CN105419320A - High glass fiber filled and reinforced nylon composite and preparation method thereof - Google Patents
High glass fiber filled and reinforced nylon composite and preparation method thereof Download PDFInfo
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- CN105419320A CN105419320A CN201510802747.3A CN201510802747A CN105419320A CN 105419320 A CN105419320 A CN 105419320A CN 201510802747 A CN201510802747 A CN 201510802747A CN 105419320 A CN105419320 A CN 105419320A
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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
- B29C2948/92704—Temperature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses a high glass fiber filled and reinforced nylon composite and a preparation method thereof. The high glass fiber filled and reinforced nylon composite is prepared from, by weight, 35%-45% of PA66 resin, 3%-5% of PA6 resin, 0.3%-0.5% of an antioxidant, 0.2%-0.5% of a coupling reagent, 0.5%-1% of a lubricating agent and 50%-60% of glass fibers. The preparation method includes the steps that all the raw materials are added into an extruder, subjected to melt plastification, extruded through an extruder die head and then subjected to water-cooling bracing granulation, and finally the product nylon composite is obtained. The impact strength of the nylon composite can reach 190 J/M or above, the tensile strength of the nylon composite can reach 215 MPA or above, the bending strength of the nylon composite can reach 330 MPA or above, and the nylon composite has high strength and hydrolysis resistance; the glass fibers are better dispersed into the matrix resin through specific screw configuration, and thus the obtained nylon composite is good in rigidity, has a granular surface appearance and can reduce floating fibers on the surface of an injection-moulded product.
Description
Technical field
The present invention relates to a kind of high glass fibre filling Reinforced Nylon matrix material and preparation method thereof.
Background technology
Nylon is the abbreviation of polyamide resin, owing to having amide group, has certain polarity, exist owing to having firmly hydrogen bond in its structure, make nylon fusing point higher, and stable chemical nature, and then be widely used in industries such as automobile, household electrical appliances, building materials.Then along with the development of science and technology, nylon material is more and more harsher in the service requirements in the fields such as automobile, household electrical appliances, building, common strongthener can not meet service requirements in rigidity, intensity etc., need could meet service requirements by adding more strongthener, and add a large amount of strongtheners, in process of manufacture, there will be strongthener and matrix resin disperses problem of non-uniform, injection surface also there will be a large amount of floating fine, and then does not reach the desirable effect of expection.
Summary of the invention
The present invention is confined to process issues in the market for solving, it adds high glass fiber content filling reinforced nylon 6 dragon, there is processing to extrude difficulty, glass fibre in matrix resin, disperse bad and injection surface to float fine serious problem, propose a kind of high glass fibre filling Reinforced Nylon matrix material and preparation method thereof.
The invention provides a kind of high glass fibre filling Reinforced Nylon matrix material, containing weight ratio be respectively 35% ~ 45% PA66 resin, 3% ~ 5% PA6 resin, 0.3% ~ 0.5% oxidation inhibitor, 0.2% ~ 0.5% coupling agent, 0.5% ~ 1% lubricant and 50% ~ 60% glass fibre.
The shock strength of described nylon composite materials is more than 190J/M, and tensile strength is more than 215MPA, and flexural strength is more than 330MPA.
The present invention also provides a kind of high glass fibre filling Reinforced Nylon composite material and preparation method thereof, and the preparation method of this nylon composite materials comprises the following steps:
Step one: weight ratio is respectively the PA66 resin of 35% ~ 45%, 3% ~ 5% PA6 resin, the oxidation inhibitor of 0.3% ~ 0.5%, the coupling agent of 0.2% ~ 0.5% and 0.5% ~ 1% lubricant join in mixing tank simultaneously, join in forcing machine after mixing
Step 2: glass fibre is joined in forcing machine according to the ratio that weight ratio is 50% ~ 60%;
Step 3: the material in forcing machine is carried out fusion plastification, then extrudes rear water cooling bracing granulation by extruder die head, obtains product nylon composite materials.
The forcing machine of step 3 kind is meshing in the same way type twin screw extruder, has straight-tooth gear dish and angular gear dish, makes the high glass fibre filling Reinforced Nylon matrix material of preparation have specific screw rod configuration, the dispersion of screw rod reinforced glass fiber in matrix resin.
Joined in forcing machine by main feeding manner after the raw material in mixing tank being mixed in step one.
Glass fibre is joined in forcing machine by side feeding manner by step 2.
In step 3, the temperature of fusion plastification is 210 DEG C ~ 280 DEG C.
In step 3 fusion plastification process in shown in the temperature of fusion plastification in each district of forcing machine sees the following form:
In step 3, water-cooled temperature is normal temperature tank temperature.
The advantage that the present invention has is: nylon composite materials provided by the invention there is the high and hydrolytic resistance of intensity, its shock strength can reach more than 190J/M, and tensile strength can reach more than 215MPA, and flexural strength can reach more than 330MPA.By specific screw rod configuration (screw combinations arrangement), glass fibre is better scattered in matrix resin, obtains good rigidity, there is good particle surface outward appearance and the nylon composite materials of injection-molded item surface floating fiber can be reduced.
Accompanying drawing explanation
Fig. 1: the structural representation of the straight-tooth gear dish of forcing machine in the present invention;
Fig. 2: the structural representation of the angular gear dish of forcing machine in the present invention.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, can better understand the present invention and can be implemented, but illustrated embodiment is not as a limitation of the invention to make those skilled in the art.
The invention provides a kind of high glass fibre filling Reinforced Nylon matrix material, composition containing following weight ratio, be respectively the PA66 resin of 35% ~ 45%, 3% ~ 5% PA6 resin, 0.3% ~ 0.5% oxidation inhibitor, 0.2% ~ 0.5% coupling agent, 0.5% ~ 1% lubricant and 50% ~ 60% glass fibre.
Nylon composite materials provided by the invention has the high and hydrolytic resistance of intensity, hydrolysis can be crossed and test resistance to deicing fluid test in 135 DEG C, 48 hours, the shock strength of this nylon composite materials can reach more than 190J/M, tensile strength can reach more than 215MPA, flexural strength can reach more than 330MPA, glass fibre is better scattered in matrix resin, obtains good rigidity, and the outward appearance with particle surface can reduce injection-molded item surface floating fiber problem.
Described oxidation inhibitor divides and comprises primary antioxidant and auxiliary antioxidant, and primary antioxidant is Hinered phenols, and in the present invention, primary antioxidant used is 1098 of BASF production, and auxiliary antioxidant is phosphoric acid lipid, preferred BASF168.The proportioning (weight) of primary antioxidant and auxiliary antioxidant is general between 1:2-1:3, and both arrange in pairs or groups and use better than being used alone a kind of effect, and it does not have effect to be used alone auxiliary antioxidant, must use competence exertion effect with primary antioxidant.Described coupling agent is silane coupling agent, the one in selected commercially available KH550, KH560.The preferred silicone lubricant of described lubricant, the one in preferred DOW CORNING silicone powder, silicone master batch or both interworkings use the requirement of imponderability part.Described glass fibre is alkali-free short glass fiber, and the multiple material HP-3 in preferred Chongqing, filament diameter is 13um.
The present invention also provides a kind of preparation method of high glass fibre filling Reinforced Nylon matrix material, specifically comprises following process:
Step one: first weight ratio is respectively in starting material the PA66 resin of 35% ~ 45%, 3% ~ 5% PA6 resin, the oxidation inhibitor of 0.3% ~ 0.5%, the coupling agent of 0.2% ~ 0.5% and 0.5% ~ 1% lubricant join in mixing tank simultaneously, join in forcing machine by main feeding manner after mixing;
Step 2: be that 50% ~ 60% ratio joins in forcing machine by side feeding manner according to raw-material weight ratio by glass fibre; Wherein, without grain size size requirements time these starting material in step one and two add before mixing, only need before blanking to stir.
Step 3: the fusion plastification material in forcing machine being carried out 200 DEG C ~ 270 DEG C.In the process of fusion plastification, the temperature of the fusion plastification in each district of forcing machine sees the following form shown in 1, after fusion plastification completes, extrudes rear water cooling bracing granulation by extruder die head.Obtain product height glass fibre filling Reinforced Nylon matrix material.The temperature range of concrete water-cooled is normal temperature (20 DEG C ~ 25 DEG C) tank temperature.All not doing specific requirement for wherein fusion time, pressure and granulation size, is normal experiment available data.
Wherein, add after in raw material to forcing machine through step one and step 2, carry out in fusion plastification process at material, material roughly arranges as shown in table 1 below in forcing machine each district major temperature:
Table 1: forcing machine each district major temperature
High glass fibre filling Reinforced Nylon matrix material prepared by the present invention has specific screw rod configuration, after adding glass fibre, by the dispersion of screw rod reinforced glass fiber in matrix resin of forcing machine, the shearing of specific configuration comprises straight-tooth gear dish, angular gear dish (K45/5/56, K60/4/44), as depicted in figs. 1 and 2, forcing machine is mould assembly twin screw extruder in the same way, toothed disc is as the one of shearing elements in forcing machine, it is more eager to excel in whatever one does than other shearing elements with the dispersive ability of matrix resin to glass fibre, enclose and shear dispersion section screw combinations array data in table 1.
Table 1: shear the different screw rod configuration of dispersion section to product appearance with the impact of transitivity
Remarks: ZME represents toothed disc shearing elements.Wherein 56 helical pitches representing shearing elements in ZME56/28,28 length representing shearing elements, more such as K45/5/56, represent block shearing elements, angle is 45 °, and length is 56mm, 5 pieces altogether, and every block thickness is 56/5=12.2mm.
The material auxiliary agent that high glass fibre filling Reinforced Nylon matrix material prepared by the present invention uses is for buying in market, and price is low, easily realizes volume production.
The present invention also provides another one embodiment, provides the high glass fibre filling Reinforced Nylon composite material compositions of different added ingredients with following table 2:
Table 2: high glass fibre filling Reinforced Nylon composite material compositions
| Recipe ingredient | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| PA66 resin | 43.50% | 43.50% | 35.50% |
| PA6 resin | 5% | 5% | 3% |
| Silane coupling agent KH550 | 0.20% | 0.20% | 0.20% |
| Primary antioxidant 1098 | 0.20% | 0.20% | 0.20% |
| Auxiliary antioxidant 168 | 0.10% | 0.10% | 0.10% |
| Lubricant silicone master batch | 1% | 1% | 1% |
| Glass fibre | 50% | 50% | 60% |
The embodiment of table 1 in correspondence, its physicals refers to table 3
Table 3: high glass fibre filling Reinforced Nylon matrix material
| Test item | Examination criteria | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 3 |
| Density | ASTM D792 | 1.55 | 1.55 | 1.6 | 1.55 | 1.6 |
| Tensile strength | ASTM D638 | 215 | 210 | 230 | 210 | 230 |
| Elongation at break | ASTM D638 | 2 | 2 | 2.5 | 2 | 2.3 |
| Flexural strength | ASTM D790 | 330 | 320 | 360 | 310 | 330 |
| Modulus in flexure | ASTM D790 | 12500 | 12000 | 15500 | 12000 | 14500 |
| Izod notched impact strength | ASTM D256 | 19 | 18 | 24 | 16 | 21 |
| Glass/glass fibre content | 50 | 50 | 60 | 50 | 60 |
High glass fibre filling Reinforced Nylon matrix material prepared by the present invention, not only particle outward appearance is closely knit, and the mechanical property of materials is excellent, has anti-hydrolytic performance, and heat resistance is good.The present invention replace steel in automobile, household electrical appliance etc. can widespread use, and its important applied field is sanitaryware, due to the processing characteristics of the special rigidity of material, creep resistance, intensity, hydrolytic resistance and excellence, successful Application is on sanitaryware cold and hot water pipe fitting.It is polyphenyl ether material that the present invention can replace metal and high temperature plastics PPS to add fine 40%(PPS, and this rigidity of material is strong, and shrinking percentage is low, can substituted metal goods, but this material price is higher).On vehicle structure accessory, owing to having high temperature tolerance, anti-hydrolytic performance, be used successfully to cooling water car groove, vehicle turbine intercooler material, not only reduced production cost, and reduce auto parts machinery weight, the object of energy-saving and emission-reduction can also be reached.
The present invention reintroduces an embodiment, this embodiment provides a kind of high glass fibre filling Reinforced Nylon matrix material, containing weight ratio be respectively 40% PA66 resin, 4% PA6 resin, 0.4% oxidation inhibitor, 0.3% coupling agent, 0.7% lubricant and 54.6% glass fibre.Described preparation method carries out fusion plastification after each material composition is joined forcing machine, extrudes rear water cooling bracing granulation, finally obtain product nylon composite materials by extruder die head.The shock strength of this nylon composite materials can reach more than 190J/M, tensile strength can reach more than 215MPA, flexural strength can reach more than 330MPA, there is the high and hydrolytic resistance of intensity, by specific screw rod configuration, glass fibre is better scattered in matrix resin, obtains good rigidity, there is the outward appearance of particle surface and the nylon composite materials of injection-molded item surface floating fiber can be reduced.
The present embodiment also provides a kind of preparation method of high glass fibre filling Reinforced Nylon matrix material, specifically comprises following process:
Step one: first weight ratio is respectively in starting material the PA66 resin of 40%, 4% PA6 resin, the oxidation inhibitor of 0.4%, coupling agent, 0.7% lubricant of 0.3% join in mixing tank simultaneously, join in forcing machine by main feeding manner after mixing;
Step 2: be that 54.6% ratio joins in forcing machine by side feeding manner according to raw-material weight ratio by glass fibre; Wherein, without grain size size requirements time these starting material in step one and two add before mixing, only need before blanking to stir.
Step 3: the fusion plastification material in forcing machine being carried out 250 DEG C.In the process of fusion plastification, the temperature of the fusion plastification in each district of forcing machine sees the following form shown in 4, after fusion plastification completes, extrudes rear water cooling bracing granulation by extruder die head.Obtain product height glass fibre filling Reinforced Nylon matrix material.The temperature range of concrete water-cooled is normal temperature (25 DEG C) tank temperature.All not doing specific requirement for wherein fusion time, pressure and granulation size, is normal experiment available data.
Wherein, add after in raw material to forcing machine through step one and step 2, carry out in fusion plastification process at material, material roughly arranges as shown in table 4 below in forcing machine each district major temperature:
Table 4: forcing machine each district major temperature
| 1st district | 2nd district | 3rd district | 4th district | 5th district | 6th district | 7th district | 8th district | 9th district | 10th district |
| 220℃ | 230℃ | 270℃ | 280℃ | 270℃ | 270℃ | 250℃ | 240℃ | 225℃ | 270℃ |
High glass fibre filling Reinforced Nylon matrix material prepared by the present embodiment has specific screw rod configuration, after adding glass fibre, by the dispersion of screw rod reinforced glass fiber in matrix resin of forcing machine, the shearing of specific configuration comprises straight-tooth gear dish, angular gear dish (K45/5/56, K60/4/44).Forcing machine is mould assembly twin screw extruder in the same way, and toothed disc is as the one of shearing elements in forcing machine, and it is more eager to excel in whatever one does than other shearing elements with the dispersive ability of matrix resin to glass fibre.
The above embodiment is only that protection scope of the present invention is not limited thereto in order to absolutely prove the preferred embodiment that the present invention lifts.The equivalent alternative or conversion that those skilled in the art do on basis of the present invention, all within protection scope of the present invention.Protection scope of the present invention is as the criterion with claims.
Claims (9)
1. one kind high glass fibre filling Reinforced Nylon matrix material, it is characterized in that, containing weight ratio be respectively 35% ~ 45% PA66 resin, 3% ~ 5% PA6 resin, 0.3% ~ 0.5% oxidation inhibitor, 0.2% ~ 0.5% coupling agent, 0.5% ~ 1% lubricant and 50% ~ 60% glass fibre.
2. high glass fibre filling Reinforced Nylon matrix material according to claim 1, is characterized in that, the shock strength of described nylon composite materials is more than 190J/M, and tensile strength is more than 215MPA, and flexural strength is more than 330MPA.
3. a high glass fibre filling Reinforced Nylon composite material and preparation method thereof, it is characterized in that, the preparation method of this nylon composite materials comprises the following steps:
Step one: weight ratio is respectively the PA66 resin of 35% ~ 45%, 3% ~ 5% PA6 resin, the oxidation inhibitor of 0.3% ~ 0.5%, the coupling agent of 0.2% ~ 0.5% and 0.5% ~ 1% lubricant join in mixing tank simultaneously, join in forcing machine after mixing
Step 2: glass fibre is joined in forcing machine according to the ratio that weight ratio is 50% ~ 60%;
Step 3: the material in forcing machine is carried out fusion plastification, then extrudes rear water cooling bracing granulation by extruder die head, obtains product nylon composite materials.
4. high glass fibre filling Reinforced Nylon matrix material according to claim 3, it is characterized in that, the forcing machine of step 3 kind is meshing in the same way type twin screw extruder, there is straight-tooth gear dish and angular gear dish, the high glass fibre filling Reinforced Nylon matrix material of preparation is made to have specific screw rod configuration, the dispersion of screw rod reinforced glass fiber in matrix resin.
5. high glass fibre filling Reinforced Nylon matrix material according to claim 3, be is characterized in that, by main feeding manner joined in forcing machine after being mixed by the raw material in mixing tank in step one.
6. high glass fibre filling Reinforced Nylon matrix material according to claim 3, it is characterized in that, glass fibre is joined in forcing machine by side feeding manner by step 2.
7. the preparation method of high glass fibre filling Reinforced Nylon matrix material according to claim 3, is characterized in that, in step 3, the temperature of fusion plastification is 210 DEG C ~ 280 DEG C.
8. the preparation method of high glass fibre filling Reinforced Nylon matrix material according to claim 6, is characterized in that, in step 3 fusion plastification process in shown in the temperature of fusion plastification in each district of forcing machine sees the following form:
。
9. the preparation method of high glass fibre filling Reinforced Nylon matrix material according to claim 3, is characterized in that, in step 3, water-cooled temperature is normal temperature tank temperature.
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Cited By (5)
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| CN111621151A (en) * | 2020-07-09 | 2020-09-04 | 东莞市奥能工程塑料有限公司 | High-rigidity high-bonding-strength nylon reinforced material and preparation method thereof |
| CN111718576A (en) * | 2019-03-19 | 2020-09-29 | 上海术博新材料技术有限公司 | High-strength friction-resistant nylon composite material and preparation method thereof |
| CN112029264A (en) * | 2020-09-11 | 2020-12-04 | 广州辰东新材料有限公司 | High-rigidity long-chain nylon composite material and preparation method thereof |
| WO2021057372A1 (en) * | 2019-09-25 | 2021-04-01 | 广东格瑞新材料股份有限公司 | High-rigidity nylon composite material and preparation method therefor |
| CN113667300A (en) * | 2021-09-14 | 2021-11-19 | 四川恒领皓睿塑胶科技有限公司 | Glass fiber reinforced engineering plastic and preparation method thereof |
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| CN111718576A (en) * | 2019-03-19 | 2020-09-29 | 上海术博新材料技术有限公司 | High-strength friction-resistant nylon composite material and preparation method thereof |
| WO2021057372A1 (en) * | 2019-09-25 | 2021-04-01 | 广东格瑞新材料股份有限公司 | High-rigidity nylon composite material and preparation method therefor |
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| CN112029264B (en) * | 2020-09-11 | 2023-01-20 | 广州辰东新材料有限公司 | High-rigidity long-chain nylon composite material and preparation method thereof |
| CN113667300A (en) * | 2021-09-14 | 2021-11-19 | 四川恒领皓睿塑胶科技有限公司 | Glass fiber reinforced engineering plastic and preparation method thereof |
| CN113667300B (en) * | 2021-09-14 | 2023-09-19 | 四川恒领皓睿塑胶科技有限公司 | Glass fiber reinforced engineering plastic and preparation method thereof |
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