CN109943068A - A kind of high-temperature-resnylont nylont material and plating nylon material and its preparation method and application - Google Patents
A kind of high-temperature-resnylont nylont material and plating nylon material and its preparation method and application Download PDFInfo
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- CN109943068A CN109943068A CN201910244242.8A CN201910244242A CN109943068A CN 109943068 A CN109943068 A CN 109943068A CN 201910244242 A CN201910244242 A CN 201910244242A CN 109943068 A CN109943068 A CN 109943068A
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Abstract
The invention belongs to polymeric material field, a kind of high-temperature-resnylont nylont material and plating nylon material and its preparation method and application are specifically disclosed.The high temperature resistant plating nylon material is made of PA6T, potassium titanate crystal whisker, mineral and optional high temperature resistant antioxidant, contain kaolin in the mineral, the weight ratio of the PA6T, potassium titanate crystal whisker and mineral are 100:(0.1~30): (20~50).Nylon material provided by the invention not only heat distortion temperature and notch impact strength with higher, but also the problem of big nylon water absorption rate, hardly possible plating can be solved perfectly, also there is good electroplating effect under 170~190 DEG C of this high temperature, the rear surface of plating is relatively smooth, product quality is high, to widen electroplating plastic in the application of hot environment.
Description
Technical field
The invention belongs to polymeric material field, specifically disclose a kind of high-temperature-resnylont nylont material and plating nylon material and
Preparation method and application.
Background technique
Good metal-like not only may be implemented in plastic electroplating product, but also can also mitigate product weight, is effectively changing
Kind plastics appearance and it is decorative simultaneously, also improve its electricity, heat and in terms of performance, but plastic material is used in plating
Selection but to comprehensively consider the processing performance of material, mechanical performance, material cost, electroplating cost, the complexity of plating with
And the factors such as dimensional accuracy.Mainstream plated material is using ABS, PC/ABS as substrate at present, but with the development of society, life
The flat raising of running water, requirement of the people to product is higher and higher and more and more diversified, ABS, PC/ABS plated material thermal deformation
Temperature is lower, is unable to satisfy some higher temperature applications occasions.Nylon material has extremely excellent as one of five large-engineering materials
Different mechanical performance.However, the water absorption rate of common nylon is big, but cannot be largely used to be electroplated always, and need to build special
Electroplating assembly line, equipment investment is big, and as substrate, at plating, this is high than plating ABS, PC/ABS for electroplating cost.
CN108219450A discloses a kind of nylon material, the component containing following weight percent meter: nylon resin 23
~75%, PA1335 5~10%, glass fibre 0~35%, filling mineral 20~30%, lubricant 0~1%, antioxidant 0~
1%.Wherein, PA1335 is a kind of amorphous nylon material, preferable with the compatibility of nylon, it is therefore an objective to reduce the crystallization of nylon
Property, increase the dimensional stability of nylon material, to improve the apparent property of nylon material, reduces surface floating fiber.The glass
The addition of fiber can be improved the intensity and modulus of nylon material, be conducive to the application that plating increases nylon material.The filling
Mineral are the MD1250WC10012 with unique dimensions and acid-base property by specially treated, and it is plating resistance can to assign nylon
Can, and the Conventional filler mineral equally as wollastonite and talcum powder do not have electroplating effect then and (say referring to CN108219450A
Bright book [0090] section).In addition, although the nylon material provided in CN108219450A has preferable electricity at a lower temperature
Effect is plated, resulting materials surface is substantially without floating fibre, but heat distortion temperature still needs to be further increased, and works as electroplating temperature
It is higher to be then difficult to realize plating when for example reaching 170~190 DEG C, it is unable to satisfy some higher temperature applications occasions.
Summary of the invention
The purpose of the invention is to overcome, existing nylon material heat distortion temperature is lower, is difficult to realize 170~190
The defect being electroplated under DEG C this high temperature, and providing a kind of has higher heat distortion temperature and in 170~190 DEG C of this high temperature
There is down high-temperature-resnylont nylont material of good electroplating effect and preparation method thereof and be electroplated by the high-temperature-resnylont nylont material and obtain
Plating nylon material and its preparation method and application.
Glass fibre is generally needed to be added in existing nylon material, and the use of glass fibre can make gained nylon material
There is floating fibre on surface, rough.In this regard, although the prior art has introduction that can introduce amorphous nylon for example, by CN108219450A
The mode that material PA1335, for another example CN10569447A introduce inorganic crystal whisker improves this problem, but in view of the addition of glass fibre
The intensity and modulus of nylon material can be significantly improved, therefore it typically is the necessary components of nylon material, indispensable.So
And the present inventor has found after further investigation, the nylon material containing glass fibre is since there are many on surface
Trichobothrium, these trichobothriums can seriously affect its high temperature resistant plating performance, be cannot achieve at all in 170~190 DEG C of this higher temperatures
Under be electroplated.The present inventor also found after further investigation, use this kind of specific nylon resin of PA6T
Under the premise of, when all potassium titanate crystal whisker being used to substitute in glass fibre, it is equipped with containing kaolinic mineral and optionally resistance to
High-temperature antioxidant, and the weight ratio of PA6T, potassium titanate crystal whisker and mineral is controlled in 100:(0.1~30): when (20~50), institute
Nylon material heat distortion temperature with higher and high temperature resistant plating performance, be fully able to 170~190 DEG C of receiving this
Higher electroplating temperature.Based on this, the present invention is completed.
Specifically, the present invention provides a kind of high temperature resistants, and nylon material is electroplated, wherein nylon material is electroplated in the high temperature resistant
It is made of PA6T, potassium titanate crystal whisker, mineral and optional high temperature resistant antioxidant, kaolin is contained in the mineral, it is described
The weight ratio of PA6T, potassium titanate crystal whisker and mineral are 100:(0.1~30): (20~50).
Further, the weight ratio of the PA6T, potassium titanate crystal whisker, mineral and high temperature resistant antioxidant be 100:(10~
15): (30~40): (0~5).
Further, the PA6T is at least one of PA6T/6, PA6T/66 and PA6T/6I.
Further, the PA6T be PA6T/6 and the mixture of PA6T/66 or be PA6T/66 and PA6T/6I it is mixed
Close object.
Further, in the mixture of the PA6T/6 and PA6T/66 PA6T/66 and PA6T/6 weight ratio be 9:1~
6:4。
Further, the weight ratio of PA6T/66 and PA6T/6I is 9:1 in the mixture of the PA6T/66 and PA6T/6I
~6:4.
Further, the potassium titanate crystal whisker is crystal whisker of hexa potassium titanate.
Further, the diameter of the potassium titanate crystal whisker is 0.2~0.6 μm, and length is 3~20 μm.
Further, kaolinic content is not less than 30wt% in the mineral.
Further, the mineral are the mixture of kaolin or kaolin and wollastonite.
Further, the kaolin is calcined kaolin.
Further, the calcination temperature of the calcined kaolin is 500~700 DEG C, and partial size is 2000~5000 mesh.
Further, the high temperature resistant antioxidant is selected from least one of H161,1098, S9228 and HP-136.
The present invention also provides the preparation methods of high temperature resistant plating nylon material, and this method includes mixing each component
Uniformly.
The present invention also provides a kind of preparation methods that nylon material is electroplated, wherein this method includes by above-mentioned high temperature resistant
The profile of plating nylon material is electroplated.
Further, the temperature of the plating is 170~190 DEG C.
The present invention also provides plating nylon materials prepared by the above method.
In addition, the application the present invention also provides the plating nylon material as sanitaryware.
Nylon material provided by the invention not only heat distortion temperature and notch impact strength with higher, but also can
The problem of big nylon water absorption rate, hardly possible plating is solved perfectly, also has good electroplating effect, electricity under 170~190 DEG C of this high temperature
The rear surface of plating is relatively smooth, and product quality is high, to widen electroplating plastic in the application of hot environment.
Specific embodiment
The present invention is described more fully below.
In the present invention, the high temperature resistant plating nylon material is by PA6T, potassium titanate crystal whisker, mineral composition, Huo Zheyou
PA6T, potassium titanate crystal whisker, mineral and high temperature resistant antioxidant composition.Wherein, the weight of the PA6T, potassium titanate crystal whisker and mineral
Than for 100:(0.1~30): (20~50), preferably 100:(0.5~25): (25~45), more preferably 100:(5~20):
(25~40), most preferably 100:(10~15): (30~40).And the weight ratio of the PA6T and high temperature resistant antioxidant can be
100:(0~5), preferably 100:(0.01~4), more preferably 100:(0.05~3) and, most preferably 100:(0.1~1).
In the present invention, the PA6T can be at least one of for PA6T/6, PA6T/66 and PA6T/6I, preferably
The mixture of PA6T/6 and PA6T/66 or mixture for PA6T/66 and PA6T/6I, corresponding nylon material has at this time
More excellent high temperature resistant plating performance.When the PA6T is the mixture of PA6T/6 and PA6T/66, PA6T/66 and PA6T/
6 weight ratio is preferably 9:1~6:4, more preferably 8:2~6:4, most preferably 7:3.When the PA6T be PA6T/66 and
When the mixture of PA6T/6I, the weight ratio of PA6T/66 and PA6T/6I are preferably 9:1~6:4, more preferably 8:2~6:4, most
Preferably 7:3.Wherein, the relative viscosity of PA6T/6, PA6T/66 and PA6T/6I these types nylon resin be both preferably 2.0~
2.4.In the present invention, the test temperature of the relative viscosity is 25 ± 0.1 DEG C, and reference medium is the sulfuric acid of 96 ± 0.15wt%
Aqueous solution.
In the present invention, the potassium titanate crystal whisker is preferably crystal whisker of hexa potassium titanate.In addition, the diameter of the potassium titanate crystal whisker
Preferably 0.2~0.6 μm, length is preferably 3~20 μm.
In the present invention, contain kaolin in the mineral, preferably kaolinic content is not less than 30wt%, for example, can
Think 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%,
80wt%, 85wt%, 90wt%, 95wt%, 100wt%.A preferred embodiment of the invention, the mineral are height
The mixture of ridge soil or kaolin and wollastonite.When the mineral are the mixture of kaolin and wollastonite, wherein kaolinite
The content of soil is not less than 30wt%, such as can be the above percentage composition, and therefore not to repeat here.In addition, the kaolin is preferred
For calcined kaolin, corresponding nylon material has higher heat distortion temperature and superior high temperature resistant plating resistance at this time
Energy.The calcination temperature of the calcined kaolin can be 500~700 DEG C, and partial size can be 2000~5000 mesh.In the present invention
In, the wollastonite can be unmodified wollastonite, or the wollastonite after being modified by existing method.
The specific example of the high temperature resistant antioxidant includes but is not limited to: in H161,1098, S9228 and HP-136 extremely
Few one kind.
In addition, the high temperature resistant plating nylon material can be pellet and existing various profiles.
The preparation method of the high temperature resistant plating nylon material provided by the invention includes being uniformly mixed each component.Its
In, the mixing can be mixed with hand operated mixing, can also be carried out in existing various mixing apparatus.The mixed condition with
So that above several components form uniform system.In the mixed process, above several components can be with random order
Mixing mixes for example, above several components can be added in mixing vessel one by one in any order, can also will be with
Any in upper several components two or more add other components after mixing and continuess to mix uniformly.According to the present invention one
Kind specific embodiment, described be blended in the double screw extruder with bilateral feed system carries out, and in mixed process, first will
PA6T and optional high temperature resistant antioxidant are added from the main spout of double screw extruder, and by potassium titanate crystal whisker and mineral from
Bilateral spout is added, these raw materials are granulated through melting extrusion up to the nylon material.Wherein, the twin-screw goes out the length of machine
Diameter ratio can be (36~48): 1, extrusion temperature can be 280~320 DEG C, and screw speed can be 260~400r/min, feed
Expect that revolving speed can be 15~30r/min.In addition, the preparation method of high temperature resistant plating nylon material provided by the invention can also wrap
Include the step of pellet is molded into shape product (such as plate, column material, profile shapes etc.).
The preparation method of plating nylon material provided by the invention includes carrying out the profile of high temperature resistant plating nylon material
Plating.Wherein, the plating can use the electroplating technology of ABS, PC/ABS, and electroplate liquid used can be with prior art phase
Together.In addition, the electroplating temperature can be 170~190 DEG C.
In addition, the application the present invention also provides the plating nylon material as sanitaryware.
The embodiment of the present invention is described below in detail, the examples of the embodiments are intended to be used to explain the present invention, and cannot
It is interpreted as limitation of the present invention.In the examples where no specific technique or condition is specified, described according to the literature in the art
Technology or conditions or carried out according to product description.Reagents or instruments used without specified manufacturer is that can lead to
Cross the conventional products of commercially available acquisition.
In following embodiment and comparative example, the relative viscosity that the relative viscosity of PA6T/6 is 2.0, PA6T/66 is 2.4,
The relative viscosity of PA6T/6I is 2.2.
Embodiment 1
PA6T (PA6T/66 and PA6T/6 according to weight ratio 7:3 match the mixture to be formed) and H161 is squeezed from twin-screw
The main spout of machine is added out, and by potassium titanate crystal whisker (diameter is 0.2~0.6 μm and length is 3~20 μm) and calcines kaolinite
Native (calcination temperature is 500 DEG C and partial size is 2000~5000 mesh) is added from bilateral spout, sets double screw extruder temperature
280~320 DEG C, 260~400r/min of screw speed, 15~30r/min of feeding revolving speed, the above raw material is through melting extrusion, water cooling
Tie rod pelletizing can obtain nylon material, wherein the dosage of each component is as shown in table 1.
Embodiment 2
By PA6T (PA6T/66 and PA6T/6I according to weight ratio 7:3 match the mixture to be formed) and S9228 from twin-screw
The main spout of extruder is added, and potassium titanate crystal whisker (diameter is 0.2~0.6 μm and length is 3~20 μm) and calcining is high
Ridge soil (calcination temperature is 700 DEG C and partial size is 2000~5000 mesh) is added from bilateral spout, sets double screw extruder temperature
280~320 DEG C, 260~400r/min of screw speed, 15~30r/min of feeding revolving speed are spent, the above raw material is through melting extrusion, water
Cold drawn bar pelletizing can obtain nylon material, wherein the dosage of each component is as shown in table 1.
Embodiment 3
PA6T (PA6T/66 and PA6T/6 according to weight ratio 6:4 match the mixture to be formed) and 1098 is squeezed from twin-screw
The main spout of machine is added out, and by potassium titanate crystal whisker (diameter is 0.2~0.6 μm and length is 3~20 μm) and calcines kaolinite
Native (calcination temperature is 600 DEG C and partial size is 2000~5000 mesh) is added from bilateral spout, sets double screw extruder temperature
280~320 DEG C, 260~400r/min of screw speed, 15~30r/min of feeding revolving speed, the above raw material is through melting extrusion, water cooling
Tie rod pelletizing can obtain nylon material, wherein the dosage of each component is as shown in table 1.
Embodiment 4
Nylon material is prepared according to the method for embodiment 1, unlike, all PA6T/66 of PA6T obtain nylon material
Material, wherein the dosage of each component is as shown in table 1.
Embodiment 5
Nylon material is prepared according to the method for embodiment 1, unlike, by calcined kaolin using the mixed of identical weight part
Mineral (kaolin and unmodified wollastonite are according to mixture obtained by mass ratio 1:1) substitution is closed, obtains nylon material, wherein each
The dosage of component is as shown in table 1.
Embodiment 6
Nylon material is prepared according to the method for embodiment 5, unlike, it is added without high temperature resistant antioxidant H161, obtains Buddhist nun
Imperial material, wherein the dosage of each component is as shown in table 1.
Comparative example 1
Nylon material is prepared according to the method for embodiment 6, unlike, the dosage of each component is not in the scope of the present invention
It is interior, obtain reference nylon material, wherein the dosage of each component is as shown in table 1.
Comparative example 2
Nylon material is prepared according to the method for embodiment 6, unlike, potassium titanate crystal whisker is used to the glass of identical weight part
Glass fiber substitution, obtains reference nylon material, wherein the dosage of each component is as shown in table 1.
Comparative example 3
Nylon material is prepared according to the method for embodiment 6, unlike, nylon PA6T is substituted with nylon PA6, obtains reference
Nylon material, wherein the dosage of each component is as shown in table 1.
Comparative example 4
Nylon material is prepared according to the method for embodiment 6, unlike, it will be by kaolin and unmodified wollastonite according to matter
It measures and is substituted than mixed mineral obtained by 1:1 using the unmodified wollastonite of identical weight part, obtain reference nylon material, wherein each
The dosage of component is as shown in table 1.
Table 1 (dosage of each component, in parts by weight)
| Project | PA6T | Potassium titanate crystal whisker | Mineral | High temperature resistant antioxidant |
| Embodiment 1 | 100 | 15 | 30 | 0.5 |
| Embodiment 2 | 100 | 10 | 35 | 0.5 |
| Embodiment 3 | 100 | 12 | 40 | 0.5 |
| Embodiment 4 | 100 | 15 | 30 | 0.5 |
| Embodiment 5 | 100 | 15 | 30 | 0.5 |
| Embodiment 6 | 100 | 15 | 30 | - |
| Comparative example 1 | 100 | 40 | 60 | - |
| Comparative example 2 | 100 | Glass fibre 15 | 30 | - |
| Comparative example 3 | 100 | 15 | 30 | - |
| Comparative example 4 | 100 | 15 | Unmodified wollastonite 30 | - |
Test case
Nylon material obtained by Examples 1 to 6 and 1~4 gained reference nylon material of comparative example are molded into standard respectively
Batten simultaneously carries out simply supported beam notch impact strength and heat distortion temperature test (1.8MPa) in accordance with the following methods, while by the above Buddhist nun
Imperial material and reference nylon material are molded into the plastic plate with a thickness of 3mm, later on the surface of these plastic plates at 180 DEG C
It is lower to use identical electroplating technology successively electric plated with copper, three layers of nickel, chromium coating, totally 5.5 μm, plating nylon material is obtained, later
Apparent mass and binding force of cladding material to coating are tested in accordance with the following methods:
(1) notch impact strength: carrying out according to method disclosed in ISO179-1, and acquired results are shown in Table 2；
(2) heat distortion temperature: carrying out according to method disclosed in ISO 75, and acquired results are shown in Table 2；
(3) apparent mass: using the apparent mass after visually observing nylon material before plating, acquired results are shown in Table 2；
(4) binding force of cladding material: the method with reference to disclosed in GB/T 23447 successively presses plating nylon material test sample such as
Lower step is handled: it is dried 15 minutes at being dried 30 minutes, 15 DEG C at being dried 15 minutes, -30 DEG C at being dried 30 minutes, 15 DEG C at 70 DEG C,
Be repeated in above step, observe sample surfaces after circulation 5 times, sample surfaces without the hot spot being visually observed, crackle, rise
It steeps, peel off, fading, deforming then to be qualified, acquired results are shown in Table 2.
Table 2
From the results shown in Table 2, nylon material provided by the invention passes through the PA6T of special ratios, potassium titanate is brilliant
Palpus, mineral and optional high temperature resistant antioxidant are used cooperatively, the not only thermal deformation with higher of thus obtained nylon material
Temperature and notch impact strength, but also the problem of nylon difficulty is electroplated can be solved perfectly, with very excellent high temperature resistant electricity
It plates performance (can be with resistance to 180 DEG C of high temperature).In addition, the nylon material surface after plating is relatively smooth, binding force is good, product matter
Amount is high, the great prospects for commercial application of the product.It can be seen that from the comparison of embodiment 1 and embodiment 4~5 when PA6T is preferably
When the mixture of the mixture or PA6T/66 of PA6T/6 and PA6T/66 and PA6T/6I or when mineral preferably calcine it is high
When the soil of ridge, it is more advantageous to the raising (reflecting by heat distortion temperature) of gained nylon material high temperature resistant plating performance.From implementation
The comparison of example 1 and embodiment 6 can be seen that when the nylon material preferably also contains high temperature resistant antioxidant, can prevent material
Xanthochromia occurs for material degradation in extrusion process, it is ensured that material physical property.Comparison from embodiment 6 and comparative example 1~4 can
Out, the PA6T of special ratios, potassium titanate crystal whisker, mineral and high temperature resistant antioxidant with the use of to nylon material heat-resisting quantity
Can raising play the role of it is vital (in comparative example 1 proportion of each component not within the scope of the present invention, notched-impact resistance
Can be poor, product destruction easily occurs for electroplating process, is not able to satisfy customer requirement, and coating physical property is unqualified；Comparative example 2 uses glass
Fiber is also easy to produce floating fibre, will cause poor plating and plating binding force decline；Comparative example 3 substitutes nylon PA6T using nylon PA6,
Heat distortion temperature is too low can not to carry out high temperature plating；Mineral used in comparative example 4 are different from the present invention, and coating combines after plating
Power test failure).
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art are not departing from the principle of the present invention and objective
In the case where can make changes, modifications, alterations, and variations to the above described embodiments within the scope of the invention.
Claims (10)
1. nylon material is electroplated in a kind of high temperature resistant, which is characterized in that the high temperature resistant plating nylon material is brilliant by PA6T, potassium titanate
Must, mineral and optional high temperature resistant antioxidant composition, contain kaolin in the mineral, the PA6T, potassium titanate crystal whisker and
The weight ratio of mineral is 100:(0.1~30): (20~50).
2. nylon material is electroplated in high temperature resistant according to claim 1, which is characterized in that the PA6T, potassium titanate crystal whisker, mine
The weight ratio of object and high temperature resistant antioxidant is 100:(10~15): (30~40): (0~5).
3. nylon material is electroplated in high temperature resistant according to claim 1 or 2, which is characterized in that the PA6T be PA6T/6,
At least one of PA6T/66 and PA6T/6I；Preferably, the PA6T is PA6T/6 and the mixture of PA6T/66 or is
The mixture of PA6T/66 and PA6T/6I；Preferably, PA6T/66 and PA6T/6 in the mixture of the PA6T/6 and PA6T/66
Weight ratio be 9:1~6:4；Preferably, in the mixture of the PA6T/66 and PA6T/6I PA6T/66 and PA6T/6I weight
Amount is than being 9:1~6:4.
4. nylon material is electroplated in high temperature resistant according to claim 1 or 2, which is characterized in that the potassium titanate crystal whisker is six
Potassium titanate crystal whisker；The diameter of the potassium titanate crystal whisker is 0.2~0.6 μm, and length is 3~20 μm.
5. nylon material is electroplated in high temperature resistant according to claim 1 or 2, which is characterized in that kaolinic in the mineral
Content is not less than 30wt%；Preferably, the mineral are the mixture of kaolin or kaolin and wollastonite；Preferably, institute
Stating kaolin is calcined kaolin；Preferably, the calcination temperature of the calcined kaolin be 500~700 DEG C, partial size be 2000~
5000 mesh.
6. nylon material is electroplated in high temperature resistant according to claim 1 or 2, which is characterized in that the high temperature resistant antioxidant choosing
From at least one of H161,1098, S9228 and HP-136.
7. the preparation method of the plating nylon material of high temperature resistant described in any one of claim 1~6, which is characterized in that should
Method includes being uniformly mixed each component.
8. a kind of preparation method that nylon material is electroplated, which is characterized in that this method includes will be any one in claim 1~7
The profile of high temperature resistant plating nylon material described in is electroplated；Preferably, the temperature of the plating is 170~190 DEG C.
9. nylon material is electroplated as made from method according to any one of claims 8.
10. application of the plating nylon material as claimed in claim 9 as sanitaryware.
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| CN116218205A (en) * | 2023-03-03 | 2023-06-06 | 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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