CN107663372B - A kind of polyamide compound and preparation method thereof for environment-protection electroplating - Google Patents
A kind of polyamide compound and preparation method thereof for environment-protection electroplating Download PDFInfo
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- CN107663372B CN107663372B CN201710844128.XA CN201710844128A CN107663372B CN 107663372 B CN107663372 B CN 107663372B CN 201710844128 A CN201710844128 A CN 201710844128A CN 107663372 B CN107663372 B CN 107663372B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Abstract
The present invention provides a kind of polyamide compounds for environment-protection electroplating, including following raw material by weight percentage: polyamide containing aromatic ring 40%~90%, thermoplastic elastomer (TPE) 3%~20%, fatty polyamide 0~20%, coupling agent 0%~2%, inorganic mineral powder 0%~40%；Wherein, the melt index of the thermoplastic elastomer (TPE) is higher than the melt index of polyamide containing aromatic ring and fatty polyamide；The present invention also provides the preparation methods of the polyamide compound for environment-protection electroplating；Polyamide compound of the invention has more excellent plating resistance and mechanical property, and the potassium permanganate coarsening solution processing of environmental protection can be used, be suitble to the development of environment-protection electroplating, after plating, it can reach 10N or more with the plating binding force that coating layer surface is electroplated, and ensure using safe.
Description
Technical field
The invention belongs to technical field of polymer materials more particularly to a kind of polyamide compound for environment-protection electroplating and
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, is by backbone structure
It is no to be divided into polyamide containing aromatic ring and fatty polyamide containing aromatic rings, wherein there is the same or portion in the amine or acid of nylon raw material
Divide and contains aromatic rings Shi Weihan aromatic ring polyamide.Polyamide containing aromatic ring includes semiaromatic polyamide composition and its copolymer, such as PA6T/
66, PA6/6T, PA9T, PA10T, PA12T etc.；It also include fully aromatic polyamide, such as aramid fiber 1313, Fanglun l414 etc..Containing virtue
Ring polyamide contains aromatic rings in strand compared to fatty polyamide, be remarkably improved the heat resistance of nylon, rigidity,
Solvent resistance etc..At present on the market, polyamide containing aromatic ring, which is mainly studied, is composite strengthening aspect, and can be used for water power plating contains virtue
Ring polyamide product is not yet reported that.
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) polyurethane-type thermoplastic elastomer is one kind of polyurethane rubber, is divided into
Polyester-type and polyether-type.The structure of its macromolecular chain is by polarity polyurethane or polyureas segment (hard section) and aliphatic polyester or to gather
Ether segment (soft segment) is alternately constituted.Lightly crosslinked structure between the hydrogen bond crosslinks and macromolecular chain of intermolecular formation, so that this
Kind high molecular material has plasticity with the variation of temperature.It is that this kind of elastomer is most prominent that hardness is high, wearability is good, elasticity is good
The characteristics of.
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 its 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 polyamide for environment-protection electroplating
Compound, using aliphatic polyamide resin and Semi-aromatic polyamide resin as matrix resin, by adding special thermoplastic
Property elastomer, so that elastomer is evenly distributed on resin surface during mixed and modified.Polyamide compound of the invention is not
In the case where adding miberal powder, it can also be used to which electroplating processes are coated carrying out surface metalation by electroplating technology, obtain high-strength
Degree, high temperature resistant, low water suction, dimensionally stable product, binding force especially is electroplated with fabulous substrate.Of the invention another
Purpose is to provide a kind of preparation method of polyamide compound for environment-protection electroplating.A further object of the present invention is to provide one
Kind polyamide material can be electroplated with ABS electroplating technology.
To achieve the goals above, the invention adopts the following technical scheme:
A kind of polyamide compound for environment-protection electroplating, including following raw material by weight percentage:
Wherein, the melt index of the thermoplastic elastomer (TPE) is higher than the melt index of the polyamide containing aromatic ring.
Preferably, the fatty polyamide refers to that polyamide is (e.g., aliphatic derived from one or more aliphatic diamines
C6-C20Alkylenediamine, alicyclic diamine, preferably diamines include bis(p-aminocyclohexyl)methane, 1,6- hexamethylene diamine, 2- first
Base pentanediamine, 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, azelaic acid,
Dodecanedioic acid or their derivative) and/or one or more aliphatic lactams, amino acid (such as 11- aminododecane
Acid, caprolactam and lauric lactam).
It is further preferred that the fatty polyamide is selected from PA6, PA66, PA6/66, PA56, PA 46, PA 610, PA
612、PA 11、PA 12、PA 910、PA 912、PA 913、PA 914、PA 915、PA 616、PA 936、PA 1010、PA
1012、PA 1013、PA 1014、PA 1210、PA 1212、PA 1213、PA 1214、PA1313、PA 614、PA 613、PA
615, one of PA 616 and PA 613 or a variety of.
It is further preferred that the fatty polyamide be selected from PA6, PA66, PA6/66, PA56, PA610, PA612,
One of PA1010, PA1212, PA11, PA12, PA1313 or a variety of.
Preferably, the polyamide containing aromatic ring can be by aromatic acid (such as terephthalic acid (TPA)) and aliphatic binary
Acid (such as diamines) polycondensation forms or aromatic diamine (such as p-phenylenediamine) and aliphatic diamine (such as adipic acid) polycondensation and
At.
It is further preferred that the polyamide containing aromatic ring be PA4T, PA6T/66, PA6T/6I, PA9T, PA10T,
One of PA12T, PA12T/12I, PA13T, PA13T/13I, MXD6 or a variety of.
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, wherein the melt index of thermoplastic elastomer (TPE) be > 2g/10min, test condition: 220 DEG C, 2.16kg；
The melt index of the thermoplastic elastomer (TPE) is higher than the melt index of fatty polyamide and the polyamide containing aromatic ring, is conducive to
In mixed and modified and injection molding, thermoplastic elastomer (TPE) is distributed in the surface layer of polyamide compound to external migration.
Preferably, the inorganic mineral powder is selected from aluminium oxide, silica, talcum powder, titanium oxide, zinc oxide, montmorillonite and height
At least one of ridge soil.It is further preferred that the inorganic mineral powder is selected from talcum powder, aluminium oxide, silica, zinc oxide, illiteracy
At least one of de- soil.The partial size mesh number of the inorganic mineral powder is greater than 1500 mesh.Particularly preferred, the inorganic mineral powder is put down
Equal partial size is 0.1~1 μm, and partial size mentioned here refers to the median particle diameter measured using laser particle analyzer measuring method
(D50), 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.
The modified inorganic mineral powder of coupling agent 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 will be containing 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 to drying, but needs to increase additional equipment.
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-(the third oxygen of 2,3- 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 between 3: 1 to 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 fire retardant additive amount is no more than the 20% of polyamide compound total weight.Halogenated flame retardant is to non-reinforced and increasing
Very effectively, it can be used in conjunction with strong nylon with synergistic metal oxide, metal salt, phosphorus-containing compound or carbon forming agent.But
Halogenated flame retardant will also result in the similar thing that nylon chain is cracked into flammable monomer or is caused by hydrogen halides (HX) or be catalyzed.Halogen
Flame retardant it is usually used be chlorinated flame retardants and brominated flame retardant；Chlorinated flame retardants are mainly that hexacholorocyclopentadiene and ring are pungent
The binary addition product that Diels-Alder reaction generates occurs for diene, and bis- (hexacholorocyclopentadiene) cyclooctane, it is in nylon
It is the most frequently used.Brominated flame retardant is commonly decabromodiphenylethane, and effect is not it is obvious that but by three oxidations two when exclusive use
After the synergistic effect of antimony, 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 fire 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 antioxidant additive amount is no more than the 2% of polyamide compound total weight.The antioxidant
Can be divided into primary antioxidant and auxiliary antioxidant, primary antioxidant refer to the compounds such as the aromatic amine that can eliminate free radical and hindered phenol and its
Derivative, auxiliary antioxidant refer to the organic compound containing p and s of energy hydroperoxide decomposition.The primary antioxidant choosing
From four [methyl-β-(3,5- di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol esters, β-(3,5- di-t-butyl -4- hydroxyls
Phenyl) propionic acid n-octadecyl alcohol ester, N, N '-is bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine it is a kind of or
It is a variety of.The auxiliary antioxidant is selected from three [2.4- di-tert-butyl-phenyl] phosphite esters, diphosphorous acid pentaerythrite distearyl alcohol
One or both of ester.
It is further preferred that the nucleating agent additive amount is no more than the 1% of polyamide compound total weight.The nucleating agent
For ethylene acrylic acid co polymer, optimal ethylene-methacrylic acid copolymer sodium ion derivative.The main function of nucleating agent 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 polyamide compound for environment-protection electroplating, comprising the following steps:
(1) aromatic ring polyamide will be contained, fatty polyamide is mixed with thermoplastic elastomer (TPE), in autoclave, close
It in mill or extruder, 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. polyamide compound of the invention has more excellent plating resistance and power relative to existing plating grade nylon
Phenomena such as learning performance, being in the plating process not in blistering, point, orange peel, material surface is smooth；And temperature tolerance improves,
Material is unlikely to deform when high temperature is electroplated, and meets the requirement of high temperature plating；
2. polyamide compound of the invention can be handled using existing ABS plastic electroplating technology, come from enterprise's production
It says, equipment investment is few, and electroplating cost is low, greatly improves product competitiveness；
3. thermoplastic elastomer (TPE) additive amount is few in polyamide compound of the invention, it is distributed in the surface layer of polyamide,
The fundamental characteristics of polyamide substrate can be kept, in addition, thermoplastic elastomer (TPE) is easy to be plated liquid medicine corrosion, is generated similar
The hole of " bait throwing in " effect of ABS, and then improve binding force of cladding material；
4. polyamide compound of the invention not only can be electroplated Cr VI coarsening solution with existing ABS and carry out at plating
Reason can also use the potassium permanganate coarsening solution processing of environmental protection, be suitble to the development of environment-protection electroplating；
5. polyamide compound of the invention after plating, reaches with the plating binding force that coating layer surface is electroplated
10N or more has been ensured using safe；
6. this product high temperature resistance is excellent, short-term highest is resistant to 280 DEG C of high 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 " ASTM D 638-2008 plastic tensile performance standard test method ", prepares dumbbell shaped
Sample, having a size of 160*10*4mm, gauge length 50mm, tensile speed 50m/min, the longitudinal axis is stretched.Record drawing when sample destroys
Stretch intensity and corresponding elongation at break.The sample should be placed in front of the test 23 ± 2 DEG C (73.4 ± 3.6 ℉), 50 ±
Under 5% relative humidities, the adjusting not less than 40 hours is carried out.During the tensile test, sample stretches until being fractured into
Only, record elongation between gages apart from percentage be elongation at break.
The test method of impact strength
The test of impact strength according to " standard test method of the Chalpy impact performance detection of ASTM D256 plastics " 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.The standard sample molding material is wide in the range of 3.17~12.7mm (0.125~0.500in).In addition, ruler
Very little all samples less than 12.7mm (0.500in) all should be compared with short face open gap.All pressing mold samples should all be parallel to mould
Pressure applies open gap on the face in direction.Make notch one side parallel with another side by removing a small amount of material in process
Degree is within 0.025mm (0.001in), within the allowable deviation to maintain sample depth.The standard sample is in open gap
Afterwards, it needs to be placed under 23 ± 2 DEG C of (73.4 ± 3.6 ℉), 50 ± 5% relative humidities before test, adjusts and be not less than 40 hours.Examination
When testing, need to be tested under 23 ± 2 DEG C of (73.4 ± 3.6 ℉), 50 ± 5% 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.
Load heat distortion temperature
The test of load heat distortion temperature is carried out according to " measurement of ISO 75-2-2013 plastics deflection under load temperature ",
Test pressure is 1.8Mpa, and temperature when degree of deformation reaches 0.34mm is its heat distortion temperature.
It is raw materials used in embodiment:
PA6T/66: the D3000 resin of Jiangmen Dezhongtai Engineering Plastics Technology Co., Ltd.；
PA6: the M2500I of newly meeting Mei Da polyamide fibre limited liability company；
PA12T: the T3000 resin of Jiangmen Dezhongtai Engineering Plastics Technology Co., Ltd.
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 polyamide compound for environment-protection electroplating, including following raw material (raw material gross weight by weight percentage
10KG):
PA6T/66 90%,
TPE 10%.
The preparation method of the above-mentioned polyamide compound for environment-protection electroplating, comprising the following steps:
PA6T/66 and TPE are added in double screw extruder by main feeder and carry out melt polymerization, tie rod pelletizing is
Obtain polyamide compound of the invention.
Embodiment 2
A kind of polyamide compound for environment-protection electroplating, including following raw material (raw material gross weight by weight percentage
10KG):
The preparation method of the above-mentioned polyamide compound for environment-protection electroplating, comprising the following steps:
(1) PA6T/66 and TPE are added in double screw extruder by main feeder and carry out melt polymerization, tie rod is cut
Grain obtains blend, spare；
(2) inorganic mineral powder aluminium oxide is added in high mixer, inorganic mineral powder aluminium oxide temperature is made to be increased to 120 DEG C, then plus
Enter Silane coupling agent KH550 reaction, 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 aluminium oxide by step (2) processing is added in the feeder of side, after mixing, temperature control is melted under the conditions of 315 DEG C
Melt extrusion, pelletizing, twin-screw revolving speed is 350RPM to get polyamide compound of the invention.
Embodiment 3
A kind of polyamide compound for environment-protection electroplating, including following raw material (raw material gross weight by weight percentage
10KG):
The preparation method of the above-mentioned polyamide compound for environment-protection electroplating, comprising the following steps:
(1) PA12T and TP0 are added in double screw extruder by main feeder and carry out melt polymerization, tie rod pelletizing
Blend is obtained, it is spare；
(2) inorganic mineral powder aluminium oxide is added in high mixer, inorganic mineral powder aluminium oxide temperature is made to be increased to 120 DEG C, then plus
Enter Silane coupling agent KH550 reaction, 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 aluminium oxide 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 305 DEG C, pelletizing, twin-screw revolving speed are 250RPM to get polyamide compound of the invention.
Embodiment 4
A kind of polyamide compound for environment-protection electroplating, including following raw material (raw material gross weight by weight percentage
10KG):
The preparation method of the above-mentioned polyamide compound for environment-protection electroplating, comprising the following steps:
(1) by PA12T, PA6 and TPU by carrying out melt polymerization in mixer, tie rod pelletizing obtains blend, standby
With；
(2) inorganic mineral powder talcum powder is added in high mixer, inorganic mineral powder talcum powder temperature is made to be increased to 105 DEG C, then plus
Enter titanate coupling agent reaction, 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
It is added after the inorganic mineral powder talcum powder that step (2) are handled is mixed with carbon fiber in the feeder of side, temperature is controlled in 295 DEG C of items
Melting extrusion under part, pelletizing, twin-screw revolving speed are 300RPM to get polyamide compound of the invention.
Embodiment 5
A kind of polyamide compound for environment-protection electroplating, including following raw material (raw material gross weight by weight percentage
10KG):
The preparation method of the above-mentioned polyamide compound for environment-protection electroplating, comprising the following steps:
(1) by PA12T, PA6 and TPU by carrying out melt polymerization in mixer, tie rod pelletizing obtains blend, standby
With；
(2) inorganic mineral powder talcum powder, aluminium oxide are added in high mixer, make inorganic mineral powder talcum powder, aluminium oxide temperature liter
Up to 105 DEG C, 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
Inorganic mineral powder talcum powder, the aluminium oxide by step (2) processing are added in the feeder of side, after mixing, temperature is controlled in 295 DEG C of items
Melting extrusion under part, pelletizing, twin-screw revolving speed are 300RPM 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 polyamide compound for environment-protection electroplating, comprising the following steps:
(1) PA6T/66 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 320 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) PA6T/66 and SEED are added in double screw extruder by main feeder, while added in the feeder of side
Enter the inorganic mineral powder aluminium oxide handled by step (1), temperature controls melting extrusion under the conditions of 230 DEG C, pelletizing, and twin-screw turns
Speed is 300RMP 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) PA12T 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.
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.
Binding force test result is electroplated in the polyamide compound 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 polyamide compound for environment-protection electroplating, which is characterized in that including following raw material by weight percentage:
Wherein, the melt index of the thermoplastic elastomer (TPE) is higher than the melt index of the polyamide containing aromatic ring；
The thermoplastic elastomer (TPE) is polyester elastomer.
2. the polyamide compound according to claim 1 for environment-protection electroplating, which is characterized in that the polyamides containing aromatic ring
Polyimide resin be selected from PA4T, PA6T/66, PA6T/6I, PA9T, PA10T, PA12T, PA12T/12I, PA13T, PA13T/13I,
At least one of MXD6.
3. the polyamide compound according to claim 1 for environment-protection electroplating, which is characterized in that the aliphatic polyamides
Polyimide resin is in PA6, PA66, PA6/66, PA56, PA610, PA612, PA1010, PA1212, PA11, PA12, PA1313
It is at least one.
4. the polyamide compound according to claim 1 for environment-protection electroplating, which is characterized in that wherein thermoplastic elastic
The melt index of body be > 2g/10min, test condition: 220 DEG C, 2.16kg.
5. the polyamide compound according to claim 1 for environment-protection electroplating, which is characterized in that the inorganic mineral powder choosing
From at least one of talcum powder, aluminium oxide, silica, zinc oxide, montmorillonite.
6. the polyamide compound according to claim 5 for environment-protection electroplating, which is characterized in that the inorganic mineral powder is
Inorganic mineral powder after coupling agent modified.
7. the polyamide compound for environment-protection electroplating according to claim 1 or 6, which is characterized in that the coupling agent
Selected from epoxy silane coupling, amino silane coupling agent, sulfydryl one type of silane coupling agent, urea groups one type of silane coupling agent, isocyanide
Esters of gallic acid silane coupling agent, titanate coupling agent, boric acid ester coupler, aluminium titanium composite coupler, in aluminate coupling agent extremely
Few one kind.
8. the polyamide compound according to claim 1 for environment-protection electroplating, which is characterized in that the polyamide is compound
Object further includes one of fibre reinforced materials, fire retardant, nucleating agent and antioxidant or a variety of.
9. the preparation method of the polyamide compound according to claim 1 to 8 for environment-protection electroplating, special
Sign is, comprising the following steps:
(1) aromatic ring polyamide will be contained, fatty polyamide is mixed with thermoplastic elastomer (TPE), in autoclave, mixer
Or in extruder, 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, 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/CN2017/112365 WO2019056547A1 (en) | 2017-09-19 | 2017-11-22 | Polyamide complex for environmentally friendly electroplating and preparation method therefor |
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| CN109722018A (en) * | 2018-12-21 | 2019-05-07 | 金旸（厦门）新材料科技有限公司 | A kind of high rigidity low water absorbable PA/ABS alloy material and preparation method thereof |
| CN114507441A (en) * | 2021-12-24 | 2022-05-17 | 金发科技股份有限公司 | Polyamide composite material and preparation method and application 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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| CN1995142A (en) * | 2006-12-28 | 2007-07-11 | 深圳市科聚新材料有限公司 | Polyamide material and its preparing process |
| CN102276897A (en) * | 2011-06-29 | 2011-12-14 | 广州市聚赛龙工程塑料有限公司 | Polyethylene/nylon alloy composite material 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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| US20050197452A1 (en) * | 2004-02-27 | 2005-09-08 | Solvay Advanced Polymers, Llc | Safety equipment comprising an aromatic polyamide composition, and aromatic polyamide composition |
| US20070213475A1 (en) * | 2004-07-29 | 2007-09-13 | Solvay Advanced Polymers, L.L..C | Impact Modified Polyamide Compositions |
| CN101418097B (en) * | 2007-10-23 | 2011-05-11 | 广州金发科技股份有限公司 | Polypropylene compound capable of plating and preparation method thereof |
| CN104662094B (en) * | 2012-10-12 | 2016-09-28 | 尤尼吉可株式会社 | Semiaromatic polyamide composition film |
| KR101823204B1 (en) * | 2015-08-24 | 2018-03-09 | 롯데첨단소재(주) | Thermoplastic resin compositon and molded parts using the same |
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| CN1995142A (en) * | 2006-12-28 | 2007-07-11 | 深圳市科聚新材料有限公司 | Polyamide material and its preparing process |
| CN102276897A (en) * | 2011-06-29 | 2011-12-14 | 广州市聚赛龙工程塑料有限公司 | Polyethylene/nylon alloy composite material 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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