CN110294928A - A kind of high glass mine fiber content high glaze polyamide material and its prepare raw material and preparation method and application - Google Patents
A kind of high glass mine fiber content high glaze polyamide material and its prepare raw material and preparation method and application Download PDFInfo
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- CN110294928A CN110294928A CN201910642993.5A CN201910642993A CN110294928A CN 110294928 A CN110294928 A CN 110294928A CN 201910642993 A CN201910642993 A CN 201910642993A CN 110294928 A CN110294928 A CN 110294928A
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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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
- C08K7/14—Glass
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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
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/168—Zinc halides
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
- C08K2003/3036—Sulfides of zinc
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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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
- 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
Abstract
The invention belongs to field of compound material, discloses a kind of high glass mine fiber content high glaze polyamide material and its prepare raw material and preparation method and application.The preparation method of the high glass mine fiber content high glaze polyamide material includes: S1, is pre-mixed hydrogen bond inhibitor and optional lubricant and antioxidant uniformly, obtains powder packet；Hemicrystalline polyamide, amorphous polyamides and powder packet are uniformly mixed, major ingredient is obtained；S2, the major ingredient claim metering feeding by weightless from the main spout of double screw extruder, the glass mine fiber claims metering feeding by weightless from the side spout of double screw extruder, each material in double screw extruder through melting extrusion, cross water is cooling, after pelletizing up to the high glass mine fiber content high glaze polyamide material.There is high mechanical strength and high gloss simultaneously using polyamide material obtained by method provided by the invention, be highly suitable as to the demanding shell quasi-structure component of the visual sensory effects of glossiness.
Description
Technical field
The invention belongs to field of compound material, in particular to a kind of high glass mine fiber content high glaze polyamide material and its
Prepare raw material and preparation method and application.
Background technique
Polyamide (nylon, PA) is a kind of engineering plastics of high comprehensive performance.Nylon has very high mechanical strength, resistance to
Hot, wear resistance, chemical-resistance and electrical insulating property.Nylon material automobile industry, electric industry, communications and transportation,
Each field such as machinery, aerospace is all widely used.High glaze nylon can obtain product fine by being directly molded
Appearance, such as high glaze and metal effect.Nylon base obtains high mechanical strength and high gloss effect by modified, can be with
The shell class products application for replacing part metals component, toy part and family's kitchen and bath's component etc. to require with good gloss degree.
Currently, the industrial maximum polyamide material of dosage is hemicrystalline polyamide material, such as PA6 and PA66.PA6 and
PA66 enhance by using glass mine fibers such as glass fibre, needle-shaped or whisker mineral filling-modified, can significantly improve it
Rigidity, heat resistance and the mechanical strength of modified material.
However, in the prior art, modified material usually needs to obtain higher rigidity, heat resistance and mechanical strength
A large amount of glass mine fiber is added.However, a large amount of glass mine fibers are added especially when the glass mine fiber content of addition is more than
When 50wt% or more, the surface appearance effects severe exacerbation of polyamide material is not only resulted in, such as floating fibre bad phenomenon occurs,
And also polyamide material glossiness can be made to be greatly lowered.The existing method for improving floating fine promotion glossiness effect has as follows
It is several: 1) using low-viscosity polyamides or chain-breaker or branched resin viscosity reductant etc. improve material flowability, it can be largely
It avoids floating fine phenomenon caused by because of illiquidity；2) hemicrystalline is reduced using low melting point copolyamide or amorphous polyamides
The fusing point of polyamide improves appearance；3) product appearance can also be improved to a certain extent using flat glass fiber.But it adopts
In the presence of that can not combine high mechanical strength, (such as high tensile and height lack the modified polyamide material obtained in aforementioned manners
Mouthful impact strength) and high-luster defect.
For example, CN1329448C, which discloses one kind, is used for high glaze and rigid polyamide material, it is linear containing hypocrystalline
The polyamide that polyamide, special branching graft-polyamide, amorphous polyamides, reinforcing material and conventional additives form is mixed
Close object.Although however, using this method obtain polyamide material glossiness it is preferable, need to be added in its mixture super
The branching graft-polyamide or indefiniteness polyamide material for crossing 9% or more, this kind of material, which is added, to stretch by force material dry state
Degree and notch impact strength have obvious reduction.For example, CN105419315A discloses a kind of high glass dimension hplc enhancing Buddhist nun
Imperial material, it is 5~10% nylon copolymers and 0.05~1% star-branched agent etc. which, which contains mass fraction,.However,
Although having preferable mobility and low floating fine effect using the polyamide material that this method obtains, star-branched agent is significant
While reducing nylon viscosity, also there is negative effect to the dry state tensile strength and notch impact strength of polyamide material, and
The glossiness for preparing material is relatively low.For example, CN108676355A discloses a kind of low floating fine high glaze fiber glass reinforced polyamide
Composition, it is 0.1~10% nanofiller and 0.08%~5.0% rheology tune which, which contains mass fraction,
Save agent etc..Although there is high fluidity and low floating fibre, used rheology tune using the polyamide material that this method obtains
Section agent is also to achieve the purpose that improve polyamide material mobility using hyperbranched resin visbreaking polyamide, and pass through hyperbranched
Resin carries out visbreaking to polyamide material, practical also to have a negative impact to notch impact strength under polyamide material dry state.
Summary of the invention
The purpose of the invention is to overcome existing high glass mine fiber content polyamide material that can not obtain high drawing simultaneously
The defect of intensity, high notch impact strength and high gloss is stretched, and is provided a kind of strong with high tensile, high notch shock
Degree and high gloss high glass mine fiber content high glaze polyamide material and its prepare raw material and preparation method and application.
The fibre-reinforced polyamide of high glass mine fiber content, can be by it because having high mechanical strength, rigidity and heat resistance
For replacing part metals component.For example, when the additive amount of glass mine fiber reach 50% it is even higher when, corresponding glass mine fiber
Polyamide material can obtain high rigidity and tensile strength close to even more than part metals.It is right for visual appearance component
The demanding shell quasi-structure component of the visual sensory effects of glossiness, needs to meet high mechanical strength and high gloss simultaneously.So
And as described above, when the additive amount of glass mine fiber in polyamide material reaches 50% or higher, using existing common modification
The appearance and glossiness effect for the polyamide material that method obtains are all poor, or or are obtained by sacrificing mechanical strength
The appearance and glossiness effect that must improve.The present inventor has found after further investigation, using being able to suppress
The metallic compound that hydrogen bond is formed between hemicrystalline polyamide molecule chain is modified high microsteping content polyamide material, can
To obtain high-mechanical property (such as high tensile and notch impact strength), high rigidity and unexpected good appearance simultaneously
With glossiness effect.Based on this, the present invention is completed.
Specifically, raw material is prepared the present invention provides a kind of high glass mine fiber content high glaze polyamide material, wherein
The raw material for preparing of the high glass mine fiber content high glaze polyamide material contains 15~85wt% of hemicrystalline polyamide, amorphous
0.1~5wt% of 0~10wt% of polyamide, glass 10~80wt% of mine fiber and hydrogen bond inhibitor, the hydrogen bond inhibitor is can
Inhibit the metallic compound that hydrogen bond is formed between hemicrystalline polyamide molecule chain.
Further, the high glass mine fiber content high glaze polyamide material to prepare raw material composed of the following components:
19.5~84wt% of hemicrystalline polyamide, 0~8wt% of amorphous polyamides, 15~70wt% of glass mine fiber, hydrogen bond inhibitor
0.2~0.5wt% of 0.5~1.5wt%, 0.3~0.5wt% of lubricant and antioxidant.
Further, the high glass mine fiber content high glaze polyamide material to prepare raw material composed of the following components:
20~50wt% of hemicrystalline polyamide, 0.5~8wt% of amorphous polyamides, 45~70wt% of glass mine fiber, hydrogen bond inhibitor
0.2~0.5wt% of 0.5~1.5wt%, 0.3~0.5wt% of lubricant and antioxidant.
Further, the hemicrystalline polyamide be selected from PA6, PA66, PA11, PA12, PA46, PA56, PA610,
At least one of PA612 and PA1010, preferably PA6.
Further, the amorphous polyamides are PA6I and/or PA MACM12, preferably PA6I.
Further, the relative viscosity R.V. of the hemicrystalline polyamide and amorphous polyamides is each independently 2.4
~2.8.
Further, the glass mine fiber is selected from least one of glass fibre, acicular wollastonite and calcium sulfate crystal whiskers.
Further, the diameter of the glass mine fiber is 7~13 μm, and length is 0.2~5mm.
Further, the glass mine fiber is the short glass fiber of 7~13 μm of diameter, 3~5mm of length.
Further, the hydrogen bond inhibitor is selected from least one of lithium chloride, calcium chloride, zinc chloride and zinc sulphide,
Preferably zinc chloride and zinc sulphide are according to mass ratio 1:(5~10) compound.
Further, the lubricant in stearate, ethylene acrylic acid co polymer and amide series lubricant agent extremely
Few one kind.
Further, the antioxidant is selected from least one of 1098,168,9228,1010 and H161.
The present invention also provides a kind of preparation methods of high glass mine fiber content high glaze polyamide material, wherein the party
Method using above-mentioned high glass mine fiber content high glaze polyamide material prepare raw material as raw material and the following steps are included:
S1, mixing: the hydrogen bond inhibitor and optional lubricant and antioxidant are pre-mixed uniformly, powder is obtained
Packet；The hemicrystalline polyamide, amorphous polyamides and powder packet are uniformly mixed, major ingredient is obtained；
S2, melting extrusion are granulated: the major ingredient claims metering feeding, institute by weightless from the main spout of double screw extruder
It states glass mine fiber and claims metering feeding by weightless from the side spout of double screw extruder, each material passes through in double screw extruder
Melting extrusion is crossed after water cooling, pelletizing up to the high glass mine fiber content high glaze polyamide material.
The present invention also provides high glass mine fiber content high glaze polyamide materials prepared by the above method.
In addition, the present invention also provides the high glass mine fiber content high glaze polyamide materials as shell class product system
The application of standby raw material.
Beneficial effects of the present invention are as follows:
The present invention is being added hydrogen bond inhibitor in polyamide material and is rationally controlling the ratio between each material, may be implemented
In the case where not broken polyamide molecule chain and reduction molecular weight, the mechanical performance of reinforced polyamide material is sufficiently kept, together
When by part inhibited to be formed due to the hydrogen bond between polyamide molecule chain, polyamide crystallizing power is lowered, polyamide material light
Damp degree can be improved significantly.That is, high glass mine fiber content reinforced polyamide material provided by the invention can obtain simultaneously
Obtain high-mechanical property (such as high tensile and notch impact strength), high rigidity and unexpected good appearance and glossiness
Effect may be substituted for part metals component, toy part and family's kitchen and bath's component etc. with the outer of good gloss degree requirement
Shell class product.Speculate its reason, it may be possible to due to: the addition of hydrogen bond inhibitor is able to suppress part hemicrystalline polyamide molecule
Hydrogen bond is formed between chain, can not only slow down the crystallization rate of hemicrystalline polyamide material and reduces the crystallinity of polyamide,
And be conducive to flowing and dispersion of the glass mine fiber in polyamide, and then polyamide material machinery can not influenced by force
Improve the floating fine phenomenon and glossiness of high microsteping content polyamide on the basis of degree.
Specific embodiment
There is no particular limitation for type of the present invention to the hemicrystalline polyamide and amorphous polyamides.The hypocrystalline
Property polyamide can be the high polymer containing amide group and partially crystallizable in existing various macromolecular main chain repetitive units,
Specific example includes but is not limited to: in PA6, PA66, PA11, PA12, PA46, PA56, PA610, PA612, PA1010 etc. extremely
Few one kind, preferably PA6.The amorphous polyamides can be to contain amide groups in existing various macromolecular main chain repetitive units
The high polymer of group and non-crystalline, specific example includes but is not limited to: PA6I and/or PA MACM12, preferably PA6I.Institute
The relative viscosity R.V. for stating hemicrystalline polyamide and amorphous polyamides is preferably each independently 2.4~2.8.In the present invention
In, the test condition of the relative viscosity includes that temperature is 25 DEG C, and reference medium is the sulfuric acid of concentration 98wt%.In addition, described
The content of hemicrystalline polyamide is 15~85wt%, preferably 19.5~84wt%, more preferably 20~50wt%.It is described non-
The content of brilliant polyamide is 0~10wt%, preferably 0~8wt%, more preferably 0.5~8wt%.
In the present invention, the glass mine fiber can for it is existing it is various can be as the glass fibers of aramid reinforcement
Dimension and/or mineral fibres, specific example include but is not limited to: in glass fibre, acicular wollastonite and calcium sulfate crystal whiskers extremely
Few one kind.The diameter of the glass mine fiber is preferably 7~13 μm, and length is preferably 0.2~5mm.The glass mine fiber is especially excellent
It is selected as the dedicated short glass fiber of nylon, diameter is preferably 7~13 μm, and length is preferably 3~5mm.In addition, the glass mine is fine
The content of dimension is 10~80wt%, preferably 15~70wt%, more preferably 45~70wt%.
In the present invention, the hydrogen bond inhibitor is the metallization for being able to suppress hemicrystalline polyamide material and forming hydrogen bond
Object is closed, at least one of lithium chloride, calcium chloride, zinc chloride and zinc sulphide, more preferably zinc chloride and zinc sulphide are preferably selected from
Compound, most preferably zinc chloride and zinc sulfate are according to mass ratio 1:(5~10) compound.The hydrogen bond inhibitor can be with
Slow down the crystallization rate of polyamide material and reduce the crystallinity of polyamide, is conducive to stream of the glass mine fiber in polyamide
Dynamic and dispersion, and then the floating fine phenomenon and glossiness of high microsteping content polyamide material can be improved.In addition, the hydrogen bond inhibits
The content of agent is 0.1~5wt%, preferably 0.5~1.5wt%.
There is no particular limitation for type of the present invention to the lubricant, various can improve polyamide to be existing
The auxiliary agent of material greasy property, specific example include but is not limited to: stearate, ethylene acrylic acid co polymer and amides profit
At least one of lubrication prescription.The content of the lubricant is preferably 0.3~0.5wt%.
In the present invention, the antioxidant can be selected from at least one of 1098,168,9228,1010 and H161.It is described
The content of antioxidant is preferably 0.2~0.5wt%.
The preparation method of high glass mine fiber content high glaze polyamide material provided by the invention the following steps are included:
S1, mixing: the hydrogen bond inhibitor and optional lubricant and antioxidant are pre-mixed uniformly, powder is obtained
Packet；The hemicrystalline polyamide, amorphous polyamides and powder packet are uniformly mixed, major ingredient is obtained；
S2, melting extrusion are granulated: the major ingredient claims metering feeding, institute by weightless from the main spout of double screw extruder
It states glass mine fiber and claims metering feeding by weightless from the side spout of double screw extruder, each material passes through in double screw extruder
Melting extrusion is crossed after water cooling, pelletizing up to the high glass mine fiber content high glaze polyamide material.
It should be noted that the lubricant and antioxidant can be added selectively according to the actual situation, when without being added
When lubricant and antioxidant, directly hemicrystalline polyamide, amorphous polyamides and hydrogen bond inhibitor can be carried out in step S1
It is uniformly mixed and obtains major ingredient.
In step sl, the mixing can be mixed with hand operated mixing, can also be using existing various mixing apparatus (such as height
Fast blender, low-speed mixer etc.) carry out mechanical mixture.The mixed condition so that more than several components formed integrally
System.Before melting extrusion, by the hemicrystalline polyamide, amorphous polyamides, hydrogen bond inhibitor and optional anti-
Oxygen agent and the uniform purpose of mix lubricant be in order to enable hydrogen bond inhibitor full and uniform dispersion in polyamide matrix to keep away
Exempt from that local concentration is excessively high, to be more advantageous to the hydrogen bond inhibitory effect for obtaining reasonable proportion-controllable.
In step s 2, the double screw extruder includes a main spout and side spout, wherein the master feeds
Material mouth is located at the leading portion of the double screw extruder, and side spout is normally at the middle section of the double screw extruder.For example, working as
The double screw extruder is when including the double screw extruder in 3rd area 11 Qu Zhishi, and the main spout is usually located at one
Area, side spout are usually located at 5th area or 6th area.Major ingredient is obtained from main spout by polyamide and powder packet after mixing
It is accurately fed in such a way that weighing balance measures weightlessness, and glass mine fiber is then smart in such a way that weighing balance measures weightlessness from side spout
Really charging.
The present invention also provides high glass mine fiber content high glaze polyamide materials prepared by the above method.It is described
High glass mine fiber content high glaze polyamide material is with high-mechanical property (such as high tensile and notch impact strength), height
Rigid and unexpected good appearance and glossiness effect, may be substituted for part metals component, toy part and family
The shell class product that there is front yard kitchen and bath's component etc. good gloss degree to require.
In addition, the present invention also provides the high glass mine fiber content high glaze polyamide materials as shell class product system
The application of standby raw material.
The embodiment of the present invention is described below in detail, the examples of the embodiments are intended to be used to explain the present invention, and cannot
It is interpreted as limitation of the present invention.In the examples where no specific technique or condition is specified, described according to the literature in the art
Technology or conditions or carried out according to product description.Reagents or instruments used without specified manufacturer is that can lead to
Cross the conventional products of commercially available acquisition.
In following embodiment and comparative example: hemicrystalline polyamide is the PA6 that relative viscosity R.V. is 2.4, amorphous polyamides
Amine is the PA6I that relative viscosity is 2.4.Glass mine fiber is the staple glass that filament diameter is 10~13 μm and length is 3~5mm
Fiber.Hydrogen bond inhibitor is the compound that zinc chloride and zinc sulphide are formed according to mass ratio 1:9.Lubricant is calcium stearate.It is anti-
Oxygen agent is 1098.Double screw extruder is the double screw extruder with main spout and side spout, and specially draw ratio is
The Rhea RXT-65 of 40:1 comprising Shi Yiqu, main spout are located at an area, and side spout is located at 5th area.
Examples 1 to 4
S1, mixing: hydrogen bond inhibitor, lubricant and antioxidant are put into high-speed mixer, with revolving speed 600r/min
2min is mixed, is sufficiently mixed and is formed uniformly powder packet, it is spare；PA6, PA6I and above-mentioned powder packet are put into low-speed mixer
In, with revolving speed 100r/min mixing 5min, it is sufficiently mixed and is formed uniformly major ingredient, it is spare；
S2, melting extrusion are granulated: claim the major ingredient to metering feeding by weightless from the main spout of double screw extruder,
Individually claim short glass fiber to metering feeding from the side spout of double screw extruder by weightless；Double screw extruder it is each
Duan Wendu is respectively as follows: 210 DEG C, 235 DEG C, 250 DEG C, 250 DEG C, 245 DEG C, 245 DEG C, 245 DEG C, 235 DEG C, 225 DEG C, 225 DEG C, head
Temperature is 250 DEG C, screw speed 400r/min；Material sufficiently fuses under the shearing, mixing and conveying of screw rod, finally passes through
High glass mine fiber content high glaze polyamide material pellet is made after crossing water cooling, pelletizing in extrusion, tie rod.Wherein, each component
Dosage is as shown in table 1.
Comparative example 1
High glass mine fiber content high glaze polyamide material pellet is prepared according to the method for embodiment 1, unlike, by hydrogen
Key inhibitor is substituted using the PA6 resin of identical weight part, remaining condition is same as Example 1, obtains the high glass mine fiber of reference
Content high glaze polyamide material pellet.Wherein, the dosage of each component is as shown in table 1.
Comparative example 2
High glass mine fiber content high glaze polyamide material pellet is prepared according to the method for embodiment 4, unlike, by hydrogen
Key inhibitor is substituted using the PA6I resin of identical weight part, remaining condition is same as Example 4, obtains the high glass mine fiber of reference
Content high glaze polyamide material pellet.Wherein, the dosage of each component is as shown in table 1.
Comparative example 3~4
High glass mine fiber content high glaze polyamide material pellet is prepared according to the method for Examples 1 to 4, unlike,
It is main that by addition amorphous polyamides PA6I and the hyperbranched resin viscosity reductant with three-dimensional structure, (it can reduce strand
Between entanglement, specially morning source resin-like nylon lubricant, trade mark CYD-701D) improve glossiness, the specific steps are as follows:
S1, mixing: antioxidant, lubricant and CYD-701D are put into high-speed mixer, mixed with revolving speed 600r/min
2min is closed, is sufficiently mixed and is formed uniformly powder packet, it is spare；PA6, PA6I and above-mentioned powder packet are put into low-speed mixer,
With revolving speed 100r/min mixing 5min, it is sufficiently mixed and is formed uniformly major ingredient, it is spare；
S2, melting extrusion are granulated: claim the major ingredient to metering feeding by weightless from the main spout of double screw extruder,
Individually claim short glass fiber to metering feeding from the side spout of double screw extruder by weightless；Double screw extruder it is each
Duan Wendu is respectively as follows: 210 DEG C, 235 DEG C, 250 DEG C, 250 DEG C, 245 DEG C, 245 DEG C, 245 DEG C, 235 DEG C, 225 DEG C, 225 DEG C, head
Temperature is 250 DEG C, screw speed 400r/min；Material sufficiently fuses under the shearing, mixing and conveying of screw rod, finally passes through
The high glass mine fiber content high glaze polyamide material pellet of reference is made after crossing water cooling, pelletizing in extrusion, tie rod.Wherein, each group
The dosage divided is as shown in table 1.
Test case
It will be by the high glass mine fiber content high glaze polyamide material pellet of Examples 1 to 4 gained and by comparative example 1~4
The high glass mine fiber content high glaze polyamide material pellet of gained reference, which is placed in 90 DEG C of blast driers, dries 4 hours, later
By the particle after drying, injection molding obtains test bars at a temperature of 245~270 DEG C respectively, the correlated performance test of test bars and
Test method and acquired results are as shown in table 2.
1 dosage of each component of table (wt%)
Table 2
Remarks: in table 2 ,+it is good degree ,+The more the better；It is undesirable level ,-much more bad.
It can be seen that Examples 1 to 4 from the data of table 2 and comparative example 1~4 prepare identical thickness under identical Shooting Technique
Template is spent, for Examples 1 to 4 due to joined hydrogen bond inhibitor, template contact clarity is higher, and this also illustrates hydrogen bond suppression is added
Material crystalline ability decreases after preparation, limits crystal and grows up, and transparency increases.Examples 1 to 4 is added hydrogen bond and inhibits
Agent partially inhibits form hydrogen bond between polyamide PA6 strand to a certain extent, hydrogen bond formed be suppressed after, polyamide
The crystallizing power of PA6 is consequently also weakened, and crystalline rate and crystallinity reduce.The modified polyamide material that Examples 1 to 4 obtains
With significantly superior anti-floating fibre effect and 60 ° of considerably higher angle glossiness.In addition, common 50% glass fibers in comparative example 1
The peak crystallization T of dimension enhancing PA6cAbout 179 DEG C of temperature, and hydrogen bond inhibitor is added in embodiment 1 and makes hemicrystalline polyamide PA6
Crystallization peak temperature and crystallization onset temperature reduce 6 DEG C, and embodiment 1 crystallizes half-peak breadth and increases 3 DEG C.From comparative example 2~4
Result can be seen that increase amorphous polyamides material PA6I additive amount and be added viscosity reductant, to promoted polyamide material
Glossiness have certain effect, but the impact strength of modified material can be produced bigger effect, and glossiness effect is changed
It is kind general.To sum up, the hydrogen bond inhibitor that Examples 1 to 4 is added can obtain high while utmostly keeping toughness of material
The high gloss of fibre-reinforced polyamide material.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art are not departing from the principle of the present invention and objective
In the case where can make changes, modifications, alterations, and variations to the above described embodiments within the scope of the invention.
Claims (10)
1. a kind of high glass mine fiber content high glaze polyamide material prepares raw material, which is characterized in that the high glass mine fiber
Content high glaze polyamide material prepare raw material contain 15~85wt% of hemicrystalline polyamide, amorphous polyamides 0~
0.1~5wt% of 10wt%, glass 10~80wt% of mine fiber and hydrogen bond inhibitor, the hydrogen bond inhibitor are to be able to suppress half hitch
The metallic compound of hydrogen bond is formed between crystalline substance polyamide molecule chain.
2. high glass mine fiber content high glaze polyamide material according to claim 1 prepares raw material, which is characterized in that
The high glass mine fiber content high glaze polyamide material to prepare raw material composed of the following components:
Hemicrystalline polyamide: 19.5~84wt%；
Amorphous polyamides: 0~8wt%；
Glass mine fiber: 15~70wt%
Hydrogen bond inhibitor: 0.5~1.5wt%；
Lubricant: 0.3~0.5wt%；
Antioxidant: 0.2~0.5wt%.
3. high glass mine fiber content high glaze polyamide material according to claim 2 prepares raw material, which is characterized in that
The high glass mine fiber content high glaze polyamide material to prepare raw material composed of the following components:
Hemicrystalline polyamide: 20~50wt%；
Amorphous polyamides: 0.5~8wt%；
Glass mine fiber: 45~70wt%
Hydrogen bond inhibitor: 0.5~1.5wt%；
Lubricant: 0.3~0.5wt%；
Antioxidant: 0.2~0.5wt%.
4. the preparation of high glass mine fiber content high glaze polyamide material according to any one of claims 1 to 3 is former
Material, which is characterized in that the hemicrystalline polyamide is selected from PA6, PA66, PA11, PA12, PA46, PA56, PA610, PA612
At least one of with PA1010, preferably PA6；The amorphous polyamides are PA6I and/or PA MACM12, preferably PA6I；
The relative viscosity R.V. of the hemicrystalline polyamide and amorphous polyamides is each independently 2.4~2.8.
5. the preparation of high glass mine fiber content high glaze polyamide material according to any one of claims 1 to 3 is former
Material, which is characterized in that the glass mine fiber is selected from least one of glass fibre, acicular wollastonite and calcium sulfate crystal whiskers；It is excellent
Selection of land, the diameter of the glass mine fiber are 7~13 μm, and length is 0.2~5mm；Preferably, the glass mine fiber be diameter 7~
13 μm, the short glass fiber of 3~5mm of length.
6. the preparation of high glass mine fiber content high glaze polyamide material according to any one of claims 1 to 3 is former
Material, which is characterized in that the hydrogen bond inhibitor is selected from least one of lithium chloride, calcium chloride, zinc chloride and zinc sulphide, preferably
Be zinc chloride and zinc sulphide according to mass ratio 1:(5~10) compound.
7. high glass mine fiber content high glaze polyamide material according to claim 2 or 3 prepares raw material, feature exists
In the lubricant is selected from least one of stearate, ethylene acrylic acid co polymer and amide series lubricant agent；The antioxygen
Agent is selected from least one of 1098,168,9228,1010 and H161.
8. a kind of preparation method of high glass mine fiber content high glaze polyamide material, which is characterized in that this method is wanted with right
High glass mine fiber content high glaze polyamide material prepares raw material as raw material and packet described in asking any one of 1~7
Include following steps:
S1, mixing: the hydrogen bond inhibitor and optional lubricant and antioxidant are pre-mixed uniformly, powder packet is obtained；It will
The hemicrystalline polyamide, amorphous polyamides and powder packet are uniformly mixed, and obtain major ingredient；
S2, melting extrusion are granulated: the major ingredient claims metering feeding, the glass by weightless from the main spout of double screw extruder
Mine fiber claims metering feeding by weightless from the side spout of double screw extruder, and each material is in double screw extruder through melting
It squeezes out, cross after water cooling, pelletizing up to the high glass mine fiber content high glaze polyamide material.
9. the high glass mine fiber content high glaze polyamide material being prepared by method according to any one of claims 8.
10. high glass mine fiber content high glaze polyamide material as claimed in claim 9 prepares raw material as shell class product
Using.
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