CN107663371B - A kind of fatty polyamide compound and preparation method thereof for environment-protection electroplating - Google Patents
A kind of fatty polyamide compound and preparation method thereof for environment-protection electroplating Download PDFInfo
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- CN107663371B CN107663371B CN201710844109.7A CN201710844109A CN107663371B CN 107663371 B CN107663371 B CN 107663371B CN 201710844109 A CN201710844109 A CN 201710844109A CN 107663371 B CN107663371 B CN 107663371B
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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
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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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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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract
The present invention provides a kind of fatty polyamide compounds for environment-protection electroplating, including following raw material by weight percentage: aliphatic polyamide resin 40%~90%, thermoplastic elastomer (TPE) 3%~20%, coupling agent 0%~2%, inorganic mineral powder 0%~40%；Wherein, high melt index of the melt index of the thermoplastic elastomer (TPE) than aliphatic polyamide resin.The present invention also provides the preparation methods of the fatty polyamide compound for environment-protection electroplating.Fatty polyamide compound of the invention can use the potassium permanganate coarsening solution processing of environmental protection, be suitble to the development of environment-protection electroplating, after plating, can reach 10N or more with the plating binding force that coating layer surface is electroplated, ensured using safe.
Description
Technical field
The present invention relates to polyamide compound, especially a kind of fatty polyamide compound for environment-protection electroplating and its
Preparation method.
Background technique
Plastic electroplating can make surface of plastic products have metallic luster, beautiful, play decoration function, improve product surface
Mechanical strength, prolong the service life；Make plastic products to the extraneous factors such as light and atmosphere stability with higher, is not easy old
Change；Make plastics that there is conductive, magnetic conduction and weldability.Plastic electroplating product can be used for aerospace, shipbuilding, automobile, electronics electricity
The industries such as device, building decoration, toy and daily necessity, purposes are very extensive.
There are two types of common plastic cement products electroplating technologies: water power plating and vacuum ion plating.
Vacuum plating specifically includes that vacuum evaporation, sputtering plating and ion plating several types.They are all utilized in vacuum item
Under part, various metals and nonmetal film are deposited on plastic surface by the modes such as distilling or sputtering, in this way may be used
To obtain very thin overlay coating, while the outstanding advantages for having the fast adhesive force of speed good, but price is also higher, Ke Yijin
The metal types of row operation are less, are generally used to make the functional coating of higher gears product.
Water power plating main technique is the product of plating will to be needed to be put into chemical-electrical plating solution to be electroplated.Water power plating because technique compared with
Simply, the requirement from equipment to environment is without vacuum ion plating harshness, to be widely used.It can be used for water power plating plastic bag
Include: ABS, nylon, polycarbonate and polystyrene etc., wherein maximum with ABS dosage, electroplating effect is best, and technique is most mature.
Polyamide (polyamide, PA) is commonly referred to as nylon (Nylon), it is in polymer macromolecule chain containing weight
The heterochain polymer general name of complex structure unit amide group (NHCO-), mainly by binary acid and diamine or amino acid lactams
It is obtained through polycondensation, autohemagglutination, is to develop earliest, the maximum thermoplastic engineering plastic of usage amount.PA kind is more, can by backbone structure
It is divided into fatty polyamide, semiaromatic polyamide composition, fully aromatic polyamide, polyamide containing heteroaromatic and alicyclic polyamides
Amine is semi-aromatic nylon when wherein having in the amine or acid of nylon raw material equally containing phenyl ring, when two kinds of raw materials all contain phenyl ring
For Wholly aromatic polyamide.Semi-aromatic or fully aromatic polyamide are remarkably improved the heat resistance and rigidity of nylon.With aliphatic
Polyamide is similar, and aromatic polyamide can also be formed by Amino acid from polycondensation by binary acid and diamine polycondensation, half virtue
Fragrant polyamide can be formed by aromatic acid (such as terephthalic acid (TPA)) and aliphatic dibasic acids (such as nonamethylene diamine) polycondensation, such as Buddhist nun
Imperial 9T.
Thermoplastic elastomer (TPE) (TPE) is a kind of by glassy state or semi-crystalline thermoplastic resin and soft elastomer institute group
At block copolymer, had both the high resiliency of rubber and the thermoplastic processing of thermoplastic resin, be known as " third generation synthesize rubber
Glue ".It, which is structurally characterized in that, is made of different resin section and rubber segments chemical bond, and resin section relies on active force formation between segment
It manages " crosslinking ", rubber segments are the high resiliency segments with the larger ability of rotating freely, and plastics and rubber segments are arranged with order appropriate
It arranges, link up.Due to the invertibity of this polymer chain architecture feature and cross-linked state, thermoplastic elastomer (TPE) is shown at normal temperature
Show the physical mechanical properties such as the elasticity, intensity and deformation behavior of vulcanized rubber, the physical crosslinking of plastics section is with temperature at high temperature
Variation and be in reversible change, it is shown that the processing characteristics of thermoplastic.The TPE of industrialized production mainly has at present: benzene second
Alkenes, olefines, polyurethanes, polyesters, polyvinyl chloride, phthalein amine, diene class and organic fluoride class etc..
Styrene analog thermoplastic elastomer (TPS or SBC) refers to that by polystyrene chain segment be hard section (S), polybutadiene alkene
Chain is the triblock copolymer (SDS) or segmented copolymer of soft segment (D).Major product therein is using soft segment as polybutadiene
(B) block copolymer (SBS), using polyisoprene as the block copolymer (SIS) of soft segment and the plus hydrogenated product of SBS (SEBS)
Deng.SBS thermoplastic elastomer (TPE) is the block copolymer of styrene and butadiene, there is the title of third generation synthetic rubber, it has good
Good tensile strength and elasticity, rub resistance, endurance, easy dyeing and quality-high and inexpensive feature, can directly be molded or extrusion forming.
Main application: 1. producing rubber product, 2. makees improvement agent for synthesis resin, 3. makees adhesive, 4. makees asphalt modifier.SBS conduct
Research in terms of modifier has very much, Tan can it is superfine with a small amount of SBS respectively with polypropylene, polyethylene blend, can obviously change
The cryogenic property and impact strength of kind product.Addition SBS can be such that polystyrene impact resistance greatly increases, and make the transparency
There are improvement, the superfine people's calcium carbonate of Tan's energy and SBS modified synergic PS, reduces costs.SIS production technology and SBS are essentially identical,
Therefore many SBS devices are provided simultaneously with the ability for producing SIS in the world.But it is said from production process, production SIS difficulty is higher than SBS,
Thus and not all SBS device can all produce SIS simultaneously, and the kind trade mark is considerably less than SBS.
Polyolefins thermoplastic elastomer (TPO) is made of rubber and polyolefin, and usual rubber component is ethylene-propylene-diene monomer
Glue (EPDM), nitrile rubber (NBR) and butyl rubber.Polyolefin component is mainly polypropylene (PP) and polyethylene (PE).TPO exists
Caoutchouc elasticity is presented under room temperature, density is small, bending elastic modulus is high, good fluidity, has excellent weatherability, resistance to ozone, resistance to
Ultraviolet light and good high temperature resistant, the features such as low-temperature impact-resistant performance is good, it is easy processing, at low cost, reusable, it is a kind of comprehensive
Close material of good performance.
Polyurethane-type thermoplastic elastomer (TPU) is one kind of polyurethane rubber, is divided into polyester-type and polyether-type.It divides greatly
The structure of subchain is alternately made of polarity polyurethane or polyureas segment (hard section) and aliphatic polyester or polyether segment (soft segment).
Lightly crosslinked structure between the hydrogen bond crosslinks and macromolecular chain of intermolecular formation, so that this high molecular material is with temperature
Variation has plasticity.It is the most prominent feature of this kind of elastomer that hardness is high, wearability is good, elasticity is good.
Polyester-type thermoplastic elastomer (TPEE) is a kind of soft containing aromatic polyester hard section and aliphatic polyester or polyethers
The block copolymer of section.The ratio of hard section and soft segment determines the hardness and physical mechanical property of thermoplastic polyester elastomer.Firmly
Section forms physics crosslinking points, meets with stresses, and soft segment is the high resiliency segment being freely distributed, contribution elasticity.Elasticity is good by TPEE, resistance to
Mill, anti-flexural property is excellent, has excellent heat resistance, and low-temperature flexibility is good, and low temperature impact strength is high.
Plastic electroplating refers to the processing technology for coating the coat of metal in frosting with chemical plating and electric plating method.Plastics
Product remains the big feature of light plastic, high production efficiency, design flexibility after electroplated metal layer；Assign it simultaneously
Protective, dicoration, wearability and thermal conductivity, therefore plastic electroplating technique is widely used in electronics, optical instrument, lathe button
With the various aspects such as light industrial goods.Metal is replaced with plastic electroplating metal layer, it is significant in terms of engineer application, not only realize
Lightweight more greatly reduces cost.
ABS is amorphous macromolecule material, and appearance is in ivory white, and opaque, odorless, tasteless is nontoxic, has fabulous electricity
Performance is plated, is fabulous non-metal electroplating material.The content of butadiene has a significant impact to electroplating effect in ABS plastic, generally
For the ABS of plating, butadiene mass fraction cannot be below 10%, generally should be 18%~24%.In electroplating process, ABS
The elastomer phase (also referred to as rubber phase) that middle butadiene is formed is etched and " bait throwing in " effect can be generated in plating by forming many
Hole, this bottleneck lock catch shape hole can greatly enhance the binding force of coating.
The electroplating technology of ABS plastic is the following steps are included: first step destressing, it is therefore an objective to which object is because of note after reducing plating
The deformation moulding the internal stress of generation and may occurring；Second step is oil removing, and majority removes product using alkalinity or acid degreaser
In processing or transportational process, greasy dirt, release agent and some sundries for influencing subsequent operation be infected with.The main mesh of oil removing
Be that degreasing is deoiled, while reducing its surface tension, assign its surface hydrophilicity；Third step roughening, the purpose of roughening are to improve
Surface roughness, increase surface area makes frosting become hydrophilic from hydrophobic to increase the binding force of the coat of metal and plastics,
Each section is by water uniform wet, so as to uniform adsorption metal ion.There are two types of the chemistry roughening formulas that ABS product is widely used:
One is Cr03-H2S04-H2O etch system；One is Cr03–H2S04-H3P04Etch system, wherein all containing Cr VI at
Point.Cr VI is the property swallowed poisonous substance/extremely toxic object of imbedibility, and skin contact may cause allergy；It is more likely to cause inherited genetic
Defect, sucking are potentially carcinogenic, and have lasting risk to environment；The sensitization of 4th step, the i.e. divalent of absorbing and reducing on the surface of the material
Tin ion is prepared for activation；5th step is activating and reducing, first adsorbs one layer of noble metal for having catalytic activity on the surface of the material
Layer, such as Ag, are then restored, and surface-active can be improved, and accelerate deposition velocity, it is noted that need to be by material surface
Activating solution cleans up, and prevents post-order process from being stained；6th step is chemical plating, i.e., formation coating is uniform on the surface of the material, connects
The good coat of metal of continuous property, provides safeguard for plating；7th step is plating, generallys use three kinds of copper, nickel and chromium metals in material
Expect surface recombination plating, forms final surface decoration layer.
Currently, traditional plating grade nylon material passes through mainly using fatty polyamide (based on PA6) resin as substrate
A certain proportion of inorganic mineral powder filling is added, it is carried out coating modification is electroplated.In carrying out electroplating process, electroplate liquid is first rouge
Fat polyamide resin swelling, then penetrate into the internal inorganic mineral powder in material and corrode, shaggy effect is formed, for increasing
It is powered on the surface binding force of metal cladding and nylon base.It is usually to utilize sulfuric acid solution and chromic acid in the surface treatment of polyamide
It carries out, such as United States Patent (USP) US5,324,766.But using heavy metal chromic acid for worker great harmfulness, and also can be right
Environment generates larger pollution.The organic components contained in intumescent system and added other chemical substances, can be by nylon plastic(s)
In certain filler materials remove, since not every filler material can remove, cause certain nylon plastic(s)s more difficult or not
It can plating.In the plating of nylon, roughening is the key factor for influencing Deposit appearance quality and binding force, workpiece with expansion process
Surface is uniformly roughened effect, can have the postorder decorative coating of good combination power to lay a solid foundation to obtain.Table
Whether face roughening is uniform, directly determines the electroplating quality of nylon workpiece surface.There are biggish for existing plating grade nylon material
Defect is: 1. need using dedicated nylon electroplating liquid medicine；2. substrate plating binding force is not high, it is unable to satisfy metal plated articles
The requirement of adhesiveness；3. production is not flexible, at high cost, conventional nylon electroplating technology cost is about 2.4 yuan/DM, and ABS galvanizer
Skill cost is about 1.2 yuan/dm.Therefore market is broad using no ABS.
Summary of the invention
In view of the problems of the existing technology, it is an object of the present invention to provide a kind of aliphatic for environment-protection electroplating
Polyamide compound, the resin based on aliphatic polyamide resin are changed by adding special thermoplastic elastomer (TPE) in mixing
Property during so that elastomer is evenly distributed on resin surface.Polyamide compound of the invention in the case where not adding miberal powder,
It can also be used for electroplating processes, be coated carrying out surface metalation by electroplating technology, obtain high intensity, high temperature resistant, low water suction, ruler
Especially binding force is electroplated with fabulous substrate in very little stable product.It is a further object to provide one kind to be used for
The preparation method of the fatty polyamide compound of environment-protection electroplating.It is compound that a further object of the present invention is to provide a kind of polyamide
Object can be electroplated with ABS electroplating technology.
To achieve the goals above, the invention adopts the following technical scheme:
A kind of fatty polyamide compound for environment-protection electroplating, including following raw material by weight percentage:
Wherein, the melt index of thermoplastic elastomer (TPE) is higher than the melt index of aliphatic polyamide resin.
Preferably, the aliphatic polyamide resin number refers to polyamide derived from one or more aliphatic diamines (such as
Aliphatic C6-C20Alkylenediamine, alicyclic diamine, preferably diamines include bis(p-aminocyclohexyl)methane, 1,6- hexamethylene diamine,
2 methyl pentamethylenediamine, 2- methyl octamethylenediamine, trimethyl 1,6- hexamethylene diamine, 1,8- octamethylenediamine, 1,9- nonamethylene diamine, 1,10- decamethylene diamine,
1,12- dodecamethylene diamine and meta-xylene base diamines) and one or more dicarboxylic acids (e.g., adipic acid, decanedioic acid, nonyl two
Acid, dodecanedioic acid or their derivative) and/or one or more aliphatic lactams, amino acid (such as 11- amino 12
Alkanoic acid, caprolactam and lauric lactam).
It is further preferred that the fatty polyamide is selected from PA6, PA46, PA56, PA66, PA610, PA612,
PA613, PA614, PA615, PA616, PA11, PA12, PA910, PA912, PA913, PA914, PA915, PA936, PA1010,
At least one of PA1012, PA1013, PA1014, PA1210, PA1212, PA1213, PA1214.
It is highly preferred that the fatty polyamide is selected from PA6, PA56, PA66, PA610, PA612, PA11, PA12,
At least one of PA1010, PA1212.
Preferably, the thermoplastic elastomer (TPE) is in polyolefin elastomer, polyester elastomer and polystyrene elastomers
It is at least one.
It is further preferred that the thermoplastic elastomer (TPE) can carry out maleic anhydride, silicone (silane), chlorine, amine, propylene
The chemical modifications such as acid, epoxide and use.
It is further preferred that the polyolefin elastomer is that the alkene such as ethylene, propylene, butadiene, diolefinic monomer is equal
Substance obtained from poly- or copolymerization etc..It is further preferred that the polyolefin elastomer is selected from ethylene/propylene/diene rubber
(EPDM), the blend of ethylene-propylene rubber (EPM) or EPDM and EPM, ethene-alpha-olefin copolymer, ethene improved-α-alkene
Hydrocarbon copolymer, reactor directly prepare one of thermoplastic polyolefin (reactor TPO) or a variety of.As above-mentioned ethylene-
Alpha olefin copolymer, such as ethylene and propylene, 1- butylene, 1- amylene, 1- hexene, 1- heptene, 1- octene, 1- nonyl can be enumerated
The copolymer of the alpha-olefins such as alkene, 1- decene.In addition, can enumerate as above-mentioned ethene improved-alpha olefin copolymer by above-mentioned second
Alkene-alpha olefin copolymer polymer lateral chain or polymer ends maleic anhydride, silicone (silane), chlorine, amine, acrylic acid, ring
Substance obtained from the chemical modifications such as oxygen compound.
It is further preferred that the polystyrene elastomers are selected from Styrene-Butadiene-Styrene Block Copolymer
(SBS), styrene-ethylene butylene-styrene block copolymer (SEBS), styreneisobutylene block copolymer (SIB), benzene
In ethylene-isobutylene-styrene block copolymer (SIBS), styrene-ethylene propylene-styrene block copolymer (SEPS)
It is one or more.
It is further preferred that the polyester elastomer is copolyether-ester block copolymer or copolyester-ester block's copolymer.Tool
The polyester elastomer of body is selected from by dimethyl terephthalate (DMT), 1,4-butanediol, polytetramethylene ether diol (PTMG)
Raw material, substance as obtained from transesterification, polycondensation reaction etc..It is highly preferred that the polyester elastomer is poly- naphthalenedicarboxylic acid fourth
Diol ester (PBN) based elastomers, polybutylene terephthalate (PBT) (PBT) based elastomers etc..
Preferably, the melt index of the thermoplastic elastomer (TPE) is 220 DEG C of > 2g/10min, 2.16kg；The thermoplasticity
The melt index of elastomer is higher than the melt index of aliphatic polyamide resin, is conducive in mixed and modified and injection molding, thermoplastic
Property elastomer is distributed in the surface layer of polyamide material to external migration.
Preferably, the inorganic mineral powder be in aluminium oxide, silica, talcum powder, titanium oxide, montmorillonite and kaolin extremely
Few one kind.It is further preferred that the inorganic mineral powder in talcum powder, aluminium oxide, silica, zinc oxide, montmorillonite extremely
Few one kind.Particularly preferred, the average grain diameter of the inorganic mineral powder is 0.1~1 μm, and partial size mentioned here refers to using laser
The median particle diameter (D50) of particle size analyzer measuring method measurement, and the size distribution of the inorganic oxide miberal powder is in normal distribution.
In the present invention, the granularity of such as above-mentioned inorganic mineral powder is not able to satisfy Spreading requirements, then needs to carry out at depolymerization it
Reason while when disaggregation processing should ensure that depolymerization between mineral powder granular, avoids that it is broken, because of inorganic mineral powder after broken as far as possible
In since there are a large amount of fine particle, specific surface area be will be further increased, cause the reunion between inorganic mineral powder to increase, it is unfavorable
Evenly dispersed in polyamide compound in it, inorganic mineral powder primarily serves the mechanical strength for increasing material and durothermic work
With.
It is further preferred that the inorganic mineral powder is inorganic mineral powder after coupling agent modified, wherein coupling agent with it is inorganic
The weight ratio of miberal powder is 1:20-1:100.
Coupling agent contains reactive group, its one end can form covalent bond or hydrogen bond with the hydroxyl of inorganic material, another
End forms hydrogen bond with organic material or generates covalent bond.To by organically connected of the interface of inorganic material and organic material
Come, improves the properties of composite material.
Preferably, the coupling agent is selected from epoxy silane coupling, amino silane coupling agent, the coupling of sulfydryl one type of silane
Agent, urea groups one type of silane coupling agent, isocyanates silane coupling agent, titanate coupling agent, boric acid ester coupler, the compound idol of aluminium titanium
Join at least one of agent, aluminate coupling agent, inorganic mineral powder is modified.
Coupling agent modified inorganic mineral powder is carried out using the methods of common infusion process, spray process, spray-on process, in the present invention
Its method of modifying is not particularly limited.According to process step design, can be used arbitrarily makes inorganic mineral powder and the solution containing coupling agent
The method for more uniformly contacting, adsorbing.
Infusion process is put miberal powder into the solution containing coupling agent, due to surface tension effect and generate capillary pressure
Power, make Liquid Penetrant to inside capillary to which coupling agent gradually in miberal powder surface and micro- pore diffusion and adsorbs, when dipping is flat
After weighing apparatus, remaining solution is removed by the methods of dry or roasting.Spray process and spraying rule are by there are also the liquid of coupling agent
Body is sprayed directly on miberal powder surface, and due to the difference of jet expansion, spray process drop is larger, applies in general to bulk material and grain
Shape material, and spray-on process is suitable for powder material more.The advantages of infusion process is that active constituent utilization rate is high, at low cost, producer
Method is simple, but dry process may result in the migration of active component, and spray process and spray-on process processing miberal powder efficiency are more
Height is also easier in equipment that is dry, but needing to increase additional.
The specific epoxy silane coupling includes vinyltrimethoxysilane, ethenylphenyl trimethoxy silicon
Alkane, γ-methacryloxypropyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, 4- glycidol
Base butyl trimethoxy silane, γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane.The amino silane coupling agent packet
Include gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, N- β (amino-ethyl) gamma-amino propyl three
Methoxy silane, N-3- (4- (3- amino propoxyl group) butoxy) propyl -3- TSL 8330, gamma-amino third
Ethyl triethoxy silicane alkane, N- β (amino-ethyl) gamma-amino propyl trimethoxy silicane, N-3- (4- (3- amino propoxyl group) fourth oxygen
Base) propyl -3- TSL 8330.The isocyanates silane coupling agent includes γ-isocyanates propyl three
Ethoxysilane, isocyanate propyl trimethoxysilane.The urea groups one type of silane coupling agent includes three ethoxy of γ-ureido-propyl
Base silane, γ-ureido-propyl trimethoxy silane.The titante coupling agent includes answering for three iso stearate isopropyl titanates
With object, three stearic acid isopropyl titanates, Di(dioctylpyrophosphato) ethylene titanate, (the dioctyl coke phosphorus of isopropyl three
Sour acyloxy) titanate esters, isopropyl three (dodecyl benzenesulfonyl) titanate esters, three oleic acid acyloxy titanate esters of isopropyl are different
Propyl three (dioctyl phosphoric acid acyloxy) titanate esters, two oleic acid acyloxy of isopropyl (dioctyl phosphoric acid acyloxy) titanate esters.
Preferably, the fatty polyamide compound further includes fibre reinforced materials, fire retardant, nucleating agent and anti-oxidant
One of agent is a variety of.
In the present invention, the fibre reinforced materials includes one of glass fibre, carbon fiber, aramid fiber, wollastonite
Or it is a variety of.The additive amount of the fibre reinforced materials is no more than the 40% of fatty polyamide compound total weight.
Wherein, the glass fibre have non-circular cross sections, refer to long axis be in the longitudinally perpendicular state of fiber and
The glass fibre of the longest straight line distance in cross section taken in correspondence.The non-circular cross sections having on the direction vertical with long axis
The short axle of longest linear distance in cross section taken in correspondence.The non-circular cross sections of the fiber can have various shapes, including cocoon
Shape (number eight) shape, rectangular shape, elliptical shape, half elliptic shape, rough triangular shaped, polygonal shape and length
Square configuration.Those skilled in the art can understand that cross section can have other shapes.The long axis length and the short axle
The ratio of length is preferably in the range of about between 1.5: 1 and about 6: 1.The ratio is more preferably between 2:1 and 5:1, but more excellent
Selected introductions are in 3:1 between about 4:1.The glass fibre can for long glass fibres, chopped strand, crushing short glass fibre
Form or other suitable forms known to those skilled in the art.
The carbon fiber is in acrylonitrile base carbon fiber, asphalt base carbon fiber, viscose base carbon fibre or phenolic aldehyde carbon fiber
It is one or more.The atomic structure of carbon fiber is similar to graphite, and carbon atomic layer is arranged with regular hexagonal shaped pattern, layer and layer it
Between so that interlayer spacing is reached 0.344nm due to the presence of sp3 key.The tensile strength of carbon fiber is 2-7GPa, and elasticity modulus is
200-900GPa, density 1.78g/cm3.Carbon fiber can be T300, T700, T800, T1000 of Toray, can also be with
It is the P-1002K of CytecThronel series, P-100S2K, P-1202K, P-120S2K etc..
The aramid fiber is poly- phenyl-diformyl phenylenediamine, is a kind of novel synthetic fibers, is broadly divided into the fragrant acyl of contraposition
Amine fiber (PPTA) and meta position aramid fiber (PMIA).
The wollastonite is avirulent natural minerals, and the wollastonite of nature output is usually fibrous, needle-shaped or puts
Penetrate shape aggregate, the plate or sheet-pile shape that monocrystal extends along b axis.Solubility of the wollastonite in neutral water is low, and oil absorption is low,
Without the crystallization water, hygroscopicity is small, and without dehydration problem when heating, fusing point is high, and thermal expansion coefficient is small, and heat-resistant stability is good, corrosion-resistant,
Weather-resistant, mechanical performance and electrical property are good.After potting resin, good stability of the dimension, rub resistance, flatness；With cunning
The laminal filters such as mountain flour, mica are compared, and have the characteristics that the resistance to scratching in surface.Good dispersion of the wollastonite in resin, under intensity
Drop degree is small, and melt strength is low after packing material.Due to the reduction of hygroscopicity and viscosity, the molding processibility of material is also improved
Energy.Preferably, wollastonite partial size is 200-800 mesh；More preferable 400-600 mesh.Wollastonite of the invention changes for silane coupling agent
The wollastonite of property.
It is further preferred that the fire retardant includes one of halogenated flame retardant, halogen-free flame retardants and fire retarding synergist
Or it is a variety of.The additive amount of the fire retardant is no more than the 20% of fatty polyamide compound total weight.Halogenated flame retardant is not to
Very effectively, it can make jointly with synergistic metal oxide, metal salt, phosphorus-containing compound or carbon forming agent for enhancing and enhancing nylon
With.But halogenated flame retardant will also result in nylon chain and be cracked into flammable monomer or be caused by hydrogen halides (HX) or be catalyzed similar
Thing.Halogenated flame retardant it is usually used be chlorinated flame retardants and desertization fire retardant；Chlorinated flame retardants are mainly chlordene ring penta 2
The binary addition product that alkene and cyclo-octadiene generation Diels-Alder reaction generate, bis- (hexacholorocyclopentadiene) cyclooctane, it
It is the most frequently used in nylon.Brominated flame retardant is commonly decabromodiphenylethane, and effect is not it is obvious that but passing through when exclusive use
After the synergistic effect of antimony oxide, effect is clearly.
Halogen-free flameproof agent addition agent is mainly based on phosphorus series compound and metal hydroxides.The preferably described nothing of the present invention
Halogen fire retardant is phosphorus-nitrogen containing flame retardant, preferably one of melamine cyanurate, hypophosphites or ammonium polyphosphate or a kind of
More than, further preferred ammonium polyphosphate, wherein phosphorus content is not less than 19%.
The flame retardant synergist includes siloxanes, metal oxide (such as silica, boehmite, aluminium oxide, oxidation
Iron, titanium oxide, manganese oxide, magnesia, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, tin oxide, oxidation
Antimony, nickel oxide, copper oxide and tungsten oxide, antimony oxide, di-iron trioxide), metal powder (such as aluminium, iron, titanium, manganese, zinc,
Molybdenum, cobalt, bismuth, chromium, tin, antimony, nickel, copper and tungsten) and metal salt (such as barium metaborate, zinc carbonate, zinc borate, magnesium carbonate, carbon
Sour calcium and barium carbonate).
It is further preferred that the additive amount of the antioxidant is no more than the 2% of fatty polyamide compound total weight.Institute
Primary antioxidant and auxiliary antioxidant can be divided by stating antioxidant, and primary antioxidant refers to that the aromatic amine that can eliminate free radical and hindered phenol etc. are changed
Object and its derivative are closed, auxiliary antioxidant refers to the organic compound containing p and s of energy hydroperoxide decomposition.The master
Antioxidant is selected from four [methyl-β-(3,5- di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol esters, β-(3,5- bis- tertiary fourths
Base -4- hydroxy phenyl) propionic acid n-octadecyl alcohol ester, N, N '-is bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) oneself
Diamines is one or more.The auxiliary antioxidant is selected from three [2.4- di-tert-butyl-phenyl] phosphite esters, diphosphorous acid Ji Wusi
One or both of alcohol distearyl alcohol ester.
It is further preferred that the additive amount of the nucleating agent is no more than the 1% of fatty polyamide compound total weight.Institute
Stating nucleating agent is ethylene acrylic acid co polymer, optimal ethylene-methacrylic acid copolymer sodium ion derivative.The master of nucleating agent
Acting on is the crystallization rate for improving nylon material, improves the tensile strength and bending modulus of material, enhances intensity.
The preparation method of the above-mentioned fatty polyamide compound for environment-protection electroplating, comprising the following steps:
(1) aliphatic polyamide resin is mixed with thermoplastic elastomer (TPE), in autoclave, mixer or extruder
It is interior, it is reacted, obtains blend, it is spare；
(2) inorganic mineral powder is added in high mixer, is increased to 105 DEG C or more to inorganic mineral powder temperature, adds coupling agent
Reaction, reaction time are 10-30 minutes, are taken out stand-by；
(3) blend that step (1) obtains is added in double screw extruder, while is added and is handled by step (2)
Inorganic mineral powder, after mixing, squeeze out pelletizing to get.
Beneficial effects of the present invention:
1. fatty polyamide compound of the invention can be handled using existing ABS plastic electroplating technology, from enterprise
For production, equipment investment is few, and electroplating cost is low, substantially increases product competitiveness；
2. thermoplastic elastomer (TPE) additive amount is few in fatty polyamide compound of the invention, it is distributed in polyamide
Surface layer can keep the fundamental characteristics of polyamide substrate, in addition, thermoplastic elastomer (TPE) is easy to be plated liquid medicine corrosion, produce
The hole of " bait throwing in " effect of raw Similar to ABS, and then improve binding force of cladding material；
3. fatty polyamide compound of the invention not only can be electroplated Cr VI coarsening solution with existing ABS and carry out electricity
Plating can also use the potassium permanganate coarsening solution processing of environmental protection, be suitble to the development of environment-protection electroplating；
4. fatty polyamide compound of the invention is after plating, with the plating binding force that coating layer surface is electroplated
It can reach 10N or more, ensured using safe；
5, this product resistance to low temperature is excellent, minimum to be resistant to -50 DEG C of low temperature, can widen electroplated product use scope.
Specific embodiment
In order to better understand the present invention, invention is described in detail combined with specific embodiments below.
The test method of tensile strength
Tensile strength is carried out according to " ISO 527-2012 plastic tensile performance test methods ", prepares dumbbell-shaped specimen, is drawn
Stretching speed is 2mm/min, and the longitudinal axis stretches.Record tensile strength when sample destroys and corresponding elongation at break.The sample
It should be placed under 23 ± 2 DEG C of (73.4 ± 3.6 ℉), 50 ± 5% relative humidities, be carried out not less than 40 hours before the test
Adjusting.During the tensile test, sample stretches until fracture, and record elongation between gages is to be broken apart from percentage
Elongation.
The test method of impact strength
The test of impact strength according to " standard test method of the Chalpy impact performance detection of 180 plastics of ISO " into
Row.In test, it is broken standard sample by the swing of standard pendulum, the energy that the sample fracture recorded absorbs is exactly it
Impact strength.All pressing mold samples all should be parallel to molding apply direction face on open gap.By going in process
Make notch on one side with the depth of parallelism of another side within 0.025mm (0.001in), except a small amount of material to maintain sample depth
Allowable deviation within.The standard sample need to be placed in after open gap, before test 23 ± 2 DEG C (73.4 ± 3.6 ℉), 50 ±
Under 5% relative humidities, adjusts and be not less than 40 hours.When test, need 23 ± 2 DEG C of (73.4 ± 3.6 ℉), 50 ± 5%
It is tested under relative humidities.
The test method of binding force of cladding material
Binding force of cladding material refers to the bond strength of coating and matrix resin or intermediate deposit, i.e., the coating of per surface area from
Power required for being removed on matrix resin or intermediate deposit.By material injection at the square products of 120*60*2mm, then it is electroplated,
The bar shaped of a 10*80mm is cut out on the space of a whole page with pocket knife.It is pasted on the width of bar shaped coating with 3M gummed paper, then with omnipotent examination
Testing maximum, force required when machine test coating is separated with resin is binding force of cladding material.
The test method of bending property
Bending property test is carried out according to " measurement of ISO 178-2010 plastics bending property ".Wherein bending strength is material
Expect the maximum stress for rupturing under bend loading effect or being born when reaching regulation amount of deflection, bending modulus is material in elastic pole
The ability of bending deformation is resisted in limit, the bending strength and bending modulus unit are MPa.
Cold cycling test
It by material injection at the square products of 120*60*2mm, is then electroplated, keeps the temperature 24 hours at -50 DEG C, then 2 DEG C/
Min is warming up to 50 DEG C of constant temperature 24 hours, then 2 DEG C/min cool to -50 DEG C this be a cycle.Electricity is observed after the completion of a cycle
Whether coating and resin-bonded have loosening, if not provided, continuing next cycle.The cold cycling period time that product carries out
Number is more, and it is more excellent to represent its cold-resistant thermal shock resistance properties.
It is raw materials used in embodiment:
PA66: the EPR27 of Pingdingshan Shenma Engineering Plastic Co., Ltd.；
PA6: the M2500I of newly meeting Mei Da polyamide fibre limited liability company；
The TR55 of chemistry (China) Co., Ltd, PA12:EMS Switzerland；
Glass fibre: the 301HP of Chongqing world composite material；
Carbon fiber: the Type-45 of toray；
Silane coupling agent KH550: the A-1100 of union carbide corporation, the U.S.；
Titanate coupling agent: the KR-238S of the oil company Kenrich, the U.S.；
TPE: the G4774 of Dupont Co., Ltd；
TPU: the WHT-2195 of Yantai Wanhua Polyurethane Co., Ltd；
TPO: the CMV241 of ExxonMobil Chemical；
Talcum powder: Hangzhou Fuyang new sky dragon miberal powder Co., Ltd, 2000 mesh；
Silica: the ST-O-001-2 of the prosperous chemical reagent factory of Tianjin letter；
Aluminium oxide: the ALuna-100 of Guangzhou Science and Technology Ji Sheng Industrial Co；
Antioxidant: the SEED of Clariant chemical industry (China) Co., Ltd.
Embodiment 1
A kind of fatty polyamide compound for environment-protection electroplating, it is (former including following raw material by weight percentage
Expect gross weight 10KG):
PA6 89.5%,
TPE 10%,
SEED 0.5%.
The preparation method of the above-mentioned fatty polyamide compound for environment-protection electroplating, comprising the following steps:
(1) PA6 and TPE are added in double screw extruder by main feeder and carry out melt polymerization, tie rod pelletizing obtains
It is spare to blend；
(2) blend and SEED that step (1) obtains are added in double screw extruder by main feeder, are mixed
Afterwards, temperature controls melting extrusion under the conditions of 235 DEG C, pelletizing, and twin-screw revolving speed is 300RPM multiple to get polyamide of the invention
Close object.
Embodiment 2
A kind of fatty polyamide compound for environment-protection electroplating, it is (former including following raw material by weight percentage
Expect gross weight 10KG):
The preparation method of the above-mentioned fatty polyamide compound for environment-protection electroplating, comprising the following steps:
(1) PA6 and TPE are added in double screw extruder by main feeder and carry out melt polymerization, tie rod pelletizing obtains
It is spare to blend；
(2) inorganic mineral powder aluminium oxide is added in high mixer, so that inorganic mineral powder aluminium oxide temperature is increased 110 DEG C, adds
Silane coupling agent KH550 reaction, reaction time are 15 minutes, are taken out stand-by；
(3) blend and SEED that step (1) obtains are added in double screw extruder by main feeder, while
The inorganic mineral powder aluminium oxide by step (2) processing is added in the feeder of side, after mixing, temperature control is melted under the conditions of 240 DEG C
Melt extrusion, pelletizing, twin-screw revolving speed is 300RPM to get polyamide compound of the invention.
Embodiment 3
A kind of fatty polyamide compound for environment-protection electroplating, it is (former including following raw material by weight percentage
Expect gross weight 10KG):
The preparation method of the above-mentioned fatty polyamide compound for environment-protection electroplating, comprising the following steps:
(1) PA66 and TPO are added in double screw extruder by main feeder and carry out melt polymerization, tie rod pelletizing obtains
It is spare to blend；
(2) inorganic mineral powder silica is added in high mixer, so that inorganic mineral powder silica temperature is increased 105 DEG C, adds
Silane coupling agent KH550 reaction, reaction time are 10 minutes, are taken out stand-by；
(3) blend and SEED that step (1) obtains are added in double screw extruder by main feeder, while
The inorganic mineral powder silica and glass fibre 301HP by step (2) processing are added in the feeder of side, after mixing, temperature control
Melting extrusion under the conditions of 280 DEG C, pelletizing, twin-screw revolving speed are 350RMP to get polyamide compound of the invention.
Embodiment 4
A kind of fatty polyamide compound for environment-protection electroplating, it is (former including following raw material by weight percentage
Expect gross weight 10KG):
The preparation method of the above-mentioned fatty polyamide compound for environment-protection electroplating, comprising the following steps:
(1) PA6, PA66 and TPU are obtained into blend by carrying out melt polymerization in mixer, it is spare；
(2) inorganic mineral powder talcum powder is added in high mixer, so that inorganic mineral powder talcum powder temperature is increased 120 DEG C, adds
Titanate coupling agent reaction, reaction time are 10 minutes, are taken out stand-by；
(3) blend and SEED that step (1) obtains are added in double screw extruder by main feeder, while
The inorganic mineral powder talcum powder and carbon fiber by step (2) processing are added in the feeder of side, after mixing, temperature is controlled at 270 DEG C
Under the conditions of melting extrusion, pelletizing, twin-screw revolving speed be 250RMP to get polyamide compound of the invention.
Embodiment 5
A kind of fatty polyamide compound for environment-protection electroplating, it is (former including following raw material by weight percentage
Expect gross weight 10KG):
The preparation method of the above-mentioned fatty polyamide compound for environment-protection electroplating, comprising the following steps:
(1) PA6, PA66, PA12 and TPU are obtained into blend by carrying out melt polymerization in autoclave, it is spare；
(2) inorganic mineral powder talcum powder and aluminium oxide are added in high mixer, make inorganic mineral powder talcum powder and aluminium oxide temperature
120 DEG C are increased, titanate coupling agent reaction is added, the reaction time is 10 minutes, is taken out stand-by；
(3) blend and SEED that step (1) obtains are added in double screw extruder by main feeder, while
The inorganic mineral powder talcum powder and aluminium oxide by step (2) processing are added in the feeder of side, temperature control is melted under the conditions of 250 DEG C
Melt extrusion, pelletizing, twin-screw revolving speed is 300RMP to get polyamide compound of the invention.
Embodiment 6
A kind of fatty polyamide compound for environment-protection electroplating, it is (former including following raw material by weight percentage
Expect gross weight 10KG):
The preparation method of the above-mentioned fatty polyamide compound for environment-protection electroplating, comprising the following steps:
(1) PA12 and TPU, TPO are obtained into blend by carrying out melt polymerization in autoclave, it is spare；
(2) inorganic mineral powder talcum powder and aluminium oxide are added in high mixer, make inorganic mineral powder talcum powder and aluminium oxide temperature
120 DEG C are increased, titanate coupling agent reaction is added, the reaction time is 30 minutes, is taken out stand-by；
(3) blend and SEED that step (1) obtains are added in double screw extruder by main feeder, while
The inorganic mineral powder talcum powder and aluminium oxide by step (2) processing are added in the feeder of side, temperature control is melted under the conditions of 230 DEG C
Melt extrusion, pelletizing, twin-screw revolving speed is 300RMP to get polyamide compound of the invention.
Comparative example 1
A kind of polyamide compound, including following raw material (raw material gross weight 10KG) by weight:
The preparation method of above-mentioned polyamide compound, comprising the following steps:
(1) inorganic mineral powder aluminium oxide is added in high mixer, so that inorganic mineral powder aluminium oxide temperature is increased 120 DEG C, adds
Silane coupling agent KH550 reaction, reaction time are 10 minutes, are taken out stand-by；
(2) PA6 and SEED are added in double screw extruder by main feeder, while warp is added in the feeder of side
The inorganic mineral powder aluminium oxide of step (1) processing is crossed, temperature controls melting extrusion under the conditions of 230 DEG C, pelletizing, and twin-screw revolving speed is
300RMP is to get polyamide compound.
Comparative example 2
A kind of polyamide compound, including following raw material (raw material gross weight 10KG) by weight:
The preparation method of above-mentioned polyamide compound, comprising the following steps:
(1) inorganic mineral powder talcum powder is added in high mixer, so that inorganic mineral powder talcum powder temperature is increased 105 DEG C, adds
Silane coupling agent KH550 reaction, reaction time are 30 minutes, are taken out stand-by；
(2) PA66 and SEED are added in double screw extruder by main feeder, while are added in the feeder of side
By the inorganic mineral powder talcum powder and glass fibre 301HP of step (1) processing, temperature controls melting extrusion under the conditions of 280 DEG C,
Pelletizing, twin-screw revolving speed are 300RMP to get polyamide compound.
Test can be carried out to the lower temperature resistance of the obtained polyamide compound of embodiment 1-6 and comparative example 1-2, as a result such as table
Shown in 1.
The polyamide compound that embodiment 1-3 and comparative example 1 are obtained carries out electricity after the processing of potassium permanganate coarsening solution
Plating carries out plating binding force test to the coating formed after plating.The polyamide compound that embodiment 4-6 and comparative example 2 obtain,
It is electroplated after the processing of chromic acid coarsening solution, plating binding force test is carried out to the coating formed after plating.Test result such as table 1
It is shown.
Test can be carried out to the Physical Mechanical of the obtained polyamide compound of embodiment 1-6 and comparative example 1-2, as a result such as
Shown in table 2.
The polyamide compound plating binding force and cold cycling test result that table 1 embodiment 1-6 and comparative example 1-2 is obtained
The polyamide compound measuring mechanical property result that table 2 embodiment 1-6 and comparative example 1-2 is obtained
Claims (9)
1. a kind of fatty polyamide compound for environment-protection electroplating, which is characterized in that including it is following by weight percentage
Raw material:
Wherein, high melt index of the melt index of the thermoplastic elastomer (TPE) than aliphatic polyamide resin；
The thermoplastic elastomer (TPE) is polyester elastomer.
2. the fatty polyamide compound according to claim 1 for environment-protection electroplating, which is characterized in that the fat
Polyamide resin is derived from one or more aliphatic diamines and one or more dicarboxylic acids or one or more aliphatic
Lactams.
3. the fatty polyamide compound according to claim 2 for environment-protection electroplating, which is characterized in that the fat
Polyamide is selected from PA6, PA56, PA66, PA610, PA612, PA11, PA12, PA1010, at least one of PA1212.
4. the fatty polyamide compound according to claim 1 for environment-protection electroplating, which is characterized in that the thermoplastic
The melt index > 2g/10min of property elastomer, test condition: 220 DEG C, 2.16kg.
5. the fatty polyamide compound according to claim 1 for environment-protection electroplating, which is characterized in that described inorganic
Miberal powder is at least one of talcum powder, aluminium oxide, silica, zinc oxide and montmorillonite.
6. the fatty polyamide compound according to claim 5 for environment-protection electroplating, which is characterized in that described inorganic
Miberal powder is the inorganic mineral powder after coupling agent modified.
7. the fatty polyamide compound for environment-protection electroplating according to claim 1 or 6, which is characterized in that described
Coupling agent is selected from epoxy silane coupling, amino silane coupling agent, sulfydryl one type of silane coupling agent, the coupling of urea groups one type of silane
Agent, isocyanates silane coupling agent, titanate coupling agent, boric acid ester coupler, aluminium titanium composite coupler, aluminate coupling agent
At least one of.
8. the polyamide compound according to claim 1 for environment-protection electroplating, which is characterized in that the aliphatic polyamides
Amine compound further includes one of fibre reinforced materials, fire retardant, nucleating agent and antioxidant or a variety of.
9. the preparation side of the fatty polyamide compound according to claim 1 to 8 for environment-protection electroplating
Method, which comprises the following steps:
(1) aliphatic polyamide resin is mixed with thermoplastic elastomer (TPE), in autoclave, mixer or extruder, into
Row reaction, obtains blend, spare；
(2) inorganic mineral powder is added in high mixer, is increased to 105 DEG C or more to inorganic mineral powder temperature, add coupling agent reaction,
Reaction time is 10-30 minutes, is taken out stand-by；
(3) blend that step (1) obtains is added in double screw extruder, while the nothing handled by step (2) is added
Machine miberal powder, after mixing, squeeze out pelletizing to get.
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| PCT/CN2017/112366 WO2019056548A1 (en) | 2017-09-19 | 2017-11-22 | Aliphatic polyamide complex for environmentally friendly electroplating and preparation method therefor |
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| KR20200117385A (en) * | 2019-04-04 | 2020-10-14 | 현대모비스 주식회사 | Composition for worm wheel having excellent durability with wear resistance and worm wheel prepared using the same |
| CN110643173A (en) * | 2019-09-25 | 2020-01-03 | 广东格瑞新材料股份有限公司 | High-rigidity nylon composite material and preparation method thereof |
| CN111004497B (en) * | 2019-12-24 | 2022-03-29 | 上海中镭新材料科技有限公司 | Electroplating nylon material and preparation method thereof |
| CN114316581A (en) * | 2021-12-07 | 2022-04-12 | 合肥科拜耳新材料有限公司 | Halogen-free flame-retardant nylon 66 composition and preparation method thereof |
| CN116218205B (en) * | 2023-03-03 | 2024-03-29 | 金旸（厦门）新材料科技有限公司 | Electroplated heat-conducting nylon composite material and preparation method thereof |
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| CN101418097A (en) * | 2007-10-23 | 2009-04-29 | 广州金发科技股份有限公司 | Polypropylene compound capable of plating and preparation method thereof |
| CN106046781A (en) * | 2016-07-12 | 2016-10-26 | 江门市德众泰工程塑胶科技有限公司 | Aromatic polyamide compound for electroplating treatment and preparing method of aromatic polyamide compound |
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| CN101081929A (en) * | 2007-06-08 | 2007-12-05 | 深圳市科聚新材料有限公司 | Composite material easy for coating thermoplastic elastomer and preparation method thereof |
| CN101298518B (en) * | 2008-06-13 | 2010-07-21 | 南京鸿瑞塑料制品有限公司 | Silicon dioxide reinforced PA66 and preparation thereof |
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| US20130302615A1 (en) * | 2010-10-14 | 2013-11-14 | Lg Chem, Ltd. | Resin blend for melting process |
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| CN106046781A (en) * | 2016-07-12 | 2016-10-26 | 江门市德众泰工程塑胶科技有限公司 | Aromatic polyamide compound for electroplating treatment and preparing method of aromatic polyamide compound |
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