CN102443261A - Polyamide (PA) material modification method - Google Patents

Polyamide (PA) material modification method Download PDF

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Publication number
CN102443261A
CN102443261A CN2011100251650A CN201110025165A CN102443261A CN 102443261 A CN102443261 A CN 102443261A CN 2011100251650 A CN2011100251650 A CN 2011100251650A CN 201110025165 A CN201110025165 A CN 201110025165A CN 102443261 A CN102443261 A CN 102443261A
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China
Prior art keywords
polyamide
aramid fiber
modifying
speed
polyamide material
Prior art date
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Pending
Application number
CN2011100251650A
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Chinese (zh)
Inventor
宋伟
潘雷
刘光裕
高朝乾
刘强
马芳武
李书福
杨健
赵福全
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Zhejiang Geely Holding Group Co Ltd
Zhejiang Geely Automobile Research Institute Co Ltd
Original Assignee
Zhejiang Geely Holding Group Co Ltd
Zhejiang Geely Automobile Research Institute Co Ltd
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Priority to CN2011100251650A priority Critical patent/CN102443261A/en
Publication of CN102443261A publication Critical patent/CN102443261A/en
Pending legal-status Critical Current

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Classifications

    • 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
    • B29C48/03—Extrusion 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
    • B29C48/04—Particle-shaped
    • 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
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • 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
    • B29C2948/9259—Angular 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
    • 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
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92885—Screw or gear
    • 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
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a high molecular composite material. At present, polyamide (PA) is widely used in multiple fields and is frequently used in the automobile field. PA used as a structural material has the advantages of high mechanical property, fine solvent resistance, good workability and the like; but PA is poor in heat resistance, water resistance and dimensional stability, and accordingly needs to be modified. The invention provides a PA material modification method which comprises the following steps: thoroughly mixing all components at a mixing speed of 3000-5000r/min in a high-speed mixer, wherein the components comprise 60-80% of PA, 5-25% of polyphenyl ether and 5-25% of aromatic polyamide fiber in percentage by mass; after the high-speed stirring of 2-3 minutes, putting into a double-screw extruder for melting granulation, wherein the extrusion temperature is 250-270 DEG C, and the rotation speed of the screw is 160-200r/min; and carrying out injection molding on the dried granules in an injection molding machine. The modified PA material has favorable comprehensive mechanical property.

Description

A kind of polyamide material method of modifying
Technical field
The present invention relates to polymer composite, relate in particular to a kind of method of modifying in polyamide material.
Background technology
Polymeric amide (PA is commonly called as nylon) is the engineering plastics of one type of excellent performance, is widely used in multiple field; Polymeric amide has advantages such as mechanical property height, good, the easy processing of solvent resistance as structural material, but PA thermotolerance, water tolerance and poor dimensional stability; Need it is carried out modification; Through modification, improve its some performance, enlarge its Application Areas.In the automotive applications field, mainly carry out modification: improve the water-absorbent of nylon, improve the dimensional stability of goods in following several respects; Improve the physical strength of nylon; Improve the wear resistance of nylon, to adapt to wear-resisting demanding occasion; Improve the thermotolerance of nylon.
PA becomes the main flow of modified engineered plastic development after the modification.Nylon alloyization is to realize the high performance important channel of nylon, also is the main means of making the nylon PP Pipe Compound, improving properties of nylons.Through other superpolymer of blending, improve the water-absorbent of nylon, improve the dimensional stability of goods, and low temperature brittleness, thermotolerance and wear resistance.Thereby, the purposes of suitable car type demands of different.
In a word,, realize the high performance and the functionalization of nylon composite materials, and then promote the relevant industries product to develop to high-performance, high quality direction through above-mentioned improvement.
The Chinese patent of application number CN200310103221.3 discloses a kind of modified polyamide composition and method of making the same, relates to the technical field to the polyamide resin modification.The median size that this daiamid composition includes blend is butylbenzene pyrrole powdered rubber and the polymeric amide of 30～200nm; The weight ratio of powdered rubber and polymeric amide is 1: 99～50: 50, will comprise the component melts blend of said butylbenzene pyrrole powdered rubber and polymeric amide and makes daiamid composition.The document is a raw material with butylbenzene pyrrole powdered rubber, and as novel elastomer, butylbenzene pyrrole powdered rubber has the low characteristic of viscosity, but the polyamide material after the modification also be not best aspect the comprehensive mechanical properties such as tensile strength.
Summary of the invention
At present, polymeric amide is widely used in multiple field, and the application on automotive field is also many especially; Polymeric amide is as structural material; Have advantages such as mechanical property height, good, the easy processing of solvent resistance, but PA thermotolerance, water tolerance and poor dimensional stability need carry out modification to it; The present invention proposes a kind of polyamide material method of modifying, the polyamide material after the modification has good comprehensive mechanical properties.
The present invention realizes through following technical scheme: a kind of polyamide material method of modifying, and described method of modifying is following:
(1) component of polyamide modified material and mass percent thereof are:
Polyamide 6 0%～80%
Ppe 5%～25%
Aramid fiber 5%～25%
(2) method of modifying of polyamide material:
With each component thorough mixing in high speed mixer, mixing velocity 3000～5000r/min is after the high-speed stirring of 2～3min; Put into the twin screw extruder melt pelletization; 250～270 ℃ of extrusion temperatures, screw speed 160～200r/min uses the injection moulding machine injection moulding with dried granules.
Ppe (PPO) has many excellent properties, and is high like: physical strength, thermotolerance, water tolerance, excellent in dimensional stability, and electrical insulating property, combustion-supporting property, chemical-resistant are good.And ppe (PPO) is organic materials, can be compatible preferably with matrix, in automotive industry purposes is widely arranged simultaneously, and PPO and PA alloy, very fast at the exterior member development ratio of high-impact ability.
As preferably, described polymeric amide is selected from PA66.The hardness of nylon 66 in the nylon, rigidity are the highest, have very strong price advantage simultaneously.
The aramid fiber full name is a PPTA, belongs to organic fibre, is the abbreviation of aromatic polyamide fibre; Be a kind of novel high-tech synthon, have superstrength, high-modulus and high temperature resistant, acid-fast alkali-proof, premium properties such as in light weight, its intensity is 5～6 times of steel wire; Modulus is steel wire or spun glass 2～3 times, and toughness is 2 times of steel wire, and weight is merely about 1/5 of steel wire; Under the temperature of 560 degree, do not decompose, do not melt.It has good insulation performance property and ageing resistance, has very long life cycle.
Aramid fiber is very soft, can rise directly, be curled in the matrix, has hindered crack propagation; And when fiber break from matrix extract after, owing to friction makes waste of energy, improve impelling strength.
As preferably, described aramid fiber is selected from contraposition aramid fiber (PPTA).Because the PPTA fiber shows lyotropic liquid crystalline; It is a kind of important backbone chain type high molecule liquid crystal; Can be scattered in the isotropy matrix material of processing excellent property in the matrix better; The mechanical property that its good thermotolerance, erosion resistance are become reconciled has obtained better application in friction sealed matrix material (replacement asbestos).The most outstanding performance of p-aramid fiber is its HS, high-modulus and outstanding thermotolerance.The weight ratio tensile strength of standard P PTA aramid fiber is 6 times of steel wire, 3 times of glass, 2 times of high-strength nylon industry silk; Its tensile modulus is 3 times of steel wire, 2 times of glass, 10 times of high-strength nylon industry silk; Experience 100hr down at 200 ℃, still can keep 75% of former intensity, experience 500hr down, still can keep 95% of former intensity at 160 ℃.In view of the above, p-aramid fiber is used as lightweight, heat-stable textile structural material or composite structure strongthener mostly.
As preferably, before aramid fiber uses, earlier aramid fiber is soaked 10～15 hours with acetone after, boiled 1～1.5 hour with absolute ethyl alcohol and zero(ppm) water respectively again, use after putting into oven for drying at last.Unwashed aramid fiber surface has more dirt settling, and the dirt settling of the fiber surface after cleaning disappears basically, and fiber surface is Paint Gloss, follow-up fiber surface is carried out chemical treatment, when making it produce active site, can directly carry out activation at fiber surface.Therefore, combine well with the resin matrix interface, fiber is cleaned be necessary for making fiber.
Therefore, the present invention just is being based on the excellent properties of ppe and aramid fiber, the comprehensive excellent properties of reinforced polyamide material.
Compared with prior art; The invention has the beneficial effects as follows: its over-all properties is greatly improved with aramid fiber and ppe (PPO) modification PA; PA with its modification can make large-scale baffle plate, wheel cover and cushion plate etc., quality and the life-span that can improve component.
Embodiment
Below in conjunction with embodiment the present invention is done further explain.
Embodiment 1
(1) taking by weighing mass percent is 10% aramid fiber (PPTA Kevlar1414), 20 grams, my parent form ppta-pulp fibre (pavilion high mountain, Dingxing County science and technology green wood ltd produces); Mass percent is that 20% ppe (PPO) powder, 40 grams (GE company), limiting viscosity are that 0.43dl/g and mass percent are 70% polymeric amide (PA66) 140 grams (French Rhodia).After aramid fiber soaked 12h with acetone, boil 1h respectively, use after putting into oven for drying with absolute ethyl alcohol and zero(ppm) water.
(2) with above-mentioned each component thorough mixing in high speed mixer, mixing velocity 4000r/min.After the high-speed stirring of 2～3min, put into the twin screw extruder melt pelletization, 260 ℃ of extrusion temperatures, screw speed 180r/min.Dried granules is used the injection moulding machine injection moulding.
Embodiment 2～5
The component and the mass percent thereof of polyamide modified material are as shown in table 1, carry out the modification of polyamide material according to the method for modifying of embodiment 1.
The mass percent of table 1: embodiment 1～5 each component
Figure BDA0000044820280000031
Comparative example 1
Pure polymeric amide PA66
Comparative example 2
(1) taking by weighing mass percent is 10% aramid fiber (PPTA Kevlar1414), 20 grams, my parent form ppta-pulp fibre (pavilion high mountain, Dingxing County science and technology green wood ltd produces); Mass percent is 90% polymeric amide (PA66) 180 grams (French Rhodia).After aramid fiber soaked 12h with acetone, boil 1h respectively, use after putting into oven for drying with absolute ethyl alcohol and zero(ppm) water.
(2) with above-mentioned each component thorough mixing in high speed mixer, mixing velocity 4000r/min.After the high-speed stirring of 2～3min, put into the twin screw extruder melt pelletization, 260 ℃ of extrusion temperatures, screw speed 180r/min.Dried granules is used the injection moulding machine injection moulding.
Comparative example 3
(1) taking by weighing mass percent is that 10% ppe (PPO) powder, 40 grams (GE company), limiting viscosity are that 0.43dl/g and mass percent are 90% polymeric amide (PA66) 140 grams (French Rhodia).
(2) with above-mentioned each component thorough mixing in high speed mixer, mixing velocity 4000r/min.After the high-speed stirring of 2～3min, put into the twin screw extruder melt pelletization, 260 ℃ of extrusion temperatures, screw speed 180r/min.Dried granules is used the injection moulding machine injection moulding.
The mass percent of each component in table 2 comparative example 1～3
Figure BDA0000044820280000041
Polyamide modified material after the embodiment modification, its mechanical property is as shown in table 2.
Table 3: the mechanical property of each embodiment and comparative example contrast as follows:
Figure BDA0000044820280000051
Therefore embodiment 1 is the preferred embodiment of polyamide modified material excellent combination property.

Claims (4)

1. a polyamide material method of modifying is characterized in that, described method of modifying is following:
(1) component of polyamide modified material and mass percent thereof are:
Polyamide 6 0% ~ 80%
Ppe 5% ~ 25%
Aramid fiber 5% ~ 25%
(2) method of modifying of polyamide material:
With each component thorough mixing in high speed mixer, mixing velocity 3000 ~ 5000r/min is after the high-speed stirring of 2 ~ 3min; Put into the twin screw extruder melt pelletization; 250 ~ 270 ℃ of extrusion temperatures, screw speed 160 ~ 200 r/min use the injection moulding machine injection moulding with dried granules.
2. a kind of polyamide material method of modifying according to claim 1, it is characterized in that: described polymeric amide is selected from PA66.
3. a kind of polyamide material method of modifying according to claim 1, it is characterized in that: described aramid fiber is selected from the contraposition aramid fiber.
4. according to claim 1 or 2 or 3 described a kind of polyamide material method of modifying; It is characterized in that: before aramid fiber uses; After earlier aramid fiber being soaked 10 ~ 15 hours with acetone, boiled 1 ~ 1.5 hour with absolute ethyl alcohol and zero(ppm) water respectively again, use after putting into oven for drying at last.
CN2011100251650A 2011-01-21 2011-01-21 Polyamide (PA) material modification method Pending CN102443261A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103709742A (en) * 2012-09-29 2014-04-09 黑龙江鑫达企业集团有限公司 Modified aramid fiber reinforced PA66 material and preparation method thereof
CN110684337A (en) * 2018-07-04 2020-01-14 中蓝晨光化工研究设计院有限公司 High-performance scratch-resistant polyamide/polyphenyl ether composite material and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103709742A (en) * 2012-09-29 2014-04-09 黑龙江鑫达企业集团有限公司 Modified aramid fiber reinforced PA66 material and preparation method thereof
CN103709742B (en) * 2012-09-29 2016-03-23 黑龙江鑫达企业集团有限公司 A kind of modification of aramid fiber reinforced plastic PA66 material and preparation method thereof
CN110684337A (en) * 2018-07-04 2020-01-14 中蓝晨光化工研究设计院有限公司 High-performance scratch-resistant polyamide/polyphenyl ether composite material and preparation method thereof
CN110684337B (en) * 2018-07-04 2022-05-03 中蓝晨光化工研究设计院有限公司 High-performance scratch-resistant polyamide/polyphenyl ether composite material and preparation method thereof

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Application publication date: 20120509