CN107501920A - It is a kind of to improve composition of fiberglass reinforced PA 6 for floating fine phenomenon and preparation method thereof - Google Patents
It is a kind of to improve composition of fiberglass reinforced PA 6 for floating fine phenomenon and preparation method thereof Download PDFInfo
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- CN107501920A CN107501920A CN201610425990.2A CN201610425990A CN107501920A CN 107501920 A CN107501920 A CN 107501920A CN 201610425990 A CN201610425990 A CN 201610425990A CN 107501920 A CN107501920 A CN 107501920A
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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
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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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
- C08K2201/016—Additives defined by their aspect ratio
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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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
Abstract
The invention discloses a kind of composition of fiberglass reinforced PA 6 for improving floating fine phenomenon and preparation method thereof, it is prepared by weight by following components：PA6, PA66, glass fibre, magnesium sulfate crystal whisker, toughener, nucleator, silicone oil.By enhancing the compatibility between glass fibre after magnesium sulfate crystal whisker and silicone oil mixing, and similar anchoring node is formd between glass fibre, nylon resin, that is crosslinking points, improve the bond state of glass and resin, the separation of glass and resin is reduced, makes glass flowing synchronous with resin in process, is not easy to rip, the exposed of glass is greatly reduced, and the mechanical strength of PA6 compositions is improved by adding PA66.
Description
Technical field
The invention belongs to field of polymer composite material, and in particular to a kind of to improve 6 groups of fiberglass reinforced PA for floating fine phenomenon
Compound and preparation method thereof.
Background technology
Polyamide (PA, being commonly called as nylon) is that DuPont develops resin for fiber at first, real in nineteen thirty-nine
Now industrialize.Polyamide starts to develop and produce injection-molded item the 1950s, meets downstream industry system with substituted metal
Product lightweight, the requirement for reducing cost.PA has a good combination property, including mechanical property, heat resistance, wear resistance, resistance to
Chemicals and self lubricity, and coefficient of friction is low, also certain anti-flammability, it is easy to process.
Currently in order to strengthening PA6 toughness and reducing its production cost, appropriate glass is mostly added inside nylon material
Fibre is modified to it, but adds and then easily occur the problem of floating fine after glass.It is usually to be made by glass emergence on the surface to float fine phenomenon
Into white glass floats during plastic melt filling flow and is exposed to appearance, is just formed and put on plastic surface after shaping to be condensed
Shape white vestige is penetrated, can be more obvious because shade deviation increases when plastic is black.So floating fine phenomenon not only influences PA
The cosmetic look of product, have an effect on its performance as resistance to rolled-up stock.
The content of the invention
It is an object of the invention to provide a kind of composition of fiberglass reinforced PA 6 for improving floating fine phenomenon and preparation method thereof.
Technical scheme is as follows：
The invention provides a kind of composition of fiberglass reinforced PA 6 for improving floating fine phenomenon, made by weight by following components
It is standby to form：
The intrinsic viscosity range of described PA6 sections is 0.6-1.0dl/g；
Described glass fibre is short glass fiber, Length of Glass Fiber 2-5mm, a diameter of 7-13 microns of glass；
Described magnesium sulfate crystal whisker moisture≤0.1%, oil absorption≤25 (g/100g), draw ratio 70.
Described toughener is selected from maleic anhydride grafted ethene-octene copolymer, ethylene-methyl acrylate copolymer or second
One or more in alkene-methyl acrylate-GMA；
The nucleator is sodium benzoate.
The preparation method of the composition of fiberglass reinforced PA 6 of fine phenomenon, this method bag are floated present invention also offers above-mentioned improvement
Include following steps：
(1) PA6 and PA66 are dried respectively；
(2) by proportioning, by dried PA6 and PA66, and magnesium sulfate crystal whisker, glass fibre, toughener, nucleator and
Silicone oil, add in high-speed mixer stir 3-5min together；
(3) well mixed material is added from the charge door of double screw extruder, through double screw extruder melting extrusion,
It is granulated, is prepared into the modified composition of fiberglass reinforced PA 6.
PA6 is to dry 4-5h under the conditions of temperature is 110-140 DEG C in the step (1)；It in temperature is 110- that PA66, which is,
4-5h is dried under the conditions of 120 DEG C；
220-250 DEG C of the area's temperature of double screw extruder one, two 225-265 DEG C of area's temperature, three area's temperature in the step (3)
235-275 DEG C, four 245-285 DEG C of area's temperature, five 240-280 DEG C of area's temperature, six 245-285 DEG C of area's temperature, head temperature 245-
285 DEG C, engine speed is 15-35HZ.
The present invention compared with the existing technology, has the advantages that：
1st, magnesium sulfate crystal whisker and silicone oil enhance the compatibility between glass fibre after mixing, and in glass fibre, Buddhist nun
Similar anchoring node, i.e. crosslinking points are formd between imperial resin, the bond state of glass and resin is improved, reduces glass and tree
The separation of fat.
2nd, due to the mechanical function thickness degree increase between the surface of glass and matrix resin, make to be in glass near surface
Matrix be easier to occur shear yielding, increase the absorption to impact energy and dissipative effect, promote glass between matrix resin
Toughening effect.So that glass is coated well in resin, glass flowing synchronous with resin in process, no
Easily rip, greatly reduce the exposed of glass.
3rd, magnesium sulfate crystal whisker and silicone oil reduce glass emergence on the surface, so as to correspondingly reduce the friction of glass and screw rod, make
The moment of torsion of screw rod also decreases, easy to process.
4th, PA66 has higher fusing point, and it can also keep stronger strength and stiffness in higher temperature, so in the present invention
PA66 is added to improve the mechanical strength of PA6 compositions.
5th, the composition of modification fiberglass reinforced PA 6 prepared by the present invention has excellent mechanical property.
Embodiment
The present invention is further illustrated with reference to embodiments.
Measuring mechanical property method：
Composition prepared by the present invention is molded into test examination using injection molding machine of plastic using GB standards at 230-270 DEG C
Sample, the size (length x width x thickness) of its test bars are respectively：Tensile bars (dumbbell shape), 170.0 × 10.0 ×
4.0；Bending batten, 80.0 × 10.0 × 4.0；Non-notch impact batten, 80.0 × 10.0 × 4.0；Notch shock batten, 80.0
× 10.0 × 4.0, v-notch, notch depth 1/5.
In temperature be (23 ± 2) DEG C, in the standard environment that humidity is (50 ± 5) % after placement 16h after test bars shaping
Tested, test environment is (23 ± 2) DEG C, humidity is (50 ± 5) %.
Tensile strength and elongation at break：Tested by GB 1040, draw speed 5mm/min.
Bending strength and bending modulus：Tested by GB 9341, rate of bending 1.25mm/min.
Simply supported beam notch impact strength：Tested by GB 1043.
Glass fiber content：Tested by GB 9345.
Embodiment 1
(1) by PA6 in 110 DEG C of temperature, dry 4h；PA66 is in 110 DEG C of temperature, dry 4h；
(2) weigh dry 60 parts of PA6,1 part of PA66,25 parts of glass fibre, 5 parts of magnesium sulfate crystal whisker, 5 parts
Sodium benzoate, 5 parts of silicone oil；
(3) material weighed up in above-mentioned steps (2) is stirred into 3min in high-speed mixer；
(4) charge door of double screw extruder and then by above-mentioned well mixed material is added；
(5) material is granulated through double screw extruder melting extrusion；
The processing technology of described double screw extruder is：230 DEG C of one area's temperature of double screw extruder, two area's temperature 245
DEG C, three 255 DEG C of area's temperature, four 265 DEG C of area's temperature, five 260 DEG C of area's temperature, six 265 DEG C of area's temperature, 265 DEG C of head temperature, main frame
Rotating speed is 15HZ.The performance test results are shown in Table 1.
Embodiment 2
(1) by PA6 in 110 DEG C of temperature, dry 4h；PA66 is in 110 DEG C of temperature, dry 4h；
(2) weigh 40 parts dry of PA6,10 parts of PA66,30 parts of glass fibre, 15 parts of magnesium sulfate crystal whisker, 5 parts
Toughener maleic anhydride grafted ethene-octene copolymer, 10 parts of sodium benzoate, 10 parts of silicone oil；
(3) material weighed up in above-mentioned steps (2) is stirred into 3min in high-speed mixer；
(4) charge door of double screw extruder and then by above-mentioned well mixed material is added；
(5) material is granulated through double screw extruder melting extrusion；
The processing technology of described double screw extruder is：220 DEG C of one area's temperature of double screw extruder, two area's temperature 225
DEG C, three 235 DEG C of area's temperature, four 245 DEG C of area's temperature, five 240 DEG C of area's temperature, six 245 DEG C of area's temperature, 245 DEG C of head temperature, main frame
Rotating speed is 15HZ.The performance test results are shown in Table 1.
Embodiment 3
(1) by PA6 in 140 DEG C of temperature, dry 4-5h；PA66 is in 120 DEG C of temperature, dry 5h；
(2) weigh 40 parts dry of PA6,5 parts of PA66,35 parts of glass fibre, 10 parts of magnesium sulfate crystal whisker, 3 parts
Toughener ethylene-methyl acrylate copolymer, 5 parts of sodium benzoate, 5 parts of silicone oil；
(3) material weighed up in above-mentioned steps (2) is stirred into 3min in high-speed mixer；
(4) charge door of double screw extruder and then by above-mentioned well mixed material is added；
(5) material is granulated through double screw extruder melting extrusion；
The processing technology of described double screw extruder is：240 DEG C of one area's temperature of double screw extruder, two area's temperature 255
DEG C, three 265 DEG C of area's temperature, four 275 DEG C of area's temperature, five 270 DEG C of area's temperature, six 275 DEG C of area's temperature, 275 DEG C of head temperature, main frame
Rotating speed is 35HZ.The performance test results are shown in Table 1.
Embodiment 4
(1) by PA6 in 120 DEG C of temperature, dry 5h；PA66 is in 120 DEG C of temperature, dry 5h；
(2) weigh 30 parts dry of PA6,5 parts of PA66,45 parts of glass fibre, 10 parts of magnesium sulfate crystal whisker, 5 parts
Sodium benzoate, 5 parts of silicone oil；
(3) material weighed up in above-mentioned steps (2) is stirred into 5min in high-speed mixer；
(4) charge door of double screw extruder and then by above-mentioned well mixed material is added；
(5) material is granulated through double screw extruder melting extrusion；
The processing technology of described double screw extruder is：250 DEG C of one area's temperature of double screw extruder, two area's temperature 265
DEG C, three 275 DEG C of area's temperature, four 285 DEG C of area's temperature, five 280 DEG C of area's temperature, six 285 DEG C of area's temperature, 285 DEG C of head temperature, main frame
Rotating speed is 35HZ.The performance test results are shown in Table 1.
Comparative example 1
(1) by PA6 in 110 DEG C of temperature, dry 4h；PA66 is in 110 DEG C of temperature, dry 4h；
(2) 50 parts dry of PA6,5 parts of PA66,35 parts of glass fibre, 5 parts of toughener ethylene-propylene are weighed
Sour methyl terpolymer, 5 parts of sodium benzoate；
(3) material weighed up in above-mentioned steps (2) is stirred into 3min in high-speed mixer；
(4) charge door of double screw extruder and then by above-mentioned well mixed material is added；
(5) material is granulated through double screw extruder melting extrusion；
The processing technology of described double screw extruder is：220 DEG C of one area's temperature of double screw extruder, two area's temperature 225
DEG C, three 235 DEG C of area's temperature, four 245 DEG C of area's temperature, five 240 DEG C of area's temperature, six 245 DEG C of area's temperature, 245 DEG C of head temperature, main frame
Rotating speed is 35HZ.The performance test results are shown in Table 1.
Comparative example 2
(1) by PA6 in 140 DEG C of temperature, dry 5h；PA66 is in 120 DEG C of temperature, dry 5h；
(2) it is brilliant that 40 parts dry of PA6,5 parts of PA66,35 parts of glass fibre, 10 parts of calcium sulfate magnesium sulfate are weighed
Palpus, 5 parts of toughener ethylene-methyl acrylate copolymer, 5 parts of sodium benzoate；
(3) material weighed up in above-mentioned steps (2) is stirred into 5min in high-speed mixer；
(4) charge door of double screw extruder and then by above-mentioned well mixed material is added；
(5) material is granulated through double screw extruder melting extrusion；
The processing technology of described double screw extruder is：220 DEG C of one area's temperature of double screw extruder, two area's temperature 225
DEG C, three 235 DEG C of area's temperature, four 245 DEG C of area's temperature, five 240 DEG C of area's temperature, six 245 DEG C of area's temperature, 245 DEG C of head temperature, main frame
Rotating speed is 35HZ.The performance test results are shown in Table 1.
Comparative example 3
(1) by PA6 in 120 DEG C of temperature, dry 5h；PA66 is in 120 DEG C of temperature, dry 5h；
(2) 40 parts dry of PA6,5 parts of PA66,35 parts of glass fibre, 5 parts of toughener ethylene-propylene are weighed
Sour methyl terpolymer, 5 parts of sodium benzoate；
(3) material weighed up in above-mentioned steps (2) is stirred into 5min in high-speed mixer；
(4) charge door of double screw extruder and then by above-mentioned well mixed material is added；
(5) material is granulated through double screw extruder melting extrusion；
The processing technology of described double screw extruder is：220 DEG C of one area's temperature of double screw extruder, two area's temperature 225
DEG C, three 235 DEG C of area's temperature, four 245 DEG C of area's temperature, five 240 DEG C of area's temperature, six 245 DEG C of area's temperature, 245 DEG C of head temperature, main frame
Rotating speed is 35HZ.The performance test results are shown in Table 1.
Table 1
The comparison of embodiment and comparative example can be seen that fiberglass reinforced PA composition produced by the present invention from upper table 1
Bending modulus, tensile strength, elongation at break, simply supported beam notch impact strength obviously higher than material prepared by comparative example, and
And article surface is bright, without floating fibre.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using this hair
It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to implementation here
Example, for those skilled in the art according to the announcement of the present invention, not departing from improvement that scope made and modification all should be
Within protection scope of the present invention.
Claims (8)
1. a kind of improve the composition of fiberglass reinforced PA 6 for floating fine phenomenon, it is characterised in that：Prepared by weight by following components and
Into：
PA6 30-60 parts,
PA66 1-10 parts,
Glass fibre 25-45 parts,
Magnesium sulfate crystal whisker 5-15 parts,
Toughener 0-5 parts,
Nucleator 5-10 parts,
Silicone oil 5-10 parts.
A kind of 2. composition of fiberglass reinforced PA 6 for improving floating fine phenomenon according to claim 1, it is characterised in that：It is described
PA6 section intrinsic viscosity range be 0.6-1.0 dl/g.
A kind of 3. composition of fiberglass reinforced PA 6 for improving floating fine phenomenon according to claim 1, it is characterised in that：It is described
Glass fibre be short glass fiber, its length is 2-5mm, a diameter of 7-13 microns.
A kind of 4. composition of fiberglass reinforced PA 6 for improving floating fine phenomenon according to claim 1, it is characterised in that：It is described
Moisture≤0.1% of magnesium sulfate crystal whisker, oil absorption≤25 (g/100g), draw ratio 70.
A kind of 5. composition of fiberglass reinforced PA 6 for improving floating fine phenomenon according to claim 1, it is characterised in that：It is described
Toughener be selected from maleic anhydride grafted ethene-octene copolymer, ethylene-methyl acrylate copolymer or ethylene-acrylic acid first
One or more in ester-GMA.
A kind of 6. composition of fiberglass reinforced PA 6 for improving floating fine phenomenon according to claim 1, it is characterised in that：It is described
Nucleator is sodium benzoate.
7. a kind of preparation method as claimed in claim 1 for improving the composition of fiberglass reinforced PA 6 for floating fine phenomenon, its feature exist
In：Its step is as follows：
（1）PA6 and PA66 are dried respectively；
（2）By proportioning, by dried PA6 and PA66, and magnesium sulfate crystal whisker, glass fibre, toughener, nucleator and silicon
Oil, add in high-speed mixer stir 3-5min together；
（3）Well mixed material is added from the charge door of double screw extruder, through double screw extruder melting extrusion, made
Grain, is prepared into the modified composition of fiberglass reinforced PA 6.
8. preparation method according to claim 7, it is characterised in that：The step（1）It in temperature is 110- that middle PA6, which is,
4-5h is dried under the conditions of 140 DEG C；PA66 is to dry 4-5h under the conditions of temperature is 110-120 DEG C；
The step（3）Middle 220-250 DEG C of the area's temperature of double screw extruder one, two 225-265 DEG C of area's temperature, three area temperature 235-
275 DEG C, four 245-285 DEG C of area's temperature, five 240-280 DEG C of area's temperature, six 245-285 DEG C of area's temperature, head temperature 245-285
DEG C, engine speed is 15-35HZ.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610425990.2A CN107501920A (en) | 2016-06-14 | 2016-06-14 | It is a kind of to improve composition of fiberglass reinforced PA 6 for floating fine phenomenon and preparation method thereof |
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| CN201610425990.2A CN107501920A (en) | 2016-06-14 | 2016-06-14 | It is a kind of to improve composition of fiberglass reinforced PA 6 for floating fine phenomenon and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111892813A (en) * | 2020-07-28 | 2020-11-06 | 横店集团得邦工程塑料有限公司 | Low-odor reinforced toughened flame-retardant PA6 composite material and preparation method thereof |
| CN113980463A (en) * | 2021-11-15 | 2022-01-28 | 上海良勤实业有限公司 | High-toughness PA66 material and preparation method thereof |
| CN115819966A (en) * | 2022-12-12 | 2023-03-21 | 江苏尚艾新材料科技有限公司 | Wear-resistant reinforced nylon material and preparation method thereof |
| CN113980463B (en) * | 2021-11-15 | 2024-04-26 | 上海良勤实业有限公司 | High-toughness PA66 material and preparation method thereof |
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| CN101955653A (en) * | 2010-10-29 | 2011-01-26 | 南京鸿瑞塑料制品有限公司 | Enhanced conductive nylon material and preparation method thereof |
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| CN105646939A (en) * | 2014-11-10 | 2016-06-08 | 合肥杰事杰新材料股份有限公司 | Application of basic magnesium sulfate whiskers as flame-retardant anti-dripping agent of composition |
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| CN101851417A (en) * | 2009-03-31 | 2010-10-06 | 上海金发科技发展有限公司 | Low-cost and high-performance glass fiber reinforced nylon 6 composite material and preparation method thereof |
| US20130061739A1 (en) * | 2010-02-11 | 2013-03-14 | Wun Chet Davy Cheong | Energy dissipation composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111892813A (en) * | 2020-07-28 | 2020-11-06 | 横店集团得邦工程塑料有限公司 | Low-odor reinforced toughened flame-retardant PA6 composite material and preparation method thereof |
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| CN113980463A (en) * | 2021-11-15 | 2022-01-28 | 上海良勤实业有限公司 | High-toughness PA66 material and preparation method thereof |
| CN113980463B (en) * | 2021-11-15 | 2024-04-26 | 上海良勤实业有限公司 | High-toughness PA66 material and preparation method thereof |
| CN115819966A (en) * | 2022-12-12 | 2023-03-21 | 江苏尚艾新材料科技有限公司 | Wear-resistant reinforced nylon material and preparation method thereof |
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Application publication date: 20171222 |