CN105694444B - A kind of long basalt fibre enhancing PA6 composites and its melt impregnation preparation method - Google Patents
A kind of long basalt fibre enhancing PA6 composites and its melt impregnation preparation method Download PDFInfo
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- CN105694444B CN105694444B CN201610207580.0A CN201610207580A CN105694444B CN 105694444 B CN105694444 B CN 105694444B CN 201610207580 A CN201610207580 A CN 201610207580A CN 105694444 B CN105694444 B CN 105694444B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
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- 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
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention belongs to field of compound material, specifically a kind of long basalt fibre enhancing PA6 composites and its melt impregnation preparation method.The composite is prepared by the raw material of following weight percents, 15 ~ 50wt% long basalt fibre, 48 ~ 80wt% PA6 master batches and 2 ~ 5wt% processing aid；The processing aid is silane coupler.Compared with prior art, the melt impregnation preparation method of the long basalt fibre enhancing PA6 composites of the present invention, realize that resin is sufficiently impregnated to fiber by the concave-convex wheel structure design of dip roll, with reference to the temperature regulating device of impregnation mold, the accurate control to melt temperature can be achieved.Long basalt fibre enhancing PA6 composites prepared by the present invention, it is tightly combined between fiber and resin matrix, mechanical property and friction and wear behavior are excellent, can solve the performance deficiency of PA6 matrixes, give full play to the enhancing effect and superiority of effectiveness of basalt fibre, processing method is simple, has industrial applications prospect.
Description
Technical field
The invention belongs to field of compound material, specially a kind of long basalt fibre enhancing PA6 composites and its melting
Impregnation preparation method.
Background technology
As one of four large-engineering plastics, nylon (PA) have high intensity, high-wearing feature, oil resistant, weak acid resistant, self-lubricating,
The performance advantage such as insulation and easy processing, is widely used in the industries such as automobile, machinery, electrical equipment, building, light industry.But PA
Hygroscopicity is big, and product size stability is poor, and intensity and rigidity can not show a candle to metal, in some particular applications, as mining machinery,
When transmission equipment, transmission parts etc., anti-wear performance wretched insufficiency.Current energy-conserving and environment-protective theory is rooted in the hearts of the people, to mould Dai Gangcheng
For a trend obvious all the more, by the nylon material of enhancing, its corrosion-resistant, dimensional stability, specific strength are more excellent,
Combination property is even better than common iron.At present, a large amount of enhancings have been carried out to PA both at home and abroad to be modified, method of modifying selects glass more
Fiber, carbon fiber are as reinforcing material, and still, glass fiber reinforcement PA can not fully meet the requirement of performance, and carbon is fine
Tie up expensive, cause manufacturing cost to increase, novel enhanced fiber and its composite technology of preparing are badly in need of research and development.
Nearly ten years, basalt fibre has become the novel enhanced material of great competitiveness in composite.It is fine with carbon
The high performance fibers such as dimension, aramid fiber, superhigh molecular weight polyethylene fibers are compared, and basalt fibre is except with high intensity and height
Outside the characteristics of modulus, also with heat-resisting quantity is good, good in oxidation resistance, radiation resistance is excellent, thermal acoustic insulation effect is good, filterability is good,
Compression strength and shear strength are high, are adapted under various environment and the excellent properties such as use.In addition, basalt fibre is cost-effective,
Harmless in production process for the pure natural inorganic non-metallic material of unartificial synthesis, life of product length, is that one kind can meet state
The low cost of people's economic base industry development demand, high-performance, green new material.
Long-fiber-reinforced thermoplastics (LFRT) are a kind of tencel enhancing technologies quickly grown in recent years, due to
The damage of fiber, breaking degree are reduced to minimum in preparation process, and LFRT has than conventional staple reinforced thermoplastics
More excellent mechanical property and hot property, and long fibre is mutually wound, and forms a kind of fiber reinforcement, can limit anisotropy
Shrink, significantly reduce warpage, improve the dimensional stability of product.Basalt fibre is applied to nylon reinforcements, borrowed simultaneously
Fiber reinforced thermoplastics (LFRT) technology of growth encourage, the performance advantage of basalt fibre can be given full play to, so as to significantly extend
The application of the engineering plastics such as nylon.
A kind of cost of present invention offer is low, fiber impregnation is abundant, long basalt fibre simple to operate enhancing PA6 composite woods
Material and its melt impregnation preparation method, homogeneous impregnation of the resin to basalt fibre, institute can be realized by modulation process parameter
The interface cohesion of the composite of preparation, fiber and resin is firm, and mechanical property, friction and wear behavior etc. are excellent, has wider
Wealthy application prospect.
The content of the invention
In order to overcome the performance deficiency of PA6 composites and deficiency, the invention provides a kind of long basalt fibre to strengthen
PA6 composites and its melt impregnation preparation method.
The present invention is achieved by the following technical solutions：A kind of long basalt fibre enhancing PA6 composites, are under
What the raw material of row percentage by weight was prepared, 15~50wt% long basalt fibre, 48~80wt% PA6 master batches and
2~5wt% processing aid；The processing aid is silane coupler.
Silane coupler of the silane coupler preferably containing amino, NCO or epoxy radicals.
For further description technical scheme, the invention provides a kind of long basalt fibre to strengthen
The melt impregnation preparation method of PA6 composites, it uses above-mentioned raw materials, is prepared according to following processing step：Will be long profound
Military rock fiber is drawn and deployed from the long fibre volume on support, is incorporated into by deflector roll and spacing deflector roll in temperature control impregnation mold
Dip roll on, PA6 master batches and processing aid are squeezed into temperature control impregnation mold by extruder, regulate and control temperature control impregnation mold in
Temperature and carry-over pinch rolls speed, the fibre bundle after dipping enters bosh by the guide roller of bosh porch
Cool down on interior pressure roller, through being granulated, dry, then obtain long basalt fibre enhancing PA6 composites.
When it is implemented, the temperature in the temperature control impregnation mold is 225~250 DEG C, the pulling speed of basalt fibre
For 5~35mm/s.Preferable temperature and speed can ensure that PA6 master batches and processing aid are sufficiently mixed in the molten state, from
And make it that dipping material is uniform to the dipping of fiber.
In order to preferably make dipping material uniform impregnation of fiber, preferable each installation direction of dip roll and fibre bundle
Moving direction is perpendicular, coordinates between adjacent dip roll in top-bottom cross.During concrete application, the number of the dip roll is 2~8
It is individual.
Compared with prior art, long basalt fibre enhancing PA6 composites provided by the invention overcome PA6 matrixes
Performance deficiency, the enhancing effect and superiority of effectiveness of basalt fibre are given full play to, the long basalt fibre enhancing provided
The melt impregnation preparation method of PA6 composites, realize resin to the abundant of fiber by the concave-convex wheel structure design of dip roll
Dipping, with reference to the temperature regulating device of impregnation mold, the accurate control to melt temperature can be achieved.Long basalt prepared by the present invention is fine
Dimension enhancing PA6 composites, are tightly combined, mechanical property and friction and wear behavior are excellent, can solve between fiber and resin matrix
The certainly performance deficiency of PA6 matrixes, the enhancing effect and superiority of effectiveness of basalt fibre are given full play to, processing method is simple, tool
There is industrial applications prospect.
Brief description of the drawings
Fig. 1 is used the structural representation of device by melt impregnation preparation method of the present invention.In figure：1- supports, 2- length are fine
Dimension volume, 3- deflector rolls, the spacing deflector rolls of 4-, 5- extruders, 6- temperature control impregnation molds, 7- dip rolls, 8- boshes, 9- guide rollers,
10- carry-over pinch rolls, 11- pelleters, 12- pressure rollers.
Fig. 2 is long basalt fibre/PA6 composite Tensile fracture stereoscan photographs prepared by the embodiment of the present invention 1.
Show that the interface cohesion of fiber and resin matrix is firm in figure, illustrate the long basalt fibre enhancing PA6 composites of the present invention
Melt impregnation preparation method can be sufficiently impregnated fiber.
Embodiment
Referring to Fig. 1, melt impregnation preparation method of the present invention is completed using following device, and described device includes peace
Support 1 equipped with some long fibres volume 2, the temperature control impregnation mold 6 being connected with the port of export of extruder 5, is installed on support 1 successively
Deflector roll 3 and spacing deflector roll 4 between temperature control impregnation mold 6, some dip rolls 7 being installed in temperature control impregnation mold 6, set
In the bosh 8 of the port of export of temperature control impregnation mold 6, the pressure roller 12 being installed in bosh 8, bosh is respectively arranged in
8 porch and two guide rollers 9 in exit, are installed on the carry-over pinch rolls 10 in the exit of bosh 8 and are installed on carry-over pinch rolls 10
The pelleter 11 of discharge end.
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
Embodiment 1：
Fibre bundle is drawn and deployed from the long fibre volume 2 on support 1, by deflector roll 3, spacing deflector roll 4 is incorporated into control
In warm impregnation mold 6, supporting extruder 5 is connected with temperature control impregnation mold 6, and extruder 5 is by PA6 (80wt%), γ-aminopropyl
Triethoxysilane (5wt%) squeezes into temperature control impregnation mold 6 (dip roll 7 totally 2), by the temperature of temperature control impregnation mold 6
Adjust to the speed of 250 DEG C, carry-over pinch rolls 10 and be set as 35mm/s, so that the content of long basalt fibre is 15wt%.Will dipping
Fibre bundle afterwards is directed through bosh 8 and cooled down, and is granulated in pelleter 11, dries, then obtains long basalt fibre
Strengthen PA6 composites.Gained composite is injection moulded to obtain standard batten, test obtains the mechanics of composite and rubbed
Polishing machine is wiped, is shown in Table 1.
Embodiment 2：
Fibre bundle is drawn and deployed from the long fibre volume 2 on support 1, by deflector roll 3, spacing deflector roll 4 is incorporated into control
In warm impregnation mold 6, supporting extruder 5 is connected with temperature control impregnation mold 6, and extruder 5 is sweet by PA6 (48wt%), γ-shrink
Oily ether oxygen propyl trimethoxy silicane (2wt%) squeezes into temperature control impregnation mold 6 (dip roll 7 totally 5), by temperature control dipping former
Temperature adjustment to the speed of 235 DEG C, carry-over pinch rolls 10 of tool 6 is set as 16mm/s, so that the content of long basalt fibre is
50wt%.Fibre bundle after dipping is directed through into bosh 8 to be cooled down, is granulated in pelleter 11, dries, then obtains
Long basalt fibre strengthens PA6 composites.Gained composite is injection moulded to obtain standard batten, test obtains composite wood
The mechanics and friction and wear behavior of material, are shown in Table 1.
Embodiment 3：
Fibre bundle is drawn and deployed from the long fibre volume 2 on support 1, by deflector roll 3, spacing deflector roll 4 is incorporated into control
In warm impregnation mold 6, supporting extruder 5 is connected with temperature control impregnation mold 6, and extruder 5 is by PA6 (48wt%), γ-isocyanic acid
Propyl-triethoxysilicane (3wt%) squeezes into temperature control impregnation mold 6 (dip roll 7 totally 8, by the temperature of temperature control impregnation mold 6
Degree regulation to the speed of 230 DEG C, carry-over pinch rolls 10 is set as 10mm/s, so that the content of long basalt fibre is 49wt%.Will leaching
Fibre bundle after stain is directed through bosh 8 and cooled down, and is granulated in pelleter 11, dries, then it is fine to obtain long basalt
Dimension enhancing PA6 composites.Gained composite is injection moulded to obtain standard batten, test obtain composite mechanics and
Friction and wear behavior, it is shown in Table 1.
Embodiment 4：
Fibre bundle is drawn and deployed from the long fibre volume 2 on support 1, by deflector roll 3, spacing deflector roll 4 is incorporated into control
In warm impregnation mold 6, supporting extruder 5 is connected with temperature control impregnation mold 6, and extruder 5 is by PA6 (58wt%), γ-isocyanic acid
Propyl-triethoxysilicane (2wt%) squeezes into temperature control impregnation mold 6 (dip roll 7 totally 8), by temperature control impregnation mold 6
Temperature adjustment to the speed of 225 DEG C, carry-over pinch rolls 10 is set as 5mm/s, so that the content of long basalt fibre is 40wt%.Will leaching
Fibre bundle after stain is directed through bosh 8 and cooled down, and is granulated in pelleter 11, dries, then it is fine to obtain long basalt
Dimension enhancing PA6 composites.
Each raw material cited by the present invention can realize the present invention, and the bound value of each raw material and its interval value can
Realize the present invention, embodiment numerous to list herein.
Table 1 strengthens the mechanical property and frictional property of PA6 composites for the long basalt fibre obtained by embodiment 1,2,3
Energy.Compare each item data of mechanical property can be seen that the present invention prepare long basalt fibre enhancing PA6 composites have it is excellent
Different mechanical property；Compare coefficient of friction and wear rate can be seen that the friction system of long basalt fibre enhancing PA6 composites
Number and wear rate are below the enhancing PA6 composites that are chopped, and illustrate that long basalt fibre can more effectively improve PA6 matrixes
Friction and wear behavior.The data of consolidated statement 1 understand that melt impregnation preparation method of the present invention can obtain mechanical property and friction
The more excellent long basalt fibre enhancing PA6 composites of performance, therefore there is promotional value.
Table 1
Note：Coefficient of friction and wear rate are that sample measures (ASTM Standard on HT-1000 friction wear testing machines
G99-95), test condition is：Normal temperature, 20N, 1000r/min.Comparative example 1 is：By 10wt% chopped basalt fibre (diameter
7um, long 50um) and 90wt% PA6 master batches premixing after, extruded by extruder in 230 DEG C of melt blendings, cooling and dicing,
Dry, then obtain the basalt fibre enhancing PA6 composites that are chopped, gained composite is injection moulded to obtain standard batten,
Test obtains the mechanics and friction and wear behavior of composite；Comparative example 2 is：20wt% chopped basalt fibre (diameter
7um, long 50um) and 80wt% PA6 master batches premixing after, extruded by extruder in 230 DEG C of melt blendings, after cooling and dicing
The basalt fibre enhancing PA6 composites that are chopped are obtained through drying, injection；Comparative example 3 is：30wt% is chopped basalt fibre
After the premixing of (diameter 7um, long 50um) and 70wt%PA6 particles, extruded by extruder in 230 DEG C of melt blendings, cooling is cut
Grain, dry, then obtain the basalt fibre enhancing PA6 composites that are chopped, gained composite is injection moulded to obtain standard sample
Bar, test obtain the mechanics and friction and wear behavior of composite.
Claims (4)
- A kind of 1. melt impregnation preparation method of long basalt fibre enhancing PA6 composites, it is characterised in that the composite wood Material is prepared by the raw material of following weight percents, 15 ~ 50wt% long basalt fibre, 48 ~ 80wt% PA6 master batches with And 2 ~ 5wt% silane coupler；The silane coupler is the silane coupler containing amino, NCO or epoxy radicals, is melted Melt impregnation preparation method to prepare using following devices and technique：Described device includes being provided with some long fibre volumes（2）Support（1）, with extruder（5）The temperature control that the port of export is connected Impregnation mold（6）, support is installed on successively（1）With temperature control impregnation mold（6）Between deflector roll（3）With spacing deflector roll（4）, installation In temperature control impregnation mold（6）Interior some dip rolls（7）, it is arranged at temperature control impregnation mold（6）The bosh of the port of export（8）, It is installed on bosh（8）Interior pressure roller（12）, it is respectively arranged in bosh（8）Porch and two guide rollers in exit （9）, it is installed on bosh（8）The carry-over pinch rolls in exit（10）And it is installed on carry-over pinch rolls（10）The pelleter of discharge end （11）；The melt impregnation preparation technology is：By long basalt fibre from support（1）On long fibre volume（2）Middle extraction is simultaneously opened up Open, by deflector roll（3）With spacing deflector roll（4）It is incorporated into temperature control impregnation mold（6）Interior dip roll（7）On, extruder（5）Will PA6 master batches and processing aid squeeze into temperature control impregnation mold（6）It is interior, adjust temperature control impregnation mold（6）Interior temperature and traction Roller（10）Speed, the fibre bundle after dipping passes through bosh（8）The guide roller of porch（9）Enter bosh（8） Interior pressure roller（12）Cooled down, in pelleter（11）Middle granulation, dry, then obtain long basalt fibre enhancing PA6 composite woods Material.
- 2. a kind of melt impregnation preparation method of long basalt fibre enhancing PA6 composites according to claim 1, its It is characterised by, the temperature control impregnation mold（6）Interior temperature is 225 ~ 250 DEG C, and the pulling speed of basalt fibre is 5 ~ 35mm/ s。
- 3. a kind of melt impregnation preparation method of long basalt fibre enhancing PA6 composites according to claim 1, its It is characterised by, each dip roll（7）Installation direction and fibre bundle moving direction it is perpendicular, adjacent dip roll（7）Between be in Top-bottom cross coordinates.
- 4. a kind of melt impregnation preparation method of long basalt fibre enhancing PA6 composites according to claim 2, its It is characterised by, the dip roll（7）Number be 2 ~ 8.
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| CN201610207580.0A CN105694444B (en) | 2016-04-05 | 2016-04-05 | A kind of long basalt fibre enhancing PA6 composites and its melt impregnation preparation method |
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| CN109822777B (en) * | 2019-02-27 | 2021-07-09 | 南京特塑复合材料有限公司 | Continuous fiber impregnation method |
| CN109732807B (en) * | 2019-02-27 | 2023-06-20 | 南京特塑复合材料有限公司 | Elliptical impregnating device with continuous fibers in multiple motion states |
| CN111057369A (en) * | 2019-12-12 | 2020-04-24 | 会通新材料股份有限公司 | Carbon fiber reinforced polyamide composite material pre-soaked basalt fiber cloth and preparation method thereof |
| CN111662545B (en) * | 2020-07-09 | 2023-03-21 | 四川拜赛特高新科技有限公司 | Long basalt fiber reinforced thermoplastic resin composite master batch, and preparation method and application thereof |
| CN112063167B (en) * | 2020-09-21 | 2023-04-11 | 四川谦宜复合材料有限公司 | Long basalt fiber thermoplastic consumable for 3D printing, and preparation method and preparation device thereof |
| CN112549586B (en) * | 2020-11-11 | 2022-12-27 | 青岛海力威新材料科技股份有限公司 | Static infiltration device for rapid pultrusion of composite material |
| CN112847924B (en) * | 2021-01-07 | 2022-06-10 | 中广核俊尔(浙江)新材料有限公司 | Low-emission, low-fiber-floating, low-warpage and ultra-dispersed long glass fiber polyamide composite material and preparation method thereof |
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| CN102477177A (en) * | 2010-11-29 | 2012-05-30 | 辽宁杰事杰新材料有限公司 | High-performance continuous synthetic fiber reinforced thermoplastic composite and preparation method thereof |
| CN103289374A (en) * | 2013-05-22 | 2013-09-11 | 江苏金发科技新材料有限公司 | Basalt continuous fiber reinforced nylon material and preparation method thereof |
| CN104723582A (en) * | 2015-03-27 | 2015-06-24 | 解廷秀 | Manufacture equipment for continuous fiber reinforced thermoplastic composite material and application thereof |
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|---|---|---|---|---|
| US5424104A (en) * | 1990-11-30 | 1995-06-13 | Mitsui Petrochemical Industries, Ltd. | Thermoplastic resin composition and use thereof |
| CN102477177A (en) * | 2010-11-29 | 2012-05-30 | 辽宁杰事杰新材料有限公司 | High-performance continuous synthetic fiber reinforced thermoplastic composite and preparation method thereof |
| CN103289374A (en) * | 2013-05-22 | 2013-09-11 | 江苏金发科技新材料有限公司 | Basalt continuous fiber reinforced nylon material and preparation method thereof |
| CN104723582A (en) * | 2015-03-27 | 2015-06-24 | 解廷秀 | Manufacture equipment for continuous fiber reinforced thermoplastic composite material and application thereof |
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