CN114957973B - Automobile water chamber material and preparation method thereof - Google Patents
Automobile water chamber material and preparation method thereof Download PDFInfo
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- CN114957973B CN114957973B CN202210648572.5A CN202210648572A CN114957973B CN 114957973 B CN114957973 B CN 114957973B CN 202210648572 A CN202210648572 A CN 202210648572A CN 114957973 B CN114957973 B CN 114957973B
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- 239000000463 material Substances 0.000 title claims abstract description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920002647 polyamide Polymers 0.000 claims abstract description 87
- 239000004952 Polyamide Substances 0.000 claims abstract description 86
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000835 fiber Substances 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 230000002787 reinforcement Effects 0.000 claims abstract description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 10
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 6
- 229920001577 copolymer Polymers 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 19
- CSVBIURHUGXNCS-UHFFFAOYSA-N 6-azaniumylhexylazanium;terephthalate Chemical compound NCCCCCCN.OC(=O)C1=CC=C(C(O)=O)C=C1 CSVBIURHUGXNCS-UHFFFAOYSA-N 0.000 claims description 17
- 238000002844 melting Methods 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 17
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 12
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 12
- 239000000155 melt Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000010907 mechanical stirring Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 7
- 239000003365 glass fiber Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 6
- 150000003077 polyols Chemical class 0.000 claims description 6
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 5
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 4
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 claims description 2
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 claims description 2
- 229920002748 Basalt fiber Polymers 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000000945 filler Substances 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 68
- 238000006136 alcoholysis reaction Methods 0.000 abstract description 17
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 16
- 125000003118 aryl group Chemical group 0.000 abstract description 10
- 230000007062 hydrolysis Effects 0.000 abstract description 10
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 10
- 238000002791 soaking Methods 0.000 abstract description 9
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 8
- 229920002302 Nylon 6,6 Polymers 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- 229920002292 Nylon 6 Polymers 0.000 description 4
- 229910001508 alkali metal halide Inorganic materials 0.000 description 4
- 150000008045 alkali metal halides Chemical class 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 231100001010 corrosive Toxicity 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000001291 vacuum drying 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
-
- 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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Abstract
The invention relates to the field of high polymer materials, in particular to an automobile water chamber material and a preparation method thereof. The raw materials for preparing the automobile water chamber material comprise first polyamide, second polyamide, fiber reinforcement material and polyalcohol; the first polyamide and the second polyamide are copolymers of terephthalic acid, hexamethylenediamine and caprolactam, and the difference between the reduced viscosity of the first polyamide and the reduced viscosity of the second polyamide is 0.1 to 0.8dl/g. Polyamide with lower viscosity is adopted to improve the fluidity before forming, so that the surface of a finished product does not float fiber; the polyamide with the aromatic ring macromolecular structure and the large pi conjugated bond thereof can slow down hydrolysis and alcoholysis reaction, and the polyamide with the aromatic ring macromolecular structure is matched with each other in different viscosities, so that the alcoholysis resistance of the prepared automobile water chamber material can be further improved. The tensile strength of the automobile water chamber material after being soaked in glycol is as follows: the ratio of tensile strength before ethylene glycol soaking is greater than 0.65.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to an automobile water chamber material and a preparation method thereof.
Background
With the development trend of light weight in the automobile industry and the increasingly strict environmental protection recovery requirements, more and more automobile components (such as a radiating water tank of an automobile) begin to adopt nylon parts to replace metal and thermosetting plastics. Because the upper cover and the lower cover of the radiating water tank of the automobile belong to large-sized parts, the upper cover and the lower cover of the radiating water tank of the automobile are required to have high fluidity and smooth surface in injection molding. In addition, because the working environment of the radiator tank of the automobile is a high-low temperature coolant environment, the upper cover material and the lower cover material (automobile water chamber material) of the radiator tank of the automobile are required to be resistant to the corrosion of glycol and other chemical corrosives, and meanwhile, the workpiece is required to be free from cracking in the assembly process, so that the requirements on the alcoholysis resistance and the impact strength of the materials are high. The alcoholysis resistance of the existing automobile water chamber material is still not ideal. Meanwhile, most of upper and lower cover materials (namely automobile water chamber materials) of an automobile radiator water tank used in the automobile industry are aliphatic nylon as base material resin, and an alcoholysis resistance agent is added to meet the performance requirements. If PA66 is adopted as base material resin, copper iodide alcoholysis-resistant agent is added to meet the performance requirement; or adopting PA66 and other aliphatic Ni Long Shuzhi, and adding alkali metal halide as alcoholysis resisting agent to reach the performance requirement. However, due to the increasingly stringent environmental protection requirements at present, the industry has increasingly strict control on halogen contained in plastic raw materials.
Therefore, it is needed to provide an automobile water chamber material and a preparation method thereof, wherein the automobile water chamber material has the advantages of high fluidity, alcoholysis resistance, no halogen and other heavy metal ions and excellent performance.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides the automobile water chamber material and the preparation method thereof, the automobile water chamber material has the advantages of high fluidity, alcoholysis resistance, no halogen and other heavy metal ions and excellent performance, the prepared 4mm test rod of the automobile water chamber material is tested according to ISO527 after being soaked in glycol refrigerating fluid at 135 ℃ for 300 hours, the 4mm test rod has tensile strength of more than or equal to 110MPa, and the tensile strength after being soaked in glycol: the ratio of tensile strength before ethylene glycol soaking is greater than 0.65.
The invention is characterized in that: the polyamide with lower viscosity is adopted to improve the fluidity before forming, so that the possibility of surface floating fiber is reduced, the macromolecular structure of the aromatic ring and the large pi conjugated bond thereof can slow down hydrolysis and alcoholysis reaction, and the polyamide with the macromolecular structure of the aromatic ring is matched with each other with different viscosities, so that the alcoholysis resistance of the prepared automobile water chamber material can be further improved.
The first aspect of the invention provides an automobile water chamber material, wherein the raw materials for preparing the automobile water chamber material comprise first polyamide, second polyamide, fiber reinforcement and polyalcohol; the first polyamide and the second polyamide are copolymers of terephthalic acid, hexamethylenediamine and caprolactam, the difference between the reduced viscosity of the first polyamide and the reduced viscosity of the second polyamide is 0.1-0.8dl/g, and the difference between the melting point of the first polyamide and the melting point of the second polyamide is 10-100 ℃.
Compared with the prior art, the automobile water chamber material and the preparation method thereof have the following beneficial effects: polyamide with lower viscosity is adopted to improve the fluidity before forming, so that the surface of a finished product does not float fiber; the polyamide with the aromatic ring macromolecular structure and the pi conjugated bond thereof can slow down hydrolysis and alcoholysis reactions, and the polyamide with the aromatic ring macromolecular structure is matched with each other in different viscosities, so that the alcoholysis resistance of the prepared automobile water chamber material can be further improved, and the same effect can be achieved in performance even though polyamine hydrolysis resistance agents and alkali metal halides are not added. The prepared 4mm test rod of the automobile water chamber material is soaked in glycol refrigerating fluid at 135 ℃ for 300 hours and then tested according to ISO527, and the 4mm test rod has tensile strength of 110MPa or more and tensile strength after being soaked in glycol: the ratio of tensile strength before ethylene glycol soaking is greater than 0.65.
Preferably, the reduced viscosity of the first polyamide is from 0.7 to 2dl/g; the reduced viscosity of the second polyamide is 0.2 to 0.6dl/g.
Preferably, the difference between the reduced viscosity of the first polyamide and the reduced viscosity of the second polyamide is between 0.5 and 0.8dl/g.
Preferably, the raw materials for preparing the automobile water chamber material comprise, by weight, 40-80 parts of first polyamide, 0.1-5 parts of second polyamide, 20-50 parts of fiber reinforcement material and 0.1-5 parts of polyalcohol; further preferably, the raw materials of the automobile water chamber material comprise, by weight, 43-80 parts of first polyamide, 0.5-3 parts of second polyamide, 25-45 parts of fiber reinforcement material and 1-3 parts of polyol; still more preferably, the raw materials of the automobile water chamber material comprise 48-68 parts by weight of first polyamide, 0.5-3 parts by weight of second polyamide, 25-45 parts by weight of fiber reinforcement material and 1-3 parts by weight of polyol.
Preferably, the raw materials of the first polyamide comprise 65-75 parts by weight of terephthalic acid-hexamethylenediamine salt (6T salt), 25-35 parts by weight of caprolactam, 15-25 parts by weight of water, 0.1-1 part by weight of acetic acid and 0.05-0.5 part by weight of sodium hypophosphite; the raw materials of the second polyamide comprise, by weight, 55-64 parts of terephthalic acid-hexamethylenediamine salt (6T salt), 25-35 parts of caprolactam, 15-25 parts of water, 0.1-1 part of acetic acid and 0.05-0.5 part of sodium hypophosphite.
Preferably, the melting point of the first polyamide is 220-280 ℃; further preferably, the first polyamide has a melting point of 230-280 ℃; still more preferably, the first polyamide has a melting point of 250-280 ℃.
Preferably, the second polyamide has a melting point of 220-280 ℃; further preferably, the second polyamide has a melting point of 220-250 ℃.
Preferably, the difference between the melting point of the first polyamide minus the melting point of the second polyamide is 30-60 ℃.
Preferably, the fiber reinforcement material comprises at least one of glass fiber, carbon fiber, aramid fiber, LCP (liquid crystal polymer) fiber and basalt fiber; further preferably, the glass fibers are ECS301 HP type glass fibers and/or T435TM type glass fibers of Mount Taishan glass fibers of Chongqing composite Co., ltd.
Preferably, the surface of the fiber reinforced material is also treated by a silane coupling agent.
Preferably, the fiber strength of the fiber reinforced material is greater than or equal to 18cN/dtex; further preferably, the fiber strength of the fiber reinforcement is 35cN/dtex or more.
Preferably, the polyol includes at least one of pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, trimethylolpropane, and di (trimethylolpropane); further preferably, the polyol comprises dipentaerythritol. Dipentaerythritol can play a certain crosslinking role, reduce the hydrolysis of substances such as ethylene glycol and the like on materials, and prevent the reduction of mechanical properties of the materials caused by the rapid reduction of the molecular weight of the materials.
Preferably, the 4mm test bar of the automobile water chamber material is soaked in glycol freezing solution at 135 ℃ for 300 hours and then tested according to ISO527, the tensile strength of the 4mm test bar is more than or equal to 110MPa, and more preferably, the tensile strength of the 4mm test bar is more than or equal to 110MPa and less than or equal to 250MPa; still more preferably, the 4mm test bar has a tensile strength of 120MPa or more and 200MPa or less.
Preferably, the tensile strength of the automobile water chamber material after being soaked in glycol is as follows: the ratio of tensile strength before soaking in glycol is more than 65%.
Preferably, the halogen content of the automobile water chamber material is less than 10ppm.
Preferably, the thin-wall flow length of the automobile water chamber material is more than 50mm; further preferably, the thin-wall flow length of the automobile water chamber material is more than 50mm and less than 100mm.
Preferably, the automobile water chamber material is tested according to ISO180, and the notch impact strength of the cantilever beam is more than 10kj/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Further preferably, the automobile water chamber material is tested according to ISO180, and the notched Izod impact strength is greater than 10kj/m 2 Less than 20kj/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Still further preferably, the automotive header stock has a notched Izod impact strength greater than 10kj/m when tested according to ISO180 2 15kj/m or less 2 。
The second aspect of the invention also provides a preparation method of the automobile water chamber material, which is optionally one of the following steps: and (3) melting and blending the first polyamide, the second polyamide and the polyalcohol to obtain a melt, adding the fiber reinforcement into the melt, mixing, extruding and cooling to obtain the automobile water chamber material.
Preferably, the temperature of the melt blending is 260-300 ℃; further preferably, the melt blending temperature is 270-290 ℃; still more preferably, the melt blending temperature is 280 ℃.
Preferably, the preparation method of the first polyamide comprises the following steps: adding terephthalic acid-hexamethylenediamine salt, caprolactam, water, acetic acid and sodium hypophosphite into an autoclave with a mechanical stirring and vacuumizing device, heating to a reaction temperature of 200-240 ℃, keeping the temperature at the reaction temperature, keeping the pressure, exhausting the gas, decompressing to normal pressure, starting vacuumizing after reacting for 0.3-0.7 hour under the normal pressure, keeping the negative pressure between-0.05 and-0.5 MPa for 0.5-1.5 hours, and discharging to obtain the first polyamide; further preferably, the preparation method of the first polyamide comprises the following steps: adding terephthalic acid-hexamethylenediamine salt (6T salt), caprolactam, water, acetic acid and sodium hypophosphite into an autoclave with a mechanical stirring and vacuumizing device, uniformly heating to a reaction temperature of 200-240 ℃ within 1.5-2.5 hours, keeping the temperature for 1.5-2.5 hours, keeping the pressure and exhausting for 2.5-3.5 hours under 1.5-2.5MPa, reducing the pressure to normal pressure under 0.5-1.5MPa per hour, reacting for 0.3-0.7 hours under normal pressure, vacuumizing, keeping the negative pressure between-0.05 and-0.5 MPa for 0.5-1.5 hours, and discharging to obtain the first polyamide.
Preferably, the preparation method of the second polyamide comprises the following steps: adding terephthalic acid-hexamethylenediamine salt, caprolactam, water, acetic acid and sodium hypophosphite into an autoclave with a mechanical stirring and vacuumizing device, heating to a reaction temperature of 200-240 ℃, keeping the temperature and the pressure at the reaction temperature, exhausting the air, decompressing to normal pressure, and discharging to obtain the second polyamide; further preferably, the preparation method of the second polyamide comprises the following steps: adding terephthalic acid-hexamethylenediamine salt (6T salt), caprolactam, water, acetic acid and sodium hypophosphite into an autoclave with a mechanical stirring and vacuumizing device, uniformly heating to a reaction temperature of 200-240 ℃ within 1.5-2.5 hours, keeping the temperature at the reaction temperature for 1.5-2.5 hours, keeping the pressure and exhausting for 2.5-3.5 hours under 1.5-2.5MPa, and discharging after depressurizing to normal pressure at 0.5-1.5MPa per hour to obtain the second polyamide.
Preferably, the preparation method of the terephthalic acid-hexamethylenediamine salt comprises the following steps: mixing terephthalic acid and water, pulping, heating to 35 ℃, then uniformly adding hexamethylenediamine in a molten state until the PH value in the reaction solution is 7.8-8.2, and controlling the temperature of the reaction solution to be 75-80 ℃ in the reaction process; cooling to 20-27 ℃ after the reaction is finished, centrifugally separating the separated crystals, and vacuum drying for 24 hours to obtain the terephthalic acid-hexamethylenediamine salt.
Preferably, the apparatus used in the preparation method is a double-screw extruder, the screw speed of the double-screw extruder is 250-350rpm, and the throughput is 100-150kg/h; further preferably, the twin-screw extruder has a screw speed of 290-310rpm and a throughput of 110-130kg/h.
Preferably, the extruded form is lace-like or strand-like.
Preferably, the cooling mode is water bath cooling.
The third aspect of the invention provides an application of any of the automobile water chamber materials in preparing an automobile.
Compared with the prior art, the invention has the following beneficial effects:
polyamide with lower viscosity is adopted to improve the fluidity before forming, so that the surface of a finished product does not float fiber; the polyamide with the aromatic ring macromolecular structure and the pi conjugated bond thereof can slow down hydrolysis and alcoholysis reactions, and the polyamide with the aromatic ring macromolecular structure is matched with each other in different viscosities, so that the alcoholysis resistance of the prepared automobile water chamber material can be further improved, and the same effect can be achieved in performance even though polyamine hydrolysis resistance agents and alkali metal halides are not added. The prepared 4mm test rod of the automobile water chamber material is soaked in glycol refrigerating fluid at 135 ℃ for 300 hours and then tested according to ISO527, and the 4mm test rod has tensile strength of 110MPa or more and tensile strength after being soaked in glycol: the ratio of tensile strength before ethylene glycol soaking is greater than 0.65.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
Twin screw extruder, CTE 50, available from Coperion; glass fiber, ECS301 HP, available from Chongqing composite Co., ltd; LCP fiber from Jiangmen Dezhongtai engineering plastics technology Co., ltd; PANT D5000, from Deltai engineering plastics technologies Co., ltd.
Examples 1 to 5, comparative examples 1 to 5
Automobile water chamber material and preparation method thereof
Preparation of terephthalic acid-hexamethylenediamine salt: 30 parts of terephthalic acid and 100 parts of water are mixed, beaten and heated to 35 ℃, then hexamethylenediamine in a molten state is added uniformly until the PH value in the reaction solution is 7.8-8.2, and the temperature of the reaction solution is controlled to be 75-80 ℃ in the reaction process. Cooling to 25 deg.c, centrifuging to separate out crystal, and vacuum stoving at 80 deg.c for 24 hr to obtain terephthalic acid-hexamethylenediamine salt (6T salt).
Preparation of the first polyamide: 70kg of terephthalic acid-hexamethylenediamine salt, 30kg of caprolactam, 20kg of high-purity water, 0.5kg of acetic acid and 0.1kg of sodium hypophosphite are added into a 200L autoclave with a mechanical stirring and vacuumizing device, the temperature is uniformly increased to 220 ℃ within 2 hours, the temperature is kept constant for 2 hours at 220 ℃, then the pressure is maintained and exhausted for 3 hours under 2MPa, the pressure is reduced to normal pressure at 1MPa per hour, the vacuum pumping is started after the reaction is carried out for half an hour under the normal pressure, and the discharging is carried out after the negative pressure is kept for-0.1 MPa for 1 hour, so that the first polyamide is prepared. The first polyamide has a melting point of 275 ℃ and reduced viscosity: 1.2dl/g.
Preparation of the second polyamide: 60kg of terephthalic acid-hexamethylenediamine salt, 40kg of caprolactam, 20kg of high-purity water, 0.5kg of acetic acid and 0.1kg of sodium hypophosphite are added into a 200L autoclave with a mechanical stirring and vacuumizing device, the temperature is uniformly increased to 220 ℃ within 2 hours, the temperature is kept constant for 2 hours at 220 ℃, then the pressure is maintained and exhausted for 3 hours at 2MPa, and then the pressure is reduced to normal pressure at 1MPa per hour and then the materials are discharged, so that the second polyamide is prepared. The second polyamide has a melting point of 235 ℃, reduced viscosity: 0.45dl/g.
Preparing an automobile water chamber material: melt blending a first polyamide, a second polyamide, a polyol or other polyamide (PA 66, PA6, PANT D5000) in a 50mm twin screw extruder to produce a melt, adding a fiber reinforcement to the melt by a screw side feeder to produce a compound, operating at 280 ℃, with a screw speed of 300rpm, throughput of 120 kg/h; the compounded mixture was extruded in the form of laces or strands and cooled in a water bath, then chopped into pellets and packed into sealed aluminum lined bags to prevent moisture absorption. The specific raw material component contents of each example and comparative example are shown in Table 1 below.
TABLE 1 raw material component contents of examples 1-5, comparative examples 1-5
PA66 is PA66 engineering plastic (Polyamide 66); PA6 is nylon 6 (Polyamide 6); PANT D5000 is PA6T/66, melting point 310 ℃, reduced viscosity 1dl/g.
Performance test of automobile water chamber material: the prepared examples 1-5 and comparative examples 1-5 were subjected to performance tests for judging thin wall flow length, notched impact strength, tensile strength after ethylene glycol immersion, halogen content and surface appearance, respectively, and the corresponding performance test results of the corresponding examples 1-5 and comparative examples 1-5 are shown in Table 2 below.
Notched impact strength was tested according to ISO 180; tensile strength was tested according to ISO 527; the tensile strength after soaking in ethylene glycol is specifically as follows: a4 mm test bar was prepared from the polyamide composition and tested according to ISO527 after immersion in a glycol refrigerant at 135℃for 300 hours. The tensile strength/tensile strength after ethylene glycol soaking is also the tensile strength after ethylene glycol soaking: ratio of tensile strength before ethylene glycol soak.
TABLE 2 results of the corresponding Performance tests for examples 1-5, comparative examples 1-5
Polyamide with lower viscosity is adopted to improve the fluidity before forming, so that the surface of a finished product does not float fiber; the polyamide with the aromatic ring macromolecular structure and the pi conjugated bond thereof can slow down hydrolysis and alcoholysis reactions, and the polyamide with the aromatic ring macromolecular structure is matched with each other in different viscosities, so that the alcoholysis resistance of the prepared automobile water chamber material can be further improved, and the same effect can be achieved in performance even though polyamine hydrolysis resistance agents and alkali metal halides are not added. The prepared 4mm test rod of the automobile water chamber material is soaked in glycol refrigerating fluid at 135 ℃ for 300 hours and then tested according to ISO527, and the 4mm test rod has tensile strength of 110MPa or more and tensile strength after being soaked in glycol: the ratio of tensile strength before ethylene glycol soaking is greater than 0.65.
Dipentaerythritol can play a certain crosslinking role, reduce the hydrolysis of substances such as ethylene glycol and the like on materials, and prevent the reduction of mechanical properties of the materials caused by the rapid reduction of the molecular weight of the materials.
Comparative example 6
Automobile water chamber material and preparation method thereof
Comparative example 6 differs from example 1 in that: in the preparation of the second polyamide, the amount of terephthalic acid-hexamethylenediamine salt added was 55kg and the amount of caprolactam added was 45kg, with the aim of modifying the reduced viscosity of the second polyamide.
The second polyamide was tested for melting point 245 ℃, reduced viscosity: 0.28dl/g; thin wall flow length of automobile water chamber material is 63mm, and notch impact strength is 13kj/m 2 The tensile strength is 170MPa, the tensile strength after being soaked in glycol is 95MPa, the tensile strength/tensile strength after being soaked in glycol is 0.56, the halogen content is 0ppm, and the surface is good.
In addition, when the second polyamide is present in the automobile header stock at a ratio exceeding 5wt/%, the initial mechanical strength of the automobile header stock may be reduced, i.e., the tensile strength in Table 2.
Claims (7)
1. The automobile water chamber material is characterized by comprising, by weight, 40-80 parts of a first polyamide, 0.1-5 parts of a second polyamide, 20-50 parts of a fiber reinforcement material and 0.1-5 parts of a polyol;
the raw materials for preparing the first polyamide comprise, by weight, 65-75 parts of terephthalic acid-hexamethylenediamine salt, 25-35 parts of caprolactam, 15-25 parts of water, 0.1-1 part of acetic acid and 0.05-0.5 part of sodium hypophosphite; the raw materials for preparing the second polyamide comprise, by weight, 55-64 parts of terephthalic acid-hexamethylenediamine salt, 25-35 parts of caprolactam, 15-25 parts of water, 0.1-1 part of acetic acid and 0.05-0.5 part of sodium hypophosphite;
the polyalcohol comprises at least one of pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, trimethylolpropane and di (trimethylolpropane);
the first polyamide, the second polyamide is a copolymer of terephthalic acid, hexamethylenediamine and caprolactam, the difference of the reduced viscosity of the first polyamide minus the reduced viscosity of the second polyamide is 0.75dl/g, and the difference of the melting point of the first polyamide minus the melting point of the second polyamide is 40 ℃.
2. The automotive water filler of claim 1, wherein the fiber reinforcement comprises at least one of glass fiber, carbon fiber, aramid fiber, LCP fiber, basalt fiber.
3. The method for preparing the automobile water chamber material according to any one of claims 1 to 2, which is characterized in that the method for preparing the automobile water chamber material comprises the following steps: and (3) melting and blending the first polyamide, the second polyamide and the polyalcohol to obtain a melt, adding the fiber reinforcement into the melt, mixing, extruding and cooling to obtain the automobile water chamber material.
4. A method of preparation according to claim 3, wherein the first polyamide is prepared by: adding terephthalic acid-hexamethylenediamine salt, caprolactam, water, acetic acid and sodium hypophosphite into an autoclave with a mechanical stirring and vacuumizing device, heating to a reaction temperature of 200-240 ℃, keeping the temperature and the pressure of the reaction, exhausting the air, decompressing to normal pressure, reacting for 0.3-0.7 hour under the normal pressure, vacuumizing, keeping the negative pressure between-0.05 and-0.5 MPa for 0.5-1.5 hours, and discharging to obtain the first polyamide.
5. A process according to claim 3, wherein the process for preparing the second polyamide comprises: adding terephthalic acid-hexamethylenediamine salt, caprolactam, water, acetic acid and sodium hypophosphite into an autoclave with a mechanical stirring and vacuumizing device, heating to a reaction temperature of 200-240 ℃, keeping the temperature and the pressure at the reaction temperature, exhausting the air, decompressing to normal pressure, and discharging to obtain the second polyamide.
6. A production method according to claim 3, characterized in that the apparatus used in the production method is a twin-screw extruder having a screw speed of 250-350rpm and a throughput of 100-150kg/h.
7. Use of the automotive water chamber material according to any one of claims 1-2 for the preparation of an automobile.
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| CN102112525A (en) * | 2008-07-30 | 2011-06-29 | 纳幕尔杜邦公司 | Heat resistant molded or extruded thermoplastic articles |
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| CN103987782A (en) * | 2011-12-16 | 2014-08-13 | 三菱瓦斯化学株式会社 | Molded article |
| CN111117233A (en) * | 2019-12-31 | 2020-05-08 | 会通新材料(上海)有限公司 | Polyamide 56 composition resistant to corrosion of automobile coolant and preparation method and application thereof |
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| CN102112525A (en) * | 2008-07-30 | 2011-06-29 | 纳幕尔杜邦公司 | Heat resistant molded or extruded thermoplastic articles |
| CN102471506A (en) * | 2009-07-30 | 2012-05-23 | 纳幕尔杜邦公司 | Heat resistant polyamide composite structures and processes for their preparation |
| CN102471505A (en) * | 2009-07-30 | 2012-05-23 | 纳幕尔杜邦公司 | Heat resistant semi-aromatic polyamide composite structures and processes for their preparation |
| CN102827471A (en) * | 2011-06-17 | 2012-12-19 | Ems专利股份公司 | Semiaromatic moulding masses and their applications |
| CN103987782A (en) * | 2011-12-16 | 2014-08-13 | 三菱瓦斯化学株式会社 | Molded article |
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