizer627A, 15 kilograms of Ke Laien fire retardant OP1311 are by the mono-spiral shell of draw ratio 20:1After the plasticizing of bar extruder, be transported to low-temperature melt immersion slot by mouth mould, described low temperature is moltenIn the groove of body immersion slot, temperature is 240 DEG C, and described low-temperature melt immersion slot length is1m；
The 3rd step: 20 kilograms of PPG companies are produced to continuous long glass fiber Tufrov4510 pass through the high-temperature fusant groove and in the first step successively with 50mm/min speedLow-temperature melt groove in two steps, long glass fibres is used after drawing from melt tank and infiltratingPelleter is cut into the particle of the long homogeneous of 12mm, obtains composite B, and its performance is as tableShown in 2:
The performance of table 2 composite B
| Performance | Unit | Testing standard | Test result |
| Density (23 DEG C) | g/cm3 | ISO 1183 | 1.39 |
| Glass fiber content (750 DEG C, 30min) | ％ | ISO 3451/1 | 20 |
| HDT(1.80MPa) | ℃ | ISO75/1-93 | 210 |
| Hot strength | MPa | ISO527/2-93 | 170 |
| Bending modulus | MPa | ISO178/2-93 | 7500 |
| Notched Izod impact strength | KJ/m2 | ISO179/2-93 | 29.0 |
| Anti-flammability | -- | UL94 | 1.6mmV-0 |
| CTI value | V | IEC 60112 | 600 |
Embodiment tri-:
The first step: 20 kilograms of polyamide 6 Volgamid27 are passed through to draw ratio 20:After 1 single screw extrusion machine plasticizing, be transported to high-temperature fusant immersion slot by mouth mould, described inIn the groove of high-temperature fusant immersion slot, temperature is 340 DEG C, and described high-temperature fusant immersion slotLength is 2.5m;
Second step: by 33.5 kilograms of polyamide 6 Volgamid27,5 kilograms of flexibilizerBondyram7003,1010,0.7 kilogram of phosphorous acid of 0.8 kilogram of phenols heat stabilizerEster antioxidant 627A, 10 kilograms of Ke Laien fire retardant OP1230 and 5 kilograms fire-retardantAgent MPP carries by mouthful mould by the plasticizing of draw ratio 20:1 single screw extrusion machine is rearTo low-temperature melt immersion slot, in the groove of described low-temperature melt immersion slot, temperature is arranged on245 DEG C, and described low-temperature melt immersion slot length is 1.5m;
The 3rd step: 25 kilograms of PPG companies are produced to continuous long glass fiber Tufrov4588 pass through the high-temperature fusant groove and in the first step successively with 70mm/min speedLow-temperature melt groove in two steps, long glass fibres is used after drawing from melt tank and infiltratingPelleter is cut into the particle of the long homogeneous of 12mm, obtains composite C, and its performance is as tableShown in 3:
The performance of table 3 composite C
| Performance | Unit | Testing standard | Test result |
| Density (23 DEG C) | g/cm3 | ISO 1183 | 1.43 |
| Glass fiber content (750 DEG C, 30min) | ％ | ISO 3451/1 | 25 |
| HDT(1.80MPa) | ℃ | ISO75/1-93 | 212 |
| Hot strength | MPa | ISO527/2-93 | 185 |
| Bending modulus | MPa | ISO178/2-93 | 8200 |
| Notched Izod impact strength | KJ/m2 | ISO179/2-93 | 33 |
| Anti-flammability | -- | UL94 | 1.6mmV-0 |
| CTI value | V | IEC 60112 | 550 |
Embodiment tetra-:
The first step: 20 kilograms of polyamide 6 Volgamid27 are passed through to draw ratio 20:After 1 single screw extrusion machine plasticizing, be transported to high-temperature fusant immersion slot by mouth mould, described inIn the groove of high-temperature fusant immersion slot, temperature is arranged on 360 DEG C, and described high-temperature fusant soaksProfit slot length is 2.3m;
Second step: by 22 kilograms of polyamide 6 Volgamid27,6 kilograms of flexibilizer560D, 1010,1 kilogram of monothioester antioxidant 412S of 1 kilogram of phenols heat stabilizer,15 kilograms of Ke Laien fire retardant OP1312 and 5 kilograms of fire retardant MCA pass through major diameterInfiltrate than being transported to low-temperature melt by mouth mould after the plasticizing of 20:1 single screw extrusion machineGroove, in the groove of described low-temperature melt immersion slot, temperature is arranged on 250 DEG C, and described lowTemperature melt immersion slot length is 1.3m;
The 3rd step: 30 kilograms of PPG companies are produced to continuous long glass fiber Tufrov4588 pass through the high-temperature fusant groove and in the first step successively with 70mm/min speedLow-temperature melt groove in two steps, long glass fibres is used after drawing from melt tank and infiltratingPelleter is cut into the particle of the long homogeneous of 12mm, obtains composite D, and its performance is as tableShown in 4:
The performance of table 4 composite D
| Performance | Unit | Testing standard | Test result |
| Density (23 DEG C) | g/cm3 | ISO 1183 | 1.47 |
| Glass fiber content (750 DEG C, 30min) | ％ | ISO 3451/1 | 30 |
| HDT(1.80MPa) | ℃ | ISO75/1-93 | 215 |
| Hot strength | MPa | ISO527/2-93 | 200 |
| Bending modulus | MPa | ISO178/2-93 | 9000 |
| Notched Izod impact strength | KJ/m2 | ISO179/2-93 | 38.5 |
| Anti-flammability | -- | UL94 | 1.6mmV-0 |
| CTI value | V | IEC 60112 | 500 |
Can be found out by above-described embodiment, the material that the present invention prepares gained has high flowingProperty, excellent heat resistance, high rigidity, HI high impact, high-dimensional stability, excellentFire resistance and high CTI value, its hot strength >=120MPa after testing, bendingModulus >=6500MPa, notched Izod impact strength >=20KJ/m2, heat distortion temperature(1.80MPa) >=200 DEG C, flame retardant rating reaches UL941.6mmV-0, CTIValue >=500V, and the present invention adopts the technology solution of the two melt immersion slot series connection of high low temperatureThe determined shortcoming of halogen-free flame retardants pyrolytic.
Above embodiment is only exemplary embodiment of the present invention, is not used in and limits thisBright. Those skilled in the art can be in essence of the present invention and protection domain, to thisInvention is made various amendments or is equal to replacement, this amendment or be equal to replacement and also should be considered asDrop in protection scope of the present invention.
Claims (5)
1. the preparation of continuous roving glass fiber reinforced polyamide 6 composites of halogen-free flameproofMethod, is characterized in that: comprise the following steps:
(1) 20～50wt.% of formula consumption polyamide 6 total amount is squeezed by single screw rodAfter going out machine plasticizing, be transported to high-temperature fusant immersion slot by mouth mould, described high-temperature fusant soaksIn profit groove, temperature is 300～360 DEG C, and described high-temperature fusant immersion slot length is2～2.5m；
(2) by described in (1), remain polyamide 6, formula consumption heat stabilizer,Formula consumption flexibilizer and formula consumption halogen-free flame retardants plastify by single screw extrusion machineBe transported to low-temperature melt immersion slot by mouth mould afterwards, the groove of described low-temperature melt immersion slotInterior temperature is 230～250 DEG C, and described low-temperature melt immersion slot length is 1～1.5m;
(3) formula consumption long glass fibres is complied with the speed drawing of 25～70m/minLow-temperature melt immersion slot in high-temperature fusant immersion slot in inferior entering (1) and (2),By traction infiltrate and cooling after, adopt LFT special pelleter to cut into 12mm longParticle;
The formula of continuous roving glass fiber reinforced polyamide 6 composites of described halogen-free flameproof is usedMeasure as described below, this composite by following by each component group of total weight percentBecome:
The relative viscosity of wherein said polyamide 6 is 2.0～3.0; Described long glass fibresIt is the special LFT alkali-free of polyamide 6 continuous long glass fiber.
2. the continuous roving glass fiber reinforced polyamide of halogen-free flameproof according to claim 1The preparation method of 6 composites, is characterized in that: described heat stabilizer be phenols,The compound class of acryloyl group functional group and monothioester, phosphorous acid esters, half hindered phenolAt least one in class, amine and calixarenes.
3. the continuous roving glass fiber reinforced polyamide of halogen-free flameproof according to claim 1The preparation method of 6 composites, is characterized in that: described flexibilizer is polarity listBody graft polymers, wherein polymer be polyethylene, polypropylene, ethene-α-ethene-The copolymer of octene copolymer, styrene and butadiene, polyethylene-polystyrene-poly-Propylene terpolymers, ethylene-propylene-butadiene terpolymer, ethene-acetic acid secondEnoate copolymer, vinyl-acrylate copolymer and ethylene-acrylate-metering systemAt least one in acid glycidyl ester copolymer; Described polar monomer is to gather by two keysAt least one in anhydrides monomer, acrylic monomer and the acrylic ester monomer closingKind.
4. the continuous roving glass fiber reinforced polyamide of halogen-free flameproof according to claim 3The preparation method of 6 composites, is characterized in that: described acid anhydrides that can double-bond polymerizationClass monomer is at least one in maleic anhydride, citraconic anhydride and vinyl succinic anhydride;Described acrylic monomer is at least one in acrylic acid and methacrylic acid; DescribedAcrylic ester monomer is methyl acrylate, ethyl acrylate, methyl methacrylateWith at least one in GMA.
5. the continuous roving glass fiber reinforced polyamide of halogen-free flameproof according to claim 1The preparation method of 6 composites, is characterized in that: described halogen-free flame retardants is organicAt least one in hypophosphites, melamine polyphosphate and melamine cyanurateKind.
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