CN109553964A - A kind of scratch selfreparing nylon composite materials and preparation method thereof - Google Patents
A kind of scratch selfreparing nylon composite materials and preparation method thereof Download PDFInfo
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- CN109553964A CN109553964A CN201811456305.8A CN201811456305A CN109553964A CN 109553964 A CN109553964 A CN 109553964A CN 201811456305 A CN201811456305 A CN 201811456305A CN 109553964 A CN109553964 A CN 109553964A
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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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
- C08K2201/011—Nanostructured additives
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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
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a kind of scratch selfreparing nylon composite materials and preparation method thereof, belong to high analyte field of material technology.Mainly solve the problems, such as to repair after general nylon composite material is scratched.A kind of scratch selfreparing nylon composite materials, raw material composition and mass parts are as follows: polyamide 6,70-95%；Self-repairing microcapsule, 0.5-4%；Toughener, 0-8%；Nucleating agent, 0.2-2%；Inorganic filler, 2-20%；Antioxidant, 0.2-0.8%；Other auxiliary agents, 0.5-2%.Nylon composite materials prepared by the present invention are after being made appearance device, when device surface is scratched, self-repairing microcapsule is ruptured with the formation of scratch, epoxy resin outflow in being coated on, polymerization reaction occurs and forms big strand, the scratch of device surface is filled and led up to a certain extent, to play the ability of selfreparing；Make composite nylon material surface hardness with higher additionally by substances such as addition nucleating agent, inorganic fillers, the scratch-resistant performance of the scratch selfreparing nylon material can be enhanced.
Description
[technical field]
The present invention relates to technical field of polymer materials, specially a kind of scratch selfreparing nylon composite materials and its preparation
Method.
[background technique]
In practical applications, nylon composite materials are also employed on appearance member, therefore the scratch-resistant performance of nylon composite materials
Just seem at this moment particularly significant.And the surface hardness that general scratch-resistant nylon is all raising nylon part is scraped to reduce nylon
Colored probability, but the surface of nylon part is with scratching increasing or the surface of nylon part being allowed to be scratched for number, Er Qieni
Imperial part is scratched rear unrepairable.
[summary of the invention]
The purpose of the present invention is to provide a kind of scratch selfreparing nylon composite materials, the scratch selfreparing nylon material
After being made after appearance member has scratch-resistant performance, while the appearance member made of the scratch selfreparing nylon material is scratched,
The scratch selfreparing nylon material can also be to being there is certain self-regeneration function by the place of scratching.
To solve the problems, such as to propose in background technique, it is as follows that the present invention provides technical solution: a kind of scratch selfreparing nylon
Composite material, raw material composition and parts by weight are as follows:
The relative viscosity of the polyamide 6 is 2.38~2.85, is middle low-viscosity polyamide 6.
The capsule-core of the self-repairing microcapsule is epoxy resin, and cyst wall is Lauxite.
The toughener is ethylene-octene copolymer, the ethylene propylene diene rubber copolymer of maleic anhydride, horse of maleic anhydride
Maleic anhydride grafted styrene-ethylene-butadiene-styrene copolymer, maleic anhydride, styrene ethylene butadiene-styrene
The combination of one or more of copolymer, linear low density polyethylene.
The nucleating agent be superfine talcum powder, nano silica, nanometer magnesium sulfate crystal whisker, nano zinc oxide crystal whisker and
The combination of one or more of organic nucleating agent.
The inorganic filler is the combination of one or more of superfine talcum powder, Ultramicro Barium Sulfate, palladium powder.
The antioxidant is the combination of one or more of inorganic phosphate, pentaerythritol ester, Hinered phenols.
Other described auxiliary agents are lubricant, silane coupling agent.
The present invention also provides a kind of preparation methods of above-mentioned scratch selfreparing nylon composite materials, and its technical solution is as follows:
Step 1: polyamide 6 is 3-4 hours dry in 110 DEG C of blast driers；
Step 2: by polyamide 6 and self-repairing microcapsule dried in the first step, toughener, nucleating agent, inorganic filling out
Material, antioxidant, other auxiliary agents are uniformly mixed in the sequential investment mixing machine of component according to the ratio；
Step 3: the material mixed is added to melting extrusion in double screw extruder；It is as follows that technique produces number: twin-screw
The temperature setting of extruder an are as follows: area: 130~180 DEG C；Two 220~230 DEG C of areas；3rd area: 230~240 DEG C；4th area: 230~
240℃；5th area: 220~230 DEG C；6th area: 220~230 DEG C；7th area: 220~230 DEG C；8th area: 230~240 DEG C；9th area:
230~240 DEG C；Head temperature: 235-240 DEG C, screw speed 330-360r/min；
Step 4: the compound tie rod of extrusion is immersed cooling in cold water, blower, pelleter pelletizing are crossed, is then dried, i.e.,
Obtain a kind of scratch selfreparing nylon composite materials.
Beneficial effects of the present invention:
A kind of scratch selfreparing nylon composite materials provided by the invention, can make the scratch using self-repairing microcapsule
Appearance member made of selfreparing nylon composite materials has the performance of self-regeneration after being scratched, at device damage
Epoxy resin can be released in self-repairing microcapsule, then chemical reaction quick-jointing occurs for epoxy resin at long-chain or big point
Son, and handed over the maleic anhydride grafted ethene-octene polymer molecule, maleic anhydride molecule and polyamide molecule for scraping injury
Connection, a degree of reparation in place that device surface is damaged, meanwhile, it will be certainly after long-chain or the macromolecular solidification being coupled to
The rent of repairing capsule release epoxy resin blocks no longer release epoxy resin, the remaining epoxy resin in selfreparing capsule
It does not continue to react, reparation when to scratch next time retains a certain amount of epoxy resin, repairs scratch repeatedly to realize, improves
The service life of finished device is made in scratch selfreparing nylon composite materials；The scratch selfreparing nylon material is by making simultaneously
With substances such as toughener, nucleating agent and inorganic fillers, rigidity and the surface for improving the scratch selfreparing nylon material are hard
Degree, enhances the scratch-resistant performance of the scratch selfreparing nylon material.
A kind of preparation method of scratch selfreparing nylon composite materials provided by the invention, the scratch prepared using this method
Selfreparing nylon composite materials have self-repair function and stronger scratch-resistant performance.
[Detailed description of the invention]
Fig. 1 is preparation method flow diagram of the invention.
[specific embodiment]
Below in conjunction with attached drawing of the invention, the technical scheme in the embodiment of the invention is clearly and completely described.
Embodiment 1: a kind of scratch selfreparing nylon composite materials, raw material composition and parts by weight are as follows:
The preparation method of scratch selfreparing nylon composite materials, is shown in attached drawing 1, includes the following steps: described in the present embodiment
Step 1: polyamide 6 is 3-4 hours dry in 110 DEG C of blast driers；
Step 2: by polyamide 6 and self-repairing microcapsule dried in the first step, toughener, nucleating agent, inorganic filling out
Material, antioxidant, other auxiliary agents are uniformly mixed in the sequential investment mixing machine of component according to the ratio；
Step 3: the material mixed is added to melting extrusion in double screw extruder；It is as follows that technique produces number: twin-screw
The temperature setting of extruder an are as follows: area: 130~180 DEG C；Two 220~230 DEG C of areas；3rd area: 230~240 DEG C；4th area: 230~
240℃；5th area: 220~230 DEG C；6th area: 220~230 DEG C；7th area: 220~230 DEG C；8th area: 230~240 DEG C；9th area:
230~240 DEG C；Head temperature: 235-240 DEG C, screw speed 330-360r/min；
Step 4: the compound tie rod of extrusion is immersed cooling in cold water, blower, pelleter pelletizing are crossed, is then dried, i.e.,
Obtain a kind of scratch selfreparing nylon composite materials.
Embodiment 2: a kind of scratch selfreparing nylon composite materials, raw material composition and parts by weight are as follows:
The preparation method of scratch selfreparing nylon composite materials, is shown in attached drawing 1, includes the following steps: described in the present embodiment
Step 1: polyamide 6 is 3-4 hours dry in 110 DEG C of blast driers；
Step 2: by polyamide 6 and self-repairing microcapsule dried in the first step, toughener, nucleating agent, inorganic filling out
Material, antioxidant, other auxiliary agents are uniformly mixed in the sequential investment mixing machine of component according to the ratio；
Step 3: the material mixed is added to melting extrusion in double screw extruder；It is as follows that technique produces number: twin-screw
The temperature setting of extruder an are as follows: area: 130~180 DEG C；Two 220~230 DEG C of areas；3rd area: 230~240 DEG C；4th area: 230~
240℃；5th area: 220~230 DEG C；6th area: 220~230 DEG C；7th area: 220~230 DEG C；8th area: 230~240 DEG C；9th area:
230~240 DEG C；Head temperature: 235-240 DEG C, screw speed 330-360r/min；
Step 4: the compound tie rod of extrusion is immersed cooling in cold water, blower, pelleter pelletizing are crossed, is then dried, i.e.,
Obtain a kind of scratch selfreparing nylon composite materials.
Embodiment 3: a kind of scratch selfreparing nylon composite materials, raw material composition and parts by weight are as follows:
The preparation method of scratch selfreparing nylon composite materials, is shown in attached drawing 1, includes the following steps: described in the present embodiment
Step 1: polyamide 6 is 3-4 hours dry in 110 DEG C of blast driers；
Step 2: by polyamide 6 and self-repairing microcapsule dried in the first step, toughener, nucleating agent, inorganic filling out
Material, antioxidant, other auxiliary agents are uniformly mixed in the sequential investment mixing machine of component according to the ratio；
Step 3: the material mixed is added to melting extrusion in double screw extruder；It is as follows that technique produces number: twin-screw
The temperature setting of extruder an are as follows: area: 130~180 DEG C；Two 220~230 DEG C of areas；3rd area: 230~240 DEG C；4th area: 230~
240℃；5th area: 220~230 DEG C；6th area: 220~230 DEG C；7th area: 220~230 DEG C；8th area: 230~240 DEG C；9th area:
230~240 DEG C；Head temperature: 235-240 DEG C, screw speed 330-360r/min；
Step 4: the compound tie rod of extrusion is immersed cooling in cold water, blower, pelleter pelletizing are crossed, is then dried, i.e.,
Obtain a kind of scratch selfreparing nylon composite materials.
Comparative example 1: a kind of nylon composite materials, raw material composition and parts by weight are as follows:
The preparation method of nylon composite materials described in comparative example one, includes the following steps:
Step 1: polyamide 6 is 3-4 hours dry in 110 DEG C of blast driers；
Step 2: by polyamide 6 and nucleating agent dried in the first step, inorganic filler, antioxidant, other auxiliary agents by matching
It is uniformly mixed in investment mixing machine more sequential than component；
Step 3: the material mixed is added to melting extrusion in double screw extruder；It is as follows that technique produces number: twin-screw
The temperature setting of extruder an are as follows: area: 130~180 DEG C；Two 220~230 DEG C of areas；3rd area: 230~240 DEG C；4th area: 230~
240℃；5th area: 220~230 DEG C；6th area: 220~230 DEG C；7th area: 220~230 DEG C；8th area: 230~240 DEG C；9th area:
230~240 DEG C；Head temperature: 235-240 DEG C, screw speed 330-360r/min；
Step 4: the compound tie rod of extrusion is immersed cooling in cold water, blower, pelleter pelletizing are crossed, is then dried, i.e.,
Obtain a kind of nylon composite materials.
Table one:
The raw material of embodiment 1 to 3 and comparative example 1 forms parts by weight list
Table two:
Embodiment 1 to 3 and 1 performance list of comparative example
Embodiment 1 to 3 is scratch self-repair material, by adjusting each ingredient of raw material, it will thus be seen that toughener is allowing model
Enclose that interior additive amount is more, the tensile property of material is better long；Inorganic filler add within the allowable range it is more, the rigidity of material and
Surface hardness is also bigger.Self-repairing microcapsule additive amount is more, also better for the scratch repair ability of material.
It observes by visual observation, be 1000 μm of partial size, core materials used in the embodiment 1 to 3 is epoxy resin, capsule
Wall is the self-repairing microcapsule of Lauxite, can achieve 90% for scratch of the depth and width in 0.5-1 millimeters of ranges
Repair rate；It can achieve the repair rate of 70%-80% for scratch of the depth and width in 1-1.5 millimeters of ranges；For
Depth and width can achieve the repair rate of 30%-40% in 1.5-2 millimeters of scratch；Certainly, if the depth and width of scratch
Spend it is identical, scratch length be much larger than self-repairing microcapsule partial size, be limited on nylon material matrix epoxy in self-repairing microcapsule
The content of resin is relatively fewer, and epoxy resin flows in scratch and fills and leads up scratch part, and therefore, self-repairing microcapsule can only be repaired
The shorter scratch of length；Of course, it is possible to select the partial size and additive amount of self-repairing microcapsule according to actual needs.
After appearance device is made in scratch selfreparing nylon composite materials of the invention, the selfreparing at device damage
Epoxy resin can be released in microcapsules, then chemical reaction quick-jointing occurs for epoxy resin at long-chain or macromolecular, and
It is crosslinked with the maleic anhydride grafted ethene-octene polymer molecule, maleic anhydride molecule and polyamide molecule for scraping injury, by device
The a degree of reparation in place that part surface is damaged, meanwhile, re-glue will be reviewed one's lessons by oneself after long-chain or the macromolecular solidification being coupled to
The rent of capsule release epoxy resin blocks no longer release epoxy resin, the remaining epoxy resin in selfreparing capsule not followed by
Continuous reaction is that reparation when scratching next time retains a certain amount of epoxy resin, repairs scratch repeatedly to realize, improve scratch certainly
Repair the service life that finished device is made in nylon composite materials.Make Buddhist nun additionally by substances such as addition nucleating agent, inorganic fillers
The scratch resistance that finished device is made in the scratch selfreparing nylon material can be enhanced in imperial composite material surface hardness with higher
Flower performance.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (9)
1. a kind of scratch selfreparing nylon composite materials, it is characterised in that: its raw material composition and parts by weight are as follows:
2. a kind of scratch selfreparing nylon composite materials according to claim 1, it is characterised in that: the polyamide 6
Relative viscosity is 2.38~2.85, is middle low-viscosity polyamide 6.
3. a kind of scratch selfreparing nylon composite materials according to claim 1, it is characterised in that: the micro- glue of selfreparing
The capsule-core of capsule is epoxy resin, and cyst wall is Lauxite.
4. a kind of scratch selfreparing nylon composite materials according to claim 1, it is characterised in that: the toughener is horse
Maleic anhydride grafted ethylene-octene copolymer, maleic anhydride are grafted ethylene propylene diene rubber copolymer, maleic anhydride graft phenylethene-
Ethylene-butadiene-styrene copolymer, maleic anhydride, styrene-ethylene-butadiene-styrene copolymer, linea low density
The combination of one or more of polyethylene.
5. a kind of scratch selfreparing nylon composite materials according to claim 1, it is characterised in that: the nucleating agent is super
One of fine and smooth mountain flour, nano silica, nanometer magnesium sulfate crystal whisker, nano zinc oxide crystal whisker and organic nucleating agent are several
The combination of kind.
6. a kind of scratch selfreparing nylon composite materials according to claim 1, it is characterised in that: the inorganic filler is
The combination of one or more of superfine talcum powder, Ultramicro Barium Sulfate, palladium powder.
7. a kind of scratch selfreparing nylon composite materials according to claim 1, it is characterised in that: the antioxidant is
The combination of one or more of inorganic phosphate, pentaerythritol ester, Hinered phenols.
8. a kind of scratch selfreparing nylon composite materials according to claim 1, it is characterised in that: other described auxiliary agents
For lubricant, silane coupling agent.
9. the method for preparing any one scratch selfreparing nylon composite materials described in claim 1-8, it is characterised in that: tool
Body the following steps are included:
Step 1: polyamide 6 is 3-4 hours dry in 110 DEG C of blast driers；
Step 2: by polyamide 6 and self-repairing microcapsule dried in the first step, toughener, nucleating agent, inorganic filler, resisting
Oxygen agent, other auxiliary agents are uniformly mixed in the sequential investment mixing machine of component according to the ratio；
Step 3: the material mixed is added to melting extrusion in double screw extruder；It is as follows that technique produces number: twin-screw extrusion
The temperature setting of machine an are as follows: area: 130~180 DEG C；Two 220~230 DEG C of areas；3rd area: 230~240 DEG C；4th area: 230~240
℃；5th area: 220~230 DEG C；6th area: 220~230 DEG C；7th area: 220~230 DEG C；8th area: 230~240 DEG C；9th area: 230~
240℃；Head temperature: 235-240 DEG C, screw speed 330-360r/min；
Step 4: the compound tie rod of extrusion is immersed cooling in cold water, blower, pelleter pelletizing are crossed, is then dried to get arriving
A kind of scratch selfreparing nylon composite materials.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112592579A (en) * | 2020-11-19 | 2021-04-02 | 江苏博云塑业股份有限公司 | Rapid-forming polyamide composite material and preparation method thereof |
| CN112759908A (en) * | 2020-12-24 | 2021-05-07 | 上海金发科技发展有限公司 | Scratch-repairable high-gloss ABS (acrylonitrile-butadiene-styrene) composition and preparation method thereof |
| CN114716813A (en) * | 2022-03-23 | 2022-07-08 | 华润化学材料科技股份有限公司 | Composite material for restoring deformation memory and preparation method thereof |
| CN114874617A (en) * | 2022-06-14 | 2022-08-09 | 华东理工大学 | Functional modified nylon 66 material and preparation method thereof |
-
2018
- 2018-11-30 CN CN201811456305.8A patent/CN109553964A/en active Pending
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112592579A (en) * | 2020-11-19 | 2021-04-02 | 江苏博云塑业股份有限公司 | Rapid-forming polyamide composite material and preparation method thereof |
| CN112759908A (en) * | 2020-12-24 | 2021-05-07 | 上海金发科技发展有限公司 | Scratch-repairable high-gloss ABS (acrylonitrile-butadiene-styrene) composition and preparation method thereof |
| CN112759908B (en) * | 2020-12-24 | 2023-02-10 | 上海金发科技发展有限公司 | Scratch-repairable high-gloss ABS (acrylonitrile-butadiene-styrene) composition and preparation method thereof |
| CN114716813A (en) * | 2022-03-23 | 2022-07-08 | 华润化学材料科技股份有限公司 | Composite material for restoring deformation memory and preparation method thereof |
| CN114716813B (en) * | 2022-03-23 | 2023-10-03 | 常州华润高性能复合材料有限公司 | Deformation memory recovery composite material and preparation method thereof |
| CN114874617A (en) * | 2022-06-14 | 2022-08-09 | 华东理工大学 | Functional modified nylon 66 material and preparation method thereof |
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