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CN102002229A - Long fiber reinforced nylon composite material and preparation method thereof - Google Patents

Long fiber reinforced nylon composite material and preparation method thereof Download PDF

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Publication number
CN102002229A
CN102002229A CN2010105656080A CN201010565608A CN102002229A CN 102002229 A CN102002229 A CN 102002229A CN 2010105656080 A CN2010105656080 A CN 2010105656080A CN 201010565608 A CN201010565608 A CN 201010565608A CN 102002229 A CN102002229 A CN 102002229A
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CN
China
Prior art keywords
long fiber
fiber reinforced
reinforced nylon
matrix material
liquid crystal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2010105656080A
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Chinese (zh)
Inventor
赵安赤
王建虎
王建琴
张燎
毛光军
傅李丹
倪晓玲
王涯
张超维
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ZHEJIANG CHAOWEI NEW MATERIALS CO Ltd
Original Assignee
ZHEJIANG CHAOWEI NEW MATERIALS CO Ltd
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Priority to CN2010105656080A priority Critical patent/CN102002229A/en
Publication of CN102002229A publication Critical patent/CN102002229A/en
Pending legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001Combinations of extrusion moulding with other shaping operations
    • B29C48/0022Combinations of extrusion moulding with other shaping operations combined with cutting
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04Particle-shaped
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92857Extrusion unit
    • B29C2948/92876Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895Barrel or housing

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

The invention discloses a long fiber reinforced nylon composite material and a preparation method thereof, which belong to the field of composite materials. The process of the invention is that the long fiber reinforced nylon composite material comprises the following components in part by weight: 69 to 79 parts of nylon, 16 to 26 parts of continuous carbon fiber, 5 to 10 parts of liquid crystal polymer, 0.1 to 1 part of antioxidant, and 0.5 to 2 parts of lubricant. In the preparation method, the nylon, the liquid crystal polymer, the antioxidant and the lubricant are stirred at a high speed, and then are added into a twin-screw extruder by a feeder, simultaneously long fibers are added into the twin-screw extruder through a side feed opening, and the processing temperature is between 200 and 270 DEG C. The long fiber and liquid crystal polymer reinforced nylon composite material prepared by the method has the characteristics of high mechanical properties, high product dimensional stability and light weight, and is easy to process.

Description

A kind of long fiber reinforced Nylon matrix material and preparation method thereof
Technical field
The present invention relates to the long fiber reinforced Nylon matrix material, relate in particular to a kind of continuous carbon fibre and liquid crystal polymer Reinforced Nylon matrix material and preparation method thereof.
Background technology
Polymeric amide (hereinafter to be referred as PA), be commonly called as nylon, be one of four large-engineering plastics, have excellent comprehensive performances such as high strength, wear-resisting, oil resistant, weak acid and alkali resistance, self-lubricating, insulation, antidetonation sound-absorbing, easy-formation processing, be applied in fields such as automobile industry, electronic apparatus industry, mechanical means, construction industry, packaging industry and other consumer appliance mostly.But the PA water absorbability is big, and product size stability is low, and intensity and rigidity also are nothing like metal.For overcoming these shortcomings, people adopt fiber (as glass fibre (GF), carbon fiber (CF)) and mineral substance to strengthen PA, and wherein the reinforced effects of carbon fiber is better than glass fibre and mineral substance.Liquid crystal polymer can form the micro fiber shape under certain conditions in polymeric matrix, have the ability that strengthens polymkeric substance, but strengthen limited in one's ability.Can mix the enhancing polymkeric substance by macroscopic fiber such as carbon fiber and liquid crystal polymer, form IN-SITU HYBRID COMPOSITES, the carbon fiber enhancing plays a major role, the enhancing of liquid crystal polymer fento plays a secondary role, the expansion of blocking-up tiny crack, by this specific admixture effect, the mechanical property of matrix material often is better than carbon fiber or liquid crystal polymer strengthens polymkeric substance separately, and liquid crystal polymer can also improve the processing rheological property of polymkeric substance/carbon-fibre composite.
Chinese patent 02143127.2 disclose a kind of contain staple fibre and liquid crystal polymer mix Reinforced Nylon 6 matrix materials, overcome the shortcoming of nylon 6/ glass fiber compound material fluidity of molten difference, make this strongthener have good flowing property, can be used for preparing the meticulous product of large-scale thin wall parts and structure.
Chinese patent 200810104253.8 discloses a kind of automobile inlet manifold PP Pipe Compound with nylon/thermotropic liquid crystal polymeric amide/short fiber composite material preparation.
But what these two patents were used all is staple fibre, and the effect of staple fibre enhancing polymkeric substance is limited.And the fiber that mixes at present in the effect study also is only limited to staple fibre.
Macrofiber reinforced thermoplastics(RTP) (LFRT) is a development in recent years class high-performance thermoplastic matrix material rapidly, because damage, the breaking degree of fiber dropped to minimum in preparation process, LFRT has mechanical property and the thermal characteristics more excellent than conventional staple fibre reinforced thermoplastics(RTP), and macrofiber twines mutually, formed a kind of fiber reinforcement, can limit anisotropic shrinkage, significantly reduce warpage, improve product size stability.
Can determine that by the present invention macrofiber and liquid crystal polymer have the reinforcing effect of mixing equally, in use can also satisfy the requirement of high-strength structure parts, particularly automotive industry and the aerospace field that mechanical property and dimensional stability are had relatively high expectations.
Summary of the invention
The objective of the invention is in order to overcome the shortcoming and defect that prior art exists, and provide a kind of mechanical property good, macrofiber that dimensional stability is high and liquid crystal polymer Reinforced Nylon matrix material.
Another object of the present invention provides the preparation method of a kind of macrofiber and liquid crystal polymer Reinforced Nylon matrix material.
For realizing first purpose of the present invention, technical scheme of the present invention is: fine carbon fiber of a kind of length and liquid crystal polymer Reinforced Nylon matrix material, its composition (weight ratio) is: nylon: 69 ~ 79 parts, macrofiber: 16 ~ 26 parts, liquid crystal polymer: 5 ~ 10 parts, oxidation inhibitor: 1 part, 2 parts of lubricants.
Described nylon is nylon 6 or nylon 66.
Described macrofiber is a continuous carbon fibre.
Described liquid crystal polymer is P-hydroxybenzoic acid and ethylene glycol terephthalate copolyesters liquid crystal polymer.
Described oxidation inhibitor is the mixture of Hinered phenols antioxidant and phosphorous acid ester.
The bright lubricant that described lubricant exposes for anti-fiber.
Another object of the present invention provides the preparation method of a kind of macrofiber and liquid crystal polymer Reinforced Nylon matrix material.The concrete technical scheme that adopts is as follows:
The preparation method of a kind of macrofiber and liquid crystal polymer Reinforced Nylon matrix material:
(1) will mix in high-speed mixer according to the described ratio of quality and the number of copies of claim 1 through nylon, liquid crystal polymer, oxidation inhibitor and the lubricant of vacuum drying treatment;
(2) take by weighing macrofiber according to the described massfraction ratio of claim 1;
(3) batch mixing that step (1) is obtained is added in the twin screw extruder through feeder, simultaneously the side loading mouth of the macrofiber in the step (2) through twin screw extruder is added in the twin screw extruder, and the control processing temperature is 270 ℃ of 200 –;
(4) material that step (3) is obtained obtains the long fiber reinforced Nylon matrix material through traction, cooling, pelletizing and drying treatment.
It is compound that the present invention adopts macrofiber, liquid crystal polymer that nylon material is strengthened by technology of the present invention, obtains the long fiber reinforced Nylon matrix material.Adopt liquid crystal polymer can reduce the melt viscosity of product of the present invention, part disperses high-shear to long stapled infringement, and in conjunction with twin screw extruder be prepared, product size good stability, preparation technology be simple, efficient.
The present invention adopts macrofiber and liquid crystal polymer to mix the Reinforced Nylon matrix material, and mechanical property is good, and rigidity is big, the product size good stability, and preparation method of the present invention is simple.
Embodiment
Below by embodiment the present invention is carried out concrete description; only be used for the present invention is further specified; can not be interpreted as the qualification to protection domain of the present invention, the technician in this field can make some nonessential improvement and adjustment to the present invention according to the content of foregoing invention.
Embodiment 1
(1) will be through the nylon 6(84 of vacuum drying treatment part), oxidation inhibitor (1 part) and lubricant (2 parts) mix in high-speed mixer according to the described ratio of quality and the number of copies of claim 1;
(2) take by weighing continuous carbon fibre (16 parts) according to the described massfraction ratio of claim 1;
(3) batch mixing that step (1) is obtained is added in the twin screw extruder through feeder, simultaneously the side loading mouth of the continuous carbon fibre in the step (2) through twin screw extruder is added in the twin screw extruder, and the control processing temperature is 270 ℃ of 200 –;
(4) material that step (3) is obtained obtains the long fiber reinforced Nylon matrix material through traction, cooling, pelletizing and drying treatment.
Above-mentioned mechanical property and the mold shrinkage measurement result that makes continuous carbon fibre Reinforced Nylon 6 matrix materials sees Table 1.
 
Embodiment 2
(1) will be through the nylon 6(79 of vacuum drying treatment part), liquid crystal polymer (5), oxidation inhibitor (1 part) and lubricant (2 parts) mix in high-speed mixer according to the described ratio of quality and the number of copies of claim 1;
(2) take by weighing continuous carbon fibre (16 parts) according to the described massfraction ratio of claim 1;
(3) batch mixing that step (1) is obtained is added in the twin screw extruder through feeder, simultaneously the side loading mouth of the continuous carbon fibre in the step (2) through twin screw extruder is added in the twin screw extruder, and the control processing temperature is 270 ℃ of 200 –;
(4) material that step (3) is obtained obtains the long fiber reinforced Nylon matrix material through traction, cooling, pelletizing and drying treatment.
Above-mentioned mechanical property and the mold shrinkage measurement result that makes continuous carbon fibre and liquid crystal polymer Reinforced Nylon 6 matrix materials sees Table 1.
 
Embodiment 3
(1) will be through the nylon 6(74 of vacuum drying treatment part), liquid crystal polymer (10 parts), oxidation inhibitor (1 part) and lubricant (2 parts) mix in high-speed mixer according to the described ratio of quality and the number of copies of claim 1;
(2) take by weighing continuous carbon fibre (16 parts) according to the described massfraction ratio of claim 1;
(3) batch mixing that step (1) is obtained is added in the twin screw extruder through feeder, simultaneously the side loading mouth of the continuous carbon fibre in the step (2) through twin screw extruder is added in the twin screw extruder, and the control processing temperature is 270 ℃ of 200 –;
(4) material that step (3) is obtained obtains the long fiber reinforced Nylon matrix material through traction, cooling, pelletizing and drying treatment.
Above-mentioned mechanical property and the mold shrinkage measurement result that makes continuous carbon fibre and liquid crystal polymer Reinforced Nylon 6 matrix materials sees Table 1.
 
Embodiment 4
(1) will be through the nylon 66(84 of vacuum drying treatment part), oxidation inhibitor (1 part) and lubricant (2 parts) mix in high-speed mixer according to the described ratio of quality and the number of copies of claim 1;
(2) take by weighing continuous carbon fibre (16 parts) according to the described massfraction ratio of claim 1;
(3) batch mixing that step (1) is obtained is added in the twin screw extruder through feeder, simultaneously the side loading mouth of the continuous carbon fibre in the step (2) through twin screw extruder is added in the twin screw extruder, and the control processing temperature is 270 ℃ of 200 –;
(4) material that step (3) is obtained obtains the long fiber reinforced Nylon matrix material through traction, cooling, pelletizing and drying treatment.
Above-mentioned mechanical property and the mold shrinkage measurement result that makes continuous carbon fibre Reinforced Nylon 66 matrix materials sees Table 2.
 
Embodiment 5
(1) will be through the nylon 66(79 of vacuum drying treatment part), liquid crystal polymer (5), oxidation inhibitor (1 part) and lubricant (2 parts) mix in high-speed mixer according to the described ratio of quality and the number of copies of claim 1;
(2) take by weighing continuous carbon fibre (16 parts) according to the described massfraction ratio of claim 1;
(3) batch mixing that step (1) is obtained is added in the twin screw extruder through feeder, simultaneously the side loading mouth of the continuous carbon fibre in the step (2) through twin screw extruder is added in the twin screw extruder, and the control processing temperature is 270 ℃ of 200 –;
(4): the material that step (3) is obtained obtains the long fiber reinforced Nylon matrix material through traction, cooling, pelletizing and drying treatment.
Above-mentioned mechanical property and the mold shrinkage measurement result that makes continuous carbon fibre and liquid crystal polymer Reinforced Nylon 66 matrix materials sees Table 2.
 
Embodiment 6
(1) will be through the nylon 6(74 of vacuum drying treatment part), oxidation inhibitor (1 part) and lubricant (2 parts) mix in high-speed mixer according to the described ratio of quality and the number of copies of claim 1;
(2) take by weighing continuous carbon fibre (26 parts) according to the described massfraction ratio of claim 1;
(3) batch mixing that step (1) is obtained is added in the twin screw extruder through feeder, simultaneously the side loading mouth of the continuous carbon fibre in the step (2) through twin screw extruder is added in the twin screw extruder, and the control processing temperature is 270 ℃ of 200 –;
(4) material that step (3) is obtained obtains the long fiber reinforced Nylon matrix material through traction, cooling, pelletizing and drying treatment.
Above-mentioned mechanical property and the mold shrinkage measurement result that makes continuous carbon fibre Reinforced Nylon 66 matrix materials sees Table 2.
 
Embodiment 7
(1) will be through the nylon 6(69 of vacuum drying treatment part), liquid crystal polymer (5), oxidation inhibitor (1 part) and lubricant (2 parts) mix in high-speed mixer according to the described ratio of quality and the number of copies of claim 1;
(2) take by weighing continuous carbon fibre (26 parts) according to the described massfraction ratio of claim 1;
(3) batch mixing that step (1) is obtained is added in the twin screw extruder through feeder, simultaneously the side loading mouth of the continuous carbon fibre in the step (2) through twin screw extruder is added in the twin screw extruder, and the control processing temperature is 270 ℃ of 200 –;
(4) material that step (3) is obtained obtains the long fiber reinforced Nylon matrix material through traction, cooling, pelletizing and drying treatment.
Above-mentioned mechanical property and the mold shrinkage measurement result that makes continuous carbon fibre and liquid crystal polymer Reinforced Nylon 66 matrix materials sees Table 2.
Figure 157574DEST_PATH_IMAGE001
From table 1 and table 2, strengthen mechanical property and the dimensional stability that annex solution polycrystalline macromolecule in PA6 and the PA66 matrix material can further improve matrix material at continuous carbon fibre as can be seen.Macrofiber and liquid crystal polymer have equally to mix and strengthen the thermoplastic composite effect.

Claims (10)

1. long fiber reinforced Nylon matrix material, it is characterized in that composed of the following components, in mass fraction: nylon: 69 ~ 79 parts, macrofiber: 16 ~ 26 parts, liquid crystal polymer: 5 ~ 10 parts, oxidation inhibitor: 1 part, 2 parts of lubricants.
2. a kind of long fiber reinforced Nylon matrix material according to claim 1 is characterized in that: described nylon is nylon 6 or nylon 66.
3. a kind of long fiber reinforced Nylon matrix material according to claim 1 is characterized in that: described macrofiber is a continuous carbon fibre.
4. a kind of long fiber reinforced Nylon matrix material according to claim 1 is characterized in that: described liquid crystal polymer is P-hydroxybenzoic acid and ethylene glycol terephthalate copolyesters liquid crystal polymer.
5. a kind of long fiber reinforced Nylon matrix material according to claim 1 is characterized in that: described oxidation inhibitor is the mixture of Hinered phenols antioxidant and phosphorous acid ester.
6. a kind of long fiber reinforced Nylon matrix material according to claim 1 is characterized in that: the bright lubricant that described lubricant exposes for anti-fiber.
7. method for preparing long fiber reinforced Nylon matrix material as claimed in claim 1 is characterized in that comprising following operation:
(1) will mix in high-speed mixer according to the described ratio of quality and the number of copies of claim 1 through nylon, liquid crystal polymer, oxidation inhibitor and the lubricant of vacuum drying treatment;
(2) take by weighing macrofiber according to the described massfraction ratio of claim 1;
(3) batch mixing that step (1) is obtained is added in the twin screw extruder through feeder, simultaneously the side loading mouth of the macrofiber in the step (2) through twin screw extruder is added in the twin screw extruder, and the control processing temperature is 270 ℃ of 200 –;
(4) material that step (3) is obtained obtains the long fiber reinforced Nylon matrix material through traction, cooling, pelletizing and drying treatment.
8. the preparation method of long fiber reinforced Nylon matrix material according to claim 7 is characterized in that: described liquid crystal polymer is P-hydroxybenzoic acid and ethylene glycol terephthalate copolyesters liquid crystal polymer.
9. the preparation method of long fiber reinforced Nylon matrix material according to claim 7 is characterized in that: described oxidation inhibitor is the mixture of Hinered phenols antioxidant and phosphorous acid ester.
10. the preparation method of long fiber reinforced Nylon matrix material according to claim 7 is characterized in that: the bright lubricant that described lubricant exposes for anti-fiber.
CN2010105656080A 2010-11-30 2010-11-30 Long fiber reinforced nylon composite material and preparation method thereof Pending CN102002229A (en)

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Application Number Priority Date Filing Date Title
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102516762A (en) * 2011-12-02 2012-06-27 宁波锦海模具塑膠有限公司 Nylon composite material containing bio-based high molecules and preparation method thereof
CN102850785A (en) * 2012-10-22 2013-01-02 株洲时代新材料科技股份有限公司 Long-fiber-reinforced PA6 (polyamide 6) modified granules and preparation method thereof
CN104194328A (en) * 2014-08-19 2014-12-10 佛山市顺德区南凯新材料实业有限公司 High-gloss, high-fluidity and high-content glass fiber reinforced nylon material and preparation method thereof
CN104419062A (en) * 2013-08-29 2015-03-18 合肥杰事杰新材料股份有限公司 Organic fiber filled thermoplastic resin as well as preparation method thereof
CN107778852A (en) * 2017-11-29 2018-03-09 广东聚航新材料研究院有限公司 A kind of LCP and nylon 6 mixing composite and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102516762A (en) * 2011-12-02 2012-06-27 宁波锦海模具塑膠有限公司 Nylon composite material containing bio-based high molecules and preparation method thereof
CN102850785A (en) * 2012-10-22 2013-01-02 株洲时代新材料科技股份有限公司 Long-fiber-reinforced PA6 (polyamide 6) modified granules and preparation method thereof
CN104419062A (en) * 2013-08-29 2015-03-18 合肥杰事杰新材料股份有限公司 Organic fiber filled thermoplastic resin as well as preparation method thereof
CN104419062B (en) * 2013-08-29 2017-10-03 合肥杰事杰新材料股份有限公司 A kind of organic fiber filling thermoplastic resin and preparation method thereof
CN104194328A (en) * 2014-08-19 2014-12-10 佛山市顺德区南凯新材料实业有限公司 High-gloss, high-fluidity and high-content glass fiber reinforced nylon material and preparation method thereof
CN107778852A (en) * 2017-11-29 2018-03-09 广东聚航新材料研究院有限公司 A kind of LCP and nylon 6 mixing composite and preparation method thereof

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Application publication date: 20110406