CN110229514A - A kind of color inhibition fire-resistant polyamide composite and preparation method thereof - Google Patents
A kind of color inhibition fire-resistant polyamide composite and preparation method thereof Download PDFInfo
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L2201/02—Flame or fire retardant/resistant
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention belongs to technical field of polymer materials, more particularly to a kind of color inhibition fire-resistant polyamide composite and preparation method thereof, it is grouped as by the group of following weight percent meter: 25.0~70.0wt% of polyamide, 10~35wt% of fire retardant, 0.1~1.0wt% of aromatic binary carboxylic acid, 0.1~5.0wt% of 0.1~2.0wt% of antioxidant, 5~50wt% of reinforcing agent and function additive, it is processed and is obtained using melt blending, preparation process is simple, lower production costs are conducive to promote.Daiamid composition of the invention meets the UL-94V-0 standard for being used for high fire resistance, and does not influence tinctorial property, while the problem of improve thermotropic xanthochromia.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of color inhibition fire-resistant polyamide composite and its
Preparation method.
Background technique
The master link that polyamide (PA) refers to contains the polymer of amide group (- [NHCO] -), and most polyamide is one
The reason of kind semicrystalline polymeric, crystal zone formation is that amide groups is polar group, the amide group of these electrifications on strand
It attracts each other, can be repetitively folded to form crystal so as to cause polymer chain.But the electronics shared between some atoms of strand
And unequal, the as a result region in polymer chain with a small amount of positive charge and a small amount of negative electrical charge.
The nonpolar nature of amide groups assigns polyamide outstanding mechanical performance in polymer, but it is also its weakness.Water
Molecule is also polar, and water is ubiquitous in the environment.As previously mentioned, some atoms unequal ground shared electron, at this
In the case of kind, selfish atom is oxygen and nitrogen.When hydrone and contacting polyamide, weak bond is formed between the two, this process
It can continue to carry out, hydrone is spread by material, finds any charging zone, is had here it is polyamide exposed to weather and is inhaled
Aqueous reason.There is the problem of mechanical performance and appearance degradation after processing in the higher polyamide material of moisture content, therefore, gathers
Amide material needs to carry out predrying before processing, by the moisture control of material below 0.2%.To improve efficiency, factory
100 DEG C or more of drying temperature can be generally set, and excessively high particle temperature often results in material by " bored Huang ".
In addition, the electronic articles of polyamide production are just being more and more widely used a kind of surface-assembled for being referred to as SMT
Technology and technique, SMT are the abbreviation of Surface Mounting Technology, referred to as surface mount or surface mounting technique.
It is that (abbreviation SMC/SMD, Chinese claim for a kind of surface-assembled component by no pin or the grid array packages of short leg or ball
Sheet component) it is mounted on the surface of printed circuit board (Printed Circuit Board, PCB) or the surface of other substrates
On, the circuit load technology of welding assembly is subject to by the methods of Reflow Soldering or immersed solder.The typical surface mount process of SMT is divided into
Three steps: apply solder --- attachment component --- reflow soldering.With leaded material, nowadays the solder of early stage Reflow Soldering is all
Mainly use Lead-free Reflow Soldering.Lead-free solder fusing point is higher, and reflow soldering technique generally requires polyamide product need to be 260
It is born 4-5 minutes or so at DEG C, most polyamide article is easy to that " xanthochromia " occurs under this technique.
The reason of polyamide thermotropic xanthochromia, more convictive mechanism is to think that the terminal amino group of polyamide is aoxidized
Reaction, produces conjugated double bond (- C=C-)n, conjugated double bond is a kind of chromophore, so as to cause polyamide xanthochromia.Existing skill
Art forms a kind of polyamide substrate of low side amino mainly by blocking in the polymerizing polyamide stage to polyamide, from
And achieve the purpose that inhibit polyamide xanthochromia.Gather as Chinese patent application CN103882549A discloses the highly hygroscopic anti-xanthochromia of one kind
Nylon and its manufacturing method, by by C2~C20Carboxylic acid and the terminal amino group of polyamide polymer strand pass through generation
It chemically reacts and is formed a kind of containing 1.0 × 10-5~3.0 × 10-5The color inhibition and good fiber whiteness of mol/g terminal amino group are poly-
Nylon；CN102372921A discloses a kind of heat-resistant polyamide composition and its application, selects Amino End Group and carboxylic end group concentration
A kind of composition application outstanding with high initial whiteness and color inhibition is made in polyamide of the ratio between 0.1~0.8
In light source bracket；CN109705342A discloses a kind of color inhibition polyamide and its raw materials for production and production method, utilizes
Monofunctional isocyanates enter inside polyamide particle with organic solvent block instead to polyamide molecule chain end
It answers, terminal amino group and terminal carboxyl group is changed into a phenyl group, obtained polyamide has good yellowing resistance.
But the above-mentioned prior art has the disadvantage in that and inhibits the reaction method of terminal amino group, condition ratio in polymerization stage
Harsher unfavorable popularization.In addition, terminal amino group content is not easily controlled in a reasonable level, terminal amino group content is excessively reduced
It will lead to dying polymers difficulty, influence colour stability, and be not related to wanting for high fire resistance (reaching UL94V-0 grade)
It asks.
Summary of the invention
Based on this, relative to known heat aging-resistant polyamides moulding compound, the purpose of the invention is to provide one
Kind color inhibition fire-resistant polyamide composite the problem of not influencing tinctorial property and improve thermotropic xanthochromia simultaneously, has both height and hinders
Combustion property.
Another object of the present invention is to provide the preparation methods of above-mentioned color inhibition fire-resistant polyamide composite.
Above-mentioned purpose of the invention is achieved through the following technical solutions:
Color inhibition fire-resistant polyamide composite of the invention, is grouped as by the group of following mass percentage content:
Wherein, component (a) to the sum of component (f) mass percent is 100wt%.
(a) ingredient of the invention is polyamide, refers to that master link contains the polymerization of polar amide groups (- [NHCO] -)
Object is one or more dicarboxylic acids and one or more diamines and/or one or more amino carboxylic acids and/or one or more
The condensation polymer of the ring-opening polymerization product of cyclic lactames.
Polyamide is one or more hemicrystalline aromatic polyamides of 25.0~70.0wt% in the composition
(a1) or one or more hemicrystalline fatty polyamides of hemicrystalline aromatic polyamide (a1) and 0.0~20wt%
(a2) mixture.This is because SMT Reflow Soldering temperature is up to 260 DEG C, this unbearable high temperature of amorphous material will cause knot
Structure is severely deformed.
The hemicrystalline aromatic polyamide (a1) be formed by diamines and dicarboxylic acids and diamines and dicarboxylic acids extremely
Few one is the aromatic polyamide resin of aromatic system monomer component.
The hemicrystalline fatty polyamide (a2) is preferably by aliphatic dicarboxylic acid and aromatic diamine or aromatic series
Dicarboxylic acids is formed with aliphatic diamine, is more preferably formed by aromatic dicarboxylic acid and aliphatic diamine.
For hemicrystalline aromatic polyamide of the invention, fusing point is not less than 280 DEG C.
Fusing point of the present invention is characterized according to ISO11357-3, and using differential scanning calorimetry (DSC), in first time, heating is swept
It is measured in retouching with the sweep speed of 10 DEG C/min, wherein the highest point of endothermic peak is considered as fusing point.
The semi-aromatic repetitive unit is selected from the monomer of one or more of:
Aromatic diamine is selected from the group of following material composition: m-phenylene diamine (MPD), p-phenylenediamine, m-xylene diamine, terephthaldehyde
Bis- (amino methyl) naphthalenes of amine, 1,4-, bis- (amino methyl) naphthalenes of 1,5-, bis- (amino methyl) naphthalenes of 2,6-, 2,7- bis- (amino methyls)
Bis- (4- aminophenyl) propane of naphthalene, 4,4 '-diaminodiphenyl-methanes, 2,2-, 4,4 '-diamino diphenyl sulfones, 4,4 '-diaminos
Base diphenyl ether.
Aromatic dicarboxylic acid be selected from following material composition group: terephthalic acid (TPA), M-phthalic acid, 1,4- naphthalene dicarboxylic acids,
1,5- naphthalene dicarboxylic acids, 2,6 naphthalene dicarboxylic acid, 2,7- naphthalene dicarboxylic acids, 1,3- phenylene dioxydiacetic acid, 1,4- phenylene dioxy two
Acetic acid, 4,4 '-oxygen dibenzoic acids, diphenyl methane -4,4 '-dicarboxylic acids, diphenylethane -4,4 '-dicarboxylic acids, diphenylprop
Alkane -4,4 '-dicarboxylic acids, diphenyl ether -4,4 '-dicarboxylic acids, diphenyl sulfone -4,4 '-dicarboxylic acids, 4,4 '-diphenyl dicarboxylic acids, 4,
4 '-triphenyl dicarboxylic acids.
Dicarboxylic acids be selected from aliphatic dicarboxylic acid, including but not limited to oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid,
Pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, tridecandioic acid, tetracosandioic acid, 15
Docosandioic acid, hexadecandioic acid (hexadecane diacid), octadecane diacid, eicosane diacid, preferably adipic acid.
Diamines is selected from the diamines with four or more carbon atoms, including but not limited to butanediamine, pentanediamine, second two
Amine, tetra-methylenedimine, five methylene diamine, hexamethylene diamine, heptamethylene diamines, eight methylene diamines, nine methylene
Diamines, decamethylene diamine, 11 methylene diamines, ten dimethylene diamines, tridecane diamine, tetradecane diamines, pentadecane
Diamines, hexadecane diamines, heptadecane diamines, octadecamethylene diamine, nonadecane diamines, eicosane diamines, 2- methyl-1,8- pungent two
Amine, 2,2,4- trimethylhexamethylenediamines, 2, the aliphatic diamines such as 4,4- trimethylhexamethylenediamines, 1,3- cyclohexyl two
Amine, 1,4- cyclohexyl diamine, bis- (4- aminocyclohexyl) methane, bis- (4- aminocyclohexyl) propane, bis- (3- methyl -4- amino
Cyclohexyl) methane, (3- methyl -4- aminocyclohexyl) propane, 1,3- bis aminomethyl hexamethylene, 1,4- bis aminomethyl hexamethylene
Alkane, 5- amino -2,2,4- trimethyl -1- cyclopentanemethylamine, 5- amino -1,3,3- trimethyl-cyclohexane methylamine, bis- (aminopropans
Base) the ester ring types diamines, preferably ethylenediamine such as piperazine, bis- (amino-ethyl) piperazines, norboneol alkyl dimethyl amine.
The hemicrystalline aromatic polyamide (a1) be selected from following material composition group: it is poly- (poly- paraphenylene terephthalamide oneself
Diamines/hexamethylene adipamide) (PA6T/66), poly- (hexamethylene terephthalamide/polycaprolactam) (PA6T/6), it is poly- (adipyl oneself
Diamines/poly-6I hexamethylene isoterephalamide) (PA66/6I), poly- (6I hexamethylene isoterephalamide/polycaprolactam) (PA6I/6), poly- (ten
Dioxane amide/poly- hexamethylene terephthalamide) (PA12/6T), it is poly- (hexamethylene terephthalamide/poly-6I hexamethylene isoterephalamide/
Hexamethylene adipamide) (PA6T/6I/66), poly- (hexamethylene adipamide/polycaprolactam/poly-6I hexamethylene isoterephalamide) (PA66/
6/6I), poly- (hexamethylene terephthalamide/poly-6I hexamethylene isoterephalamide) (PA6T/6I), poly- (paraphenylene terephthalamide's nonamethylene diamine)
(PA9T), poly- (paraphenylene terephthalamide certain herbaceous plants with big flowers diamines) (PA10T)；It is preferred that poly- (hexamethylene terephthalamide/hexamethylene adipamide)
(PA6T/66), poly- (paraphenylene terephthalamide's nonamethylene diamine) (PA9T) and poly- (paraphenylene terephthalamide certain herbaceous plants with big flowers diamines) (PA10T).
The hemicrystalline fatty polyamide (a2) be the aliphatic polyamide resin formed by diamines and dicarboxylic acids,
The aliphatic polyamide resin formed by lactams or amino carboxylic acid and the aliphatic copolymerization formed by the copolymer of both
Polyamide.
Dicarboxylic acids be selected from aliphatic dicarboxylic acid, including but not limited to oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid,
Pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, tridecandioic acid, tetracosandioic acid, 15
Docosandioic acid, hexadecandioic acid (hexadecane diacid), octadecane diacid, eicosane diacid, preferably adipic acid.
Diamines is selected from the diamines with four or more carbon atoms, including but not limited to butanediamine, pentanediamine, second two
Amine, tetra-methylenedimine, five methylene diamine, hexamethylene diamine, heptamethylene diamines, eight methylene diamines, nine methylene
Diamines, decamethylene diamine, 11 methylene diamines, ten dimethylene diamines, tridecane diamine, tetradecane diamines, pentadecane
Diamines, hexadecane diamines, heptadecane diamines, octadecamethylene diamine, nonadecane diamines, eicosane diamines, 2- methyl-1,8- pungent two
The aliphatic diamines such as amine, 2,2,4- trimethylhexamethylenediamine, 2,4,4- trimethylhexamethylenediamine, 1,3- cyclohexyl two
Amine, 1,4- cyclohexyl diamine, bis- (4- aminocyclohexyl) methane, bis- (4- aminocyclohexyl) propane, bis- (3- methyl -4- amino
Cyclohexyl) methane, (3- methyl -4- aminocyclohexyl) propane, 1,3- bis aminomethyl hexamethylene, 1,4- bis aminomethyl hexamethylene
Alkane, 5- amino -2,2,4- trimethyl -1- cyclopentanemethylamine, 5- amino -1,3,3- trimethyl-cyclohexane methylamine, bis- (aminopropans
Base) the ester ring types diamines, preferably ethylenediamine such as piperazine, bis- (amino-ethyl) piperazines, norboneol alkyl dimethyl amine.
Lactams is selected from the group of following material composition: epsilon-caprolactams, oenantholcatam, hendecane lactams, in dodecane
Amide, α pyrrolidones, α-piperidones, preferably epsilon-caprolactams.
Amino carboxylic acid is selected from the group of following material composition: 6-aminocaprolc acid, 7- aminoheptylic acid, 9 aminononanoic acid, 11- amino
Hendecanoic acid, 12 amino dodecanoic acid.
The hemicrystalline fatty polyamide (a2) is selected from the group of following material composition: poly- ('epsilon '-hexanolactam)
(PA6), poly- (adipyl butanediamine) (PA46), poly- (adipyl pentanediamine) (PA56), poly- (hexamethylene adipamide) (PA66), gather
(decanedioyl pentanediamine) (PA510), poly- (two acyl pentanediamine of dodecane) (PA512), poly- (hexamethylene sebacamide) (PA610), gather
(hexamethylene dodecanoamide) (PA612), poly- (adipyl pentanediamine/'epsilon '-hexanolactam) (PA66/6), poly- (adipyl penta 2
Amine/hexamethylene sebacamide) (PA66/610), poly- (adipyl pentanediamine/hexamethylene dodecanoamide) (PA66/612), poly- (oneself
Two acyl pentanediamines/nylon 1010) (PA66/1010), it is poly- (epsilon-caprolactams/hexamethylene adipamide/decanedioyl oneself two
Amine) (PA6/66/610), poly- (epsilon-caprolactams/hexamethylene adipamide/hexamethylene dodecanoamide) (PA6/66/612), preferably
Poly- ('epsilon '-hexanolactam) (PA6) and poly- (hexamethylene adipamide) (PA66), particularly preferred poly- (hexamethylene adipamide) (PA66).
(b) ingredient of the invention is fire retardant, and the fire retardant is brominated Polystyrene (b1) or brominated Polystyrene
(b1) and the mixture of one or more synergistic flame retardants (b2)；Wherein: brominated Polystyrene (b1) its structure such as formula
(I), bromine content is 55~70wt%:
The brominated Polystyrene is produced using method known to industry and is obtained, and is divided into according to its route of synthesis
Bromination (polystyrene)/(BPS) and poly- (brominated styrene)/(PBS).Bromination (polystyrene)/(BPS) will be gathered using bromating agent
Styrene (PS) directly brominated synthetic route, raw material PS points are free radical PS and anion PS.Radical polymerization production
PS, molecule chain end can remain the unsaturated double-bond containing about 1%, be easy to form fat with bromating agent in bromination process
Race's substituent group.The bond energy of aliphatic C-Br key is relatively low, and being heated to 200 DEG C or so will be broken, heat resistance and color inhibition
Property bad, the PS of anionic polymerization production, the shortcomings that a small amount of free radical replaces occurs when overcoming bromination on main chain.It is poly-
The synthetic route of (brominated styrene)/(PBS) is that first brominated styrene monomer polymerize again, thus is avoided that bromating agent on main chain
The advantages of halogenating reaction, PBS excellent thermal stability, the disadvantage is that complex process high production cost, bromine content be not high.
It is easy from the point of view of obtaining from the angle and raw material of composition heat-resistant stability, the bromine of preferred anionic PS matrix
Change (polystyrene)/(BPS) and poly- (brominated styrene)/(PBS), bromination (the polyphenyl second of particularly preferred anion PS matrix
Alkene)/(BPS).
The synergistic flame retardant (b2) is selected from antimony oxide, antimony pentoxide, zinc oxide, aluminium oxide, magnesia, two
Silica, clay (can be natural or synthetic clay, such as hydrotalcite and other layered double-hydroxides, boehmite, kaolin),
One of magnesium silicate, sodium metaantimonate, anhydrous zinc borate and siloxanes or a variety of mixtures, preferably clay, sodium metaantimonate
And anhydrous zinc borate, further preferred anhydrous zinc borate.When in use, one or more synergistic flame retardants (b2) and brominated polyphenylene
The ratio of ethylene (b1) is 1:20~1:2, preferably 1:5~1:3.
(c) ingredient of the invention is aromatic binary carboxylic acid, the group selected from following material composition: terephthalic acid (TPA), isophthalic
Dioctyl phthalate, 1,4- naphthalene dicarboxylic acids, 1,5- naphthalene dicarboxylic acids, 2,6 naphthalene dicarboxylic acid, 2,7- naphthalene dicarboxylic acids, 1,3- phenylene dioxy diethyl
Acid, 1,4- phenylene dioxydiacetic acid, 4,4 '-oxygen dibenzoic acids, diphenyl methane -4,4 '-dicarboxylic acids, diphenylethane -4,
4 '-dicarboxylic acids, diphenyl propane -4,4 '-dicarboxylic acids, diphenyl ether -4,4 '-dicarboxylic acids, diphenyl sulfone -4,4 '-dicarboxylic acids, 4,
4 '-diphenyl dicarboxylic acids, 4,4 '-triphenyl dicarboxylic acids, preferably 2,6- naphthalene dicarboxylic acids.
(d) ingredient antioxidant of the invention, including copper stabilizer, dipentaerythritol, Hinered phenols antioxidant, be obstructed arylamine
Kind antioxidant (HALS), UV absorbers, phosphite antioxidant, phosphonite antioxidant, the alkali metal salt of fatty acid, hydroxyl
Bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzene two of thermal response product, sulfur synergist, the N of amine, tertiary amino oxides, N'-
The mixture of formamide (S-EED) and the above substance, the preferably mixture of Hinered phenols antioxidant and phosphonite antioxidant.
The antioxidant has low-heat weightless preferably under the processing of thermoplastic compounds and product operating temperature, and preferably at least 300
DEG C, and most preferably at least 350 DEG C of 10%TGA thermal weight loss temperature is characterized.
(e) ingredient of the invention is reinforcing agent.For the mechanical performance for improving daiamid composition, it can be advantageous to thereto
At least one reinforcing agent is added, it is fine that these reinforcing agents are selected from fiberfill such as glass fibre, carbon fiber, aramid fiber (aromatic polyamides)
Dimension, nonfibrous filler such as talcum powder, kaolin, clay, wollastonite, calcium carbonate, silica, barium sulfate, titanium dioxide；Enhancing
The particularly preferred glass fibre of agent.
(f) ingredient of the invention is function additive, may include such as toughener, nucleation accelerating agent, pigment, plasticizer, takes off
Mould agent etc..
The thermoplastic compounds are the blends of melting preparation, are blended using single screw rod or double screw extruder
Processing.The step of processing be extruder main spout put into following component: (a) polyamide, (c) aromatic binary carboxylic acid,
(d) antioxidant and (f) function additive, are squeezing out owner's spout and side spout, and ingredient (b) is added by forced feed machine
Fire retardant, ingredient (e) reinforcing agent is added in section side spout in an extruder.Processing temperature is set as 280~325 DEG C, and screw rod turns
Speed is set as 250~350rpm, and second from the bottom section in mouth mold vacuumize to melt, and vacuum degree control is 50~70cm-
Hg.Composition after shearing and mixing from extrusion, draw tie rod carry out cooling, metal screen out, dry, be homogenized after pack,
The moisture content of material need to be ensured lower than 0.2wt% when packaging.
Compared with prior art, the present invention the composition preparation process that the present invention announces is simple, equipment and technology is required not
Height, the raw material used are all to directly adopt commercially available commercially produced product, lower production costs, are conducive to promote.In addition, the present invention is public
The composition of cloth has anti-flammability and meets the UL-94V-0 standard for being used for high fire resistance, needs to assign composition anti-flammability
Incorporation fire retardant is modified, but fire retardant is easier to degrade and change colour compared with polyamide at high temperature.The present invention not only includes
It is stable to the color inhibition of polyamide, while providing the stable method of a kind of pair of fire retardant.
Specific embodiment
By following embodiment, the present invention will be further described.It should be appreciated that following embodiment is for illustration purposes only,
And it is not used to the present invention into limitation.
Following material is used in embodiment and comparative example:
PA6T/6T refers to N600, derives from new and Cheng Gongsi；
PA9T refers to GC51010, derives from Kuraray Corporation；
PA10T refers to VICNYL700, derives from golden hair company；
PA66 refers toU4800NC01 derives from INVISTA company；
BPS-1 refers to bromination (polystyrene) that PS is the production of free radical synthetic method, bromine content about 68.5%, commercially available product；
BPS-2 refers to bromination (polystyrene) SAYTEX HP-3010PST, PS for anionic synthesis methods production, bromine content
About 68.5%, derive from Albemarle company；
PBS refers to that poly- (brominated styrene) PBS-64HW, bromine content about 65% derive from Chemtura company；
ZB refers to anhydrous zinc borate Firebrake 500, derives from Borax company；
CLAY refers to kaolin Polyfil HG90, derives from KaMin company；
2,6-NDA refer to aromatic binary carboxylic acid 2,6- naphthalene dicarboxylic acids, purity 98%, commercially available product；
1098 refer to antioxidant RIANOX 1098, derive from Li Anlong company；
S9228 refers to antioxidantS-9228 derives from DOVER Chemical Corporation；
H161 refers to antioxidantH161 is the antioxidant of a kind of hindered phenol and phosphinate mixing, derives from
Br ü ggemann company；
GF refers to that OCV 983-10P, 10 μm of filament diameter (producer's nominal value) derive from Owens Coring
Vetrotex；
BL-CP refers to a kind of blue toner, and You Jinlun company mix matching.
Method
Preparation method
Composition as shown in Table 1 weighs each component, in the main spout investment polyamide of double screw extruder and each
Fire retardant is added by forced feed machine squeezing out owner's spout and side spout, in an extruder section side in kind function additive
Glass fibre is added in spout.
Processing temperature is set as 280~325 DEG C, and screw speed is set as 250~350rpm, at second from the bottom section of mouth mold
Vacuumize melt, vacuum degree control is 50~70cm-Hg.Composition after shearing and mixing is drawn from extrusion
Tie rod carries out cooling, metal and packs after screening out, dry and being homogenized.The moisture content of material need to be ensured lower than 0.2wt% when packaging.
Sample molded and adjusting
Sample molded and adjusting are carried out by method as defined in ISO 16396-2, mold 325 DEG C of melt temperature, mold temperature
130℃.It is sealed in aluminium foil bag after test piece molding, deposits in 23 DEG C of environment and adjust 16 hours or more.
Anti-flammability test
According to the requirement of UL-94V grades of Fire Tests, specimen size (length × width x thickness) be 125mm × 13.0mm × 0.8mm with
125mm × 13.0mm × 0.4mm, the batten are adjusted 48 hours under 23 DEG C/50% relative humidity, and 70 DEG C in an oven
It is lower to adjust 168 hours.It is tested with combustion box, burner diameter 9.5mm when test, gas flame height 20mm, each flame connect
Touching the time is 10 seconds, from recording burning time after fire.
The test of particle color inhibition
Resulting particle will be prepared to be laid in pallet, then pallet is placed in baking by thickness requirement (10 ± 2) mm of tiling
It is toasted for 150 DEG C in case, is taken out in sample point and be packed into glass culture dish, it is small that 1 is adjusted under 23 DEG C/50% relative humidity
When, color measurement is carried out with ultraviolet spectrometry colour meter, light source selects D65, characterizes chromatism data △ E with CIELab method.
The test of product color inhibition
Test piece is placed in 260 DEG C of bakings in baking oven and taken out after ten minutes, 23 by specimen size 60mm × 60mm × 2.0mm
DEG C/50% relative humidity under adjust 1 hour, carry out color measurement with ultraviolet spectrometry colour meter, light source selects D65, uses CIELab
Method characterizes chromatism data △ E.
Embodiment and comparative example
Table 1 enumerates the composition and performance test of embodiment 1 to 3 and comparative example 1 to 3.
Embodiment 1 and comparative example 1, it can be seen that the bromination (polystyrene) of anion PS matrix and free radical PS matrix
Performance of the bromination (polystyrene) in terms of heat resistanceheat resistant causes xanthochromia, the bromination (polystyrene) of anion PS matrix will be substantially better than certainly
By base PS matrix bromination (polystyrene), also show that fire-resistant polyamide composite due to containing flame retardant constituent, heat peace
It is more difficult to determine difficulty, suitable fire retardant selection is prerequisite.
Embodiment 2~3 and comparative example 2~3, it can be seen that aromatic binary carboxylic acid (2,6- naphthalene dicarboxylic acids) is in stable polyamides
Effect in terms of amine composition, the embodiment 2~3 for adding 2,6- naphthalene dicarboxylic acids are yellow regardless of causing in short time and prolonged heat resistanceheat resistant
Becoming, more un-added comparative example 2~3 has clear improvement, while can be seen that a kind of synergistic flame retardant combination clay of optimization
Addition helps to improve Flame Retardancy energy.
Table 1
Claims (10)
1. a kind of color inhibition fire-resistant polyamide composite, which is characterized in that the composition is by following mass percentage content
Group be grouped as:
Wherein, component (a) to the sum of component (f) accounts for the 100wt% of the daiamid composition；
The polyamide be hemicrystalline aromatic polyamide or
The mixture being made of the hemicrystalline aromatic polyamide and hemicrystalline fatty polyamide, and the hypocrystalline
Property fatty polyamide accounts for 0.1~20wt% of the daiamid composition；
The fire retardant be brominated Polystyrene or
Synergistic flame retardant and the brominated Polystyrene according to mass ratio 1:2~20 mixture；Wherein: the brominated polyphenylene second
Alkene is brominated (polystyrene)/(BPS), and/or poly- (brominated styrene)/(PBS) of anion PS matrix, and bromine content is
55~70wt%；The synergistic flame retardant is selected from antimony oxide, antimony pentoxide, zinc oxide, aluminium oxide, magnesia, two
One or more kinds of mixture in silica, clay, magnesium silicate, sodium metaantimonate, anhydrous zinc borate and siloxanes.
2. daiamid composition as described in claim 1, which is characterized in that the hemicrystalline aromatic polyamide fusing point
Not less than 280 DEG C.
3. daiamid composition as claimed in claim 1 or 2, which is characterized in that the hemicrystalline aromatic polyamide
Group selected from following material composition: poly- (poly- hexamethylene terephthalamide/hexamethylene adipamide), it is poly- (hexamethylene terephthalamide/
Polycaprolactam), poly- (hexamethylene adipamide/poly-6I hexamethylene isoterephalamide), poly- (6I hexamethylene isoterephalamide/polycaprolactam),
Poly- (dodecane amide/poly- hexamethylene terephthalamide), it is poly- (hexamethylene terephthalamide/poly-6I hexamethylene isoterephalamide/oneself two
Acyl hexamethylene diamine), poly- (hexamethylene adipamide/polycaprolactam/poly-6I hexamethylene isoterephalamide), poly- (hexamethylene terephthalamide/poly-
6I hexamethylene isoterephalamide), it is poly- (paraphenylene terephthalamide's nonamethylene diamine) and poly- (paraphenylene terephthalamide certain herbaceous plants with big flowers diamines).
4. daiamid composition as claimed in claim 3, which is characterized in that the hemicrystalline aromatic polyamide is selected from
Poly- (hexamethylene terephthalamide/hexamethylene adipamide), poly- (paraphenylene terephthalamide's nonamethylene diamine) and poly- (paraphenylene terephthalamide certain herbaceous plants with big flowers diamines)
Middle one or more mixture.
5. daiamid composition as described in claim 1, which is characterized in that the hemicrystalline fatty polyamide is selected from
The group of following material composition: poly- ('epsilon '-hexanolactam), poly- (adipyl butanediamine), poly- (adipyl pentanediamine), it is poly- (adipyl oneself
Diamines), poly- (decanedioyl pentanediamine), poly- (two acyl pentanediamine of dodecane), poly- (hexamethylene sebacamide), it is poly- (two acyl of dodecane oneself
Diamines), poly- (adipyl pentanediamine/'epsilon '-hexanolactam), poly- (adipyl pentanediamine/hexamethylene sebacamide), poly- (adipyl penta 2
Amine/hexamethylene dodecanoamide), poly- (adipyl pentanediamine/nylon 1010), it is poly- (epsilon-caprolactams/adipyl oneself two
Amine/hexamethylene sebacamide), poly- (epsilon-caprolactams/hexamethylene adipamide/hexamethylene dodecanoamide).
6. daiamid composition as claimed in claim 1 or 5, which is characterized in that the hemicrystalline fatty polyamide
For poly- (hexamethylene adipamide).
7. daiamid composition as described in claim 1, which is characterized in that
The brominated Polystyrene be anion PS matrix brominated (polystyrene)/(BPS), and/or
The synergistic flame retardant is the mixture of clay and anhydrous zinc borate.
8. daiamid composition as described in claim 1, which is characterized in that the fire retardant be the synergistic flame retardant and
The brominated Polystyrene according to mass ratio 1:3~5 mixture, and the bromine content of the brominated Polystyrene be 55~
70wt%.
9. daiamid composition as described in claim 1, which is characterized in that the aromatic binary carboxylic acid is selected from following object
The group of matter composition: terephthalic acid (TPA), M-phthalic acid, 1,4- naphthalene dicarboxylic acids, 1,5- naphthalene dicarboxylic acids, 2,6 naphthalene dicarboxylic acid, 2,7-
Naphthalene dicarboxylic acids, 1,3- phenylene dioxydiacetic acid, 1,4- phenylene dioxydiacetic acid, 4,4 '-oxygen dibenzoic acids, diphenylmethyl
Alkane -4,4 '-dicarboxylic acids, diphenylethane -4,4 '-dicarboxylic acids, diphenyl propane -4,4 '-dicarboxylic acids, diphenyl ether -4,4 '-two
Carboxylic acid, diphenyl sulfone -4,4 '-dicarboxylic acids, 4,4 '-diphenyl dicarboxylic acids and 4,4 '-triphenyl dicarboxylic acids；And/or
The antioxidant is selected from the group of following material composition: copper stabilizer, Hinered phenols antioxidant, is obstructed at dipentaerythritol
Arylamine kind antioxidant, UV absorbers, phosphite antioxidant, phosphonite antioxidant, the alkali metal salt of fatty acid, hydroxyl
Bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzene two of thermal response product, sulfur synergist, the N of amine, tertiary amino oxides, N'-
Formamide, and processing the 10%TGA thermal weight loss temperature that there are at least 300 DEG C with the antioxidant under product operating temperature；With/
Or
The reinforcing agent is selected from one or more of glass fibre, carbon fiber or aramid fiber (aromatic polyamides) fiber
Mixed fiberfill, and/or it is selected from talcum powder, kaolin, clay, wollastonite, calcium carbonate, silica, barium sulfate or two
The nonfibrous filler of one or more kinds of mixing in titanium oxide；And/or
The function additive one or more kinds of groups in toughener, nucleation accelerating agent, pigment, plasticizer or release agent
It closes.
10. the preparation method of any one of claim 1~9 daiamid composition, which is characterized in that by single screw rod or double
Screw extruder carries out melt blending processing and obtains；The step of processing be extruder main spout investment it is following at
Point: (a) polyamide, (c) aromatic binary carboxylic acid, (d) antioxidant and (f) function additive are squeezing out owner's spout and side feed
Ingredient (b) fire retardant is added by forced feed machine in material mouth, and ingredient (e) reinforcing agent is added in section side spout in an extruder, adds
Work temperature is 280~325 DEG C, and screw speed is 250~350rpm, and second from the bottom section in mouth mold vacuumize to melt,
Vacuum degree control is 50~70cm-Hg, and the composition after shearing and mixing squeezes out, carries out cooling, metal after traction tie rod
Screen out, dry, be homogenized after pack, the moisture content of material is lower than 0.2wt% when packaging.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112521749A (en) * | 2020-12-19 | 2021-03-19 | 杭州本松新材料技术股份有限公司 | Semi-aromatic nylon composition and preparation method thereof |
| WO2021106888A1 (en) * | 2019-11-28 | 2021-06-03 | 株式会社クラレ | Polyamide resin composition and molded object thereof |
| CN113845657A (en) * | 2021-10-27 | 2021-12-28 | 中仑塑业（福建）有限公司 | Semi-aromatic polyamide resin and preparation method thereof |
| CN114410108A (en) * | 2022-01-26 | 2022-04-29 | 江苏晋伦塑料科技有限公司 | Halogen-free flame-retardant semi-aromatic polyamide composition and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1894320A (en) * | 2003-12-19 | 2007-01-10 | 雅宝公司 | Flame retardant compositions and their use |
| CN101175821A (en) * | 2005-05-16 | 2008-05-07 | 三井化学株式会社 | Flame retardant polyamide composition |
| CN102604377A (en) * | 2012-02-17 | 2012-07-25 | 金发科技股份有限公司 | Polyamide composition with flame retardance and thermoplasticity |
| CN102796366A (en) * | 2011-12-08 | 2012-11-28 | 上海耐特复合材料制品有限公司 | Non-antimony flame-retardant polyamide composite material and preparation method and application thereof |
| CN104231622A (en) * | 2014-10-09 | 2014-12-24 | 晋德塑料科技(东莞)有限公司 | Low-precipitate flame-retarded polyamide composition and preparation method thereof |
| CN107922731A (en) * | 2015-08-28 | 2018-04-17 | 乐天尖端材料株式会社 | Thermoplastic resin composition and mechanograph prepared therefrom |
| CN109312153A (en) * | 2016-06-30 | 2019-02-05 | 尤尼吉可株式会社 | Thermoplastic resin composition and the formed body being molded with |
-
2019
- 2019-06-28 CN CN201910573855.6A patent/CN110229514A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1894320A (en) * | 2003-12-19 | 2007-01-10 | 雅宝公司 | Flame retardant compositions and their use |
| CN101175821A (en) * | 2005-05-16 | 2008-05-07 | 三井化学株式会社 | Flame retardant polyamide composition |
| CN102796366A (en) * | 2011-12-08 | 2012-11-28 | 上海耐特复合材料制品有限公司 | Non-antimony flame-retardant polyamide composite material and preparation method and application thereof |
| CN102604377A (en) * | 2012-02-17 | 2012-07-25 | 金发科技股份有限公司 | Polyamide composition with flame retardance and thermoplasticity |
| CN104231622A (en) * | 2014-10-09 | 2014-12-24 | 晋德塑料科技(东莞)有限公司 | Low-precipitate flame-retarded polyamide composition and preparation method thereof |
| CN107922731A (en) * | 2015-08-28 | 2018-04-17 | 乐天尖端材料株式会社 | Thermoplastic resin composition and mechanograph prepared therefrom |
| CN109312153A (en) * | 2016-06-30 | 2019-02-05 | 尤尼吉可株式会社 | Thermoplastic resin composition and the formed body being molded with |
Non-Patent Citations (1)
| Title |
|---|
| 霍然等: "《建筑火灾安全工程导论》", 30 September 2009, 中国科学技术大学出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021106888A1 (en) * | 2019-11-28 | 2021-06-03 | 株式会社クラレ | Polyamide resin composition and molded object thereof |
| CN112521749A (en) * | 2020-12-19 | 2021-03-19 | 杭州本松新材料技术股份有限公司 | Semi-aromatic nylon composition and preparation method thereof |
| CN113845657A (en) * | 2021-10-27 | 2021-12-28 | 中仑塑业（福建）有限公司 | Semi-aromatic polyamide resin and preparation method thereof |
| CN113845657B (en) * | 2021-10-27 | 2023-05-23 | 中仑塑业（福建）有限公司 | Semi-aromatic polyamide resin and preparation method thereof |
| CN114410108A (en) * | 2022-01-26 | 2022-04-29 | 江苏晋伦塑料科技有限公司 | Halogen-free flame-retardant semi-aromatic polyamide composition and preparation method and application thereof |
| CN114410108B (en) * | 2022-01-26 | 2023-10-27 | 江苏晋伦塑料科技有限公司 | Halogen-free flame-retardant semi-aromatic polyamide composition, and preparation method and application thereof |
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