CN105968801A - High-performance modified polyamide composite material and preparation method thereof - Google Patents
High-performance modified polyamide composite material and preparation method thereof Download PDFInfo
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- CN105968801A CN105968801A CN201610292627.8A CN201610292627A CN105968801A CN 105968801 A CN105968801 A CN 105968801A CN 201610292627 A CN201610292627 A CN 201610292627A CN 105968801 A CN105968801 A CN 105968801A
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- modified polyamide
- performance modified
- polyamide compoiste
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- butyl
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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
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- 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
-
- 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
-
- 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
-
- 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
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Abstract
The invention provides a high-performance modified polyamide composite material. The high-performance modified polyamide composite material comprises, by weight, 8-12% of nylon 6, 30% of glass fibers, 10-20% of polyphenylene sulfide, 0.5-4% of a filler, 1-5% of a compatilizer, 0.1-0.5% of a processing auxiliary agent and the balance nylon 66. The invention also provides a preparation method of the high-performance modified polyamide composite material. The high-performance modified polyamide composite material can be used for machinery, apparatuses and instruments, automobile parts, electrical and electronic products, railway, household electrical appliance, communication, spinners, physical culture leisure articles, oil pipes, fuel tanks and precision engineering products.
Description
Technical field
The invention belongs to materialogy field, relate to a kind of polyamide resin material, a kind of high-performance modified
Polyamide compoiste material and preparation method thereof.
Background technology
Polyamide, English name is polyamide, is called for short PA.Being commonly called as nylon (Nylon), it is macromolecular main chain
Repetitive contains the general name of the high polymer of amide group.Polyamide tool high-tensile；Resistance to tough, resistance to impact is special excellent；From
Lubricant nature, wearability are good, resistance to chemical reagents is excellent；Low-temperature characteristics is good；Tool self-extinguishment.Owing to nylon PA plastic material has a lot of spies
Property, therefore, it is widely used in machinery, instrument and meter, automobile component, electric, railway, household electrical appliances, communication, frame, physical culture are stopped
Not busy articles for use, oil pipe, fuel tank and some precision engineering goods.
But polyamide is also because of hygroscopic, poor dimensional stability, and the shortcomings such as low temperature tolerance ability deficiency limit it and answer
Use field.
The Technical comparing of fiber reinforcement and Inorganic Fillers Filled modification PA engineering plastics is ripe, through glass fiber reinforcement
After, its mechanical property can be greatly enhanced.But the serious wear that too high GF (glass fibre) content is to equipment, and note
Molded processing is the most difficult, and particularly thin-gage goods is difficult to be full of die cavity.This is owing to the addition of GF makes MFR (melt flow
Speed) decline, for complex-shaped and thin-gage goods, it is difficult to molding.
PPS (polyphenylene sulfide) is the thermoplastic special engineering plastic of a kind of excellent combination property, and its outstanding feature is resistance to height
Temperature, corrosion-resistant, radiation hardness, mechanical performance and electrical property are excellent.Water absorption and the oil absorption of PPS are the least, molding shrinkage and
Linear expansion coefficient is little, and its product size is stable, and warpage is little, though moist at some, in the environment of greasy dirt and corrosive gas,
PPS remains to keep its dimensional stability.Polyphenylene sulfide is matched with polyamide, it is possible to the performance of comprehensive both plastics, but 2
The compatibility planting material is poor.
Summary of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of high-performance modified polyamide compoiste material
And preparation method thereof
The invention provides a kind of high-performance modified polyamide compoiste material, by weight percentage, its raw material forms such as
Under:
Concrete, by weight percentage, its raw material composition is as follows:
Further, the feature viscosity number of described nylon 66 resin be 2.4-2.9 (concrete, can use Luo Diya's
27AE1B)；
Further, the feature viscosity number of described nylon 6 resin be 2.4-3.0 (concrete, can use collection contain
4407)；
Further, described glass fibre is the alkali-free glass fibre of a diameter of 10-20 micron；
Further, described polyphenylene sulfide be straight chain type, degree of crystallinity >=60 thermoplastic (concrete, can adopt
With the PPS-HB of Deyang).
Further, described filler is selected from: glass microballoon, Kaolin, Pulvis Talci, MoS2, wollastonite, in Muscovitum
Any one or two or more combination.
Further, described compatilizer uses POE grafted maleic anhydride, Research of Grafting Malaic Anhydride Onto Polyethylene, ethylene, propylene
Acid butyl ester, ethylene acrylic acid co polymer, maleic anhydride grafting level SEBS in one or more kinds of combinations (concrete,
Can the FG1901 that rises of the section of employing).
Further, described processing aid is made up of antioxidant, lubricant and flow ability modifying agent.
Concrete, described antioxidant is β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive octadecanol ester；Four
[β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester；Double (2.4-di-tert-butyl-phenyl) tetramethylolmethane；2,6-
Di-t-butyl-4-4 cresol；Three (2,4-di-tert-butyl-phenyl) phosphite ester；Sulfur generation three propanoic acid dilauryls；Or sulfur is for dipropyl
Any one or two or more combination in the double stearic alcohol ester of acid.
Concrete, described lubricant is any one or two kinds in E wax, calcium stearate, silicone master batch or PETS
Above combination.
Concrete, described flow ability modifying agent is VTECNSF 600.
Present invention also offers the preparation method of above-mentioned a kind of high-performance modified polyamide compoiste material, claim according to weight ratio
Take each reaction raw materials, then add raw materials into the mixing of high mixer high-speed stirred, be then added to the main feeder of extruder, then add
Enter in double screw extruder to carry out basis pelletize, extruder temperature distribution as follows: extruder temperature be followed successively by 260 DEG C, 285
℃、290℃、290℃、290℃、285℃、275℃、265℃、250℃、270℃；Screw rod revolution is 420r/min, and feeding turns
Speed is 20HZ, through water-cooled, pelletizing after material extrusion, then packs.
The present invention uses compounding for PA66 and PA6, and based on PA66, PA6 is dispersion phase, when using glass fiber reinforcement, produces
The bending strength of product is slightly below the pure PA66 of glass fiber reinforcement, but its impact strength exceeds 10%, and processing fluidity is changed
Kind, widen processing temperature.The present invention selects the alkali-free glass fibre of a diameter of 10-20 micron.If glass fiber diameter is too
Slightly, poor with the caking property of PA, cause product mechanical properties decrease；If glass fibre is too thin, easily it is cut into carefully by threaded rod shear
Micropowder, thus lose the effect of fiber.
The present invention is combined by adjusting screw rod and rotating speed goes the length controlling glass fibre at 2-3mm.Ensure the property of product
Energy and outward appearance.The present invention adds PPS, and the mechanical performance of its excellence and chemical property compensate for the deficiency of polyamide, it is provided that it increases
The stretching of strong material, bending and thermal deformation.Flow ability modifying agent uses VTECNSF600, VTECNSF600 to be a kind of based on nanometer skill
Art, aims at the super flow ability modifying agent of a new generation of nylon exploitation, can improve the mobility of nylon product, melting nylon material
Index doubles or several times, improves simultaneously or eliminate the surface floating fiber of reinforced nylon goods, improves goods glossiness, improvement
Outward appearance.MoS2 does not only have good wear-resistant effect, the most certain potentiation, can effectively improve the friction mill of polyamide
Consumption characteristic, MoS2 has nucleation to polyamide, can promote the crystallization granular of PA66, improves rigidity and the hardness of PA66.
FG1901 is that maleic anhydride grafting level SEBS has stronger impact resistance and tear resistance, can improve the toughness of material, SEBS
The compatilizer of plastic blend can be made by being blended in tenacity increased nylon (PA6), PC, PPO, polyester (PET, PBT), PP, also be a kind of
Compatible toughening agents.
The present invention compares with prior art, and its technological progress is significant.The material of the present invention has the mechanicalness of excellence
Energy, high flowing, good presentation quality and the moulding processability of excellence, can be widely applied to machinery, instrument and meter, automobile
Parts, electric, railway, household electrical appliances, communication, frame, Leisure Sport articles for use, oil pipe, fuel tank and some precision engineering goods.
Detailed description of the invention
Below in conjunction with example, the invention will be further described.
Comparative example 1
Each raw-material weight number is shown in Table 1
PA resin is added high mixer high-speed stirred 2 minutes with GF, FG, (various auxiliary agent), and the master joining extruder feeds
Glassware, is then added in double screw extruder carry out basis pelletize.The distribution of this extruder temperature is as follows: extruder temperature is successively
It it is 260 DEG C, 285 DEG C, 290 DEG C, 290 DEG C, 290 DEG C, 285 DEG C, 275 DEG C, 265 DEG C, 250 DEG C, 270 DEG C；Screw rod revolution is 420r/
Min, feeding rotating speed is 20HZ, through water-cooled, pelletizing after material extrusion, then packs.Pellet, at air dry oven, is done for 120 DEG C
Dry 6 hours, then prepared test bars by injection machine.
Embodiment 1～4
Each raw material weight number is shown in Table 1, according to the processes in comparative example 1 and prepare test bars.(following raw material
It is marketable material)
The raw material weight percent proportioning of table 1 embodiment 1～4
Composition properties test result in table 2 embodiment and comparative example
| Performance indications | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 |
| Hot strength | 136 | 142 | 146 | 134 | 140 |
| Bending strength | 235 | 245 | 249 | 230 | 240 |
| Notch impact strength | 11 | 9.5 | 8.5 | 10.3 | 10 |
| Thermal deformation | 242 | 248 | 253 | 241 | 240 |
| Melt index | 18 | 18 | 16 | 20 | 11 |
Embodiment 1 and comparative example 1 compare, it can be seen that the addition of PA6 can improve the impact strength of material.Embodiment 2
Compare with comparative example 1, it can be seen that the addition of PPS can improve thermal deformation and the stretching of material, bending strength.Embodiment 3 He
Embodiment 2 compares, it can be seen that along with the stretch bending increasing material of PPS increases therewith, impact strength has declined.Implement
Example 4 and comparative example 1 compare, it can be seen that the addition of VTECNSF600 can improve the flow rate of material, and mechanical property has
Being declined, thermal property is unaffected.The optimization formula of the present invention is embodiment 2.
Claims (10)
1. a high-performance modified polyamide compoiste material, it is characterised in that by weight percentage, its raw material composition is as follows:
Nylon 6 8-12%；
Glass fibre 30%；
Polyphenylene sulfide 10-20%；
Implant 0.5-4%；
Compatilizer 1-5%；
Processing aid 0.1-1.5%；
Nylon66 fiber surplus.
2. a high-performance modified polyamide compoiste material, it is characterised in that by weight percentage, its raw material composition is as follows:
Nylon66 fiber 43%；
Nylon 6 10%；
Glass fibre 30%；
Polyphenylene sulfide 10%；
Implant 2%；
Compatilizer 4%；
Processing aid 1%.
The high-performance modified polyamide compoiste material of one the most according to claim 1, it is characterised in that: described nylon66 fiber
The feature viscosity number of resin is 2.4-2.9, and the feature viscosity number of described nylon 6 resin is 2.4-3.0.
The high-performance modified polyamide compoiste material of one the most according to claim 1, it is characterised in that: described glass fibers
Dimension is the alkali-free glass fibre of a diameter of 10-20 micron.
The high-performance modified polyamide compoiste material of one the most according to claim 1, it is characterised in that: described polyphenylene sulfide
Ether is the thermoplastic of straight chain type, degree of crystallinity >=60.
The high-performance modified polyamide compoiste material of one the most according to claim 1, it is characterised in that: described filler
It is selected from: glass microballoon, Kaolin, Pulvis Talci, MoS2, wollastonite, any one or the two or more combination in Muscovitum.
The high-performance modified polyamide compoiste material of one the most according to claim 1, it is characterised in that: described compatilizer
Use POE grafted maleic anhydride, Research of Grafting Malaic Anhydride Onto Polyethylene, ethylene butyl acrylate, ethylene acrylic acid co polymer, maleic acid
One or more kinds of combinations in acid anhydride grafting level SEBS.
The high-performance modified polyamide compoiste material of one the most according to claim 1, it is characterised in that: described processing helps
Agent is made up of antioxidant, lubricant and flow ability modifying agent.
The high-performance modified polyamide compoiste material of one the most according to claim 8, it is characterised in that: described antioxidant
For β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive octadecanol ester；Four [β-(3,5-di-tert-butyl-hydroxy phenyls)
Propanoic acid] pentaerythritol ester；Double (2.4-di-tert-butyl-phenyl) tetramethylolmethane；2,6-di-t-butyl-4-4 cresol；Three (2,4-bis-
Tert-butyl-phenyl) phosphite ester；Sulfur generation three propanoic acid dilauryls；In the double stearic alcohol ester of thio-2 acid any one or two
Plant above combination；Described lubricant be any one or two kinds in E wax, calcium stearate, silicone master batch or PETS with
On combination；Described flow ability modifying agent is VTECNSF 600.
10. the preparation method of a kind of high-performance modified polyamide compoiste material described in claim 1, it is characterised in that: according to
Weight ratio weighs each reaction raw materials, then adds raw materials into the mixing of high mixer high-speed stirred, is then added to the main feeding of extruder
Device, is then added in double screw extruder carry out basis pelletize, and extruder temperature distribution is as follows: extruder temperature is followed successively by
260℃、285℃、290℃、290℃、290℃、285℃、275℃、265℃、250℃、270℃；Screw rod revolution is 420r/
Min, feeding rotating speed is 20HZ, through water-cooled, pelletizing after material extrusion, then packs.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610292627.8A CN105968801A (en) | 2016-05-05 | 2016-05-05 | High-performance modified polyamide composite material and preparation method thereof |
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|---|---|---|---|
| CN201610292627.8A CN105968801A (en) | 2016-05-05 | 2016-05-05 | High-performance modified polyamide composite material and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106548825A (en) * | 2016-12-08 | 2017-03-29 | 应剑军 | A kind of glass fibre high temperature-resistant cable and preparation method thereof |
| CN108070248A (en) * | 2016-11-18 | 2018-05-25 | 合肥杰事杰新材料股份有限公司 | A kind of medium-alkali glass fiber enhancing nylon reclaimed materials and preparation method thereof |
| CN108659528A (en) * | 2018-04-24 | 2018-10-16 | 嘉兴希卡姆复合材料有限公司 | A kind of high-performance polyphenylene sulfide and polyamide alloy material and preparation method thereof |
| CN109694573A (en) * | 2018-12-29 | 2019-04-30 | 浙江普利特新材料有限公司 | A kind of high intensity, high tenacity, mechanical resistant oil are for oil sump glass fiber reinforced nylon material and preparation method thereof |
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| US20090275683A1 (en) * | 2008-04-30 | 2009-11-05 | Cheil Industries Inc. | Flame Retardant Thermoplastic Resin Composition |
| CN101619168A (en) * | 2009-08-12 | 2010-01-06 | 深圳市华力兴工程塑料有限公司 | Modified polyphenylene sulfide resin and preparation method thereof |
| CN103224706A (en) * | 2013-04-09 | 2013-07-31 | 浙江俊尔新材料股份有限公司 | Polyphenylene sulfide composite material, preparation method and molding method thereof |
| CN103525088A (en) * | 2013-07-31 | 2014-01-22 | 宁波泛龙塑料新材料有限公司 | Polyphenylene sulfide composite material and preparation method thereof |
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2016
- 2016-05-05 CN CN201610292627.8A patent/CN105968801A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090275683A1 (en) * | 2008-04-30 | 2009-11-05 | Cheil Industries Inc. | Flame Retardant Thermoplastic Resin Composition |
| CN101619168A (en) * | 2009-08-12 | 2010-01-06 | 深圳市华力兴工程塑料有限公司 | Modified polyphenylene sulfide resin and preparation method thereof |
| CN103224706A (en) * | 2013-04-09 | 2013-07-31 | 浙江俊尔新材料股份有限公司 | Polyphenylene sulfide composite material, preparation method and molding method thereof |
| CN103525088A (en) * | 2013-07-31 | 2014-01-22 | 宁波泛龙塑料新材料有限公司 | Polyphenylene sulfide composite material and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108070248A (en) * | 2016-11-18 | 2018-05-25 | 合肥杰事杰新材料股份有限公司 | A kind of medium-alkali glass fiber enhancing nylon reclaimed materials and preparation method thereof |
| CN106548825A (en) * | 2016-12-08 | 2017-03-29 | 应剑军 | A kind of glass fibre high temperature-resistant cable and preparation method thereof |
| CN108659528A (en) * | 2018-04-24 | 2018-10-16 | 嘉兴希卡姆复合材料有限公司 | A kind of high-performance polyphenylene sulfide and polyamide alloy material and preparation method thereof |
| CN109694573A (en) * | 2018-12-29 | 2019-04-30 | 浙江普利特新材料有限公司 | A kind of high intensity, high tenacity, mechanical resistant oil are for oil sump glass fiber reinforced nylon material and preparation method thereof |
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