CN106146830A - A kind of multilamellar modified cast nylon material - Google Patents
A kind of multilamellar modified cast nylon material Download PDFInfo
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- CN106146830A CN106146830A CN201510209468.6A CN201510209468A CN106146830A CN 106146830 A CN106146830 A CN 106146830A CN 201510209468 A CN201510209468 A CN 201510209468A CN 106146830 A CN106146830 A CN 106146830A
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Abstract
The present invention relates to a kind of multilamellar modified cast nylon material, it includes at least two-layer in wearing layer, toughening layer and enhancement layer；The material of described wearing layer is wear-resisting nylon monomer-cast nylon；The material of described toughening layer is toughness reinforcing nylon monomer-cast nylon；The material of described enhancement layer is for strengthening nylon monomer-cast nylon.This multilamellar modified cast nylon material has different performances in different aspects, it is possible to meets part difference and uses the position requirement to different performance.
Description
Technical field
The present invention relates to belong to polymeric material field, be specifically related to a kind of multilamellar modification casting Buddhist nun
Dragon material and preparation method thereof.
Background technology
Along with chemical industry and the development of mechanical industry, the engineering plastics such as nylon build life its people
Consumption in product is increasing, the metallic element of some keys progressively by low-density, high-performance,
The nylon material part of low price substitutes, and makes the performance of product improve, and weight, cost significantly subtract
Low, thus promoted the fast development of " to mould Dai Gang ".
Nylon monomer-cast nylon, also known as MC nylon or monomer moulding casting nylon, English name is Monomer
Cast Nylon.Nylon monomer-cast nylon is to be urged by melted raw material caprolactam monomer alkaline matter
Agent, makes together with the auxiliary agents such as activator and treats poly-monomer, be directly injected in the mould of preheating,
A kind of nylon material that material obtains in the reaction of mould rapid polymerization.By rapid polymerization, make to water
The molecular weight ratio common nylon of casting nylon is substantially improved, and decreases defect, promotes nylon material
Performance.
And along with the progress of industrial technology level, the requirement of nylon monomer-cast nylon performance is got over by people
Come the highest.Such as, it is desirable to its have preferable wearability, intensity, toughness, ageing resistance,
Thermostability, dimensional stability etc..The pure nylon monomer-cast nylon that performance is single has been difficult to meet current work
Require that of industry technology.
For improving the performance of nylon monomer-cast nylon, people have carried out multiple modification to nylon monomer-cast nylon,
The a certain performance of nylon monomer-cast nylon is such as improved by adding filler.By adding anti-friction wear-resistant
Solid particulate lubricant (graphite, MoS2Deng), the coefficient of friction of nylon monomer-cast nylon can be reduced,
Improve its wearability；By adding various fibers (carbon fiber, glass fibre etc.), can improve
The intensity of nylon monomer-cast nylon；By adding Nano compound granule (nanometer Al2O3, nano-TiO2
Deng) or elastomer (PP, SBS etc.), the impact flexibility of nylon monomer-cast nylon can be improved.
But, when using a certain item performance that said method improves nylon monomer-cast nylon, may result in
The decline of other performance.Such as, when addition particle lubricant improves properties of antifriction and wear resistance, may
Toughness of material can be caused to decline.When adding the glass fibre raising strength of materials, it is also possible to cause
The decline of toughness of material.
If add multiple filler in nylon monomer-cast nylon simultaneously, multinomial performance may be improved.But,
The filler added is the most, and material system is the most complicated, and design difficulty is the highest, not only can increase cost,
It is also possible to reduce stability and the reliability of material.
Summary of the invention
For one or more problem present in prior art, it is an object of the invention to carry
For a kind of multilamellar modified cast nylon material, a further object of the present invention is to provide a kind of by upper
State the part that multilamellar modified cast nylon material is made, it is also another object of the present invention to provide one
Plant the method preparing above-mentioned multilamellar modified cast nylon material.
To this end, first aspect present invention provides a kind of multilamellar modified cast nylon material, it includes
At least two-layer in wearing layer, toughening layer and enhancement layer, the material of described wearing layer is resistance to
Mill nylon monomer-cast nylon, the material of described toughening layer is toughness reinforcing nylon monomer-cast nylon, the material of described enhancement layer
For strengthening nylon monomer-cast nylon；
Preferably, described wear-resisting nylon monomer-cast nylon, toughness reinforcing nylon monomer-cast nylon, enhancing nylon monomer-cast nylon are each
It is modified making to nylon monomer-cast nylon independently by one or more in following method of modifying
For obtaining: modification by copolymerization, blending and modifying, filling-modified, chemical modification；
Preferably, between described wearing layer, toughening layer or enhancement layer by successively casting (such as
Successively spun casting) method be combined；
Preferably, each layer of described multilamellar nylon monomer-cast nylon material is followed successively by wearing layer and enhancement layer,
Or it is followed successively by wearing layer and toughening layer, or is followed successively by wearing layer, enhancement layer and toughening layer.
Described multilamellar modified cast nylon material can need to carry out according to performance applications multiple
The independent assortment of modified layer, if " wearing layer+enhancement layer " combination application is in top load high abrasion
Part, " wearing layer+toughening layer " combination application is resistance in elastic packing wear part and damping
Mill part, " wearing layer+toughening layer+enhancement layer " combination application is wear-resisting in inside, outside high-strength,
Core has the part of certain toughness.
In one embodiment, the multilamellar modified cast nylon material of the aforementioned any one of the present invention,
Containing (being such as filled with) abrasion resistance modifier in described wear-resisting nylon monomer-cast nylon,
Preferably, described abrasion resistance modifier is kollag and/or fluid lubricant；
Described kollag can be graphite granule and/or MoS2Granule；
Described fluid lubricant can be in base oil, mineral oil, lubricating oil and grease
One or more (be selected from poly-diethylene glycol ether base grease oils and fats, perfluoroether basis profit
One or more in lubricating oil fat, Polyethylene Glycol lubricant grease and polyolefin base lubricant grease).
In a specific embodiment, wear-resisting nylon monomer-cast nylon of the present invention has with next
Item or multinomial performance index:
A) wear extent≤4mg, preferably≤3mg, more preferably≤2mg；
B) coefficient of friction≤0.5, preferably≤0.4, more preferably≤0.3.
In a specific embodiment, wear-resisting nylon monomer-cast nylon of the present invention is by acyl in oneself
Amine, catalyst, activator and abrasion resistance modifier are made.Wherein caprolactam and abrasion resistance modifier
Mass ratio be preferably 100:3～15.
In one embodiment, the multilamellar modified cast nylon material of the aforementioned any one of the present invention,
Containing (being such as filled with) reinforced modifier in described enhancing nylon monomer-cast nylon,
The diameter that described reinforced modifier is preferably fiber and/or whisker, fiber or whisker is preferred
Being 1～4 μm, length is preferably 50～200 μm；
Preferably, one or more in carbon fiber, glass fibre and CNT of fiber；
Preferably, whisker, selected from organic crystalline palpus and/or inorganic crystal whisker, is selected from cellulose brilliant
Palpus, poly-4-HBA fat whisker, butyl polyacrylate-styrene whisker, graphite whisker and
One or more in poly-potassium titanate crystal whisker；
Preferably, described reinforced modifier processes through surface conditioning agent, described surface conditioning agent
One or more of silane coupler, titanate coupling agent and aluminate coupling agent can be selected from.
In a specific embodiment, described enhancing nylon monomer-cast nylon of the present invention has
The most one or more performance indications:
C) hot strength >=70MPa, preferably >=90MPa, more preferably >=110MPa；
D) bending strength >=90MPa, preferably >=110MPa, more preferably >=130MPa；
E) compressive strength >=80MPa, preferably >=100MPa, more preferably >=120MPa.
In a specific embodiment, enhancing nylon monomer-cast nylon of the present invention is by acyl in oneself
Amine, catalyst, activator and reinforced modifier are made.Wherein caprolactam and reinforced modifier
Mass ratio be preferably 100:10～20.
In one embodiment, the multilamellar modified cast nylon material of the aforementioned any one of the present invention,
Containing (being such as filled with) plasticized modifier in described toughness reinforcing nylon monomer-cast nylon,
Described plasticized modifier is preferably nano-particle and/or elastomer, the particle diameter of nano-particle
Being preferably 20～50nm, the particle diameter of elastomer is preferably 0.2～0.5 μm；
Preferably, described nano-particle is selected from nanometer Al2O3, nano-TiO2, Nano-meter SiO_22、
One or more of nano zircite and nano-calcium carbonate；
Preferably, described nano zircite or nano-calcium carbonate are receiving through titanate esters modification
Rice zirconium oxide or nano-calcium carbonate, the consumption of described titanate esters is preferably nano zircite or nanometer
The 0.5% of weight of calcium carbonate～3% (such as 2.5%)；
Preferably, described elastomer is preferably thermoplastic elastomer (TPE), such as can be selected from PP,
POE, POE-g-GMA, EVA, EVA-g-MAH, EPDM, SBS and EPR's
One or more.
In a specific embodiment, described toughness reinforcing nylon monomer-cast nylon of the present invention has
The most one or more performance indications:
F) elongation at break >=20%, preferably >=40%, more preferably >=60%；
G) impact strength >=10KJ/m2, preferably >=12KJ/m2, preferably >=14KJ/m2。
In a specific embodiment, toughness reinforcing nylon monomer-cast nylon of the present invention is by acyl in oneself
Amine, catalyst, activator and plasticized modifier are made.Wherein caprolactam and plasticized modifier
Mass ratio be preferably 100:10～20.
In a preferred embodiment, the multilamellar modification casting Buddhist nun of the aforementioned any one of the present invention
Dragon material, the mass ratio of wherein said caprolactam, catalyst and activator is preferably
100:0.2～0.5:0.2～0.5.
Preferably, described catalyst is alkaline matter, be preferably selected from alkali metal, alkaline-earth metal,
One or more of metal-oxide or derivant, are more preferably selected from NaOH, KOH, ethanol
Sodium, Feldalat NM one or more.
Preferably, described activator is selected from isocyanates, is preferably selected from aromatic isocyanate
Or one or more of aliphatic isocyanates, it is more preferably selected from toluene di-isocyanate(TDI) (TDI)
Or one or more in isophorone diisocyanate (IPDI).
In a preferred embodiment, heretofore described enhancing nylon monomer-cast nylon, toughness reinforcing
Nylon monomer-cast nylon or wear-resisting nylon monomer-cast nylon can also contain compatilizer respectively.Compatilizer can allow and change
Property agent is better dispersed in nylon material.Preferably, compatilizer can be rubber-plastic elastomer
Graft copolymer, as POE-g-MAH, SEBS-g-MAH, POE-g-GMA,
EPDM-g-MAH etc..In the preparation, it is added as needed on compatilizer, can allow modifying agent
It is better dispersed in nylon material.
In one embodiment, the multilamellar modified cast nylon material of the aforementioned any one of the present invention,
The preparation method of the most wear-resisting nylon monomer-cast nylon, toughness reinforcing nylon monomer-cast nylon or enhancing nylon monomer-cast nylon is:
1) in melted caprolactam, add catalyst, stir, be dehydrated；
2) as required, add selected from abrasion resistance modifier, reinforced modifier and plasticized modifier
In one or more modifying agent, alternatively, add compatilizer while modifying agent adding,
Agitating heating, continuation dehydration,
3) add activator, then cast, prepare.
Preferably, step 1) in, melted caprolactam is warming up to 125 ± 5 DEG C, adds
Catalyst, stirs and is dehydrated 30-45min；
Preferably, step 2) in, the temperature of described agitating heating is 135 ± 5 DEG C；
Preferably, in step 3, during casting, first mould is preheating to 170 ± 5 DEG C, then enters
Row casting；Preferably, after having cast, insulation polymerization, holding temperature is preferably 130～150 DEG C,
Such as 140 ± 5 DEG C, temperature retention time is preferably 60～120min.
In one embodiment, the multilamellar modified cast nylon material of the aforementioned any one of the present invention,
Wherein the thickness of wearing layer, enhancement layer or toughening layer is 10～50mm,
Preferably, in described multilamellar modified cast nylon material, in parts by weight, wearing layer
Being 20～30 parts, enhancement layer is 20～40 parts, and toughening layer is 40～50 parts.
Second aspect present invention provides a kind of part, and it is changed by the multilamellar of the aforementioned any one of the present invention
Property nylon monomer-cast nylon material is made.Described part is preferably power transmission shaft, ring flange, lining, axle
Set, pipeline, pulley (such as two-phase pulley), slide block, slideway, multilamellar modified cast nylon
Plate, multilamellar modified cast nylon rod or multilamellar modified cast nylon pipe.
Described two-phase pulley is the pulley being made up of mutually two materials, and such as metal-nylon is double
Phase pulley, is made up of with nylon mutually metal phase, and wherein nylon can be that the present invention is aforementioned arbitrary mutually
The multilamellar modified cast nylon of item.
Preferably, the internal layer of described lining is wearing layer, and middle level is enhancement layer, and outer layer is toughness reinforcing
Layer.
Preferably, the internal layer of described pipeline is wearing layer, and outer layer is enhancement layer or toughening layer.
Preferably, the main part of described sleeve, pulley or slide block includes enhancement layer and/or increasing
Tough layer, at least part of surface is wearing layer.
Preferably, the main part of described ring flange includes enhancement layer and/or toughening layer, seals
Face is wearing layer.
Preferably, the sandwich layer of described multilamellar modified cast nylon rod is toughening layer, and intermediate layer is for increasing
Strong layer, outer layer is wearing layer.
Preferably, each layer of described multilamellar modified cast nylon plate is followed successively by wearing layer, enhancement layer
And toughening layer.
Preferably, the internal layer of described multilamellar modified cast nylon pipe is wearing layer, and intermediate layer is for increasing
Strong layer, outer layer is toughening layer.
Third aspect present invention provides the multilamellar modification of the aforementioned any one of a kind of present invention of preparation to water
The method of casting nylon material, the method is wearing layer, toughening layer or enhancement layer to be led to as required
Method composite molding after successively casting (the most successively spun casting).
In one embodiment, the method for third aspect present invention, it includes, waters wear-resisting
That casts nylon, toughness reinforcing nylon monomer-cast nylon or enhancing nylon monomer-cast nylon treats that poly-monomer the most successively pours into
In mould；
Preferably, treat described in poly-monomer include molten caprolactam, catalyst, activator and
Corresponding modifying agent；
Preferably, treat that what poly-monomer poured into mould is spaced apart 1～3 minute for every kind.
Preferably, after needed poly-monomer pours into mould, insulation polymerization, holding temperature is preferred
Being 130～150 DEG C, such as 140 ± 5 DEG C, temperature retention time is preferably 60～120min.
Unless stated otherwise, in the present invention, all numbers are parts by weight, and percentage ratio is weight
Percentage ratio.
Unless stated otherwise, heretofore described common nylon monomer-cast nylon refers to be not added with any modification
The nylon monomer-cast nylon of agent.
In the present invention, unless stated otherwise, the english abbreviation of material has well known in the art containing
Justice.Preferably, the english abbreviation in the present invention can have English full name as shown in table 1 or
Chinese.
Table 1
Beneficial effects of the present invention
Compared with the nylon monomer-cast nylon material of single modification, multilamellar modified cast nylon of the present invention has
The performance of multinomial improvement.Compared with being simultaneously introduced multiple filler modified nylon monomer-cast nylon, the present invention
Multilamellar nylon material not only has the performance of multinomial improvement, and has difference in different aspects
Performance, it is possible to meet part difference use the position requirement to different performance.Due to the present invention
The phase structure of each layer of nylon material is relatively easy, and modified filler used is relatively fewer, therefore originally
Invention multilamellar modified cast nylon performance is the most more stable, and cost is the lowest.
Contrast traditional using and extrude Shooting Technique, repeatedly casting, the multilamellar nylon of repeatedly molding
Material, the nylon material of the present invention uses monovalent anion polymerization casting process, direct casting one
Secondary molding.The two is compared, and molecular weight and the consistency of nylon material of the present invention are higher, mechanical property
Can be more preferable；Each nylon layer matrix is all to obtain, respectively with lactam monomers anionic polymerisation
Can also be combined by caprolactam monomer anionic polymerisation between nylon layer, therefore this
Bright nylon material each bed boundary binding ability is more preferable.And, damping material one-time continuous of the present invention is watered
The preparation method of type casting moulding, this features simple and practical process, it is easy to accomplish.
The multilamellar modified cast nylon material of the present invention can be prepared as various component of machine.And
And, it is also possible to according to the difformity of parts, size, purposes, use environment, use and want
Ask, the kind of flexible design wearing layer, toughening layer or enhancement layer, the number of plies or ordering,
Difference use the corresponding optimal performance of Position Design modification of nylon layer, thus obtain low cost,
High-performance, nylon parts with strong points.
When the part top layer of part requires high friction and wear behavior, and part top layer requires high tenacity,
When core requires high intensity, the wearing layer that multilamellar modified cast nylon material of the present invention provides, increase
Tough layer and enhancement layer all can meet the performance requirement of part diverse location.
In one embodiment, the performance of the present invention each layer nylon is as shown in table 1.
Table 1 nylon of the present invention each layer performance
More specifically, the multilamellar modified cast nylon material of the present invention can be used for manufacturing internal layer requirement
High-wearing feature, middle level require that high intensity, outer layer require the damping anti-wearing liner of high tenacity；Available
Require that high-wearing feature, one side require the ring flange of damping high tenacity in manufacturing one side；Can be used for making
Make internal layer requirement high-wearing feature, outer layer requirement high voltage bearing wear resistant nylon pipeline；Can be used for manufacturing
One side requires high-wearing feature, one side to require, and the wear sleeves such as the wear-resisting slideway of high-mechanic, two-phase are sliding
The components of machine such as wheel and slide block.
In sum, each layer matrix material of the multilamellar modified cast nylon material that the present invention provides
Being all nylon monomer-cast nylon, each layer of material is combined by direct casting, one-shot forming.Material possesses many
Improve while performance, molecular weight and consistency is higher, mechanical property more preferable, interface cohesion
Power is strong, and amount of modifier is few, low cost, and designability is strong, stability good.Meanwhile,
This nylon material uses one-time continuous cast molding, and Technology is simple and practical, it is easy to accomplish.
Accompanying drawing explanation
Accompanying drawing described herein is used for providing a further understanding of the present invention, constitutes the application
A part, the schematic description and description of the present invention is used for explaining the present invention, not structure
Become inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 is the cross-sectional view of multilamellar modified cast nylon plate.
Fig. 2 is the cross-sectional view of multilamellar modified cast nylon rod.
Detailed description of the invention
Below by drawings and Examples, technical scheme is done and further retouches in detail
State.
Embodiment 1 (wearing layer 20 weight %+ enhancement layer 40 weight %+ toughening layer 40 weight %):
(1) weigh the caprolactam raw material of 320kg, add in melt tank, be heated to completely
Melted.
(2) it is warming up to 125 DEG C, adds the Feldalat NM of 0.9kg, open agitating device, open
Dehydration device, 40min is to being dehydrated completely in dehydration, it is thus achieved that activation caprolactam.
(3) the activation caprolactam of 64kg is transferred in 1# retort, adds 5.12kg
Polyethylene Glycol lubricant grease, continue dehydration, be heated with stirring to 140 DEG C.
(4) the activation caprolactam of 128kg is transferred in 2# retort, adds 19.2kg
Poly-(BA-St) whisker, continue dehydration, be heated with stirring to 140 DEG C.
(5) the activation caprolactam of 128kg is transferred in 3# retort, adds 19.2kg
EVA-g-MAH, continue dehydration, be heated with stirring to 140 DEG C.
(6) in 1# molten mass, 0.32kg toluene di-isocyanate(TDI) (TDI) is added, rapidly
It is cast to preheat in the mould of 170 DEG C；After 1～3min, 2# molten mass adds 0.64kg
Activator toluene di-isocyanate(TDI) (TDI), be cast to rapidly in above-mentioned mould；1～3min
After, 3# molten mass adds the activator toluene di-isocyanate(TDI) (TDI) of 0.64kg, fast
Speed is cast in above-mentioned mould, casts according to this, until having cast.
(5) at 145 DEG C of insulation 120min, mould being completed polyreaction, the demoulding i.e. obtains
The multilamellar modification casting of wearing layer 20 weight %+ enhancement layer 40 weight %+ toughening layer 40 weight %
Nylon material composite, its various performance parameters is shown in Table 2.
Table 2 embodiment 2 multilamellar modified cast nylon material each layer performance
| Inspection project | Wearing layer | Enhancement layer | Toughening layer | Test standard |
| Hot strength MPa | 72 | 110 | 80 | GB/T1040.2/1A-2006 |
| Bending strength MPa | 86 | 130 | 96 | GB/T9341-2008 |
| Compressive strength MPa | 85 | 115 | 85 | GB/T1041-2008 |
| Elongation at break % | 16 | 18 | 68 | GB/T1040.2/1A-2006 |
| Impact strength KJ/m2 | 8 | 8.5 | 15 | GB/T1043.1/1-2008 |
| Confficient of static friction (dry state) | 0.15 | 0.39 | 0.48 | GB/T3960-1983 |
| Wear extent (2h) mg | 2.0 | 3.2 | 3.4 | GB/T3960-1983 |
Embodiment 2 (wearing layer 30 weight %+ toughening layer 20 weight %+ enhancement layer 50 weight %):
(1) weigh the caprolactam raw material of 100kg, add in melt tank, be heated to completely
Melted.
(2) it is warming up to 120 DEG C, adds the Feldalat NM of 0.4kg, open agitating device, open
Dehydration device, 30min is to being dehydrated completely in dehydration, it is thus achieved that activation caprolactam.
(3) the activation caprolactam of 50kg is transferred in 1# retort, adds 5kg's
Poly-potassium titanate crystal whisker, continues dehydration, is heated with stirring to 135 DEG C.
(4) the activation caprolactam of 20kg is transferred in 2# retort, adds 2kg's
EVA-g-MAH, continues dehydration, is heated with stirring to 135 DEG C.
(5) the activation caprolactam of 30kg is transferred in 3# retort, adds 1.5kg's
Polyolefin base lubricant grease, continues dehydration, is heated with stirring to 135 DEG C.
(6) in 1# molten mass, 0.15kg toluene di-isocyanate(TDI) (TDI) is added, rapidly
It is cast to preheat in the mould of 170 DEG C；After 1～3min, 2# molten mass adds 0.08kg
Activator toluene di-isocyanate(TDI) (TDI), be cast to rapidly in above-mentioned mould；1～3min
After, 3# molten mass adds the activator of 0.1kg, is cast to rapidly in above-mentioned mould, depends on
This casting, until having cast.
(5) at 140 DEG C of insulation 60min, mould being completed polyreaction, the demoulding i.e. obtains resistance to
The multilamellar modification casting Buddhist nun of mill layer 30 weight %+ toughening layer 20 weight %+ enhancement layer 50 weight %
Dragon composites, its various performance parameters is shown in Table 3.
Table 3 embodiment 3 nylon each layer performance
Embodiment 3
Embodiment 3 provides a kind of multilamellar modified cast nylon plate, this multilamellar Buddhist nun's modification casting dragon plate
Prepared by the multilamellar modified cast nylon of the present invention.Fig. 1 illustrates the cross-sectional view of this nylon sheet,
As it is shown in figure 1, each layer of this multilamellar nylon sheet is followed successively by toughening layer 1, enhancement layer 2 and wear-resisting
Layer 3.
The intermediate layer of this multilamellar nylon sheet is enhancement layer 2, has higher mechanical strength, side
Surface layer is toughening layer 1, has higher impact resistance, and opposite side surface layer is wearing layer 3,
There is higher wear resistance.This multilamellar modification composite nylon plate has enhancing matrix and
Side is wear-resisting, side shock resistance, is applicable to the working environment of various complexity.
Embodiment 4
Embodiment 4 provides a kind of multilamellar modified cast nylon rod, this multilamellar Buddhist nun's modification casting dragon rod
Prepared by the multilamellar modified cast nylon of the present invention.Use spun casting layer-by-layer casting can obtain this
Multilamellar modified cast nylon rod described in embodiment, first carries out outermost cast, then by
Layer cast, finally realizes the cast of core.Fig. 2 illustrates the cross-sectional view of this multilamellar nylon rod,
As in figure 2 it is shown, each layer that this multilamellar nylon rod is from inside to outside is followed successively by toughening layer 1, enhancement layer 2
With wearing layer 3.
The sandwich layer of this multilamellar nylon rod is toughening layer 1, has higher toughness, and intermediate layer is for increasing
Strong layer 2, has higher mechanical strength, and surface layer is wearing layer 3, has higher wear-resistant
Performance.This multilamellar nylon rod has toughness reinforcing matrix, the intermediate layer of enhancing and wear-resisting surface layer,
It is applicable to the working environment of Various Complex.
Finally should be noted that: above example only in order to technical scheme to be described and
Non-to its restriction；Although the present invention being described in detail with reference to preferred embodiment, affiliated
The those of ordinary skill in field is it is understood that still can enter the detailed description of the invention of the present invention
Row is revised or portion of techniques feature is carried out equivalent；Without deviating from technical solution of the present invention
Spirit, it all should be contained in the middle of the technical scheme scope that the present invention is claimed.
Claims (18)
1. a multilamellar modified cast nylon material, it include selected from wearing layer, toughening layer and
At least two-layer in enhancement layer, the material of described wearing layer is wear-resisting nylon monomer-cast nylon, described toughness reinforcing
The material of layer is toughness reinforcing nylon monomer-cast nylon, and the material of described enhancement layer is for strengthening nylon monomer-cast nylon.
2. according to the multilamellar modified cast nylon material of right 1, wherein said wear-resisting casting Buddhist nun
Nylon monomer-cast nylon imperial, toughness reinforcing, enhancing nylon monomer-cast nylon are independently of one another by selected from following method of modifying
In one or more be modified preparing to nylon monomer-cast nylon: modification by copolymerization, blending and modifying,
Filling-modified, chemical modification.
3. according to the multilamellar modified cast nylon material of right 1 or 2, wherein said wearing layer,
It is combined by the method for successively casting (the most successively spun casting) between toughening layer or enhancement layer.
4. according to the multilamellar modified cast nylon material of any one of right 1 to 3, wherein said
Each layer of multilamellar nylon monomer-cast nylon material is followed successively by wearing layer and enhancement layer, or is followed successively by wearing layer
And toughening layer, or it is followed successively by wearing layer, enhancement layer and toughening layer.
5. according to the multilamellar modified cast nylon material of any one of right 1 to 4, described wear-resisting
Containing (being such as filled with) abrasion resistance modifier in nylon monomer-cast nylon,
Preferably, described abrasion resistance modifier is kollag and/or fluid lubricant；
Preferably, described kollag is graphite granule and/or MoS2Granule；
Preferably, described fluid lubricant is selected from base oil, mineral oil, lubricating oil and lubrication
One or more in fat (are selected from poly-diethylene glycol ether base grease oils and fats, perfluoroether
One or many in plinth lubricant grease, Polyethylene Glycol lubricant grease and polyolefin base lubricant grease
Kind)；
Preferably, wear-resisting nylon monomer-cast nylon is by caprolactam, catalyst, activator and wear-resisting modification
Agent is made,
Preferably, the mass ratio of caprolactam and abrasion resistance modifier is preferably 100:3～15.
6. according to the multilamellar modified cast nylon material of right 5, wherein said wear-resisting casting
Nylon has following one or more performance indications:
A) wear extent≤4mg, preferably≤3mg, more preferably≤2mg；
B) coefficient of friction≤0.5, preferably≤0.4, more preferably≤0.3.
7. according to the multilamellar modified cast nylon material of any one of right 1 to 6, described enhancing
Containing (being such as filled with) reinforced modifier in nylon monomer-cast nylon,
Preferably, described reinforced modifier is preferably fiber and/or whisker, fiber or whisker
Diameter is preferably 1～4 μm, and length is preferably 50～200 μm；
Preferably, one or more in carbon fiber, glass fibre and CNT of fiber；
Preferably, whisker, selected from organic crystalline palpus and/or inorganic crystal whisker, is selected from cellulose brilliant
Palpus, poly-4-HBA ester whisker, butyl polyacrylate-styrene whisker, graphite whisker and
One or more in poly-potassium titanate crystal whisker；
Preferably, described reinforced modifier processes through surface conditioning agent, described surface conditioning agent
One or more of silane coupler, titanate coupling agent and aluminate coupling agent can be selected from；
Preferably, nylon monomer-cast nylon is strengthened by caprolactam, catalyst, activator and enhancing modified
Agent is made；
Preferably, the mass ratio of caprolactam and reinforced modifier is preferably 100:10～20.
8. according to the multilamellar modified cast nylon material of right 7, wherein said enhancing casting Buddhist nun
Dragon has following one or more performance indications:
C) hot strength >=70MPa, preferably >=90MPa, more preferably >=110MPa；
D) bending strength >=90MPa, preferably >=110MPa, more preferably >=130MPa；
E) compressive strength >=80MPa, preferably >=100MPa, more preferably >=120MPa.
9. according to the multilamellar modified cast nylon material of any one of right 1 to 8, described toughness reinforcing
Containing (being such as filled with) plasticized modifier in nylon monomer-cast nylon,
Preferably, described plasticized modifier is preferably nano-particle and/or elastomer, nanometer
The particle diameter of grain is preferably 20～50nm, and the particle diameter of elastomer is preferably 0.2～0.5 μm；
Preferably, described nano-particle is selected from nanometer Al2O3, nano-TiO2, Nano-meter SiO_22、
One or more in nano zircite and nano-calcium carbonate；
Preferably, described nano zircite or nano-calcium carbonate are receiving through titanate esters modification
Rice zirconium oxide or nano-calcium carbonate, the consumption of described titanate esters is preferably nano zircite or nanometer
The 0.5% of weight of calcium carbonate～3% (such as 2.5%)；
Preferably, described elastomer is preferably thermoplastic elastomer (TPE), such as can be selected from PP,
In POE, EVA, POE-g-GMA, EVA-g-MAH, EPDM, SBS and EPR
One or more；
Preferably, toughness reinforcing nylon monomer-cast nylon is by caprolactam, catalyst, activator and toughening modifying
Agent is made；
Preferably, the mass ratio of caprolactam and plasticized modifier is preferably 100:10～20.
10. according to the multilamellar modified cast nylon material of right 9, wherein said toughness reinforcing casting Buddhist nun
Dragon has following one or more performance indications:
F) elongation at break >=20%, preferably >=40%, more preferably >=60%；
G) impact strength >=10KJ/m2, preferably >=12KJ/m2, preferably >=14KJ/m2。
The multilamellar modified cast nylon material of 11. any one of claim 5-10, wherein said
Enhancing nylon monomer-cast nylon, toughness reinforcing nylon monomer-cast nylon or wear-resisting nylon monomer-cast nylon in can also contain phase respectively
Hold agent, compatilizer is preferably the graft copolymer of rubber-plastic elastomer, as POE-g-MAH,
SEBS-g-MAH, POE-g-GMA, EPDM-g-MAH etc..
The multilamellar modified cast nylon material of 12. any one of claim 5-11, wherein said
The mass ratio of caprolactam, catalyst and activator be preferably 100:0.2～0.5:0.2～0.5；
Preferably, described catalyst is alkaline matter, be preferably selected from alkali metal, alkaline-earth metal,
One or more of metal-oxide or derivant, are more preferably selected from NaOH, KOH, ethanol
Sodium, Feldalat NM one or more；
Preferably, described activator is selected from isocyanates, is preferably selected from aromatic isocyanate
Or one or more of aliphatic isocyanates, more preferably toluene di-isocyanate(TDI) (TDI)
Or isophorone diisocyanate (IPDI).
The multilamellar modified cast nylon material of 13. any one of claim 1-12 is the most wear-resisting
The preparation method of nylon monomer-cast nylon, toughness reinforcing nylon monomer-cast nylon or enhancing nylon monomer-cast nylon is:
1) in melted caprolactam, add catalyst, stir, be dehydrated；
2) as required, add selected from abrasion resistance modifier, reinforced modifier and plasticized modifier
In one or more modifying agent, alternatively, add compatilizer while modifying agent adding,
Agitating heating, continuation dehydration；
3) add activator, then cast, prepare；
Preferably, step 1) in, melted caprolactam is warming up to 125 ± 5 DEG C, adds
Catalyst, stirs and is dehydrated 30-45min；
Preferably, step 2) in, the temperature of described agitating heating is 135 ± 5 DEG C；
Preferably, step 3) in, during described casting, first mould is preheating to 170 ± 5 DEG C；
Then cast；
Preferably, after having cast, insulation polymerization, holding temperature is preferably 130～150 DEG C,
Such as 140 ± 5 DEG C, temperature retention time is preferably 60～120min.
The multilamellar modified cast nylon material of 14. any one of claim 1～13 is the most wear-resisting
The thickness of layer, enhancement layer or toughening layer is 10～50mm,
Preferably, in described multilamellar modified nylon materials, in parts by weight, wearing layer is
20～30 parts, enhancement layer is 20～40 parts, and toughening layer is 40～50 parts.
15. 1 kinds of parts, it is by the multilamellar modified cast nylon of any one of claim 1～14
Material is made；
Preferably, described part is power transmission shaft, ring flange, lining, axle sleeve, pipeline, pulley
(such as metal-nylon two-phase pulley), slide block, slideway, multilamellar modified cast nylon plate, many
Layer modified cast nylon rod or multilamellar modified cast nylon pipe；
Preferably, the internal layer of described lining is wearing layer, and middle level is enhancement layer, and outer layer is toughness reinforcing
Layer；
Preferably, the internal layer of described pipeline is wearing layer, and outer layer is enhancement layer or toughening layer；
Preferably, the main part of described sleeve, pulley or slide block includes enhancement layer and/or increasing
Tough layer, at least part of surface is wearing layer；
Preferably, the main part of described ring flange includes enhancement layer and/or toughening layer, seals
Face is wearing layer；
Preferably, the sandwich layer of described multilamellar modified cast nylon rod is toughening layer, and intermediate layer is for increasing
Strong layer, outer layer is wearing layer；
Preferably, each layer of described multilamellar modified cast nylon plate is followed successively by wearing layer, enhancement layer
And toughening layer；
Preferably, the internal layer of described multilamellar modified cast nylon pipe is wearing layer, and intermediate layer is for increasing
Strong layer, outer layer is toughening layer.
16. 1 kinds of multilamellar modified cast nylon materials preparing any one of claim 1～14
Method, the method be by wearing layer, toughening layer or enhancement layer as desired by successively casting (by
Layer spun casting) method composite molding.
The method of 17. claim 16, it includes, by wear-resisting nylon monomer-cast nylon, toughness reinforcing casting
Nylon or strengthen nylon monomer-cast nylon treat that poly-monomer is the most successively poured in mould.
The method of 18. claim 16 or 17, wherein said treat poly-monomer include melted oneself
Lactams, catalyst, activator and corresponding modifying agent；
Preferably, treat that what poly-monomer poured into mould is spaced apart 1～3 minute for every kind；
Preferably, after needed poly-monomer pours into mould, insulation polymerization, holding temperature is preferred
Being 130～150 DEG C, such as 140 ± 5 DEG C, temperature retention time is preferably 60～120min.
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| CN107434916A (en) * | 2017-08-29 | 2017-12-05 | 株洲时代新材料科技股份有限公司 | A kind of semi-trailer support supporting leg bushing and preparation method thereof |
| CN108407164A (en) * | 2018-04-18 | 2018-08-17 | 南通通州湾新材料科技有限公司 | Ceramic-plastic composite structure preparation method and electronic equipment casing |
| CN108487876A (en) * | 2018-04-09 | 2018-09-04 | 雅安万利橡塑密封技术有限责任公司 | The production technology of Operating Pressure annular space dynamic sealing wearing piece |
| CN111844575A (en) * | 2020-07-31 | 2020-10-30 | 淮安市建工尼龙制品有限公司 | Metal bushing integrated nylon wheel pouring method |
| CN115008845A (en) * | 2022-05-31 | 2022-09-06 | 西安高强绝缘电气有限责任公司 | Tree-like structure composite core and preparation tool and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107434916A (en) * | 2017-08-29 | 2017-12-05 | 株洲时代新材料科技股份有限公司 | A kind of semi-trailer support supporting leg bushing and preparation method thereof |
| CN108487876A (en) * | 2018-04-09 | 2018-09-04 | 雅安万利橡塑密封技术有限责任公司 | The production technology of Operating Pressure annular space dynamic sealing wearing piece |
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| CN115008845A (en) * | 2022-05-31 | 2022-09-06 | 西安高强绝缘电气有限责任公司 | Tree-like structure composite core and preparation tool and preparation method thereof |
| CN116554571A (en) * | 2023-04-27 | 2023-08-08 | 浙江大晋新材料科技有限公司 | High-strength plastic bucket and preparation method thereof |
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