CN103044901B - High-fluidity halogen-free flame retardant reinforced nylon composite material and preparation method thereof - Google Patents

High-fluidity halogen-free flame retardant reinforced nylon composite material and preparation method thereof Download PDF

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CN103044901B
CN103044901B CN201210546631.4A CN201210546631A CN103044901B CN 103044901 B CN103044901 B CN 103044901B CN 201210546631 A CN201210546631 A CN 201210546631A CN 103044901 B CN103044901 B CN 103044901B
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nylon
halogen
free flame
flame retardant
fluidity
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CN103044901A (en
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杨克俭
甘典松
胡天辉
宋克东
张志军
卢宏伟
姜其斌
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Zhuzhou Times Engineering Plastics Industry Co Ltd
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Zhuzhou Times New Material Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B29B9/14—Making granules characterised by structure or composition fibre-reinforced
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7461—Combinations of dissimilar mixers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion

Abstract

The invention discloses a high-fluidity halogen-free flame retardant reinforced nylon composite material and a preparation method thereof. According to the invention, high-fluidity nylon resin containing chain structural nylon 6 is adopted as matrix resin; 4.9 to 29.5 parts of halogen-free flame retardant and 0.1 to 0.5 part of antioxidant are added in a mixing machine for evenly mixing; the obtained mixture is melted and extruded through a screw extruder; a reinforcement component is added in the extruding process; and finally, a novel halogen-free flame retardant reinforced nylon composite material of the high-fluidity halogen-free flame retardant reinforced nylon composite material is obtained through drawing, cooling and pelletizing. The flame retardant reinforced nylon composite material has the characteristics of high melt fluidity, good environmental friendliness and flame retardance, good electric performance, excellent mechanical performance and the like; and obtained products have excellent surface performance, low warpage and high smoothness. The material can be widely applied in the field of electric plastic parts, such as casings, breakers, wire connection boxes, socket switches and the like of semiconductor devices such as IGBT (Insulated Gate Bipolar Transistor) and the like.

Description

A kind of high workability halogen-free flame-retardant reinforced nylon matrix material and preparation method thereof
Technical field
The present invention relates to a kind of halogen-free flame-retardant composite material, particularly a kind of high workability halogen-free flame-retardant reinforced nylon matrix material preparation method extremely.
Background technology
Reinforced Nylon material has the advantages that physical and mechanical properties is high, heat-resistant stability good, electric property is good, is widely used in the industries such as automobile, electric, defence and military and mechanical means.But due to the oxygen index of Reinforced Nylon material not high (25% left and right), and combustionvelocity is fast, in combustion processes, can produce a large amount of dense smoke and molten drop, propagating flame very easily, greatly limited its application at special dimensions such as electronic apparatuss, therefore, the flame retardant resistance of raising Reinforced Nylon material is extremely urgent.
At present, the flame-retardant system that Reinforced Nylon material is conventional comprises halogenated flame retardant, phosphorus flame retardant, nitrogen phosphorus flame retardant and inorganic combustion inhibitor.The flame retarding efficiency of halogenated flame retardant is high, consumption is few, performance impact to material is little, but it is owing to producing a large amount of toxic gases in thermal destruction and combustion processes, application is subject to the brute force restriction of the laws and regulations such as the ROHS of European Union and WEEE instruction, the non-halogen inexorable trend that has become the fire-retardant development of nylon of fire retardant.But existing three kinds of halogen-free flame-retardant systems all exist that fire retardant addition is large, fire retardant and matrix resin and the series of problems such as enhancement component consistency is poor, cause fluidity of molten variation, be difficult to process; The phenomenons such as flame retarding efficiency is not high, material mechanical performance obviously reduces, product surface is poor.In order to address the above problem, conventionally adopt to fire retardant carry out physical and chemical modified, composite and additional compatilizer is realized.As mentioned in Chinese patent 200610150960, using the metallic ion modified polyphosphoric acid melamine salt (M-MPP) through ultrafining treatment is halogen-free flame retardants, improve the poor problem of consistency of fire retardant and PA66, prepared all good fiberglass reinforced fire retardant nylon 66 materials of mechanical property and flame retardant properties.And for example in Chinese patent 200710069275, mention and adopt the multipolymer of unsaturated carboxylic acid and ABS as compatilizer and rheology modifier, melamine phosphate, poly organic silicon oxide compound and inorganic, metal oxide are flame-retardant system, effectively improve consistency and the fluidity of molten of glass fibre and nylon resin, prepare there is highly effective flame-retardant, the mechanical property of excellence and the glass fiber reinforced flame retardant polyamide material of electric property.Yet all also there is the problem that suitability is not strong in these methods.
Summary of the invention
The halogen-free flame-retardant reinforced nylon matrix material that the technical problem to be solved in the present invention is to provide a kind of high flame retardant efficiency and excellent Miscibility is preparation method extremely.Adopt halogen-free flame-retardant reinforced nylon matrix material prepared by this technology of preparing to there is the features such as fluidity of molten is high, environmental protection flame retardant performance is good, good electrical property, mechanical property excellence.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme:
This matrix material is pressed massfraction, forms as follows:
Nylon resin: 20-80;
Enhancement component: 10-50;
Halogen-free flame retardants: 9.9-29.5;
Oxidation inhibitor: 0.1-0.5;
Wherein this nylon resin is at least to contain the high-fluidity nylon composition of branched structure nylon 6, and wherein, nylon composite comprises side chain nylon 6 and linear nylon 6, nylon 66, nylon 11, nylon 12, nylon 46, nylon 612, a kind of or its combination of nylon 1212 or aromatic nylon (nylon 10T); Side chain Nylon 6 is that branching unit initiator and hexanolactam prepare by hydrolytic polymerization, and wherein, branching unit structure of initiator is a kind of or its combination in dendroid branched structure, star-branched structure or dissaving structure; Branching unit initiator molecule type be aliphatics, aromatic series or heterocyclic molecule in a kind of or its combination; The end group of branching unit initiator is a kind of of amino, carboxyl or hydroxyl; Functional group's degree of branching unit initiator is between 3-16.
The relative viscosity of side chain Nylon 6 is 1.2-3.0, kinematic viscosity (230 oC, 500s -1) between 10Pa.s-1000 Pa.s.
Enhancement component comprises fortifying fibre and inorganic mineral filler, and wherein, fortifying fibre is alkali free glass fibre, flaxen fiber, a kind of in aramid fiber or carbon fiber; Inorganic mineral filler is a kind of or its combination in glass microballon, molybdenumdisulphide, halloysite, talcum powder, mica, barium sulfate, calcium stearate, graphite, silicon-dioxide, polynite or kaolin.
Halogen-free flame retardants comprises the agent of alkylphosphonic fire-retardant, the fire-retardant agent of phosphorus nitrogen and inorganic fire-retardant agent, and wherein, the agent of alkylphosphonic fire-retardant comprises alkyl hypophosphite, alkyl metaphosphate and alkyl phosphite; The agent of phosphorus nitrogen fire-retardant comprises trimeric cyanamide-poly-phosphate (MP), trimeric cyanamide-polyphosphoric acid salt (MPP), cyanurate and trimeric cyanamide-focusing phosphoric acid salt etc.; Inorganic fire-retardant agent comprises a kind of or its combination in ammonium polyphosphate (APP), aluminium hydroxide, magnesium hydroxide, expansible black lead, seven water and magnesium sulfate molybdenum oxide.
Oxidation inhibitor is a kind of or its combination in Hinered phenols antioxidant or phosphite ester kind antioxidant.Hinered phenols antioxidant is 2, tri-grades of butyl-4-methylphenols of 6-, two (3, tri-grades of butyl-4-hydroxy phenyls of 5-) thioether, four (β-(3, tri-grades of butyl-4-hydroxy phenyls of 5-) propionic acid) a kind of in tetramethylolmethane (antioxidant 1010), phosphite ester kind antioxidant is a kind of in the compounds such as three (2,4-di-t-butyl) phenyl-phosphites (irgasfos 168), pentanoic, Ursol D and dihydroquinoline and derivative or polymkeric substance.
The present invention also provides the preparation method of this matrix material, and this preparation method comprises following processing step:
(1) pro rata nylon resin, fire retardant, oxidation inhibitor are joined in mixing machine and makes it fully to mix;
(2) mixture step (1) being obtained and enhancement component melt extrude between 220 ℃-260 ℃ by screw extrusion press, finally by traction, cooling, pelletizing, obtain high workability halogen-free flame-retardant reinforced nylon matrix material.
This high workability halogen-free flame-retardant reinforced nylon matrix material is optional is produced into the various goods of shape in order to lower equipment: mold apparatus, injection device, gas injection equipment, injection molding apparatus, extrusion equipment and extrusioning-blow equipment, application is convenient.
High workability halogen-free flame-retardant reinforced nylon matrix material can be used for the low-voltage electrical plastic items fields such as the IGBT semiconductor components and devices plastic casing in the fields such as track traffic, boats and ships, military project, electric power network and isolating switch, terminal box, socket switch.
Compare with existing technology of preparing, in technology of preparing of the present invention, introduced the side chain Nylon 6 of high fluidity of molten and a large amount of active end groups, improved greatly matrix resin to the dipping of enhancement component and fire retardant and consistency, make enhancement component and fire retardant coated being dispersed in matrix resin completely, thereby tool of the present invention has the following advantages:
1, high, the halogen-free environmental of flame retarding efficiency, low flame radiation, smoke density are low.
2, good electric property, mechanical property excellence.
3, product surface is functional, and high gloss, without floating fine frosting phenomenon.
4, low, the good stability of the dimension of shrink of product rate, low warpage high-flatness.
5, fluidity of molten good, be easy to processing; Recipe is simple, workable, suitability is wide.
Embodiment
Below the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
Table 1 embodiment and comparison example material formula table
Parts by weight component Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Comparison example 1 Comparison example 2 Comparison example 3 Comparison example 4
Side chain nylon 6 70 40 10 10 0 0
Nylon 6 0 0 70 40 10 35
Nylon 66 10 10
Nylon 46 10 10
Nylon 10T 15 10
Glass fibre 35 60 30 35 50 30
Carbon fiber 10 15
Barium sulfate 5 5 5
Halloysite 5 5
Alkyl hypophosphite 4.9 10 4.9 10
Ammonium polyphosphate 20 9.5 20 9.5
MPP 9.5 9.5
Magnesium hydroxide 20 20
Antioxidant 1010 0.5 0.2 0.5 0.2
Irgasfos 168 0.1 0.3 0.5 0.1 0.3 0.5
As shown in table 1 is the material formula table of embodiment and comparison example, and wherein, the relative viscosity of side chain nylon 6 is 1.9, and kinematic viscosity is 100pa.s(230 ℃, 1000s -1).The preparation method of embodiment and comparison example below:
(1) aforementioned proportion joins nylon resin, fire retardant, oxidation inhibitor in mixing machine and makes it fully to mix;
(2) mixture step (1) being obtained and enhancement component melt extrude between 220 ℃-260 ℃ by screw extrusion press, finally by traction, cooling, pelletizing, obtain high workability halogen-free flame-retardant reinforced nylon matrix material.
(3) high workability halogen-free flame-retardant reinforced nylon matrix material is made standard testing batten through injection moulding and is detected.
For embodiment 1,2,3,4 and comparison example 1,2,3,4 carry out a series of tests such as mechanical property, flame retardant properties, electrical property and appearance, test result is as shown in table 2.
The material properties test result of table 2 embodiment and comparison example
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Comparison example 1 Comparison example 2 Comparison example 3 Comparison example 4
MFI（g/10min） 29.1 32.7 18.3 12.9 10.7 11.4 6.2 4.7
Lateral shrinkage (%) 0.25 0.25 0.35 0.2 0.3 0.3 0.45 0.325
Longitudinal contraction rate (%) 0.35 0.4 0.5 0.3 0.5 0.55 0.65 0.45
Tensile strength (Mpa) 165 171 185 143 153 130 144 104
Flexural strength (Mpa) 246 251 237 245 216 172 188 190
Modulus in flexure (Mpa) 11000 12000 115000 13500 9000 9800 9000 10700
Simply supported beam notched Izod impact strength (KJ/m2) 10.7 12.3 13.7 8.7 8.9 8.1 11.6 5.5
Simply supported beam unnotched impact strength (KJ/m2) 65 68 71 58.5 19.4 25 59.6 37
CTI(UL-746A) 600V 600V 500V 550V 600V 550V 500V 500V
UL94(3.2mm) V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0
UL94(1.6mm) V-0 V-0 V-0 V-0 V-0 V-1 V-1 V-1
UL94(0.8mm) V-0 V-1 V-1 V-1 V-0 V-1 V-2 V-2
Glow wire resistant (1.5mm, 960 ℃) Qualified Defective Qualified Qualified Qualified Defective Defective Qualified
Glow wire resistant (1.0mm, 960 ℃) Qualified Defective Defective Qualified Qualified Defective Defective Defective
Glow wire resistant (1.5mm, 750 ℃) NI NI Qualified NI NI Qualified Qualified Qualified
Glow wire resistant (1.0mm, 750 ℃) NI NI Qualified NI NI Qualified Qualified Qualified
Appearance Good Good Good Good Generally Generally Generally Poor
Wherein, glow wire resistant test is carried out according to standard IEC 695-2-1; The test condition of melting index (MFI) is 275 ℃, 2.16kg.
Consolidated statement 1 and table 2 are visible, with comparison example 1,2,3,4 compare, the invention process example 1,2,3, the fluidity of molten of the high workability halogen-free flame-retardant reinforced nylon matrix material in 4 has all improved nearly 3 times, and flame retarding efficiency and flame retardant properties are all significantly improved, and shrinking percentage obviously declines, appearance is good, and has better mechanical property and electrical property.This explanation the present invention adopts the high-fluidity nylon that contains side chain nylon 6 as matrix resin, can effectively solve that consistency in halogen-free flame-retardant reinforced nylon modifying process is poor, fire retardant disperses unequal problem, prepare mechanical property, flame retarding efficiency and flame retardant properties, all good halogen-free flame-retardant reinforced nylon matrix materials of electrical property, and this technology has general suitability to different halogen-free flame-retardant systems.Therefore, by technology of preparing of the present invention, obtain halogen-free flame-retardant reinforced nylon matrix material and can be widely used in the low-voltage electrical plastic items fields such as the IGBT semiconductor components and devices plastic casing in the fields such as track traffic, boats and ships, military project, electric power network and isolating switch, terminal box, socket switch.

Claims (1)

1. a high workability halogen-free flame-retardant reinforced nylon matrix material, is characterized in that, nylon resin is at least to contain the high-fluidity nylon composition of branched structure nylon 6, and nylon composite comprises side chain nylon 6 and linear nylon 10T; Matrix material by weight mark is composed of the following components:
Nylon 6:70 part;
Nylon 10T:15 part;
Carbon fiber: 10 parts;
Alkyl hypophosphite: 4.9 parts;
Irgasfos 168: 0.1 part;
Described side chain Nylon 6 is that branching unit initiator and hexanolactam prepare by hydrolytic polymerization, and wherein, branching unit structure of initiator is a kind of or its combination in dendroid branched structure, star-branched structure or dissaving structure; Branching unit initiator molecule type be aliphatics, aromatic series or heterocyclic molecule in a kind of or its combination; The end group of branching unit initiator is a kind of of amino, carboxyl or hydroxyl; Functional group's degree of branching unit initiator is between 3-16;
The relative viscosity of described side chain Nylon 6 is 1.2-3.0, kinematic viscosity (230 oC, 500s -1) between 10Pa.s-1000 Pa.s;
Preparation method comprises following processing step:
(1) pro rata nylon resin, fire retardant, oxidation inhibitor are joined in mixing machine and makes it fully to mix;
(2) mixture step (1) being obtained and enhancement component melt extrude between 220 ℃-260 ℃ by screw extrusion press, finally by traction, cooling, pelletizing, obtain high workability halogen-free flame-retardant reinforced nylon matrix material.
CN201210546631.4A 2012-12-17 2012-12-17 High-fluidity halogen-free flame retardant reinforced nylon composite material and preparation method thereof Active CN103044901B (en)

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