CN1178543A - Thermoplastic polymer composition with improved wear properties - Google Patents
Thermoplastic polymer composition with improved wear properties Download PDFInfo
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- CN1178543A CN1178543A CN 96192218 CN96192218A CN1178543A CN 1178543 A CN1178543 A CN 1178543A CN 96192218 CN96192218 CN 96192218 CN 96192218 A CN96192218 A CN 96192218A CN 1178543 A CN1178543 A CN 1178543A
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Abstract
A self-lubricating polymeric composition, characterized as a melt blend of a thermoplastic polymer and a lubricating system containing ultra high molecular weight polyethylenes, a polyester, acid metal salts, calcium salts, antioxidants and stabilizers. The composition may be prepared into shaped articles which exhibit improved surface wear resistance and coefficients of friction.
Description
The present invention relates to contain the low wearing and tearing composition of the self-lubricating of thermoplastic polymer and lubricating system, they are suitable as the moulding resin of preparation moulded products.The moulded products that is made by this composition has low frictional property and low surface abrasion rate under load.
The feature of thermoplastic polymer such as polymeric amide, polyester, polyphenylene sulfide, polyoxymethylene, polyolefine, styrene polymer and polycarbonate is that they have fabulous mechanical properties and electrical property, and good mouldability and chemical-resistant are arranged.But these polymkeric substance when for example plastics and metal interface and plastics and plastic interface rub, have incompatible nature of friction when being used for some friction occasion.Though many lubricating compositions have been used for thermoplastic polymer, so that improve the nature of friction and the abrasive nature of the moulded products that makes by these thermoplastic polymers, but, some application, as food-processing, clothing making and volatility environment, owing to may pollute, limit the application of some lubricant.
Make an effort, by before making moulded products, lubricant directly being joined nature of friction and its surface abrasion rate of minimizing of improving the goods that make by thermoplastic polymer in the polymeric matrix.Many materials have been added in the thermoplastic polymer, to improve nature of friction and abrasive nature.These materials comprise solid lubricant and fiber (as graphite, mica, silicon oxide, talcum, boron nitride and moly-sulfide), paraffin, oil and ucon oil and other polymkeric substance (as polyethylene and tetrafluoroethylene).But many kinds in these additives are added in the thermoplastic polymer with various combination, though improved nature of friction, physical properties and mechanical properties that other are required have descended.Confirmed that some additive only satisfies short-term low speed and underload requirement.But rubbing characteristicss many in these lubricants can obviously degenerate under long-term high loading.
Wish to have the thermoplastic compounds of the nontoxic self-lubricating that under high loading, has surface abrasion resistance damage and low frictional properties matter for a long time.The composition that is fit to should keep required mechanical properties and the physical properties relevant with thermoplastic polymer for a long time when manufacturing moulded products, and can be used for food-processing and clothes process industry safely.
The present invention relates to a kind of self-lubricating composition that is suitable for making low friction moulded products, it is characterized in that containing and have an appointment 70 to about 99.5% (weight) thermoplastic polymer and about 30 melt blended materials to about 0.5% (weight) lubricating system, the feature of wherein said lubricating system is to contain polyolefine, pentaerythritol tetrastearate (PETS) and the lime carbonate of ultra-high molecular weight.Processing aid without detriment to feature of the present invention can be added in the composition,, for example improve the dispersion of lubricating system in polymeric matrix to improve physical properties and working properties.
Composition can be made the moulded products of self-lubricating, for example bearing, gear, cam, roll shaft, slide plate, pulley, control lever, guide groove, transmission band chain etc., they have good nature of friction, are applicable to many application scenarios of wishing to have low frictional properties and low abradability parts.
The present invention relates to a kind of self-lubricating composition that can be made into the moulded products of good friction character.Usually, the feature of said composition is to contain to have an appointment 70 to about 99.5% (weight) thermoplastic polymer and about 30 mixtures to about 0.5% (weight) lubricating system.Be typically, said composition can contain have an appointment 85 to about 99% (weight) thermoplastic polymer and about 15 to about 1% (weight) lubricating system.Preferably, press total restatement of composition, said composition contains have an appointment 98% (weight) thermoplastic polymer and about 2% (weight) lubricating system.
The thermoplastic polymer that is applicable to self-lubricating composition of the present invention is optional from polymeric amide, polyester, polyphenylene sulfide, polyolefine, polyoxymethylene, styrene polymer and polycarbonate usually.The particularly preferred thermoplastic polymer of the present invention is a polyoxymethylene, i.e. polyacetal or yuban.Polyoxymethylene has makes them be applicable to the physical properties and the mechanical properties of many industrial applications.
Be used for polyoxymethylene of the present invention, that is: the common general feature of polyacetal or yuban is, the repetition carboxaldehyde radicals unit of following general formula is arranged
-O-CH
2-
Be applicable to the polyoxymethylene of producing the present composition very high carboxaldehyde radicals unit is arranged, promptly usually greater than about 85%.These materials can be provided with forms such as homopolymer, multipolymer, terpolymers by many manufacturerss commercial.The polyoxymethylene of Jian Shu these highly crystallines is that everybody is familiar with in this specialty hereinafter, and extensively comments.For example, the commentary of one piece of polyoxymethylene that is entitled as " polyformaldehyde resin " of being write by T.J.Dolce and J.A.Grates can be found John Wiley and Sons in polymer science and engineering encyclopedia second edition, New York, 1985, the 1 volumes, the 42-61 page or leaf.About other information of polymethanal polymer can find in French Patent 1221148 and common United States Patent (USP) 3027352,3072069,3147234 and 3210318 of authorizing.
Usually, POM-H Acetal homopolymer can prepare by the polymerization of anhydrous formaldehyde Huo trioxane.Usually by as the method for sealing with ester group or ether (for example obtaining) end or POM-H Acetal homopolymer is stablized to thermal destruction by stablizer is added to by alkane acid anhydrides (as acetic anhydride) or dialkyl ether (as dme).Commercially available POM-H Acetal homopolymer prepares by following steps: make anhydrous formaldehyde polymerization in the presence of initiator; In the presence of the sodium acetate catalyzer, make the polymer end envelope subsequently by hemiacetal end group and acetic anhydride acetylize.The method of the POM-H Acetal homopolymer of preparation end envelope is open in United States Patent (USP) 2786994 and 2998409.POM-H Acetal homopolymer is that everybody is familiar with in this specialty, and with trade(brand)name DELRIN
And TENAC
Commercially available.
The polymerization formaldehyde class of having found to be specially adapted to the present composition is the crystallization polyacetal copolymer that contains oxygen (high-carbon alkylidene group) the alternative carboxaldehyde radicals repeating unit that mainly contains with following general formula:
In the formula, R
1And R
2Respectively be the low-carbon alkyl that hydrogen, low-carbon alkyl or halogen replace, each R
3Be the methylene radical of methylene radical, carboxaldehyde radicals, low-carbon alkyl or haloalkyl replacement or the carboxaldehyde radicals of low-carbon alkyl or haloalkyl replacement, n is an integer among zero or the 1-3.Each low-carbon alkyl preferably contains 1 or 2 carbon atom.In such multipolymer, carboxaldehyde radicals constitutes the 85-99.9% repeating unit usually, adds by the trioxane ring-opening polymerization in the presence of an acidic catalyst usually.Oxygen (high-carbon alkylidene group) by carbon atom at least two adjacent rings is arranged cyclic ether or cyclic formals Yu the method for trioxane copolymerization join in the polymkeric substance.Cyclic ethers or formal add by oxygen-carbon bond fracture.Preferred oxygen (high-carbon alkylidene group) is the oxygen ethylidene, and its chemical formula is:
-O-CH
2-CH
2-
The oxygen ethylidene can pass through oxyethane or 1, the 3-dioxolane Yu the method for trioxane copolymerization be incorporated in the polymkeric substance.
Main as mentioned above is that fusing point is at least 150 ℃ thermoplastic material by carboxaldehyde radicals and the consitutional preferred crystallization polyacetal copolymer of oxygen ethylidene.They can grind or processing to about 230 ℃ of scopes about 175 usually.These multipolymers are highly crystalline normally, and its degree of crystallinity is about 40 to about 90% or higher.
Usually, polyacetal copolymer can be degraded to a certain degree by the unstable molecule end of polymer chain after preparation stablizes, and at this moment metastable C-C stops the two ends of polymer chain further to be degraded.This degraded of unstable molecule end realizes by hydrolysis usually, and is for example disclosed in the United States Patent (USP) 3219623 of authorizing Berardinelli.It is stable that the polyacetal copolymer technology that also available those skilled in the art were familiar with holds envelope, and for example uses the acetic anhydride acetylize in the presence of the sodium acetate catalyzer.
A particularly preferred class polyacetal copolymer is with trade(brand)name CELCON
Commercially available polyacetal copolymer.CELCON
The multipolymer of normally about 98% (weight) trioxane of polyacetal copolymer and about 2% (weight) dioxolane.CELCON is the registered trademark of Hoechst Celanese company.Composition of the present invention can make with the CELCON polyoxymethylene of any commercial trade mark, comprises CECON trade mark U-10, M-25, M-90, M-270 and M-450.When pressing ASTM D1238-82 test, the melt index of CELCON M-25 polyacetal copolymer is about 2.5 grams/10 minutes.The molecular weight and the melt index of M-90 polyacetal copolymer are lower than CELCON M-25.Molecular weight and the melt viscosity of CELCON M-270 are lower than CELCON M-25.
The polyoxymethylene terpolymer also can be used to produce self-lubricating composition of the present invention.These terpolymers contain carboxaldehyde radicals, oxygen (high-carbon alkylidene group), as group corresponding to following general formula:
And can with the 3rd different group of carboxaldehyde radicals and oxygen (high-carbon alkylidene group) binary polymerization.Aforesaid terpolymer can prepare by trioxane and cyclic ether or cyclic acetal and as shown in the formula the 3rd monomer reaction of the difunctional compound of glycidyl:
In the formula, Z is C-C, Sauerstoffatom, 1-8 carbon atom arranged, oxygen alkoxyl group, the oxygen cycloalkyloxy that 4-8 carbon atom arranged or the oxygen of preferred 2-4 carbon atom gather (low-carbon alkoxy), preferably have 2-4 multiple low-carbon alkoxy, each group has 1-2 carbon atom.The example of the difunctional compound that is fit to comprises ethylene glycol, 1,2-propylene glycol and 1, and the diglycidyl ether of 4-butyleneglycol, 1, the diglycidyl ether of 4-butyleneglycol is preferred.Usually, when preparing such terpolymer, by the total restatement of monomer that uses in the preparation terpolymer, preferred ratio is 99.89-89.0% (weight) trioxane, 0.1-10% (weight) cyclic ether or cyclic acetal and 0.01-1% (weight) difunctional compound.Particularly preferred polyoxymethylene terpolymer can be purchased by HoechstCelanese company by trade(brand)name CELCON U10 polymethanal polymer, it is by 1,4-butanediol diglycidyl ether linking agent, dioxolane He trioxane make, press total restatement of terpolymer, contain the repeating unit that 0.05,2.0 and 97.95% (weight) of having an appointment is obtained by these monomers respectively.Prepared terpolymer, and stablized, for example added antioxidant and formaldehyde and acid scavenger by the method that this specialty is familiar with based on carboxaldehyde radicals.Find in the patent that preparation can be drawn in the above based on the more detailed explanation of the terpolymer of carboxaldehyde radicals and method for compositions thereof.
These polymethanal polymers can be made the polymkeric substance that is suitable for preparing self-lubricating composition of the present invention by method melt blended in extruding machine or in the similar equipment in different ratio combinations.Usually, polymethanal polymer when its in molten state, promptly, be easy to and lubricating system and processing aid blend at least about following time of temperature of 170 ℃.
The feature of lubricating system of the present invention is to contain extrahigh-molecular weight polyolefins, pentaerythritol tetrastearate and lime carbonate.Extrahigh-molecular weight polyolefins can be linear polyethylene, and its degree of crystallinity is about 40%, and weight-average molecular weight is at least about 3 * 10
6(common about 5 * 10
6To about 6 * 10
6), limiting viscosity is at least about 28 deciliter/gram (measuring with ASTM No.D4020), tap density is at least about 0.5 grams per milliliter (with ASTM No.D1895 measurement) and proportion is about 0.93 grams per milliliter.Particularly preferred ultra-high molecular weight (UHMW) polyethylene that meets the FDA/USDA requirement is the Hostalen of Hoechst Celanese company (Somerville, New Jersey) classification
GUR415 UHMW polyethylene.Usually, the feature of lubricating system of the present invention is, presses total restatement of composition, contains at least about 0.1% (weight) UHMW polyethylene, 0.25% (weight) PETS with at least about 0.25% (weight) lime carbonate.Be typically, the feature of lubricating system of the present invention is, presses total restatement of composition, contains 0.2 to about 10.0% (weight) UHMW polyethylene, about 0.25 to about 2.0% (weight) PETS and about 0.25 of having an appointment to about 4.0% (weight) lime carbonate.Preferably, the feature of lubricating system is, presses total restatement of composition, contains 1.5% (weight) UHMW polyethylene of having an appointment, 1.0% (weight) PETS and about 1.0% (weight) lime carbonate.
In order to help oilness and processibility, also several other components can be joined in the composition of the present invention.Usually, various additives can mix with thermoplastic polymer with the lubricating system combination and as mixture in proportion, perhaps they directly can be added in the composition.These additives can be selected from: press total restatement of composition, (a) at least about 0.25% (weight) polyoxymethylene terpolymer; (b) at least about 0.25% (weight) hindered phenol; And (c) at least 0.05% (weight) ricinoleic acid calcium or oxystearic acid calcium.Be typically, these additives can mix by some amount with the composition of self-lubricating, press total restatement of composition, are selected from (a) about 0.25 to about 2.0% (weight) polyoxymethylene terpolymer; (b) about 0.25 to about 0.75% (weight) hindered phenol; And (c) about 0.05 to about 0.3% (weight) ricinoleic acid calcium or oxystearic acid calcium.Preferably, these additives can mix by some amount with composition, press total restatement of composition, (a) about 0.5% (weight) polyoxymethylene terpolymer; (b) about 0.4% (weight) hindered phenol; And (c) 0.01% (weight) ricinoleic acid calcium or oxystearic acid calcium.The adding of these processing aids will be followed usually and regulate thermoplastic resin quantity.Known other processing aids of those skilled in the art also can be used to help molding as silicone or fluoropolymer mould hydrojet.
The feature that is applicable to lime carbonate of the present invention is, its granularity is about 0.6 micron, and surface-area is about 7 meters
2/ gram, tap density is about 25 pounds/foot
3With proportion be about 2.7.Preferred lime carbonate is the Super-Pflex that is provided by Pfizer company
200.
Be applicable to that hindered phenol of the present invention is commonly referred to antioxidant or free radical inhibitors.Can use 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol), hexamethylene glycol-two (3,5-di-t-butyl-4-hydroxyl hydrogen laurate), four pairs of (methylene radical (3,5-di-t-butyl-4-hydroxyl hydrogen laurate)) methane, triethylene glycol-with-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester, 1,3,5-trimethylammonium-2,4,6-three (3,5-di-t-butyl-4-hydroxyl-benzyl) benzene, to octadecane-3-(4 '-hydroxyl-3 ', 5 '-di-tert-butylphenol) propionic ester, 4,4 '-methylene-bis (2, the 6-di-tert-butylphenol), 4,4 '-butylidene-two-(the 6-tertiary butyl-3-sylvan), 2,2 '-sulfo-diethyl-two-(3-(3,5-di-t-butyl-4-hydroxyl phenol)) propionic ester, distearyl-3, at least a in 5-di-tert-butyl-4-hydroxyl benzyl phosphoric acid ester and the 2-tertiary butyl-6-(the 3-tertiary butyl-5-methyl-2-hydroxybenzyl)-4-aminomethyl phenyl acrylate.But the hindered phenol that is suitable for is not limited to these compounds.Other hindered phenols of above-mentioned same type or the phenol of steric hindrance also are effective.Wherein, hexamethylene glycol-two (3,5-di-t-butyl-4-hydroxyl cortex cinnamomi acid ester) is as the Irganox that is obtained by Ciba-Geigy company
259; Four (methylene radical (3, the 5-di-t-butyl)-4-hydroxyl cortex cinnamomi acid ester) methane is as the Irganox 1010 that is obtained by Ciba-Geigy company; And triethylene glycol-two-3-(the 3-tertiary butyl-4-hydroxyl-5-aminomethyl phenyl) propionic ester, be effective as the Irganox 245 that obtains by Ciba-Geigy company. preferred hindered phenol is hexamethylene glycol-two (3,5-di-t-butyl-4-hydroxyl cortex cinnamomi acid ester).
Following examples are general remarks of the method for preparation polymer composition of the present invention.Should be appreciated that from top discussion these embodiment are as just illustration.
Embodiment 1
In order to prepare the blend of the self-lubricating composition that contains 7.9% (weight) lubricating system, use following component:
A) 90 pounds of unstabilized polyacetal copolymer sheet stocks;
B) 4.9 pounds of UHMW polyethylene;
C) 1.5 pounds of polyoxymethylene terpolymers;
D) 1.0 pounds of pentaerythritol tetrastearates (PETS);
E) 2.0 pounds of lime carbonate
F) 0.1 pound of ricinoleic acid calcium and
G) 0.5 pound of preferred hindered phenol.
Each component rolled to mix in the barrel high speed of Henschel mixing tank made mixture in 30 seconds.Mixture is extruded into wire rod in Werner and Pfleiderer twin screw ZSK extruding machine, with polyoxymethylene granulate heating and cleaning.372-387 operation down of extruding machine section, it is 415 °F that melt mixes degree, under 27 inch of mercury vacuum, screw speed is 150 rev/mins.The extrusion material wire rod generates with 38 Pounds Per Hours speed.After this, with wire rod chilling and be cut into pellet in cold water.With pellet injection moulding under setting the pressure of routine, speed and cycling time, nozzle temperature is set at 360-420 °F, and barrel temperature is set at 350-420 °F, makes diameter and be 1.25 inches disk, and each heavily about 7 gram is used for machinery and friction analysis and tests.
The disk that is used for surface abrasion resistance analysis and torsional analysis with following step preparation: clean in methanol bath; At air drying; Be weighed to 1/10 milligram.These disks are tested by the Pin-On-Disk test.In implementing these tests, it is that the machining Nylatron fiber-glass pole of 0.187 inch round tip is installed in Falex Friction and Wear Test Machine that radius will be arranged, MoelMulti-Specimen goes up on the axle, apart from the center of test plate 0.469 inch, disk is installed on the lower shaft.Apply 20 pounds of loads by disk being pressed to the circular pin top to test plate with gas cylinder.Speed of rotation is 425 rev/mins (104.3 feet per minutes).In test process, with 40 standard feet
3/ hour (SCFH) and blow to disc surfaces at a distance of 2 inches airflow is to remove abrasive dust.Test duration is 0.5-65 hour.After the test, masthead end and disk are disengaged, and take off disk, remove loose abrasive dust, weigh to measure weightlessness, i.e. the surface abrasion rate with air purge.
The moment of torsion that to measure in test process (Γ) converts frictional coefficient (f) to following equation:
f＝Γ(2.137/20)
The factor 2.137 is ratio coefficients of this trier.The result of surface abrasion rate and frictional coefficient lists Table I in.
Comparative Examples 2
As a comparison case, replace the lubricating system of embodiment 1 to prepare polymer composition, use following component with 1.5% (weight) polytetrafluoroethylene (PTFE):
A) 213.84 pounds of unstabilized polyacetal copolymer sheet stocks (97.2% (weight));
B) 1.1 pounds of polyoxymethylene terpolymer pellets (0.5% (weight));
C) 199.76 gram N, N '-ethylenebisstearamide (0.2% (weight));
D) 1.1 pounds of preferred hindered phenols (0.5% (weight));
E) 99.88 gram ricinoleic acid calcium (0.1% (weight)); And
F) 3.3 pounds of PTEE (1.5% (weight) is pressed total restatement of composition).
Press the method for embodiment 1, each component is mixed, extrusion molding and molding are made 7 gram disks, are used for weightlessness and Analysis of Friction Coefficient.Analytical results is listed in Table I.
Comparative Examples 3
As a comparison case, replace the lubricating system of embodiment 1 to prepare polymer composition, use following component with 3.0% (weight) PTFE:
A) 210.54 pounds of unstabilized polyacetal copolymer sheet stocks;
B) 1.1 pounds of polyoxymethylene terpolymer pellets;
C) 199.76 gram N, N '-ethylenebisstearamide;
D) 1.1 pounds of preferred hindered phenols;
E) 99.88 gram ricinoleic acid calcium; And
F) 6.6 pounds of PTFE (3.0% (weight) is pressed total restatement of composition).
Press the method for embodiment 1, each component is mixed, extrusion molding and molding are made 7 gram disks, are used for weightlessness and Analysis of Friction Coefficient.Analytical results is listed Table I in.
The analytical results explanation, after Pin-On-Disk test in 0.5 hour, the average weightlessness of the sample of embodiment 1 is 1.1 milligrams, tests after 17 hours, and the average weightlessness of disk is 4.3 milligrams, and frictional coefficient is 0.075; After test 65 hours, the average weightlessness of disk is 5.4 milligrams.
Show that by the wearing test result who contains the disk that PTFE makes as the composition of lubricating system surface abrasion rate and frictional coefficient are all apparently higher than the present invention.
For the polishing machine at composition in the presence of each component of lubricating system or not is described, it is as follows to have prepared several prescriptions according to the method for the foregoing description 1:
Embodiment 4
Component
% (weight)
Polyacetal copolymer 95.5
Polyoxymethylene terpolymer 0.5
Preferred hindered phenol 0.4
Ricinoleic acid calcium 0.1
UHMW polyethylene 1.5
PETS???????????????????????????????????????1.0
Lime carbonate 1.0
Embodiment 5
Component
% (weight)
Polyacetal copolymer 97
Polyoxymethylene terpolymer 0.5
Preferred hindered phenol 0.4
Ricinoleic acid calcium 0.1
UHMW polyethylene 0
PETS?????????????????????????????????????1.0
Lime carbonate 1.0
Embodiment 6
Component
% (weight)
Polyacetal copolymer 96.5
Polyoxymethylene terpolymer 0.5
Preferred hindered phenol 0.4
Ricinoleic acid calcium 0.1
UHMW polyethylene 1.5
PETS???????????????????????????????????????0
Lime carbonate 1.0
Embodiment 7
Component
% (weight)
Polyacetal copolymer 96.5
Polyoxymethylene terpolymer 0.5
Preferred hindered phenol 0.4
Ricinoleic acid calcium 0.1
UHMW polyethylene 1.5
PETS???????????????????????????????????????1.0
Lime carbonate 0
Embodiment 8
Component
% (weight)
Polyacetal copolymer 98.7
Polyoxymethylene terpolymer 0.5
Preferred hindered phenol 0.5
Ricinoleic acid calcium 0.1
N, N '-ethylenebisstearamide 0.2
UHMW polyethylene 0
PETS???????????????????????????????????????0
Lime carbonate 0
Embodiment 9
Component
% (weight)
Polyacetal copolymer 96.6
Polyoxymethylene terpolymer 0.5
Preferred hindered phenol 0.4
Ricinoleic acid calcium 0.1
UHMW polyethylene 0.4
PETS??????????????????????????????????????1.0
Lime carbonate 1.0
Embodiment 10
Component
% (weight)
Polyacetal copolymer 96.2
Polyoxymethylene terpolymer 0.5
Preferred hindered phenol 0.4
Ricinoleic acid calcium 0.1
UHMW polyethylene 0.8
PETS??????????????????????????????????????1.0
Lime carbonate 1.0
The composite mold of embodiment 4-10 is moulded test disc and carries out the Pin-On-Disk test according to the step of embodiment 1.Test-results is listed down Table I in.
Table I
| Weightlessness, milligram 1/ frictional coefficient | |||||
| Embodiment | Lubricating system % (weight) | Test period, hours 0.5 1.5 7 65 | |||
| ????1 | ?7.9 | ????1.1 | ???1.4 | ?4.3/0.075 | ????5.4 |
| ????2 | ?1.5PTFE | ????8.1 | ???15.9 | ?122/0.14 | ????181 |
| ????3 | ?3.0PTFE | ????3.4 | ???15.9 | ?87/0.13 | ????155 |
| ????4 | ?3.5 | ????1.8 | ????2.1 | ?4.2 | ????8.6 |
| ????5 | ?2.0 | ????n/d 2 | ????2 | ?45 | ????n/d |
| ????6 | ?2.5 | ????n/d | ????4.1 | ?167 | ????n/d |
| ????7 | ?2.5 | ????n/d | ????2.4 | ?64 | ????n/d |
| ????8 | ?0 | ????n/d | ????113 | ?260 | ????n/d |
| ????9 | ?2.4 | ????n/d | ????3.0 | ?6.9 | ????30.1 |
| ????10 | ?2.8 | ????n/d | ????2.8 | ?7.8 | ????12.4 |
1Load 20 pounds; Speed 104.3 feet per minutes
2N/d: No data
The explanation of last table, the embodiment 4,9 that contains UHMW polyethylene, lime carbonate and PETS and 10 composition are compared with not containing in the said components composition of any or all, and better lubricating quality is arranged in wearing test 17 with after 65 hours.
Claims (20)
1. one kind is suitable for making the self-lubricating composition that hangs down the friction moulded products, said composition contains has an appointment 70 to about 99.5% (weight) thermoplastic polymer and about 30 melt blended materials to about 0.5% (weight) lubricating system, and the latter is contained extrahigh-molecular weight polyolefins, pentaerythritol tetrastearate and lime carbonate.
2. according to the composition of claim 1, wherein thermoplastic polymer is selected from polymeric amide, polyester, polyphenylene sulfide, polyoxymethylene, styrene polymer and polycarbonate.
3. according to the composition of claim 2, wherein thermoplastic polymer is a polyoxymethylene.
4. according to the composition of claim 3, wherein polyoxymethylene is selected from:
(i) POM-H Acetal homopolymer;
(ii) contain and have an appointment 85 to about 99.9% by the polyacetal copolymer of following formula repeating unit alternative carboxaldehyde radicals repeating unit,
In the formula, each R
1And R
2Be selected from hydrogen, low-carbon alkyl and halo low-carbon alkyl (each has 1-2 carbon atom described low-carbon alkyl), each R
3Be selected from the methylene radical of methylene radical, carboxaldehyde radicals, low-carbon alkyl and haloalkyl replacement and the carboxaldehyde radicals of low-carbon alkyl and the replacement of halo low-carbon alkyl, n is an integer among the 0-3;
(iii) polyoxymethylene terpolymer, the reaction product of the diglycidyl ether linking agent of their Shi trioxanes and cyclic ether and/or cyclic acetal and following formula,
In the formula, Z is selected from the oxygen oxyalkyl units and the poly-low-carbon alkoxy unit of oxygen of C-C, oxygen, a 1-8 carbon atom; And
(iv) (i), (ii) and mixture (iii).
5. according to the composition of claim 4, wherein polyolefine is the line style ultrahigh molecular weight polyethylene(UHMWPE).
6. according to the composition of claim 5, wherein poly degree of crystallinity is at least about 40%, and molecular weight is at least about 3 * 10
6, limiting viscosity is at least about 28 deciliter/gram, and tap density is that about 0.5 grams per milliliter and proportion are at least about 0.93.
7. according to the composition of claim 6, wherein contain have an appointment 85 to about 99% (weight) polyoxymethylene and about 15 to about 1% (weight) lubricating system.
8. according to the composition of claim 7, wherein lubricating system contains at least about 0.1% (weight) ultrahigh molecular weight polyethylene(UHMWPE), at least about 0.1% (weight) pentaerythritol tetrastearate with at least about 0.1% (weight) lime carbonate.
9. composition according to Claim 8 wherein also contains: press total restatement of composition, (a) about 0.1% (weight) polyoxymethylene terpolymer; (b) about 0.1% (weight) hindered phenol; And (c) about 0.05% (weight) ricinoleic acid calcium or hydroxyl three hard acid calcium.
10. moulded products of making by the self-lubricating composition of claim 9, the weightlessness of wearing and tearing after 17 hours is about 4.2 milligrams under about 20 pounds of speed of rotation 104.3 feet per minutes and load, frictional coefficient is about 0.075.
11. a method of improving the anti-surface abrasion of thermoplastic polymer moulded products, this method may further comprise the steps:
(a) preparation contains and has an appointment 70 to about 99.5% (weight) thermoplastic polymer and the about 30 melt blending compositions to about 0.5% (weight) lubricating system, and wherein said lubricating system contains extrahigh-molecular weight polyolefins, pentaerythritol tetrastearate and lime carbonate; And
(b) described composition is made moulded products, wherein goods have improved frictional coefficient and anti-surface abrasion.
12. according to the method for claim 11, wherein thermoplastic polymer is selected from polymeric amide, polyester, polyphenylene sulfide, polyoxymethylene, styrene polymer and polycarbonate.
13. according to the method for claim 12, wherein polyoxymethylene is selected from:
(i) POM-H Acetal homopolymer;
(ii) contain and have an appointment 85 to about 99.9% by the polyacetal copolymer of the repeating unit alternative carboxaldehyde radicals repeating unit of following formula:
In the formula, each R
1And R
2Be selected from hydrogen, low-carbon alkyl and halo low-carbon alkyl, each has 1-2 carbon atom, each R described low-carbon alkyl
3Be selected from methylene radical, the carboxaldehyde radicals that methylene radical that carboxaldehyde radicals, low-carbon alkyl and halo low-carbon alkyl replace and low-carbon alkyl and halo low-carbon alkyl replace, n is an integer among the 0-3;
(iii) polyoxymethylene terpolymer, the reaction product of the diglycidyl ether linking agent of their Shi trioxanes and cyclic ether and/or cyclic acetal and following formula:
In the formula, Z is selected from the oxygen oxyalkyl units and the poly-low-carbon alkoxy unit of oxygen of C-C, oxygen, a 1-8 carbon atom; And
(iv), (i), (ii) and mixture (iii).
14. according to the method for claim 13, wherein composition contain have an appointment 85 to about 99% (weight) polyoxymethylene and about 15 to about 1% (weight) lubricating system.
15. according to the method for claim 14, wherein polyoxymethylene is a polyacetal copolymer, they contain has an appointment 85 to about 99.9% by following formula repeating unit alternative oxygen methylene radical repeating unit:
In the formula, each R
1And R
2Be selected from hydrogen, low-carbon alkyl and halo low-carbon alkyl, each has 1-2 carbon atom, each R described low-carbon alkyl
3Be selected from the methylene radical that methylene radical, carboxaldehyde radicals, low-carbon alkyl and haloalkyl replace, and the carboxaldehyde radicals of low-carbon alkyl and haloalkyl replacement, n is an integer among the 0-3.
16. according to the method for claim 15, wherein lubricating system contains at least about 0.25% (weight) ultrahigh molecular weight polyethylene(UHMWPE), at least about 0.25% (weight) pentaerythritol tetrastearate with at least about 0.25% (weight) lime carbonate.
17. according to the method for claim 16, wherein lubricating system contains 0.1% (weight) ultrahigh molecular weight polyethylene(UHMWPE) of having an appointment, about 0.1% (weight) pentaerythritol tetrastearate and about 0.1% (weight) lime carbonate.
18. according to the method for claim 17, wherein composition also contains: press total restatement of composition, (a) about 0.5% (weight) polyoxymethylene terpolymer; (b) about 0.4% (weight) hindered phenol; And (c) about 0.1% (weight) ricinoleic acid calcium or oxystearic acid calcium.
19. the moulded products by the preparation of the method for claim 18, wherein goods weightlessness of 17 hours of wearing and tearing under about 20 pounds of speed of rotation 104.3 feet per minutes and load is about 4.3 milligrams, and frictional coefficient is less than about 0.05.
20. according to the moulded products of claim 19, wherein goods are selected from bearing, gear, cam, roll shaft, slide plate, pulley, control lever, guide groove and transmission band chain.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96192218A CN1085698C (en) | 1996-02-26 | 1996-02-26 | Thermoplastic polymer composition with improved wear properties |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96192218A CN1085698C (en) | 1996-02-26 | 1996-02-26 | Thermoplastic polymer composition with improved wear properties |
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| Publication Number | Publication Date |
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| CN1178543A true CN1178543A (en) | 1998-04-08 |
| CN1085698C CN1085698C (en) | 2002-05-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96192218A Expired - Fee Related CN1085698C (en) | 1996-02-26 | 1996-02-26 | Thermoplastic polymer composition with improved wear properties |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262763A (en) * | 2014-11-03 | 2015-01-07 | 苏州钧隆塑胶有限公司 | Wear-resist plastic |
| CN106543627A (en) * | 2016-10-18 | 2017-03-29 | 成都新柯力化工科技有限公司 | A kind of high-temperature resistance plastice lubricating additive and preparation method thereof |
| CN107428114A (en) * | 2015-02-18 | 2017-12-01 | 纳幕尔杜邦公司 | Bulletproof composite laminate |
| CN110317422A (en) * | 2019-06-28 | 2019-10-11 | 浙江中达精密部件股份有限公司 | A kind of MULTILAYER COMPOSITE sliding bearing |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0148743B1 (en) * | 1984-01-06 | 1991-04-10 | Mitsui Petrochemical Industries, Ltd. | Thermoplastic resin composition |
| US4960813A (en) * | 1988-02-25 | 1990-10-02 | Hoechst Celanese Corporation | Internal lubricant for glass reinforced polyarylene sulfide |
| JP2993062B2 (en) * | 1990-07-02 | 1999-12-20 | 三菱瓦斯化学株式会社 | Oxymethylene copolymer composition |
-
1996
- 1996-02-26 CN CN96192218A patent/CN1085698C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262763A (en) * | 2014-11-03 | 2015-01-07 | 苏州钧隆塑胶有限公司 | Wear-resist plastic |
| CN107428114A (en) * | 2015-02-18 | 2017-12-01 | 纳幕尔杜邦公司 | Bulletproof composite laminate |
| CN107428114B (en) * | 2015-02-18 | 2020-12-08 | 纳幕尔杜邦公司 | Composite ballistic laminates |
| CN106543627A (en) * | 2016-10-18 | 2017-03-29 | 成都新柯力化工科技有限公司 | A kind of high-temperature resistance plastice lubricating additive and preparation method thereof |
| CN106543627B (en) * | 2016-10-18 | 2018-10-30 | 谢灵卫 | A kind of high-temperature resistance plastice lubricating additive and preparation method thereof |
| CN110317422A (en) * | 2019-06-28 | 2019-10-11 | 浙江中达精密部件股份有限公司 | A kind of MULTILAYER COMPOSITE sliding bearing |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1085698C (en) | 2002-05-29 |
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