CN108192334A - A kind of high-performance, low-warpage nylon dragon material and its preparation method and application - Google Patents
A kind of high-performance, low-warpage nylon dragon material and its preparation method and application Download PDFInfo
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- CN108192334A CN108192334A CN201711448077.5A CN201711448077A CN108192334A CN 108192334 A CN108192334 A CN 108192334A CN 201711448077 A CN201711448077 A CN 201711448077A CN 108192334 A CN108192334 A CN 108192334A
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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
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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
- 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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- Chemical Kinetics & Catalysis (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The invention discloses a kind of high-performance, low-warpage nylon dragon material and its preparation method and application, including following raw material by weight percentage：PA6/66 46~66%；Toughener 1~5%；Flat glass 30~50%；Lubricant and antioxidant 0.1~1%.Compared with prior art, advantage of the invention is that：Raw material is selected by hexamethylene diamine, adipic acid, the PA6/66 that caprolactam copolymerization forms, crystallinity compared to PA6 materials is low, after-contraction is small, it in this way can be to avoid because of the warpage issues that non-uniform after-contraction generates, glass uses flat glass, compared to conventional glass, flat glass has superior mechanical property, high-specific surface area can increase the interface binding power of glass and nylon resin, so as to increase the mechanical property of composite material, compare the cylindrical cross-section of conventional glass in the flat and thin section of flat glass, the problem of warpage caused by being orientated in nylon resin due to glass can be effectively reduced, so as to obtain high-performance, the nylon material of low warpage.
Description
Technical field
The present invention relates to by the design to composite-material formula, selection can improve composite property, reduce again
The glass and resin of condensation material warpage prepare the nylon composite materials of high-performance, low warpage, meet it in very thin computer and property
Energy phone housing and the application in the fields such as frame, sports equipment, electric appliance and electronic component, locomotive part.
Background technology
Nylon material has excellent mechanical property, chemical resistance, high-low temperature resistant, mechanical performance, processability, electrical isolation etc.
Performance is used widely in industries such as household electrical appliances, automobile, electronic apparatus, building, machinery instruments, but nylon also has water suction
Property big, water suction after the yielding, shortcomings such as acid resistance is poor, dry state notch impact strength is low, limit the use of nylon.In order to overcome
Disadvantages mentioned above meets requirement of the nylon in different parts, varying environment, and nylon is carried out using a variety of methods at present
It is modified, for promoting the performances such as the impact property of nylon material, heat distortion temperature, dimensional stability.
The modification carried out at present to nylon material mainly includes：It is toughening modifying, flame-retardant modified, alloy modification, mineral-filled
The modification modes such as modified, fiber-reinforced modified, wherein most widely used is the material of fiber-reinforced modified nylon, with fiber pair
Nylon material is modified the mechanical property that can improve nylon material, heat distortion temperature, heatproof air aging performance, dimensionally stable
The performances such as property.Fiber used in fiber reinforced nylon material mainly includes：Glass fibre, aramid fiber, carbon fiber, basalt are fine
Dimension etc., glass fibre is due to the advantages that its is cheap, mechanical strength is high, chemical-resistance is excellent, glass modified nylon materials
It is extensive in sector applications such as automobile, electronic apparatus.
Glass can play humidification, be tied mainly using itself excellent mechanical property and with the interface of nylon resin
With joint efforts, stress main body is played when glass fiber reinforced nylon material is acted on by external force；But nylon is a kind of partially crystallizable
Material, conventional glass are the fibers for having certain draw ratio cylinder, and orientation of the glass in nylon material influences nylon
The defects of contraction of material generates warpage so as to cause product, this affects glass fiber reinforced materials in ultra-thin computer, phone housing
Wait the application in products.
Invention content
The present invention provides a kind of high-performance, low-warpage nylon dragon material and preparation method thereof, with conventional glass fiber enhanced nylon
Material is compared, and increases the mechanical property of composite material, reduces the warpage properties of composite material.Nylon material is realized to power
Learn the application in performance and the more demanding computer of warpage performance, phone housing.Subtracted using a kind of copolymer nylon raw material PA6/66
The after-contraction of small nylon material compared to conventional cylindrical glass, increases glass and Buddhist nun using flat glass large specific surface area
Imperial resin boundary surface binding force increases the mechanical property of composite material, can be effective using the flat and flat section feature of flat glass
Warpage caused by solving the difference influenced on differently- oriented directivity and vertical orientated direction on shrinking percentage of the glass in nylon resin is asked
Topic.Realize application of the nylon material in products such as computer, phone housings.
The technical issues of present invention is proposed for solution, the technical solution that uses for：
A kind of high-performance, low-warpage nylon dragon material, including following raw material by weight percentage：
Further,
The material resin is the alloy of PA6/66, is that hexamethylene diamine, adipic acid, caprolactam are copolymerized, wherein, oneself
Diamines and adipic acid accounting are no more than 10%.
The toughener is maleic anhydride stem grafting polyolefin elastomer, is known and can be by multiple business
Source obtains.
The flat glass refers to fibre section non-cylindrical and flaky process is presented have large specific surface area, original
The characteristics of silk is flat and thin.
The present invention provides a kind of high-performance, the preparation method and applications of low-warpage nylon dragon material, includes the following steps：
(1) it will be weighed after raw material drying by formula rate；
(2) PA6/66, toughener, lubricant, antioxidant are uniformly mixed by homogenizer, it is spare；
(3) above-mentioned time mixed raw material is added in by the main spout of double screw extruder, by flat glass from twin-screw
The side spout of extruder adds in, and the high performance composite is obtained after the processes such as melting extrusion, granulation, drying process
Material.
Compared with prior art, advantage of the invention is that：Raw material selection is copolymerized by hexamethylene diamine, adipic acid, caprolactam
Into into PA6/66, it is low compared to the crystallinity of PA6 materials, after-contraction is small, in this way can be to avoid because of non-uniform after-contraction
The warpage issues of generation, glass use flat glass, and compared to conventional glass, flat glass has superior mechanical property, high
Specific surface area can increase the interface binding power of glass and nylon resin, so as to increase the mechanical property of composite material, flat glass
The cylindrical cross-section of conventional glass is compared in fine flat and thin section, can be effectively reduced since glass is orientated in nylon resin
Caused by warpage the problem of, so as to obtain the nylon material of high-performance, low warpage.
Specific embodiment
In order to make technical problems, technical solutions and advantageous effects to be solved by the present invention clearer, below in conjunction with reality
Example is applied, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used for explaining this hair
It is bright, it is not intended to limit the present invention.
The embodiment of the present invention uses following materials：
PA6, MF800, Jiangsu Rui Meifu Co., Ltds are
PA6/66, it is commercially available；
Toughener：Maleic anhydride stem grafting polyolefin elastomer, the good easy appearance macromolecule new material Science and Technology Ltd. in Nantong；
Conventional glass：301HP；Chongqing Polycomp International Co., Ltd
Flat glass：301T；Chongqing Polycomp International Co., Ltd
Lubricant：Silicone powder, technical grade are commercially available；
Antioxidant：Hinered phenols antioxidant 1010, CIBA companies of Switzerland；
Antioxidant：Three [2.4- di-tert-butyl-phenyls] phosphite esters 168, it is commercially available.
Properties of product test method：
Melt mass flow index (melt index)：By ISO1133-1 methods, tested under 275 DEG C, 2.16kg load.
Tensile property：By ISO527-2 methods, batten size：170*10*4mm, test speed 5mm/min.
Bending property：By ISO178-1 methods, batten size：80*10*4mm, test speed 2mm/min.
Notched impact properties：By 180 methods of ISO, batten size：80*10*4mm.
Warpage performance：The model of 150*100*1mm is molded, model is placed on horizontal desktop at 23 DEG C, 50%RH's
48h is placed in environment, by plank width be 100mm one side fix, test another side warpage peak with fixed edge pair
The angle of point line and desktop is claimed to weigh warpage performance, angle is bigger, and warpage properties are poorer.
Embodiment 1：
PA6/66 3.3kg are weighed, it is each to weigh toughener 0.15kg, antioxidant 1010 and 168 by the baking material 4h at 100 DEG C
12.5g, lubricant 25g are uniformly mixed in homogenizer, obtain resin compound, spare；
Flat glass 1.5kg is weighed, it is spare.
The resin compound that above-mentioned resin is uniformly mixed is added to double screw extruder (screw diameter by main spout
For 35mm, draw ratio L/D=36) in, flat glass is added to by side spout in double screw extruder, twin-screw extrusion
Each section of machine control temperature (being exported from charge door to head) is 200 DEG C, 210 DEG C, 225 DEG C, 225 DEG C, 225 DEG C, 225 DEG C, 225
DEG C, 225 DEG C, 225 DEG C, 225 DEG C, 225 DEG C, double screw extruder rotating speed be 360r/min, by die head squeeze out material strip pass through
After sink cooling, blast drier drying product is obtained after pelleter pelletizing.
Above-mentioned material is molded into standard after 120 DEG C of dry 4h in air dry oven under 250 DEG C of injection temperature
Batten.By the mechanical property batten of injection formed, (23 DEG C, 50%RH) is surveyed after status adjustment for 24 hours in laboratory standard environment
Examination will judge batten (the batten size of warpage performance：It 150*100*1mm) is placed on horizontal desktop at 23 DEG C, 50%RH
Environment in place 48h judged, more than test result is shown in Table 1.
Embodiment 2：
PA6/66 2.8kg are weighed, it is each to weigh toughener 0.15kg, antioxidant 1010 and 168 by the baking material 4h at 100 DEG C
12.5g, lubricant 25g are uniformly mixed in homogenizer, obtain resin compound, spare；
Flat glass 2kg is weighed, it is spare.
The resin compound that above-mentioned resin is uniformly mixed is added to double screw extruder (screw diameter by main spout
For 35mm, draw ratio L/D=36) in, flat glass is added to by side spout in double screw extruder, twin-screw extrusion
Each section of machine control temperature (being exported from charge door to head) is 200 DEG C, 210 DEG C, 225 DEG C, 225 DEG C, 225 DEG C, 225 DEG C, 225
DEG C, 225 DEG C, 225 DEG C, 225 DEG C, 225 DEG C, double screw extruder rotating speed be 360r/min, by die head squeeze out material strip pass through
After sink cooling, blast drier drying product is obtained after pelleter pelletizing.
Above-mentioned material is molded into standard after 120 DEG C of dry 4h in air dry oven under 250 DEG C of injection temperature
Batten.By the mechanical property batten of injection formed, (23 DEG C, 50%RH) is surveyed after status adjustment for 24 hours in laboratory standard environment
Examination will judge batten (the batten size of warpage performance：It 150*100*1mm) is placed on horizontal desktop at 23 DEG C, 50%RH
Environment in place 48h judged, more than test result is shown in Table 1.
Embodiment 3：
PA6/66 2.3kg are weighed, it is each to weigh toughener 0.15kg, antioxidant 1010 and 168 by the baking material 4h at 100 DEG C
12.5g, lubricant 25g are uniformly mixed in homogenizer, obtain resin compound, spare；
Flat glass 2.5kg is weighed, it is spare.
The resin compound that above-mentioned resin is uniformly mixed is added to double screw extruder (screw diameter by main spout
For 35mm, draw ratio L/D=36) in, flat glass is added to by side spout in double screw extruder, twin-screw extrusion
Each section of machine control temperature (being exported from charge door to head) is 200 DEG C, 210 DEG C, 225 DEG C, 225 DEG C, 225 DEG C, 225 DEG C, 225
DEG C, 225 DEG C, 225 DEG C, 225 DEG C, 225 DEG C, double screw extruder rotating speed be 360r/min, by die head squeeze out material strip pass through
After sink cooling, blast drier drying product is obtained after pelleter pelletizing.
Above-mentioned material is molded into standard after 120 DEG C of dry 4h in air dry oven under 250 DEG C of injection temperature
Batten.By the mechanical property batten of injection formed, (23 DEG C, 50%RH) is surveyed after status adjustment for 24 hours in laboratory standard environment
Examination will judge batten (the batten size of warpage performance：It 150*100*1mm) is placed on horizontal desktop at 23 DEG C, 50%RH
Environment in place 48h judged, more than test result is shown in Table 1.
Comparative example 1：
PA6 3.3kg are weighed, 4h is dried at 100 DEG C, it is each to weigh toughener 0.15kg, antioxidant 1010 and 168
12.5g, lubricant 25g are uniformly mixed in homogenizer, obtain resin compound, spare；
Conventional glass 1.5kg is weighed, it is spare.
The resin compound that above-mentioned resin is uniformly mixed is added to double screw extruder (screw diameter by main spout
For 35mm, draw ratio L/D=36) in, flat glass is added to by side spout in double screw extruder, twin-screw extrusion
Each section of machine control temperature (being exported from charge door to head) is 200 DEG C, 210 DEG C, 225 DEG C, 225 DEG C, 225 DEG C, 225 DEG C, 225
DEG C, 225 DEG C, 225 DEG C, 225 DEG C, 225 DEG C, double screw extruder rotating speed be 360r/min, by die head squeeze out material strip pass through
After sink cooling, blast drier drying product is obtained after pelleter pelletizing.
Above-mentioned material is molded into standard after 120 DEG C of dry 4h in air dry oven under 250 DEG C of injection temperature
Batten.By the mechanical property batten of injection formed, (23 DEG C, 50%RH) is surveyed after status adjustment for 24 hours in laboratory standard environment
Examination will judge batten (the batten size of warpage performance：It 150*100*1mm) is placed on horizontal desktop at 23 DEG C, 50%RH
Environment in place 48h judged, more than test result is shown in Table 1.
Comparative example 2：
PA6/66 3.3kg are weighed, it is each to weigh toughener 0.15kg, antioxidant 1010 and 168 by the baking material 4h at 100 DEG C
12.5g, lubricant 25g are uniformly mixed in homogenizer, obtain resin compound, spare；
Conventional glass 1.5kg is weighed, it is spare.
The resin compound that above-mentioned resin is uniformly mixed is added to double screw extruder (screw diameter by main spout
For 35mm, draw ratio L/D=36) in, flat glass is added to by side spout in double screw extruder, twin-screw extrusion
Each section of machine control temperature (being exported from charge door to head) is 200 DEG C, 210 DEG C, 225 DEG C, 225 DEG C, 225 DEG C, 225 DEG C, 225
DEG C, 225 DEG C, 225 DEG C, 225 DEG C, 225 DEG C, double screw extruder rotating speed be 360r/min, by die head squeeze out material strip pass through
After sink cooling, blast drier drying product is obtained after pelleter pelletizing.
Above-mentioned material is molded into standard after 120 DEG C of dry 4h in air dry oven under 250 DEG C of injection temperature
Batten.By the mechanical property batten of injection formed, (23 DEG C, 50%RH) is surveyed after status adjustment for 24 hours in laboratory standard environment
Examination will judge batten (the batten size of warpage performance：It 150*100*1mm) is placed on horizontal desktop at 23 DEG C, 50%RH
Environment in place 48h judged, more than test result is shown in Table 1.
Comparative example 3：
PA6 3.3kg are weighed, it is each to weigh toughener 0.15kg, antioxidant 1010 and 168 by the baking material 4h at 100 DEG C
12.5g, lubricant 25g are uniformly mixed in homogenizer, obtain resin compound, spare；
Flat glass 1.5kg is weighed, it is spare.
The resin compound that above-mentioned resin is uniformly mixed is added to double screw extruder (screw diameter by main spout
For 35mm, draw ratio L/D=36) in, flat glass is added to by side spout in double screw extruder, twin-screw extrusion
Each section of machine control temperature (being exported from charge door to head) is 200 DEG C, 210 DEG C, 225 DEG C, 225 DEG C, 225 DEG C, 225 DEG C, 225
DEG C, 225 DEG C, 225 DEG C, 225 DEG C, 225 DEG C, double screw extruder rotating speed be 360r/min, by die head squeeze out material strip pass through
After sink cooling, blast drier drying product is obtained after pelleter pelletizing.
Above-mentioned material is molded into standard after 120 DEG C of dry 4h in air dry oven under 250 DEG C of injection temperature
Batten.By the mechanical property batten of injection formed, (23 DEG C, 50%RH) is surveyed after status adjustment for 24 hours in laboratory standard environment
Examination will judge batten (the batten size of warpage performance：It 150*100*1mm) is placed on horizontal desktop at 23 DEG C, 50%RH
Environment in place 48h judged, more than test result is shown in Table 1.
Table 1：The performance test results.
It can be seen that from data shown in table and be modified by nylon raw material and glass, composite wood can be dramatically increased
Tensile strength, bending strength, the bending modulus of material, and the warpage performance of glass fiber enhanced nylon composite material is effectively improved,
By comparative example 1 and comparative example 1 as can be seen that flat 6/66 tangible mechanical property of fiberglass reinforced PA is still in warpage
Aspect of performance is substantially better than the PA6 of conventional fiberglass reinforced.It it can be seen that should by comparative example 1, embodiment 2 and embodiment 3
Method can play relatively good effect in different glass fiber content systems, by comparing embodiment 1, ratio 1, comparative example
2 and comparative example 3, warpage performance can be improved by using copolymer nylon raw material and flat glass, but flat glass is changing
The mechanical property of composite material can also be increased substantially while kind warpage, by by using copolymer nylon raw material and flat
The mode that glass combines can obtain optimal result.The high-performance that is prepared by the preparation method, low-warpage nylon dragon composite wood
Material realize the application in the products such as ultra-thin computer, phone housing, this to increase nylon application field, in electronic product
Realize that high performance, lightweight have great importance.
Claims (6)
1. a kind of high-performance, low-warpage nylon dragon material, it is characterised in that：It includes following raw material by weight percentage：
2. a kind of high-performance according to claim 1, low-warpage nylon dragon material, it is characterised in that：The material resin
It is the alloy of PA6/66, is that hexamethylene diamine, adipic acid, caprolactam are copolymerized, wherein, hexamethylene diamine and adipic acid accounting are no more than
10%.
3. a kind of high-performance according to claim 1, low-warpage nylon dragon material, it is characterised in that：The toughener is
Maleic anhydride stem grafting polyolefin elastomer.
4. a kind of high-performance according to claim 1, low-warpage nylon dragon material, it is characterised in that：The flat glass
Refer to fibre section non-cylindrical and flaky process is presented, large specific surface area, precursor are flat and thin, selected from 301T.
5. claim 1-4 one of the arbitrary high-performance, the preparation method of low-warpage nylon dragon material, it is characterised in that：Including
Following steps：
(1) it will be weighed after raw material drying by formula rate；
(2) PA6/66, toughener, lubricant, antioxidant are uniformly mixed by homogenizer, it is spare；
(3) above-mentioned mixed raw material is added in by the main spout of double screw extruder, by flat glass from double screw extruder
Side spout add in, obtained after the processes such as melting extrusion, granulation, dryings process described in high-performance composite materials.
6. according to claim 1-4 one of the arbitrary high-performance, low-warpage nylon dragon material, it is characterised in that：Applied to production
The shell of computer, mobile phone.
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| CN201711448077.5A CN108192334A (en) | 2017-12-27 | 2017-12-27 | A kind of high-performance, low-warpage nylon dragon material and its preparation method and application |
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| CN201711448077.5A CN108192334A (en) | 2017-12-27 | 2017-12-27 | A kind of high-performance, low-warpage nylon dragon material and its preparation method and application |
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Cited By (5)
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| CN112759925A (en) * | 2020-12-29 | 2021-05-07 | 金发科技股份有限公司 | Photo-thermal aging resistant flat long glass fiber reinforced polyamide composition and preparation method and application thereof |
| CN112812526A (en) * | 2021-01-26 | 2021-05-18 | 苏州塑发生物材料有限公司 | Low-warpage low-density glass fiber reinforced polylactic acid composite material and preparation method thereof |
| CN112898749A (en) * | 2021-01-26 | 2021-06-04 | 苏州塑发生物材料有限公司 | Low-warpage high-toughness glass fiber reinforced polylactic acid composite material and preparation method thereof |
| CN114456595A (en) * | 2022-03-28 | 2022-05-10 | 金发科技股份有限公司 | Low-mold-scale polyamide composite material and preparation method and application thereof |
| CN115141431A (en) * | 2022-06-27 | 2022-10-04 | 重庆长安汽车股份有限公司 | Thin-wall anti-warping composite material for LFT-D and preparation method and application thereof |
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| CN112812526A (en) * | 2021-01-26 | 2021-05-18 | 苏州塑发生物材料有限公司 | Low-warpage low-density glass fiber reinforced polylactic acid composite material and preparation method thereof |
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| CN115141431A (en) * | 2022-06-27 | 2022-10-04 | 重庆长安汽车股份有限公司 | Thin-wall anti-warping composite material for LFT-D and preparation method and application thereof |
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