CN109593352A - Ultralow water suction cold-resistant, wear-resisting nylon composite materials and its preparation method and application - Google Patents
Ultralow water suction cold-resistant, wear-resisting nylon composite materials and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to nylon composite materials technical field, specific open ultralow water suction cold-resistant, wear-resisting nylon composite materials of one kind and its preparation method and application.The ultralow water suction cold-resistant, wear-resisting nylon composite materials with including the following raw material components of parts by weight by being prepared: the first 60~80 parts of long carbon chain nylon；1~10 part of crystallinity semi-aromatic nylon；15~30 parts of reinforcing material；1~10 part of wear-resistant masterbatch；First 0.2~1.0 part of lubricant；0.3~1.0 part of antioxidant；0.5~2 part of compatilizer；2~10 parts of hydrophober；Wherein, first long carbon chain nylon is the nylon of monomer carbon atom number >=10.Ultralow water suction cold-resistant, wear-resisting nylon composite materials provided by the invention, with good dimensional stability and mechanical property, Injection Molding is good, and composite material surface is smooth and non-greasy, there is ultralow water absorbing properties and good cold-resistant, wear-resisting characteristic simultaneously, be especially suitable for that sweeper brush is made.
Description
Technical field
The present invention relates to nylon composite materials technical fields, more particularly to a kind of ultralow water suction cold-resistant, wear-resisting nylon composite wood
Material and its preparation method and application.
Background technique
Nylon is a computer MSR Information system development under the outstanding scientist's Tomas Carothers (Carothers) in the U.S. and its leader
It out, is the first synthetic fibers occurred in the world.The appearance of nylon is so that assuming an entirely new aspect for textile, its conjunction
It at the important breakthrough for being synthetic fiber industry, while being also an important milestone of polymer chemistry.
Since nylon has many characteristics, in automobile, electrical equipment, mechanical structure, transportation equipment, weaves, makes
Paper, machinery etc. are widely used.
With the miniaturization of automobile, the quickening of the high performance of electronic and electrical equipment, mechanical equipment lighting process, to Buddhist nun
The demand of dragon will be bigger, when especially nylon is as structural material, propose to its intensity, heat resistance, cold resistance etc.
Higher requirement.The inherent defect of nylon is also an important factor for limiting its application, especially for this two big product of PA6, PA66
For kind, since PA has the characteristics that highly polar, hygroscopicity is strong, poor dimensional stability, but can be improved by modified accordingly
Performance.Mainly nylon is modified by the way of adding toughener compounding in nylon material in the prior art, but
It is dispersed bad, poor compatibility between each component during each component is co-melting after a variety of materials mixing, it is intensity, toughness, anticorrosive
Property it is insufficient, material cost is higher, and demoulding is difficult, and surface gloss is poor, and processing performance is bad, unstable product quality.
The shortcomings that improve the prior art, the Chinese invention patent of Publication No. 103214843A provide a kind of long fibre increasing
Strong long carbon chain nylon and preparation method thereof, the ingredient of the nylon includes: nylon 1010 30-65%, 6 0-30% of nylon, nylon
66 0-30%, long glass fibres 30-60%, antioxidant 0.3-1%, lubricant 0.5-2%.It uses the long carbon of long glass fiber reinforced
The compound of chain nylon and common nylon effectively increases the intensity and modulus of material, obtained low water absorption rate, dimensionally stable,
The excellent composite material of resistance to low temperature, but its wear-resisting property is weak, and needs by processing twice, production cost
It is high.The Chinese invention patent of Publication No. 103602064A discloses a kind of 66/ nylon 612 of activeness and quietness wear resistant nylon and preparation side
Method and application, concrete composition ingredient and weight ratio are as follows: nylon66 fiber 10-80；Nylon 612 10-80；Glass fibre 10-60；Increase
Tough dose of 2-50；Anti-wear agent 1-50；Lubricant 0.1-10；Antioxidant 0.1-10, and the viscosity number for further disclosing the nylon66 fiber exists
Between 100-200；The viscosity number of the nylon 612 is between 90-180；The glass fibre is alkali-free glass fiber；The toughener is
Polyolefin Grafted Maleic Anhydride or ethylene-acrylate or ethylene-acrylate-maleic anhydride terpolymer or they answer
With object；The anti-wear agent is molybdenum disulfide or graphite or potassium titanate crystal whisker or polytetrafluoroethylene (PTFE) or their compound；The profit
Lubrication prescription is calcium stearate or ethylene bis stearamide or montanic acid sodium or their compound；The antioxidant is 1010 or 1098
Or 168 or their compound.Since this material uses alkali-free glass fiber as reinforcing agent, and use molybdenum disulfide, graphite, titanium
At least one of sour potassium whisker, polytetrafluoroethylene (PTFE) are used as anti-wear agent, and the composite-material abrasive performance and intensity obtained is poor.
The Chinese patent of Publication No. 104710785A discloses a kind of low wear-resisting composite nylon and its preparation method and application that absorbs water, specifically
Including following components: 100~120 parts of long carbon chain nylon, 20~35 parts of reinforcing material, 1.0~5.0 parts of anti-wear agent, lubricant 0.2
~1.0 parts, 2~10 parts of hydrophober, 0.3~1.0 part of antioxidant, although the wear-resisting composite nylon of low water suction obtained by aforementioned component
There is preferable wear-resisting property, but dimensional stability is poor, and water absorption rate is larger, tensile strength and bending strength need to be mentioned
Height does not meet and uses under to moisture exacting terms.
Summary of the invention
Harsh item cannot be met simultaneously for the performances such as water absorbing properties existing for existing nylon composite materials, cold-resistant, wear-resisting
The problem of using under part, the present invention provide ultralow water suction cold-resistant, wear-resisting nylon composite materials of one kind and preparation method thereof.
Further, the application the present invention also provides the composite material in multiple fields.
To achieve the above object of the invention, the present invention adopts the following technical scheme that:
A kind of ultralow water suction cold-resistant, wear-resisting nylon composite materials, the ultralow water suction cold-resistant, wear-resisting nylon composite materials use
It is obtained including the following raw material components of parts by weight through melting extrusion:
Wherein, first long carbon chain nylon is the nylon of monomer carbon atom number >=10.
And a kind of preparation method of ultralow water suction cold-resistant, wear-resisting nylon composite materials, it at least includes the following steps:
S01. ratio as described above weighs the first long carbon chain nylon, crystallinity semi-aromatic nylon, reinforcing material, wear-resisting
Agent master batch, the first lubricant, antioxidant, compatilizer, hydrophober；
S02. after the weighed material of step S01 being mixed, melting is added twin-screw extrude, it is blending extrusion, cold
But, pelletizing, drying are to get ultralow water suction cold-resistant, wear-resisting nylon composite materials.
And the ultralow water suction cold-resistant, wear-resisting nylon composite materials are turning to turbine, gear, sweeper brush, medical treatment
Application in instrument.
The invention has the benefit that
The present invention includes the ultralow water suction cold-resistant, wear-resisting nylon composite materials of said components, with long carbon chain nylon and crystallinity
For semi-aromatic nylon as substrate, the two combines the material for making to obtain to have good dimensional stability and mechanical property, and wear-resisting
Master batch then can be improved the wearability and Injection Molding of composite material, keeps composite material surface smooth and non-greasy, ties simultaneously
Other raw material components are closed, finally obtained material has ultralow water absorbing properties and good cold-resistant, wear-resisting characteristic.
The preparation method of ultralow water suction cold-resistant, wear-resisting nylon composite materials provided by the invention, simple process, the Buddhist nun of acquisition
Imperial composite material has the characteristics that ultralow water suction, resists cold, is wear-resisting, is suitable as the gears material such as motor turning gear, timing gears
In the fields such as material and sweeper brush, medical instrument.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
The first aspect of the present invention provides a kind of supra polymer anti-wear agent, which is a kind of mixture,
It includes have to have polymer and Nano diamond as shown in logical formula (I).
As can be polymer represented by a=30, b=10, c=30, n=20 in polymer shown in logical formula (I) and
The mixture of Nano diamond, at this point, the supra polymer anti-wear agent is only formed by two kinds of material mixings.
Polymer represented by=30, b=10, c=30, n=20 is for another example can be in polymer shown in logical formula (I)；a
=40, the mixture that polymer represented by b=8, c=30, n=20 and Nano diamond are formed, at this point, the supra polymer is resistance to
Grinding agent is formed by three kinds of material mixings.Certainly, supra polymer anti-wear agent of the invention is not limited to both cited, can also
To be the mixture of other polymers and Nano diamond represented by logical formula (I).
Wherein, a takes any integer in 30~50；B takes any integer in 1~10；C takes any in 30~50
Integer；Any integer that the value of n is 10~100.
Formula (I) compound represented, the degree of polymerization are 3500~5500, and number-average molecular weight is 1.0 × 105~4.0 × 105；Its
Viscosity at 25 DEG C is 1.0 × 106~2.0 × 106。
The second aspect of the present invention provides the preparation method of aforementioned supra polymer anti-wear agent.According to parts by weight, use as
Under raw material components preparation:
In above-mentioned raw materials component, the viscosity of dimethyl silicone polymer is about 7.5 × 104~1.5 × 105MPas, preferably
1.0×105mPa·s。
The viscosity of the tetramethyl-ring tetrasiloxane is about 8 × 104~1.0 × 105mPa·s。
The catalyst is any one of the concentrated sulfuric acid, concentrated hydrochloric acid or acetic acid.In the present invention, the concentrated sulfuric acid refers to mass fraction
>=70% sulfuric acid, and concentrated hydrochloric acid refers to the hydrochloric acid of mass fraction >=20%.The unsaturated polyester (UP) is metaphenylene unsaturated polyester (UP)
Resin, viscosity are 1.0 × 103~1.0 × 104mPa·s。
The neutralizer is one of potassium hydroxide, sodium hydroxide.The neutralizer is acid superfluous in neutralization reaction,
It prevents the presence of acid when distillation and side reaction occurs.
The average grain diameter of the Nano diamond is 3.0nm~4.0nm, purity >=95%, 230~250m of specific surface area2/
G, preferably 246.02m2/g。
The preparation method of the supra polymer anti-wear agent, comprising the following steps:
Water, part is added after mixing dimethyl silicone polymer as described above with tetramethyl-ring tetrasiloxane in step S01.
Catalyst, temperature rising reflux react 1~3h, are then evaporated under reduced pressure, obtain the polymer II as shown in reaction equation (a).
Wherein a=30~50, b=1~10, c=30~50, n=10~100.
Step S02. mixes the polymer II that step S01 is obtained with vinyl tri-phenyl-silane, it is warming up to 70~
90 DEG C, 1~4h is reacted, the polymer III as shown in reaction equation (b) is obtained.
Wherein, a=30~50, b=1~10, c=30~50.
Step S03. mixes the polymer III that step S02 is obtained with the Nano diamond, unsaturated polyester (UP),
And remaining catalyst is added, 70~90 DEG C are warming up to, 1~3h is reacted；Neutralizer is then added to neutralize, washing vacuumizes steaming
It evaporates, room temperature cures 48h or more, can be obtained such as supra polymer anti-wear agent, and specific reaction process can use reaction equation (c)
It indicates, in the supra polymer anti-wear agent, Nano diamond is mixed in the polymer of reaction equation (c) formation.
Wherein, a takes any integer in 30~50；B takes any integer in 1~10；C takes any in 30~50
Integer；Any integer that the value of n is 10~100.
The third aspect of the present invention provides a kind of ultralow water suction cold-resistant, wear-resisting nylon composite materials.The ultralow water suction is resistance to
Cold fire retardation wear-resistance nylon composite material includes the following raw material components of parts by weight, and is obtained through melting extrusion:
Wherein, first long carbon chain nylon is the nylon of monomer carbon atom number >=10.
Preferably, first long carbon chain nylon be nylon 11, nylon 12, nylon 1010, nylon 1313, nylon 1212,
One or more of nylon 612 or nylon 613, these types of nylon have good dimensional stability and mechanical property, in conjunction with
Crystallinity semi-aromatic nylon can play synergistic effect, the common dimensional stability and mechanical property for improving nylon composite materials,
When product is made in the nylon composite materials injection moulding of acquisition, product shows good dimensional stability and excellent power
Learn performance.
Preferably, the crystallinity semi-aromatic nylon is poly-meta-xylylene adipamide (PA/MAXD6 nylon), gathers to benzene
Two formyl butanediamine (PA4T), poly- hexamethylene terephthalamide (PA6T), polyamide 9T (PA9T), poly- paraphenylene terephthalamide's decamethylene diamine
At least one of (PA10T), these types of crystallinity semi-aromatic nylon is being used in conjunction with conduct with aforementioned first long carbon chain nylon
Substrate when product is made in the nylon composite materials of acquisition, has good dimensional stability and excellent mechanical property, guarantees to produce
The shape of product is not susceptible to deformation.Wherein, PA6T is the condensation polymer of aliphatic diamine and aromatic acid；PA9T is by nine
The nonamethylene diamine and terephthalic acid (TPA) of a carbon are made by melt polycondensation, nonamethylene diamine be by butadiene dimerization matsutake alcohol, indexing at
Octene ketone, through nonyl diketone processed, repeated hydrogenation ammonia reduction synthesis nonamethylene diamine is carbonylated；PA10T is terephthalic acid (TPA) and long-chain diamine
The homopolymer of decamethylene diamine.
Preferably, the reinforcing material is any one of flat glass, carbon fiber, the flat glass and/or described
The fibre diameter of carbon fiber is 6~18 μm, using both reinforcing materials as ultralow water suction cold-resistant, wear-resisting nylon composite materials
Component can be further improved the effect of the first long carbon chain nylon and crystallinity semi-aromatic nylon mechanical property, and more
It is important that material warp can be effectively prevented.If fibre diameter is excessive, the product flatness of machine-shaping is declined, and
If diameter is too small, it is unfavorable for preventing the generation of warpage.
It is further preferred that the reinforcing material is the reinforcing material silane coupler modified by Long carbon chain, through too long
The modification of carbochain silane coupling agent keeps it more excellent with other components compatibility.Wherein, described in Long carbon chain silane coupling agent
Long carbon chain refer to the silane coupling agents of carbon atom number >=10
Wear-resistant masterbatch of the present invention is to the Injection Molding for improving ultralow water suction cold-resistant, wear-resisting nylon composite materials product
Property is of crucial importance, and can greatly be improved the wear-resisting property of composite material while be reduced water absorbing properties,
From the summary of the invention of the fourth aspect of the present invention.
Preferably, first lubricant be silicone, oleamide, erucyl amide or ethylene bis stearic amide in extremely
Few one kind.The processing performance of material can be improved in first lubricant.
The addition of antioxidant can keep from heat and aoxidize.Preferably, the antioxidant is phosphorous acid esters, hindered phenol
One or more of kind antioxidant or suffocated amine antioxidant.It specifically can be irgasfos 168, antioxidant 1010, antioxidant
1076, antioxidant 1098, antioxidant Seed.
Preferably, the compatilizer is selected from ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH), high density is gathered
Vinyl Graft maleic anhydride (HDPE-g-MAH), grafted low density polyethylene maleic anhydride (LDPE-g-MAH), styrene-fourth two
At least one of alkene-styrene block copolymer grafted maleic anhydride (SBS-g-MAH).
Preferably, the hydrophober is at least one of polyolefin (PE), polyolefin copolymer, and hydrophober is added can be into
One step reduces the water absorption rate of composite nylon, such as can be maleic anhydride stem grafting polyolefin elastomer (POE-g-MAH).Hydrophober and
The combination of wear-resistant masterbatch can generate synergistic effect to water absorbing properties, further decrease water absorption rate.
The ultralow water suction cold-resistant, wear-resisting nylon composite materials obtained by said components, with half virtue of long carbon chain nylon and crystallinity
Fragrant nylon is as substrate, and the two combines the material for making to obtain to have good dimensional stability and a mechanical property, and wear-resistant masterbatch
The Injection Molding that then can be improved composite-material abrasive sum keeps composite material surface smooth and non-greasy, in combination with it
His raw material components, finally obtained material have ultralow water absorbing properties and good cold-resistant, wear-resisting characteristic.It is made into product, such as
When the products such as motor turning turbine, timing gears, medical instrument, gear of textile machine, sweeper brush are made in injection moulding, friction system
Number down to 0.15 hereinafter, and be soaked in water for 24 hours, water absorption rate, less than 0.1%, is shown less than 0.1%, size changing rate
Good performance.
Correspondingly, the present invention is on the basis of the above embodiments, it is further provided ultralow water suction cold-resistant, wear-resisting nylon is compound
The preparation method of material.
In one embodiment, it is described it is ultralow water suction cold-resistant, wear-resisting nylon composite materials preparation method the following steps are included:
The component ratio of step S11. as described above claims long carbon chain nylon, crystallinity semi-aromatic nylon, reinforcing material, resistance to
Grinding agent master batch, the first lubricant, antioxidant, compatilizer, hydrophober；
After step S12. is mixed the weighed material of step S11, melting is added twin-screw extrude, is blended and squeezes
Out, cooling, pelletizing, drying are to get ultralow water suction cold-resistant, wear-resisting nylon composite materials.
Detailed explanation is done to preparation method of the invention below.
Specifically, the reinforcing material is with other components before mixing, further include using Long carbon chain silane coupling agent into
Row is mixed and modified, by the modification of Long carbon chain silane coupling agent, keeps it more excellent with other components compatibility.Wherein, long carbon
Described Long carbon chain refers to that carbon atom number is >=10 silane coupling agent in chain silane coupling agent.
Preferably, the temperature of the melting in step S12 and blending extrusion is 210~240 DEG C, and the screw rod of extrusion turns
Speed is 470~490rpm.If extrusion temperature is excessively high, raw material is easily degraded, and if temperature is too low, not up to molten state,
It can not squeeze out.
The ultralow water suction cold-resistant, wear-resisting nylon composite materials obtained by above-mentioned preparation method, can be with by injection molding technique
Finished product is made, such as can be made and turn to turbine, timing gears, textile machine gear, sweeper brush, medical apparatus and instruments.Its
Specific injection moulding method can be such that
It is 210~240 DEG C in injection temperature, under the conditions of injection pressure is 40~80MPa, with the injection speed of 70~80mm/s
The ultralow water suction cold-resistant, wear-resisting nylon composite materials of melting are injected into mold by degree, 10~30s of pressure maintaining, cooling, demoulding,
Dry 3~5h, can be obtained moulded products at 110~130 DEG C.Obtained product coefficient of friction is down to 0.15 hereinafter, and soaking
Steep Yu Shuizhong for 24 hours, water absorption rate less than 0.1%, size changing rate less than 0.1%, it is with good performance.
The fourth aspect of the present invention provides a kind of wear-resistant masterbatch, and in parts by weight, the wear-resistant masterbatch uses such as the following group
The raw material preparation divided:
The above-mentioned supra polymer anti-wear agent being related to is from supra polymer anti-wear agent described in first aspect.
Preferably, second long carbon chain nylon is the nylon of monomer carbon atom number >=10, such as can be nylon 11, nylon
12, one or more of nylon 1010, nylon 1313, nylon 1212, nylon 612 or nylon 613.
Preferably, second lubricant be silicone, oleamide, erucyl amide or ethylene bis stearic amide in extremely
Few one kind.
Preferably, the stabilizer is lignin, carboxymethyl cellulose, number-average molecular weight 1.0 × 104~1.0 × 105
At least one of polyethylene oxide.
Preferably, the carrier is any one of polyolefin, polyolefin copolymer, such as polyethylene, polypropylene, polyphenyl second
Alkene, acrylonitrile-butadiene-styrene copolymer, as the carrier and coating function of supra polymer anti-wear agent, polyolefin is non-
Polar material, hydrophobicity is preferable, is conducive to the water absorbing properties for further decreasing its manufactured material.
The wear-resistant masterbatch the preparation method is as follows:
The carrier is added into kneader, is warming up to 100 DEG C or more, vacuumizes stirring, is cooled to 60~90 DEG C；
The supra polymer anti-wear agent, the second long carbon chain nylon, the second lubricant, stabilizer are added processed described
Kneading is stirred in carrier, kneading time 1h or more obtains wear-resistant masterbatch.
The wear-resistant masterbatch obtained by the above method, due to it includes there is above-mentioned supra polymer anti-wear agent, in use,
With good wear-resisting property and Injection Molding, when being used in composite material, composite material surface is smooth and satiny.
To better illustrate ultralow water suction cold-resistant, wear-resisting nylon composite materials provided by the invention and preparation method thereof, below
It is illustrated by embodiment.
Embodiment 1~13
To save length, the component of embodiment 1~13 is listed in Table 1 below, specific preparation method can be used such as lower section
Formula carries out:
Surface modification treatment is carried out to reinforcing material using dodecyltrimethoxysilane, obtains the modified enhancing in surface
Material；
By the modified reinforcing material in the surface and the first long carbon chain nylon, crystallinity semi-aromatic nylon, wear-resistant masterbatch, first
Lubricant, antioxidant, compatilizer, hydrophober carry out mixing treatment, obtain mixed material；
The mixed material is put into double screw extruder, is melted at 240 DEG C, blending extrusion, the screw rod of extrusion turns
Speed is 480rpm, is then cooled to room temperature, through pelletizing, drying, obtains ultralow water suction cold-resistant, wear-resisting nylon composite materials.
Wherein, wear-resistant masterbatch used in embodiment 1~13 is prepared using following method: (1) is by 15 parts of poly dimethyls
The sulfuric acid that water is added in siloxanes after mixing with 30 parts of tetramethyl-ring tetrasiloxanes, 3 parts of mass fractions are 80%, temperature rising reflux reaction
3h is then evaporated under reduced pressure, and the polymer II as shown in reaction equation (a) is obtained.
(2) mixes the polymer II that step (1) obtains with 25 parts of vinyl tri-phenyl-silanes, is warming up to 80 DEG C,
3.5h is reacted, the polymer III as shown in reaction equation (b) is obtained.
(3) obtains step (2) polymer III and 60 parts of Nano diamonds, 40 parts of M-phthalic acid type unsaturations are poly-
Ester resin is mixed, and the sulfuric acid that 2 parts of mass fractions are 80% is added, and is warming up to 80 DEG C, is reacted 3h；Hydroxide is then added
Sodium adjusts pH close to neutrality, and washing vacuumizes distillation, and room temperature cures 48h, can be obtained such as supra polymer anti-wear agent.
(4) 50 parts of polyolefin are placed in kneader by is heated to 100 DEG C, is stirred under vacuum, and is then cooled to 70 DEG C, and will
It is added thereto for 50 parts of supra polymer anti-wear agent, stirs with 5 parts of nylon, 12,1.5 parts of silicone, 0.5 part of lignin made from step (3)
It mediates, time 2h, obtains wear-resistant masterbatch.
The material component (parts by weight) of 1 embodiment 1~13 of table
Performance for the ultralow water suction cold-resistant, wear-resisting nylon composite materials of verifying acquisition will be real using injection molding technique
It applies the ultralow water suction cold-resistant, wear-resisting nylon composite materials that example 1~13 and comparative example 1 obtain and is prepared into sweeper brush respectively.
Its specific injection molding technique are as follows: injection temperature be 240 DEG C, injection pressure be 60MPa under the conditions of, with
The ultralow water suction cold-resistant, wear-resisting nylon composite materials of melting are injected into mold by the injection speed of 75mm/s, pressure maintaining 20s, cold
But, it demoulds, the dry 4h at 120 DEG C, i.e. acquisition sweeper brush.
Respective performances detection is carried out to the sweeper brush of acquisition, specific examination criteria and method are as follows:
(1) tensile strength: " measurement of plastic tensile performance " ISO 527-1-2012；
(2) bending strength: " Plastics-Oetermination of flexural properties method " ISO 178-2010；
(3) notch impact strength: " impact test method " GB/T 1043.1-2008；
(4) test of wear-resisting property: friction wear testing machine is used, mating plate is No. 45 steel loops of 40mm × 10mm, whole
It is 40-45 that body, which requires HRC after quenching, and outer round surface roughness is 0.4m, and specimen size is 16mm × 15mm × 7mm.
Experimental condition: under room temperature DRY SLIDING, revolving speed 0.42m/s uses electronics to time consuming 2h, load 196N
Balance weighs the quality after abrasion.
(5) water absorption rate: " plastic density and relative density test method ", GB/T8810-2005；
Detect the ruler under room temperature under the size changing rate of different humidity RH (20~100%), high/low temperature (- 40~100 DEG C)
Very little change rate.Specific performance testing result is as shown in table 2:
The performance parameter of the sweeper brush of the ultralow water suction cold-resistant, wear-resisting nylon composite materials preparation of 2 embodiment of table 1~13
As shown in Table 2, the abrasion loss of sweeper brush is smaller, and the product abrasion loss for being not added with wear-resistant masterbatch is then larger, explanation
The product obtained using formula of the invention is wear-resisting, self-lubrication is excellent；Soaked water absorption rate for 24 hours illustrates its suction less than 0.10%
Water rate is low, and size changing rate illustrates good stability of the dimension less than 0.10%；It follows that the ultralow water suction that the present invention obtains is resistance to
Cold fire retardation wear-resistance nylon composite material is suitable for the necks such as manufacture motor turning turbine, timing gears, medical instrument, textile machine gear
Domain is ideal sweeper brush material, with self-lubrication, low noise, cold-resistant, rub resistance, service life length, high safety and reliability
The features such as.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modification, equivalent replacement or improvement etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of ultralow water suction cold-resistant, wear-resisting nylon composite materials, which is characterized in that the ultralow water suction cold-resistant, wear-resisting nylon is multiple
It includes that the following raw material components of parts by weight are obtained through melting extrusion that condensation material, which uses:
Wherein, first long carbon chain nylon is the nylon of monomer carbon atom number >=10.
2. ultralow water suction cold-resistant, wear-resisting nylon composite materials as described in claim 1, which is characterized in that the wear-resistant masterbatch is
It is stirred using the supra polymer anti-wear agent as shown in formula (I), the second lubricant, the second long carbon chain nylon, stabilizer, carrier
It mediates,
Wherein, a=30~50, b=1~10, c=30~50, n=10~100；Second long carbon chain nylon is that free carbon is former
The nylon of subnumber >=10.
3. ultralow water suction cold-resistant, wear-resisting nylon composite materials as claimed in claim 2, which is characterized in that the supra polymer is resistance to
Grinding agent is prepared using following raw material components:
Preparation method is as follows:
Addition water, partial catalyst after dimethyl silicone polymer is mixed with tetramethyl-ring tetrasiloxane, temperature rising reflux reaction 1~
3h is then evaporated under reduced pressure, and the polymer II with general formula is obtained；
Polymer II is mixed with vinyl tri-phenyl-silane, is warming up to 70~90 DEG C, reacts 1~4h, obtains having logical
The polymer III of formula；
Polymer III is mixed with the Nano diamond, unsaturated polyester (UP), and remaining catalyst is added, is warming up to
70~90 DEG C, react 1~3h；Neutralizer is then added to neutralize, washing vacuumizes distillation, and room temperature cures 48h or more, can be obtained
Such as supra polymer anti-wear agent；
Wherein, a=30~50, b=1~10, c=30~50.
4. ultralow water suction cold-resistant, wear-resisting nylon composite materials as claimed in claim 2, which is characterized in that second lubricant
For at least one of silicone, oleamide, erucyl amide, ethylene bis stearic amide；
And/or second long carbon chain nylon is the nylon of monomer carbon atom number >=10；
And/or the stabilizer is lignin, carboxymethyl cellulose, number-average molecular weight 1.0 × 104~1.0 × 105Polycyclic
At least one of oxidative ethane；
And/or the carrier is any one of polyolefin, polyolefin copolymer.
5. ultralow water suction cold-resistant, wear-resisting nylon composite materials as claimed in claim 3, which is characterized in that the catalyst is dense
Any one of sulfuric acid, concentrated hydrochloric acid, acetic acid；
And/or the unsaturated polyester (UP) is metaphenylene unsaturated polyester resin.
6. ultralow water suction cold-resistant, wear-resisting nylon composite materials as described in claim 1, which is characterized in that half virtue of the crystallinity
Fragrant nylon is poly-meta-xylylene adipamide, poly- paraphenylene terephthalamide's butanediamine, poly- hexamethylene terephthalamide, polyamide 9T, gathers
At least one of paraphenylene terephthalamide's decamethylene diamine.
7. ultralow water suction cold-resistant, wear-resisting nylon composite materials as described in claim 1, which is characterized in that the reinforcing material is
The fibre diameter of any one of flat glass, carbon fiber, the flat glass and/or the carbon fiber is 6~18 μm；
And/or first lubricant is at least one of silicone, oleamide, erucyl amide or ethylene bis stearic amide；
And/or the antioxidant is one or more of phosphorous acid esters, Hinered phenols antioxidant or suffocated amine antioxidant；
And/or the compatilizer be selected from ethylene-octene copolymer grafted maleic anhydride, high-density polycthylene grafted maleic anhydride,
At least one in grafted low density polyethylene maleic anhydride, Styrene-Butadiene-Styrene Block Copolymer grafted maleic anhydride
Kind；
And/or the hydrophober is at least one of polyolefin, polyolefin copolymer.
8. a kind of preparation method of ultralow water suction cold-resistant, wear-resisting nylon composite materials, at least includes the following steps:
S01. the first long carbon chain nylon is weighed in the ratio as described in claim 1~7 is any, crystallinity semi-aromatic nylon, increase
Strong material, anti-wear agent master batch, the first lubricant, antioxidant, compatilizer, hydrophober；
S02. after the weighed material of step S01 being mixed, melting is added twin-screw extrude, blending extrusion, is cut at cooling
Grain, drying are to get ultralow water suction cold-resistant, wear-resisting nylon composite materials.
9. the preparation method of ultralow water suction cold-resistant, wear-resisting nylon composite materials as claimed in claim 8, which is characterized in that described
Reinforcing material further includes being mixed using Long carbon chain silane coupling agent to the reinforcing material before mixing with other components
It is modified；
And/or the melting and the temperature of blending extrusion are 210~240 DEG C, the screw speed of extrusion is 470~490rpm.
10. ultralow water suction cold-resistant, wear-resisting nylon composite materials as described in any one of claims 1 to 7 turn to turbine, gear,
Application in sweeper brush, medical instrument.
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| CN113956651A (en) * | 2021-11-20 | 2022-01-21 | 南京聚隆科技股份有限公司 | High-strength low-shrinkage nylon material for flange plate and preparation method thereof |
| CN114163812A (en) * | 2021-12-20 | 2022-03-11 | 万华化学（宁波）有限公司 | Low-temperature-resistant high-wear-resistance nylon material and preparation method and application thereof |
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