CN114479444B - Special material for automobile cylinder head cover produced by using regenerated PA66 - Google Patents
Special material for automobile cylinder head cover produced by using regenerated PA66 Download PDFInfo
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- CN114479444B CN114479444B CN202210157300.5A CN202210157300A CN114479444B CN 114479444 B CN114479444 B CN 114479444B CN 202210157300 A CN202210157300 A CN 202210157300A CN 114479444 B CN114479444 B CN 114479444B
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- 239000000463 material Substances 0.000 title claims abstract description 39
- 239000003365 glass fiber Substances 0.000 claims abstract description 26
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 23
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 19
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 18
- 239000007822 coupling agent Substances 0.000 claims abstract description 15
- 239000004677 Nylon Substances 0.000 claims abstract description 14
- 229920001778 nylon Polymers 0.000 claims abstract description 14
- 239000004970 Chain extender Substances 0.000 claims abstract description 12
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 230000007062 hydrolysis Effects 0.000 claims abstract description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 11
- 239000012745 toughening agent Substances 0.000 claims abstract description 11
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- -1 polypropylene Polymers 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000011265 semifinished product Substances 0.000 claims description 4
- 150000003568 thioethers Chemical class 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000004595 color masterbatch Substances 0.000 claims description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 10
- 230000009172 bursting Effects 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 4
- 238000003466 welding Methods 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000010008 shearing Methods 0.000 description 6
- 239000010705 motor oil Substances 0.000 description 5
- 239000004744 fabric Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000012809 cooling fluid Substances 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a special material for an automobile cylinder head cover produced by using regenerated PA 66. The traditional Chinese medicine is prepared from the following raw materials in parts by weight: 100 parts of regenerated PA66, 15-60 parts of nylon PA9T, 10-50 parts of nylon PA MXD-6, 65-150 parts of hydrolysis-resistant glass fiber, 0-30 parts of toughening agent, 0-20 parts of compatilizer, 0-7.5 parts of glass fiber exposure preventing agent, 3-10 parts of chain extender, 0.4-2.5 parts of coupling agent, 0-4 parts of heat stabilizer, 0.4-2 parts of antioxidant and 3-10 parts of black masterbatch. The invention can meet various requirements of the cylinder head cover working conditions of the automobile, such as heat resistance, printability, high strength, high impact resistance, welding bursting pressure, liquid resistance and the like, widens the field of PA66 recycling, reduces resource waste and environmental pollution, reduces material cost and can create huge economic benefits for enterprises and society.
Description
Technical Field
The invention relates to the technical field of material recycling, in particular to recycling of waste PA 66.
Background
The cylinder cover is a cover covering the engine cylinder body to prevent external impurities from entering the engine, and has a sealing function to keep engine oil inside and isolate pollutants such as dirt, moisture and the like; while isolating the engine oil from the air. During operation of the engine oil mist is formed. The cooler inner surface of the cylinder head cover collects oil mist, so that the engine oil is condensed and flows back to the engine oil shell; but also takes over the responsibility of crankcase ventilation. As the piston moves within the cylinder, pressure builds up inside the engine. If left unattended, this pressure can leak individual seals, resulting in reduced engine efficiency. This requires materials having high strength, high dimensional stability, low warpage, low linear expansion coefficient, excellent liquid resistance, high flying stone impact resistance, good welding properties, excellent burst resistance, high heat resistance, long-term heat aging properties, and printability.
At present, the performance of the regenerated PA66 material such as strength, heat resistance, liquid resistance, welding performance and dimensional stability are relatively poor, and particularly the high-temperature thermo-oxidative aging performance, liquid resistance and dimensional stability can not meet the working condition requirements of the cylinder cover. Therefore, no report is found on the application of the regenerated PA66 to the production of automobile cylinder head covers.
Disclosure of Invention
The invention provides a method for producing a special material for an automobile cylinder cover by using regenerated PA66, which can overcome the defect of the performance of the regenerated PA66 material, so that the method can be used for producing the special material for the automobile engine cover.
In order to solve the technical problems, the invention adopts the following technical scheme:
the material comprises the following raw materials in percentage by weight:
100 parts of regenerated PA66;
15-60 parts of nylon PA 9T;
10-50 parts of nylon PA MXD-6;
65-150 parts of hydrolysis-resistant glass fiber;
0-30 parts of toughening agent;
0-20 parts of compatilizer;
0 to 7.5 parts of glass fiber exposure preventing agent;
3-10 parts of chain extender;
0.4 to 2.5 parts of coupling agent;
0-4 parts of heat stabilizer;
0.4 to 2 parts of antioxidant;
3-10 parts of black color master batch.
Among the above technical schemes, more specific technical schemes may also be: the weight portions of the raw materials are as follows:
100 parts of regenerated PA66, 36 parts of nylon PA9T, 15 parts of nylon PA MXD-6, 100 parts of hydrolysis-resistant glass fiber, 12 parts of toughening agent, 8 parts of compatilizer, 3 parts of glass fiber exposure preventing agent, 3 parts of chain extender, 1.8 parts of heat stabilizer, 0.9 part of antioxidant, 1 part of coupling agent and 5 parts of black masterbatch.
Further, the regenerated PA66 is particles formed by crushing, cleaning and granulating recovered binding belts, conveyor belts and gift cloths.
Further, the relative viscosity of the nylon PA9T is more than 2.8;
the hydrolysis-resistant glass fiber is prepared by coating silane-based impregnating compound on a monofilament with a diameter of 10-13 micrometers and a length of 3-6 millimeters;
the glass fiber preventing exposure agent is modified by ethylene bis fatty acid amide;
the compatilizer is polypropylene grafted maleic anhydride with the grafting rate of more than or equal to 1.2 percent;
the coupling agent is one of a silane coupling agent, a titanate coupling agent and an aluminate coupling agent;
the heat stabilizer is an inorganic copper salt heat stabilizer, a hindered amine heat stabilizer and a hindered phenol heat stabilizer;
the antioxidant is prepared by compounding a hindered phenol antioxidant and a thioether compound antioxidant in a mass ratio of 2:1;
the black masterbatch is a masterbatch containing 50% carbon black.
Further, the chain extender is one of epoxy copolymer, isocyanate copolymer, amide copolymer and styrene-glycidyl acrylate copolymer;
the toughening agent is POE grafted maleic anhydride with the grafting rate of 1-1.5%.
Further, the preparation method comprises the following preparation steps:
A. mixing the regenerated PA66, the PA9T, the PA MXD-6, the glass fiber preventing exposure agent, the toughening agent, the compatilizer, the heat stabilizer, the chain extender, the coupling agent, the antioxidant and the black masterbatch according to the proportion to obtain a mixture;
B. b, feeding the mixture obtained in the step A by a main feed of a double-screw extruder, adding hydrolysis-resistant glass fibers from an 8 th-zone side feed port of the double-screw extruder, and extruding and plasticizing under the process conditions that the screw temperature of the double-screw extruder is 265-295 ℃, the screw speed of a main machine is 350 r-450 r/min, and the frequency of a feeder is 11-Hz Hz to obtain a semi-finished product;
C. cooling, drying, granulating, and homogenizing the obtained semi-finished product.
Further, the double-screw extruder is a homodromous double-screw extruder with the screw diameter of 65mm and the length-diameter ratio of 52:1, and the double vacuum pressures are all-0.06 MPa to 0.08 MPa.
By adopting the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1. the invention can meet the requirements of various working conditions (such as heat resistance, printability, high strength, high impact resistance, welding bursting pressure and liquid resistance) of the cylinder head cover of the automobile, widens the field of PA66 recycling, reduces the resource waste and environmental pollution, reduces the material cost and can create great economic benefits for enterprises and society.
2. The invention mainly utilizes the recycled PA66 to compound with PA9T and PA MXD-6 resin, thereby improving the comprehensive performance of the material, especially having good heat resistance, and being capable of being used for a long time at the temperature of minus 40 ℃ to 150 ℃; the liquid resistance is excellent, and the liquid can be soaked in diesel oil, engine lubricating liquid, engine cooling liquid and other liquids for a long time without the phenomena of color change, softening, catalysis and the like; high dimensional stability, and no change in size at-40 deg.C to 150 deg.C.
3. Compared with other antioxidants and heat stabilizers, the invention selects the compound prepared by compounding the hindered phenol antioxidant and the thioether compound antioxidant with the mass ratio of 2:1 as the antioxidant used in the invention and selects the inorganic copper salt heat stabilizer, the hindered amine heat stabilizer and the hindered phenol heat stabilizer as the heat stabilizer used in the invention, so that the heat stabilizer can be normally used at the high temperature of 150 ℃ for a long time.
4. According to the invention, the polypropylene grafted maleic anhydride with the grafting rate of more than or equal to 1.2% is selected as the compatilizer, so that the comprehensive performance of the material is improved, and particularly the bursting pressure and printing performance of the welded material are improved.
5. The invention ensures the length integrity of the glass fiber by adopting the design adjustment and the matched screw combination, and simultaneously, each phase is melted and dispersed better, thereby improving the comprehensive performance of the material system.
6. The invention reduces the material cost by selecting the regenerated PA66 prepared by using the ribbon, the conveyor belt and the gift cloth as the main base material, so that the product is more competitive.
Drawings
FIG. 1 is a schematic diagram showing screw combinations of extruders used in examples 1 to 3 and comparative examples 1 to 4.
FIG. 2 is a schematic diagram of the screw combination of the extruder used in comparative example 5.
In the figure, 1 is a conveying section; 2 is a melt plasticization stage; 3 is a mixing section; 4 is an exhaust homogenization section; and 5 is a metering section.
Detailed Description
The invention is further described in detail below with reference to examples;
table 1 below shows the compositions of the raw materials in parts by weight in examples 1 to 3, and Table 2 shows the compositions of the raw materials in parts by weight in comparative examples 1 to 4.
Wherein the regenerated PA66 mentioned in tables 1 and 2 is: particles formed by crushing, cleaning and granulating the binding belt, the conveyor belt and the gift cloth;
nylon PA9T: poly 1, 9 nonylene terephthalamide resin, japan colali N1006A;
nylon PA MXD-6: poly (m-xylylene adipamide) dupont 3426;
hydrolysis-resistant glass fiber: alkali-free short fibers with diameters of 10-13 micrometers and lengths of 3-6mm are coated with silane-based impregnating compound, and the boulder group ECS10-03-568H;
and (3) a compatilizer: polypropylene grafted maleic anhydride (PP-g-MAH), grafting rate not less than 1.2%, shenyang Kong Tong, KT-1;
chain extender: epoxides, basf, ADR-4468;
coupling agent: silane coupling agent KH560, morning light chemical industry;
thermal oxygen stabilizer: inorganic copper salts, b.g., blogman H336;
an antioxidant: the hindered phenols and the thioether compounds are compounded in a proportion of 2:1, basf 1010, DSTP;
glass fiber preventing exposure agent: modified ethylene bis fatty acid amide, dongguan Corp TAF;
black color master: carbon black content 50%, PE carrier, guobaote company, trade name PE2718;
toughening agent: grafting rate is 1-1.5% POE grafted maleic anhydride, and KT-10A is introduced into Shenyang family).
Table 1 shows the raw material compositions of examples 1 to 3 and comparative examples 1 to 5 were prepared as follows:
(1) Crushing, cleaning and granulating the recovered PA66 binding tape, the conveyer belt and the gift cloth by using a single screw extruder; then uniformly stirring the mixture through a 20-ton homogenizing bin to obtain regenerated PA66;
(2) The method comprises the steps of using a high-torque double-vacuum double-screw extruder with the screw diameter of 65mm and the length-diameter ratio of 52:1 in the same direction, and adjusting and combining parts such as a conveying mixing section, a side feeding fiber adding section, a mixing section, a vacuum exhaust section and the like of a screw combination of the extruder;
(3) Adding the regenerated PA66, the PA9T, the PA MXD-6, the glass fiber preventing exposure agent, the toughening agent, the compatilizer, the heat stabilizer, the chain extender, the coupling agent, the antioxidant and the black masterbatch into a high-speed mixer according to the proportion, and mixing for 5-10min;
(4) Feeding the mixture obtained in the step (3) by a main feed of a double-screw extruder, and adding hydrolysis-resistant glass fibers from a feeding port at the 8 th zone side of the double-screw extruder;
(5) The finished product is obtained after the procedures of extrusion, cooling, drying, granulating, homogenization and the like.
TABLE 1
。
TABLE 2
。
Examples 1 to 3 and comparative examples 1 to 4 were extruders using a screw combination as shown in fig. 1, in which:
conveying section 1: the SK large-lead threaded element is adopted, so that the conveying capacity of a screw is improved, the material residence time is shortened, and degradation of the regenerated PA66 due to long residence time is reduced;
melting section 2: (1) the kneading elements are reduced, the angle of the kneading elements is adjusted, the shearing capacity of the screw is reduced, and under the condition that the dispersion of each component of the system is not influenced, the overheat degradation of the regenerated PA66 caused by the high shearing capacity and the high friction force is reduced; (2) the length of the reverse thread element is reduced, the back pressure of the material is reduced, the shearing heat is reduced, the retention time of the material is shortened, and the degradation of the regenerated PA66 caused by long retention time and high shearing heat temperature is reduced;
mixing section 3, exhaust homogenizing section: the method has the advantages that part of kneading elements are reduced, a 32/96 conveying type toothed disc, a 176/88LS stretching block and a C18 toothed disc are added, so that the shearing efficiency of glass fibers is improved, the plasticizing efficiency is improved, the dispersing capacity of the glass fibers is improved, and meanwhile, the further decomposition of the regenerated PA66 caused by the temperature in a gun barrel due to excessive shearing heat is reduced, so that the comprehensive performance of a system is improved.
Comparative example 5 the same ingredients and proportions of the raw materials as in example 3 were used, except that comparative example 5 used an extruder with a screw combination as shown in fig. 2.
Table 3 shows the performance parameters of the products obtained in examples 1 to 3, and Table 4 shows the performance parameters of the products obtained in comparative examples 1 to 5.
The performance detection method comprises the following steps:
the granules prepared by the above proportion are baked for 6 hours at 145 ℃, and then the following performance tests are carried out:
1. the impact strength of the cantilever beam notch is carried out according to the GB/T1843-2008 standard, the size of the sample is 80 multiplied by 10 multiplied by 4mm, and the A-type notch is formed;
2. the thermal deformation temperature test is carried out according to the GB/T1634.2-2019 standard, the sample size is 80 multiplied by 10 multiplied by 4mm, the load is 1.82MPa, and the sample is horizontally placed;
3. the tensile property test is carried out according to GB/T1040.2-2018, the size of a sample is 150 multiplied by 10 multiplied by 4mm, and the tensile speed is 50 mm/min;
4. bending performance test is carried out according to GB/T9341-2008 standard, the sample size is 80 multiplied by 10 multiplied by 4mm, the bending speed is 2mm/min, and the span is 64 mm;
5. and (3) bursting the pressure, wherein the sample is a finished workpiece, sealing the cavity, introducing gas into the cavity until bursting, and testing the air pressure of the bursting point.
6. Ink adhesion was carried out according to GB/T9286-1998;
7. the linear expansion coefficient test is carried out according to the GB/T2572-2005 standard, along the flow direction;
8. the cold-hot alternation test is carried out according to QC/T15-92 standard, and the test requires: at room temperature, the humidity is kept at 60% for 2 hours; heating to 80 ℃ in 1 hour, and keeping the humidity at 90% for 3 hours; heating to 150 ℃ in 1 hour, and keeping for 2 hours; then cooling to-40 ℃ within 1 hour, and keeping for 1 hour; heating to room temperature within 1 hour again, and testing for 24 cycles;
9. the thermal oxidation aging performance test is carried out according to GB/T7141-2008 standard, and the test condition is 150 ℃ multiplied by 1000h;
10. the liquid resistance (diesel oil, engine lubricating fluid and engine cooling fluid) is carried out according to GB/T11547-2008 standard, and the test condition is 150 ℃ multiplied by 168 hours.
TABLE 3 Table 3
。
TABLE 4 Table 4
。
According to the above examples and comparative examples, the optimum amount of the regenerated PA66 is 35%, and the PA66 material meeting the working condition requirements of the cylinder head cover of the automobile can be prepared by adding PA with proper special performance and proper functional auxiliary agents (such as heat stabilizer, chain extender, compatibilizer and the like) and matching with proper screw combinations. Because the pure use of the belts, the conveyor belts and the gift cloth regeneration PA66 is processed for a plurality of times, even more, the parts of the PA are decomposed, and the viscosity and the performance are greatly reduced. If the regenerated PA66 is not modified by the means, the requirement of the cylinder head cover working condition of the automobile cannot be met when the regenerated PA66 material is reinforced by the glass fiber.
Claims (7)
1. The special material for the automobile cylinder head cover produced by using the regenerated PA66 is characterized by being prepared from the following raw materials in parts by weight:
100 parts of regenerated PA66;
15-60 parts of nylon PA 9T;
10-50 parts of nylon PA MXD-6;
65-150 parts of hydrolysis-resistant glass fiber;
6.5 to 30 parts of toughening agent;
4-20 parts of compatilizer;
0.6 to 7.5 parts of glass fiber exposure preventing agent;
3-10 parts of chain extender;
0.4 to 2.5 parts of coupling agent;
0.4 to 4 parts of heat stabilizer;
0.4 to 2 parts of antioxidant;
3-10 parts of black color master batch;
the extruder for producing the special material for the automobile cylinder head cover sequentially comprises a conveying section, a melting plasticizing section, a mixing section, an exhaust homogenizing section and a metering section along the conveying direction of materials,
the conveying section is formed by sequentially combining the following screw elements along the conveying direction of materials: 48/48-T, 96/96SK 2, 96/72SK, 56/56, 48/48;
the melting plasticizing section is formed by sequentially combining the following screw elements along the material conveying direction: 45 °/5/64, 45 °/5/56, 60 °/5/56, 56/56×2, 48/48, 45 °/5/48, 60 °/5/48, 90 °/5/56, 72/72, 64/64, 56/56, 45 °/5/56×2, 56/28L;
the mixing section is formed by sequentially combining the following screw elements along the material conveying direction: 96/96, 72/72, 64/64, 56/56, 32/96 toothed disc, 48/48, 30 °/7/72, 48/48×2, 176/88LS, 48/48, 56/28L;
the exhaust homogenizing section is formed by sequentially combining the following screw elements along the material conveying direction: 72/72, 64/64×2, 56/56, 30 °/7/72, 45 °/5/48, 72/72, 64/64, 56/56, C18 tooth disc×2, 48/48, 45 °/5/48, 56/28L, 96/96;
the metering section is formed by sequentially combining the following screw elements along the material conveying direction: 72/72, 64/64, 56/56X 2, 48/48X 2.
2. The special material for the automobile cylinder head cover produced by using the regenerated PA66 according to claim 1, wherein the special material is characterized by comprising the following raw materials in parts by weight:
100 parts of regenerated PA66, 36 parts of nylon PA9T, 15 parts of nylon PA MXD-6, 100 parts of hydrolysis-resistant glass fiber, 12 parts of toughening agent, 8 parts of compatilizer, 3 parts of glass fiber exposure preventing agent, 3 parts of chain extender, 1.8 parts of heat stabilizer, 0.9 part of antioxidant, 1 part of coupling agent and 5 parts of black masterbatch.
3. A special material for cylinder head covers of automobiles produced by using regenerated PA66 according to claim 1 or 2, characterized in that: the regenerated PA66 is particles formed by crushing, cleaning and granulating recovered binding tapes, conveyor belts and gift cloths.
4. A special material for a cylinder head cover of an automobile produced by using regenerated PA66 according to claim 3, wherein:
the relative viscosity of the nylon PA9T is more than 2.8;
the hydrolysis-resistant glass fiber is prepared by coating silane-based impregnating compound on a monofilament with a diameter of 10-13 micrometers and a length of 3-6 millimeters;
the glass fiber preventing exposure agent is modified ethylene double fatty acid amide;
the compatilizer is polypropylene grafted maleic anhydride with the grafting rate of more than or equal to 1.2 percent;
the coupling agent is one of a silane coupling agent, a titanate coupling agent and an aluminate coupling agent;
the heat stabilizer is an inorganic copper salt heat stabilizer, a hindered amine heat stabilizer and a hindered phenol heat stabilizer;
the antioxidant is prepared by compounding a hindered phenol antioxidant and a thioether compound antioxidant in a mass ratio of 2:1;
the black masterbatch is a masterbatch containing 50% carbon black.
5. The special material for the cylinder head cover of the automobile, which is produced by using the regenerated PA66, according to claim 4, wherein the special material comprises the following components:
the chain extender is one of epoxy copolymer, isocyanate copolymer, amide copolymer and styrene-glycidyl acrylate copolymer;
the toughening agent is POE grafted maleic anhydride with the grafting rate of 1-1.5%.
6. The special material for the cylinder head cover of the automobile, which is produced by using the regenerated PA66, according to claim 5, is characterized by comprising the following preparation steps:
A. mixing the regenerated PA66, the PA9T, the PA MXD-6, the glass fiber preventing exposure agent, the toughening agent, the compatilizer, the heat stabilizer, the chain extender, the coupling agent, the antioxidant and the black masterbatch according to the proportion to obtain a mixture;
B. b, feeding the mixture obtained in the step A by a main feed of a double-screw extruder, adding hydrolysis-resistant glass fibers from an 8 th-zone side feed port of the double-screw extruder, and extruding and plasticizing under the process conditions that the screw temperature of the double-screw extruder is 265-295 ℃, the screw speed of a main machine is 350 r-450 r/min, and the frequency of a feeder is 11-Hz Hz to obtain a semi-finished product;
C. cooling, drying, granulating, and homogenizing the obtained semi-finished product.
7. The special material for the cylinder head cover of the automobile, which is produced by using the regenerated PA66, according to claim 6, is characterized in that:
the double-screw extruder is a homodromous double-screw extruder with the screw diameter of 65mm, the length-diameter ratio of 52:1 and the double vacuum pressure of-0.06 MPa to 0.08 MPa.
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| CN118165510A (en) * | 2024-04-03 | 2024-06-11 | 浙江一马新材料有限公司 | PCR-based special material for black PA66 modified super-tough ribbon and preparation method thereof |
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