CN105017762B - Low-shrinkage low water absorption nylon 6 composite material and preparation and application thereof - Google Patents
Low-shrinkage low water absorption nylon 6 composite material and preparation and application thereof Download PDFInfo
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- CN105017762B CN105017762B CN201510500381.4A CN201510500381A CN105017762B CN 105017762 B CN105017762 B CN 105017762B CN 201510500381 A CN201510500381 A CN 201510500381A CN 105017762 B CN105017762 B CN 105017762B
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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
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a low-shrinkage low water absorption nylon 6 composite material and preparation and application thereof. The nylon 6 composite material is prepared from 14-40% of nylon 6, 20-30% of talcum powder masterbatch taking PA12 as a matrix, 25-35% of talcum powder, 5-15% of polyphenyl ether, 2-4% of compatilizer and 2-8% of flexibilizer. The preparation method of the low-shrinkage low water absorption nylon 6 composite material comprises the steps that talcum powder masterbatch is prepared; the prepared talcum powder masterbatch, the nylon 6, the polyphenyl ether, the talcum powder, the compatilizer and the flexibilizer are mixed together, and the low-shrinkage low water absorption nylon 6 composite material is prepared. According to the low-shrinkage low water absorption nylon 6 composite material and the preparation and application thereof, part talcum powder filling adopts a masterbatch form to add, dust pollution is reduced, and high filling of high mesh talcum powder in the nylon 6 is achieved; meanwhile, the polyphenyl ether is added, and the low shrinkage and the low water absorption of the nylon 6 are further reduced. According to the low-shrinkage low water absorption nylon 6 composite material and the preparation and application thereof, the technique is simple, the processing performance is good, and the prepared nylon sis has excellent low shrinkage and excellent low water absorption.
Description
Technical field
The invention belongs to modified plastics field, and in particular to a kind of low-shrinkage low water absorption nylon 6 composite material and its
Preparation and application.
Background technology
Nylon 6 (PA6) is translucent or opaque milky hemicrystalline resin.Have within the scope of wider temperature
Higher rigidity and toughness, its wearability, creep resistant and oil resistivity are good, and in many fields, tool is widely used.But, by
In the presence of the hydrophilic amide group (- NHCO-) of high density so that PA6 has very strong water absorption rate, at 23 DEG C, relative humidity 50%
Under the conditions of, its equilibrium water absorption is about 2.5%；When relative humidity is 100%, its equilibrium water absorption is up to 10%.PA6 absorbs water
Afterwards, the performance such as its mechanical performance, electric property there occurs significant change, reduce the safety in utilization and service life of product.
On the other hand, as crystalline material, PA6 equally exists the big shortcoming of shrinkage factor, and the shrinkage factor of its pure resin is 1.0～
1.5%, it is had a strong impact in the application for needing high-dimensional stability field.In order to overcome the shortcoming of the above, it has been proposed that various
Solution, and applied for Patents.
The B of Chinese patent document CN 101787204 discloses a kind of low water absorption polyamide composite and preparation method thereof.
It is placed in high-speed mixer by parts by weight polyamide 10～90%, layered silicate clay 3～10% and less than 2% additive
It is added in double screw extruder after premix 20min, by conveying, melting, shear extrusion cooling granulation, obtains polyamide/layer
Shape silicate master batch, then with styrene resin 10～60%, compatilizer 2～10% and short glass fiber 5～20% by double
Extruding pelletization in screw extruder, is obtained the daiamid composition of low water absorption.The A of Chinese patent document CN 102863786 is public
A kind of low water absorption reinforced polyamide compound of cloth and preparation method thereof, the reinforced polyamide compound based on polyamide,
Linear phenolic resin is polar resin, and glass fibre is reinforcement, add lubricant, antioxidant, obtain a kind of water absorption rate it is low,
The low water absorption reinforced polyamide compound of good stability of the dimension.A kind of high-dimensional stabilities of the B of Chinese patent CN 101857723
Daiamid composition and its preparation, using styrene base resin and polyamide alloy, and the complexing of inorganic metal compound
Effect reduces polyamide water absorption rate, to reach the purpose for realizing polyamide dimensional stability.
Although inventing above in terms of reducing polyamide water absorption rate and improving its dimensional stability there is provided effective scheme,
But still come with some shortcomings：(1) membership that adds of orientation filling (particularly glass) material causes the difference of material transverse and longitudinal contraction, draws
Play warpage；(2) addition of styrene resin brings being decreased obviously for polyamide heat distortion temperature；(3) content is filled low, no
Beneficial to the acquisition of low-shrinkage material.
The content of the invention
To solve the shortcoming and defect part of prior art, the primary and foremost purpose of the present invention is that a kind of low-shrinkage of offer is low
Water absorption rate nylon 6 composite material.
Another object of the present invention is to provide the preparation method of above-mentioned low-shrinkage low water absorption nylon 6 composite material.
It is of the invention first to prepare high-load talcum powder master batch based on PA12, then by PA6, talcum powder master batch, talcum powder, polyphenylene oxide
(PPO) and processing aid mixing, then by double screw extruder extruding pelletization, low-shrinkage low water absorption PA6 is obtained and is combined
Material.
It is yet a further object of the present invention to provide the application of above-mentioned low-shrinkage low water absorption nylon 6 composite material.
For achieving the above object, the present invention is adopted the following technical scheme that：
A kind of low-shrinkage low water absorption nylon 6 composite material, the composite is by PA6 (nylon 6), with PA12 (poly- ten
Two lactams, also known as nylon 12) based on talcum powder master batch, talcum powder, PPO (polyphenylene oxide), compatilizer and toughener composition,
With weight percent calculating, each component consumption is as follows：
In above-mentioned low-shrinkage low water absorption nylon 6 composite material composition, PA6 (nylon 6), the talcum based on PA12
The percentage by weight sum of powder master batch, talcum powder, PPO (polyphenylene oxide), compatilizer and toughener is 100%.
Preferably, the talcum powder master batch based on PA12 are grouped into by each group of following percentage by weight：
In the above-mentioned talcum powder master batch composition based on PA12, PA12 (nylon 12, also known as nylon 12), talcum
The percentage by weight sum of powder, coupling agent, antioxidant and lubricant is 100%.
In preferred scheme, described coupling agent is silane coupler, such as gamma-aminopropyl-triethoxy-silane.
In preferred scheme, the antioxidant is the compounding antioxidant system of hindered phenol, phosphite ester and mantoquita composition.
In preferred scheme, the lubricant is pentaerythritol stearate.
In preferred scheme, the talcum powder mesh number is 5000～15000 mesh.Mesh number may drop less than 5000 mesh
The adhesion of low talcum powder and resin, mesh number is more than 15000 mesh, it is difficult to prepare talcum powder master batch.
In preferred scheme, it in the melt index of 190 DEG C, 1.0Kg is 5～30g/10min's that the PA12 is
PA12。
Preferably, the relative viscosity of the nylon 6 is 2.0～3.4.Molecular weight mistake of the relative viscosity less than 2.0 nylon 6
Low, material mechanical performance is poor, and relative viscosity is higher than the poor fluidity of 3.4 nylon 6, brings processing difficulties.
Preferably, the intrinsic viscosity of the polyphenylene oxide is that 0.35～0.65dL/g (refers to be surveyed under the conditions of 25 DEG C of chloroforms
The intrinsic viscosity that examination is obtained).
Preferably, the compatilizer is PPE-g-MAH (polyphenylene oxide grafted maleic anhydride), (styrene is embedding for SEBS-g-MAH
Section copolymer grafted maleic anhydride) and PS-g-MAH (polystyrene graft maleic anhydride) at least one.
Preferably, the toughener is that SBS (SBS), SEBS are (a kind of with poly-
Styrene is end segment, with the polybutadiene ethylene-butene copolymer that obtains of hydrogenation as intermediate elastic block linear three embedding common
Polymers), in POE-g-MAH (polyethylene glycol oxide grafted maleic anhydride) and EPDM-g-MAH (ethylene-propylene-diene monomer grafted maleic anhydride)
At least one.
Preferably, the talcum powder mesh number is 5000～15000 mesh.
A kind of preparation method for preparing above-mentioned low-shrinkage low water absorption nylon 6 composite material, comprises the steps：
(1) talcum powder master batch based on PA12 are prepared；
(2) by weight percentage, talcum powder master batch by 14～40%PA6,20～30% based on PA12,25～
The mixing of 35% talcum powder, 5～15%PPO, 2～4% compatilizers and 2～8% toughener, is then extruded by double screw extruder
Granulation, is obtained low-shrinkage low water absorption nylon 6 composite material.
Preferably, step (2) the middle incorporation time is 3～5min, and the rotating speed of double screw extruder is 200～500r/
Min, temperature is 200～250 DEG C.
Preferably, the step (1) comprises the following steps：
A () by weight percentage, prepares following material：11～17%PA12,80～85% talcum powder, 0.8～1.6%
Coupling agent, 0.6～1.2% antioxidant and 0.6～1.2% lubricant；
B PA12, coupling agent, antioxidant, lubricant and half talcum powder that () weighs step (a) is added to banbury
Middle banburying is agglomerating, 160～200 DEG C of control banburying room temperature, 40～100r/min of screw speed, 5～15min of mixing time；Institute
Plus after raw material banburying is agglomerating, then remaining talcum powder is added in banbury, then 5～15min of banburying, as standby material；
C () is transported to the standby material of step (b) in single screw extrusion machine hopper, by single screw extrusion machine melting mixing
Extrusion, pelletizing obtains the talcum powder master batch based on PA12.
It is highly preferred that the rotating speed of single screw extrusion machine described in step (c) be 200～400r/min, temperature be 180～
220℃。
The low-shrinkage low water absorption nylon 6 composite material that the present invention is provided can be used to prepare to dimensional stability, machinery
The high precise part of performance and electrical performance demands, is applied to instrument and meter and the field such as electric.
Compared with prior art, the present invention has advantages below and beneficial effect：
(1) PPO is amorphism material, and water absorption rate is relatively low, and its addition is conducive to improving the dimensional stability of PA6, reduces
The water absorption rate of PA6.On the other hand, PPO excellent electric property and heat resistance can be carried while PA6 electric properties are kept
The heat resistance of high material；
(2) high mesh number talcum powder is adopted for packing material, it is possible to increase with resin boundary surface adhesion, it is to avoid stress concentration point
Occur, improve the mechanical performance of material；
(3) by carrying out female granulated processed to part talcum powder, dust pollution is reduced, when improving talcum powder and mixed with resin
The uniformity, the stability of blanking when improving extrusion processing realizes the filling of high talcum powder content；
(4) using the PA12 of low melting point high fluidity, the talcum powder master batch of high filler loading capacity, the opposing party can on the one hand be prepared
Face to can ensure that and have good compatibility with PA6, meanwhile, the low water absorbable of PA12 can also reduce the water absorption rate of PA6.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this,
Described embodiment is only a part of embodiment of the invention, rather than the embodiment of whole.Based on the enforcement in the present invention
Example, all other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made is belonged to
The scope of protection of the invention.
The embodiment of the present invention and comparative example according to standard require be molded into test with standard batten and tested.Its
In, shrinkage factor is marked according to ISO62 standards, Izod notched impact strength according to ISO294-4 standards, water absorption rate according to ISO180
Standard, heat distortion temperature is tested according to ISO75-2 standards.
The raw material used in the embodiment of the present invention and comparative example is as follows：
Nylon 6：PA6M2800 (relative viscosity 2.8), newly can Mei Da polyamide fibres limited company；
Polyphenylene oxide：LXR040 (intrinsic viscosity 0.40dL/g (25 DEG C of chloroforms)), Lanxing Chemical New Material Co., Ltd.；
Nylon 12：PA12 3014U (190 DEG C, the melt index of 1.0Kg is 9g/10min), Ube (UBE) company；
Talcum powder：HTP05L (11000 mesh), HTP1L (8100 mesh), HM4 (2200 mesh) Italy Yi meter Fa ratios
(Imifabi) company；
Glass ECS3014B：10 μm of filament diameter, Chongqing Polycomp International Co., Ltd；
Compatilizer：CX-1 (PPE-g-MAH, percent grafting 1.0%), Japan goes out light (Idemitsu) company；Toughener：
FUSN493D (POE-g-MAH), Dupont (DuPont) company；
Antioxidant：Hindered phenol 1098 (N, N'- pair-(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine),
Phosphite ester 168 (three [2.4- di-tert-butyl-phenyls] phosphite esters), Switzerland vapour bar (Ciba) company；Mantoquita H3336, German cloth
Lv Geman (Bruggolite) company；
Coupling agent：KBM-903 (gamma-aminopropyl-triethoxy-silane), Japanese SHIN-ETSU HANTOTAI (Shinetsu) company；
Lubricant：PETS (pentaerythritol stearate), dragon sand (Lonza) company of the U.S..
As shown in Table 1 and Table 2, wherein table 1 is the composition of talcum powder master batch for embodiment 1～5 and performance, and table 2 is lower shrinkage
The composition of rate low water absorption PA6 composites, table 3 for low-shrinkage low water absorption PA6 composites performance, 5 points of table 4, table
Not Wei comparative example 1～6 composition and performance, table 6 is the processability of embodiment 1～5 and comparative example 2～3.
Embodiment 1
A kind of preparation method of low-shrinkage low water absorption nylon 6 composite material, comprises the steps：
(1) talcum powder master batch based on PA12 are prepared：Prepare former by the composition and proportioning of talcum powder master batch 1 in table 1
Material, is then added to adding pressure type turnover internal mixer by the PA12 for weighing, coupling agent, antioxidant, lubricant and half talcum powder
Middle banburying is agglomerating, 160 DEG C of control banburying room temperature, screw speed 40r/min, mixing time 15min；Added raw material banburying is agglomerating
Afterwards, then remaining talcum powder it is added in banbury, then banburying 15min, as standby material；
Standby material Jing conveyer belts are sent in single screw extrusion machine hopper, are extruded by single screw extrusion machine melting mixing,
The talcum powder master batch based on PA12 are made in the air-cooled flour milling pelletizings of Jing；The rotating speed of wherein described single screw extrusion machine is
200r/min, each area's temperature is 180～220 DEG C；
(2) weigh raw material according to the component of embodiment 1 in table 2, then by PA6, the talcum powder master batch based on PA12,
Talcum powder, PPO, compatilizer and toughener are added to mixer mixing 5min, then by double screw extruder extruding pelletization, system
Low-shrinkage low water absorption nylon 6 composite material is obtained, the wherein rotating speed of double screw extruder is 200r/min, and each area's temperature is
200～250 DEG C.Obtained low-shrinkage low water absorption nylon 6 composite material performance is shown in Table 3.
Embodiment 2
A kind of preparation method of low-shrinkage low water absorption nylon 6 composite material, comprises the steps：
(1) talcum powder master batch based on PA12 are prepared：Prepare former by the composition and proportioning of talcum powder master batch 1 in table 1
Material, is then added to adding pressure type turnover internal mixer by the PA12 for weighing, coupling agent, antioxidant, lubricant and half talcum powder
Middle banburying is agglomerating, 200 DEG C of control banburying room temperature, screw speed 80r/min, mixing time 5min；Added raw material banburying is agglomerating
Afterwards, then remaining talcum powder it is added in banbury, then banburying 5min, as standby material；
Standby material Jing conveyer belts are sent in single screw extrusion machine hopper, are extruded by single screw extrusion machine melting mixing,
The talcum powder master batch based on PA12 are made in the air-cooled flour milling pelletizings of Jing；The rotating speed of wherein described single screw extrusion machine is
400r/min, each area's temperature is 180～220 DEG C；
(2) weigh raw material according to the component of embodiment 1 in table 2, then by PA6, the talcum powder master batch based on PA12,
Talcum powder, PPO, compatilizer and toughener are added to mixer mixing 3min, then by double screw extruder extruding pelletization, system
Low-shrinkage low water absorption nylon 6 composite material is obtained, the wherein rotating speed of double screw extruder is 500r/min, and each area's temperature is
200～250 DEG C.Obtained low-shrinkage low water absorption nylon 6 composite material performance is shown in Table 3.
Embodiment 3
A kind of preparation method of low-shrinkage low water absorption nylon 6 composite material, comprises the steps：
(1) talcum powder master batch based on PA12 are prepared：Prepare former by the composition and proportioning of talcum powder master batch 1 in table 1
Material, is then added to adding pressure type turnover internal mixer by the PA12 for weighing, coupling agent, antioxidant, lubricant and half talcum powder
Middle banburying is agglomerating, 180 DEG C of control banburying room temperature, screw speed 100r/min, mixing time 8min；Added raw material banburying is agglomerating
Afterwards, then remaining talcum powder it is added in banbury, then banburying 8min, as standby material；
Standby material Jing conveyer belts are sent in single screw extrusion machine hopper, are extruded by single screw extrusion machine melting mixing,
The talcum powder master batch based on PA12 are made in the air-cooled flour milling pelletizings of Jing；The rotating speed of wherein described single screw extrusion machine is
300r/min, each area's temperature is 180～220 DEG C；
(2) weigh raw material according to the component of embodiment 1 in table 2, then by PA6, the talcum powder master batch based on PA12,
Talcum powder, PPO, compatilizer and toughener are added to mixer mixing 4min, then by double screw extruder extruding pelletization, system
Low-shrinkage low water absorption nylon 6 composite material is obtained, the wherein rotating speed of double screw extruder is 350r/min, and each area's temperature is
200～250 DEG C.Obtained low-shrinkage low water absorption nylon 6 composite material performance is shown in Table 3.
Embodiment 4～5
Embodiment 4～5 is weighed after raw material respectively by table 1, table 2, prepares low-shrinkage according to the method for embodiment 1 low
Water absorption rate nylon 6 composite material.Obtained low-shrinkage low water absorption nylon 6 composite material performance is shown in Table 3.
Comparative example 1～6
Comparative example 1～6 is weighed after raw material respectively by the amount of raw material in table 4, is prepared by the conventional method of existing nylon 6
Obtain modification of nylon sample.The properties of sample of modification of nylon 6 of gained is shown in Table 5.
The composition of the talcum powder master batch of table 1
The composition of the low-shrinkage low water absorption nylon 6 of table 2
| Component | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| PA6 M2800 | 39 | 18 | 24 | 40 | 14 |
| PPO LXR040 | 5 | 15 | 10 | 5 | 15 |
| Talcum powder master batch 1 | 25 | 30 | --- | --- | --- |
| Talcum powder master batch 2 | --- | --- | 20 | 20 | --- |
| Talcum powder master batch 3 | --- | --- | --- | --- | 30 |
| HTP05L | 21 | 31 | --- | --- | --- |
| HTP1L | --- | --- | 35 | 25 | 35 |
| CX-1 | 2 | 2 | 3 | 4 | 4 |
| 493D | 8 | 4 | 8 | 6 | 2 |
The performance of the low-shrinkage low water absorption nylon 6 of table 3
The composition of contrast test PA6 of table 4
| Component | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 |
| PA6 M2800 | 100 | 49 | 24 | 31 | 12 | 37.5 |
| PPO LXR040 | --- | --- | 10 | --- | 15 | --- |
| Talcum powder master batch 1 | --- | --- | --- | 30 | --- | --- |
| Talcum powder master batch 4 | --- | --- | --- | --- | 30 | --- |
| PA12 3014U | --- | --- | 3.4 | --- | --- | --- |
| HM4 | --- | -- | --- | --- | 35 | --- |
| HTP05L | --- | 41 | --- | 31 | --- | --- |
| HTP1L | --- | --- | 51 | --- | --- | --- |
| 3014B | --- | --- | --- | --- | --- | 60.5 |
| CX-1 | --- | --- | 3 | 2 | 4 | --- |
| 493D | --- | 8 | 8 | 4 | 2 | --- |
| KBM-903 | --- | 0.7 | 0.2 | --- | --- | 0.7 |
| 1098 | --- | 0.1 | 0.04 | --- | --- | 0.1 |
| 168 | --- | 0.2 | 0.04 | --- | --- | 0.2 |
| H3336 | --- | 0.2 | 0.08 | --- | --- | 0.2 |
| PETS | --- | 0.8 | 0.24 | --- | --- | 0.8 |
The performance of contrast test PA6 of table 5
The processability of the embodiment of table 6 and comparative example
| Test example | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 2 | Comparative example 3 |
| Processability | ○ | ◎ | ○ | ○ | ◎ | ◎ | ● |
Explanation：Zero represents excellent processability；It is general that ◎ represents processability；● represent poor in processability
Contrasted by 5 groups of embodiments and comparative example 1, it is found that the obtained nylon 6 composite material of the present invention is pure with PA6
Resin is compared, and shrinkage factor and water absorption rate significantly decrease.
Processability aspect：Although comparative example 2 only adds 41% talcum powder, because mesh number is higher, processability one is caused
As (occur blanking difficulty situation), embodiment 1 adds the talcum powder of same mesh number and content, due to adopting the inventive method, plus
Work is excellent.The comparison of comparative example 3 and embodiment 3, the masterbatch method that the same explanation present invention is adopted can be obviously improved high mesh number
The processability of material under height filling content.
By comparative example 2 and comparative example 3, it is found that the present invention has three aspects using the method for addition PPO
Benefit：(1) shrinkage factor is reduced；(2) water absorption rate is reduced；(3) heat distortion temperature is improved.And in the past styrene resin is added in
While bringing above two benefits, being decreased obviously for PA6 composite thermal deformations is frequently can lead to.
By comparative example 5 and comparative example 5, it is found that can reduce PA6 composites using high mesh number talcum powder
Shrinkage factor, water absorption rate, while improve PA6 composites impact strength and heat distortion temperature.This is due to high mesh number talcum
With resin-bonded power more preferably, reduction becomes under the possibility of stress concentration point, and same mass fraction powder, and high mesh number is talcous
Particle number is more, can preferably limit the motion of PA6 strands.
By comparative example 5 and comparative example 6, it is found that the high filling (60.5%) of high mesh number prepared by the present invention increases
Strong PA6 composites have lower a shrinkage factor and water absorption rate compared with the composite of 60.5% fiberglass reinforced PA 6, and due to
The addition of PPO, the close composite of fiberglass reinforced PA 6 of heat distortion temperature.Importantly, due to the base of talcum powder transverse and longitudinal orientation
This uniformity, nylon 6 composite material transverse and longitudinal prepared by the present invention shrinks basically identical, and the horizontal stroke of the composite of fiberglass reinforced PA 6
Vertical difference in shrinkage is very big, and warpage is easily caused in actual use.
In sum, the lower shrinkage factor of PA6 composites acquisition and water absorption rate can be made from high mesh number talcum powder, while
Improve the impact strength and heat distortion temperature of material；By the way that part high mesh number talcum powder and PA12 are made into master batch, can reduce
Dust pollution improves processability during high filling content simultaneously；Add PPO resins can reduce PA6 composites shrinkage factor and
While water absorption rate, the heat distortion temperature of material is improved.The present invention can expand the purposes and application of PA6 composites.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention not by above-described embodiment
Limit, other any Spirit Essences without departing from the present invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (9)
1. a kind of low-shrinkage low water absorption nylon 6 composite material, it is characterised in that the composite is by nylon 6, with PA12
The talcum powder master batch of matrix, talcum powder, polyphenylene oxide, compatilizer and toughener are made, and with weight percent calculating, each component consumption is such as
Under：
The talcum powder master batch based on PA12 are made up of each component of following percentage by weight：
The talcum powder mesh number is 5000～15000 mesh.
2. a kind of low-shrinkage low water absorption nylon 6 composite material according to claim 1, it is characterised in that described
Coupling agent is silane coupler.
3. a kind of low-shrinkage low water absorption nylon 6 composite material according to claim 1, it is characterised in that described anti-
Oxygen agent is the compounding antioxidant system of hindered phenol, phosphite ester and mantoquita composition；The lubricant is pentaerythritol stearate.
4. a kind of low-shrinkage low water absorption nylon 6 composite material according to claim 1, it is characterised in that described
PA12 is 5～30g/10min in the melt index of 190 DEG C, 1.0Kg.
5. a kind of low-shrinkage low water absorption nylon 6 composite material according to claim 1, it is characterised in that the Buddhist nun
The relative viscosity of dragon 6 is 2.0～3.4；The intrinsic viscosity of the polyphenylene oxide is 0.35～0.65dL/g.
6. a kind of low-shrinkage low water absorption nylon 6 composite material according to claim 1, it is characterised in that the phase
It is at least one in PPE-g-MAH, SEBS-g-MAH and PS-g-MAH to hold agent；The toughener is SBS, SEBS, POE-g-
At least one in MAH and EPDM-g-MAH.
7. the preparation method of low-shrinkage low water absorption nylon 6 composite material described in any one of claim 1 to 6, its feature exists
In comprising the steps：
(1) talcum powder master batch based on PA12 are prepared；
(2) by weight percentage, talcum powder master batch by 14～40% nylon 6,20～30% based on PA12,25～
35% talcum powder, 5～15% polyphenylene oxide, 2～4% compatilizers and 2～8% toughener mixing, then by double screw extruder
Extruding pelletization, is obtained low-shrinkage low water absorption nylon 6 composite material.
8. preparation method according to claim 7, it is characterised in that the step (1) comprises the following steps：
A () by weight percentage, prepares following material：11～17%PA12,80～85% talcum powder, 0.8～1.6% are coupled
Agent, 0.6～1.2% antioxidant and 0.6～1.2% lubricant；
B PA12, coupling agent, antioxidant, lubricant and half talcum powder that () weighs step (a) is added to close in banbury
The group of being smelt, 160～200 DEG C of control banburying room temperature, 40～100r/min of screw speed, 5～15min of mixing time；Added original
After material banburying is agglomerating, then remaining talcum powder is added in banbury, 5～15min of banburying, as standby material；
C () is transported to the standby material of step (b) in single screw extrusion machine hopper, squeezed by single screw extrusion machine melting mixing
Go out, pelletizing is able to the talcum powder master batch based on PA12.
9. low-shrinkage low water absorption nylon 6 composite material described in any one of claim 1 to 6 is in instrument and meter and electric
Application in field.
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| CN107974074A (en) * | 2016-10-21 | 2018-05-01 | 合肥杰事杰新材料股份有限公司 | 6/ polyphenylene oxide composite material of nylon that a kind of proof stress turns white and preparation method thereof |
| CN106633852A (en) * | 2016-12-02 | 2017-05-10 | 长兴天晟能源科技有限公司 | Master batch capable of improving wet stability of nylon 66 resin |
| CN107641321A (en) * | 2017-09-20 | 2018-01-30 | 优矿塑新材料科技（苏州）有限公司 | A kind of PA66 carriers master batch |
| CN111484734A (en) * | 2019-12-20 | 2020-08-04 | 四川鑫达企业集团有限公司 | Mineral fiber composite reinforced nylon material with low shrinkage rate and water absorption rate and preparation method thereof |
| CN111154257B (en) * | 2020-01-19 | 2022-06-14 | 上海金山锦湖日丽塑料有限公司 | Ultralow-water-absorption PA66/PPO composition and preparation method thereof |
| CN116622227B (en) * | 2023-07-24 | 2023-09-15 | 广东永鑫华新型材料有限公司 | Preparation method of glass fiber reinforced nylon material with low water absorption |
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