CN114957973A - Automobile water chamber material and preparation method thereof - Google Patents
Automobile water chamber material and preparation method thereof Download PDFInfo
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- CN114957973A CN114957973A CN202210648572.5A CN202210648572A CN114957973A CN 114957973 A CN114957973 A CN 114957973A CN 202210648572 A CN202210648572 A CN 202210648572A CN 114957973 A CN114957973 A CN 114957973A
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- automobile
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000000463 material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920002647 polyamide Polymers 0.000 claims abstract description 89
- 239000004952 Polyamide Substances 0.000 claims abstract description 88
- 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
- 230000002787 reinforcement Effects 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 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 5
- 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 20
- 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
- 238000002156 mixing Methods 0.000 claims description 9
- 238000010907 mechanical stirring Methods 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 8
- 150000003077 polyols Chemical class 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
- 238000000034 method Methods 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
- 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 5
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 4
- 239000004977 Liquid-crystal polymers (LCPs) Substances 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
- 239000004760 aramid Substances 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 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 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 62
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 22
- 238000006136 alcoholysis reaction Methods 0.000 abstract description 17
- 238000002791 soaking Methods 0.000 abstract description 17
- 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
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000243 solution Substances 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
- 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
- 238000007710 freezing Methods 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920003231 aliphatic polyamide Polymers 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 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
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture 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
- 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- -1 halogen and the like Chemical class 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
- 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
- 238000004064 recycling Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Polyamides (AREA)
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 and polyhydric alcohol; the first polyamide and the second polyamide are copolymers of terephthalic acid, hexamethylene diamine and caprolactam, and the difference between the reduced viscosity of the first polyamide and the reduced viscosity of the second polyamide is 0.1-0.8 dl/g. The fluidity of the polyamide with lower viscosity before forming is improved, 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 reactions, and the polyamide with the aromatic ring macromolecular structure is matched with each other with different viscosities, so that the alcoholysis resistance of the prepared automobile water material can be further improved. The tensile strength of the automobile water chamber material after glycol soaking is as follows: the ratio of the tensile strength before glycol soaking is more 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 and the stricter environmental recycling requirements in the automobile industry, more and more automobile components (such as a heat dissipation 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 heat dissipation water tank of the automobile belong to large-scale parts, the upper cover and the lower cover of the heat dissipation water tank of the automobile are required to have high fluidity and smooth surfaces 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 ethylene glycol and other chemical corrosive agents, and meanwhile, the manufactured piece is required not to crack in the assembling process, so that the requirements on alcoholysis resistance and impact strength of the materials are high. The alcoholysis resistance of the existing automobile water chamber materials is still not ideal. Meanwhile, most of the materials (namely automobile water chamber materials) of the upper cover and the lower cover of the radiator water tank of the automobile used in the automobile industry at present are aliphatic nylon which is used as base material resin, and alcoholysis resistant agents are added to meet the performance requirements of the radiator water tank. If PA66 is adopted as base resin, copper iodide alcoholysis-resistant agent is added to meet the performance requirement; or aliphatic nylon resin such as PA66 and the like are adopted, and alkali metal halide is added as an alcoholysis resistance agent to meet the performance requirement. However, due to the increasingly strict environmental requirements at present, the industry has increasingly strict control on the halogen contained in the plastic raw material.
Therefore, it is highly desirable 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 heavy metal ions such as halogen and the like, and excellent performance.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides an automobile water chamber material and a 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, a 4mm test rod of the prepared automobile water chamber material is tested according to ISO527 after being soaked in 135 ℃ glycol refrigerating fluid for 300 hours, the 4mm test rod has the tensile strength of more than or equal to 110MPa, and the tensile strength after being soaked in glycol is as follows: the ratio of the tensile strength before glycol soaking is more than 0.65.
The invention conception of the invention is as follows: the polyamide with lower viscosity is adopted to improve the fluidity before forming the material so as to reduce the possibility of fiber floating on the surface, the macromolecular structure of the aromatic ring and the large pi conjugated bond thereof can slow down the hydrolysis and alcoholysis reactions, 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 material can be further improved.
The first aspect of the invention provides an automobile water chamber material, and raw materials for preparing the automobile water chamber material comprise first polyamide, second polyamide, a fiber reinforcement material and polyhydric alcohol; the first polyamide and the second polyamide are copolymers of terephthalic acid, hexamethylene diamine 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: the fluidity of the polyamide with lower viscosity before forming is improved, 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 reactions, and the polyamide with the aromatic ring macromolecular structure is matched with each other with different viscosities, so that the alcoholysis resistance of the prepared automobile water material can be further improved, and the same effect can be achieved in performance even though no polyamine hydrolysis resistant agent and alkali metal halide are added. A4 mm test rod of the prepared automobile water chamber material is soaked in a 135 ℃ glycol freezing solution for 300 hours and then is tested according to ISO527, wherein the 4mm test rod has the tensile strength of more than or equal to 110MPa and the tensile strength after glycol soaking: the ratio of the tensile strength before the ethylene glycol soaking is more than 0.65.
Preferably, the reduced viscosity of the first polyamide is 0.7 to 2 dl/g; the reduced viscosity of the second polyamide is 0.2 to 0.6 dl/g.
Preferably, the difference between the reduced viscosity of the first polyamide minus the reduced viscosity of the second polyamide is between 0.5 and 0.8 dl/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 and 0.1-5 parts of polyhydric alcohol; more preferably, the raw materials of the automobile water chamber material comprise 43-80 parts by weight of first polyamide, 0.5-3 parts by weight of second polyamide, 25-45 parts by weight of fiber reinforcement and 1-3 parts by weight of polyhydric alcohol; more preferably, the raw materials of the automobile water chamber material comprise, by weight, 48-68 parts of first polyamide, 0.5-3 parts of second polyamide, 25-45 parts of fiber reinforcement and 1-3 parts of polyol.
Preferably, the raw materials of the first polyamide comprise 65-75 parts by weight of hexamethylene diamine terephthalate (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-hexamethylene diamine 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 melting point of the first polyamide is 230-280 ℃; still more preferably, the melting point of the first polyamide is 250-280 ℃.
Preferably, the melting point of the second polyamide is 220-280 ℃; further preferably, the melting point of the second polyamide is 220-250 ℃.
Preferably, the difference between the melting point of the first polyamide minus the melting point of the second polyamide is between 30 and 60 ℃.
Preferably, the fiber reinforcement comprises at least one of glass fibers, carbon fibers, aramid fibers, LCP (liquid crystal polymer) fibers, basalt fibers; further preferably, the glass fiber is ECS301 HP type glass fiber of chongqing composite gmbh and/or T435TM type glass fiber of taishan glass fiber.
Preferably, the surface of the fiber reinforcement is further treated with a silane coupling agent.
Preferably, the fiber strength of the fiber reinforcement is more than or equal to 18 cN/dtex; further preferably, the fiber strength of the fiber reinforcement is not less than 35 cN/dtex.
Preferably, the polyol comprises at least one of pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, trimethylolpropane, ditrimethylolpropane; further preferably, the polyol comprises dipentaerythritol. The dipentaerythritol can play a certain role in crosslinking, so that the hydrolysis of substances such as ethylene glycol on the material is reduced, and the reduction of the mechanical property of the material caused by the rapid reduction of the molecular weight of the material is prevented.
Preferably, a 4mm test bar of the automobile water chamber material is soaked in a 135 ℃ glycol freezing liquid for 300 hours and then tested according to ISO527, wherein the 4mm test bar has a tensile strength of greater than or equal to 110MPa, and further preferably, the 4mm test bar has a tensile strength of greater than or equal to 110MPa and less than or equal to 250 MPa; 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 glycol soaking is as follows: the tensile strength ratio before glycol soaking is more than 65 percent.
Preferably, the halogen content of the automobile water fuel is less than 10 ppm.
Preferably, the thin-wall flow length of the automobile water chamber material is more than 50 mm; further preferably, the thin-wall flow length of the automobile water chamber material is more than 50mm and less than 100 mm.
Preferably, the automobile water chamber material is tested according to ISO180, and the impact strength of a cantilever beam notch is more than 10kj/m 2 (ii) a Preferably, the automobile water chamber material is tested according to ISO180, and the impact strength of a cantilever beam notch is more than 10kj/m 2 Less than 20kj/m 2 (ii) a More preferably, the automobile water chamber material is tested according to ISO180, and the impact strength of a cantilever beam notch is more than 10kj/m 2 15kj/m or less 2 。
The second aspect of the invention also provides an optional preparation method of the automobile water chamber material, which comprises the following steps: and melting and blending the first polyamide, the second polyamide and the polyol to prepare a melt, adding the fiber reinforcement material into the melt, mixing, extruding and cooling to prepare the automobile water chamber material.
Preferably, the temperature of the melt blending is 260-300 ℃; further preferably, the temperature of the melt blending 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-hexamethylene diamine 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 reaction temperature constant, maintaining the pressure, exhausting, reducing the pressure to normal pressure, starting vacuumizing after reacting for 0.3-0.7 hour under normal pressure, and discharging after keeping the negative pressure of-0.05-0.5 MPa for 0.5-1.5 hours to prepare the first polyamide; further preferably, the preparation method of the first polyamide comprises the following steps: adding terephthalic acid-hexamethylene diamine 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 reaction temperature at a constant temperature for 1.5-2.5 hours, maintaining the pressure and exhausting for 2.5-3.5 hours under 1.5-2.5MPa, reducing the pressure to the normal pressure under 0.5-1.5MPa per hour, reacting for 0.3-0.7 hour under the normal pressure, starting vacuumizing, keeping the negative pressure of-0.05-0.5 MPa for 0.5-1.5 hours, and then discharging to obtain the first polyamide.
Preferably, the preparation method of the second polyamide comprises the following steps: adding terephthalic acid-hexamethylene diamine 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 reaction temperature constant, maintaining the pressure, exhausting, reducing the pressure to normal pressure, and discharging to obtain second polyamide; further preferably, the preparation method of the second polyamide comprises the following steps: adding terephthalic acid-hexamethylene diamine 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 reaction temperature constant for 1.5-2.5 hours, maintaining the pressure and exhausting for 2.5-3.5 hours under 1.5-2.5MPa, reducing the pressure to normal pressure at 0.5-1.5MPa per hour, and then discharging to obtain the second polyamide.
Preferably, the preparation method of the terephthalic acid-hexamethylene diamine salt comprises the following steps: mixing terephthalic acid and water, pulping, heating to 35 ℃, then uniformly adding molten hexamethylene diamine 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; and after the reaction is finished, cooling to 20-27 ℃, and centrifugally separating and vacuum drying the separated crystal for 24h to obtain the terephthalic acid-hexamethylene diamine salt.
Preferably, the apparatus used in the preparation method is a twin-screw extruder, the screw speed of the twin-screw extruder is 250-350rpm, and the throughput is 100-150 kg/h; further preferably, the screw rotation speed of the twin-screw extruder is 290-310rpm, and the throughput is 110-130 kg/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 one of the automobile water chamber materials in preparing automobiles.
Compared with the prior art, the invention has the following beneficial effects:
the fluidity of the polyamide with lower viscosity before forming is improved, 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 reactions, and the polyamide with the aromatic ring macromolecular structure is matched with each other with different viscosities, so that the alcoholysis resistance of the prepared automobile water material can be further improved, and the same effect can be achieved in performance even though no polyamine hydrolysis resistant agent and alkali metal halide are added. A4 mm test rod of the prepared automobile water chamber material is soaked in a 135 ℃ glycol freezing solution for 300 hours and then is tested according to ISO527, wherein the 4mm test rod has the tensile strength of more than or equal to 110MPa and the tensile strength after glycol soaking: the ratio of the tensile strength before the ethylene glycol soaking is more 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 are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
Twin screw extruder, CTE 50, available from Coperion; glass fiber, ECS301 HP, available from mazaqing composites gmbh; LCP fibers from Dezhongtai engineering plastics science and technology, Jiangmen; PANT D5000, available from DEM-GOT engineering plastics science and technology, Inc., Jiangmen.
Examples 1 to 5 and comparative examples 1 to 5
Automobile water chamber material and preparation method thereof
Preparation of hexamethylenediamine terephthalate salt: 30 parts of terephthalic acid and 100 parts of water are mixed and beaten, the temperature is raised to 35 ℃, and then the hexamethylenediamine in a molten state is uniformly added 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. Uniformly cooling to 25 ℃, centrifugally separating precipitated crystals, and then drying in vacuum at 80 ℃ for 24 hours to obtain the terephthalic acid-hexamethylene diamine salt (6T salt for short).
Preparation of the first polyamide: 70kg of terephthalic acid-hexamethylene diamine 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 high-pressure kettle with a mechanical stirring and vacuumizing device, the temperature is uniformly raised to 220 ℃ within 2 hours, the temperature is kept constant at 220 ℃ for 2 hours, then pressure is maintained and the exhaust is carried out for 3 hours under 2MPa, the pressure is reduced to normal pressure per hour under 1MPa, the vacuum pumping is started after the reaction is carried out for half an hour under normal pressure, and the first polyamide is obtained by discharging after the negative pressure is maintained for 1 hour under-0.1 MPa. The first polyamide was tested to have a melting point of 275 ℃, reduced viscosity: 1.2 dl/g.
Preparation of the second polyamide: 60kg of terephthalic acid-hexamethylene diamine 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 high-pressure kettle with a mechanical stirring and vacuumizing device, the temperature is uniformly raised to 220 ℃ within 2 hours, the temperature is kept at 220 ℃ for 2 hours, then the pressure is maintained and the air is exhausted for 3 hours under 2MPa, the pressure is reduced to the normal pressure per hour under 1MPa, and then the materials are discharged to prepare the second polyamide. The second polyamide melting point was tested to be 235 ℃, reduced viscosity: 0.45 dl/g.
Preparing a water chamber material of the automobile: preparing a compound by melt blending a first polyamide, a second polyamide, a polyol or other polyamide (PA66, PA6, PANT D5000) in a 50mm twin screw extruder, adding a fibrous reinforcement to the melt by means of a screw side feeder, operating at 280 ℃, with a screw speed of 300rpm, throughput of 120 kg/h; the compounded mixture was extruded in lace or strand form and cooled in a water bath, then chopped into granules 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 to 5 and comparative examples 1 to 5
PA66 is PA66 engineering plastic (Polyamide 66); PA6 is Nylon 6(Polyamide 6); PANT D5000 is PA6T/66, melting point 310 ℃, reduced viscosity 1 dl/g.
And (3) testing the performance of the automobile water chamber material: the prepared examples 1 to 5 and comparative examples 1 to 5 were subjected to performance tests for judging the thin wall flow length, the notch impact strength, the tensile strength after glycol immersion, the halogen content and the surface appearance, respectively, and the corresponding performance test results of the examples 1 to 5 and comparative examples 1 to 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 the ethylene glycol soaking is as follows: 4mm test bars were prepared from the polyamide composition and tested according to ISO527 after immersion in 135 ℃ glycol chilled liquid for 300 hours. The tensile strength/tensile strength after glycol soaking is also the tensile strength after glycol soaking: ratio of tensile strength before glycol soaking.
TABLE 2 results of corresponding Performance test of examples 1 to 5 and comparative examples 1 to 5
The fluidity of the polyamide with lower viscosity before material forming is improved, 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 reactions, and the polyamide with the aromatic ring macromolecular structure is matched with each other with different viscosities, so that the alcoholysis resistance of the prepared automobile water material can be further improved, and the same effect can be achieved in performance even though no polyamine hydrolysis resistant agent and alkali metal halide are added. A4 mm test rod of the prepared automobile water chamber material is soaked in a 135 ℃ glycol freezing solution for 300 hours and then is tested according to ISO527, wherein the 4mm test rod has the tensile strength of more than or equal to 110MPa and the tensile strength after glycol soaking: the ratio of the tensile strength before glycol soaking is more than 0.65.
The dipentaerythritol can play a certain role in crosslinking, so that the hydrolysis of substances such as ethylene glycol on the material is reduced, and the reduction of the mechanical property of the material caused by the rapid reduction of the molecular weight of the material is prevented.
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, 55kg of hexamethylenediamine terephthalate and 45kg of caprolactam were added in order to modify the reduced viscosity of the second polyamide.
The second polyamide has a melting point of 245 ℃, reduced viscosity: 0.28 dl/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 glycol soaking is 95MPa, the tensile strength/tensile strength after glycol soaking is 0.56, the halogen content is 0ppm, and the surface is good.
In addition, when the second polyamide accounts for more than 5 wt/% of the automobile water fuel, the initial mechanical strength of the automobile water fuel, that is, the tensile strength in table 2, is decreased.
Claims (10)
1. The automobile water chamber material is characterized in that raw materials for preparing the automobile water chamber material comprise first polyamide, second polyamide, fiber reinforcement and polyhydric alcohol; the first polyamide and the second polyamide are copolymers of terephthalic acid, hexamethylene diamine 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 ℃.
2. The automobile water chamber material according to claim 1, wherein the raw materials of 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 and 0.1-5 parts of polyol.
3. The automobile water chamber material according to claim 1, wherein raw materials for preparing the first polyamide comprise, by weight, 65-75 parts of hexamethylenediamine terephthalate, 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 hexamethylene diamine terephthalate, 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.
4. The automotive water chamber material of claim 1, wherein the fiber reinforcement comprises at least one of glass fibers, carbon fibers, aramid fibers, LCP fibers, and basalt fibers.
5. The automotive water compartment charge of claim 1, wherein the polyol comprises at least one of pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, trimethylolpropane, ditrimethylolpropane.
6. The method for preparing the water tank material of the automobile as claimed in any one of claims 1 to 5, wherein the method for preparing the water tank material of the automobile comprises the following steps: and melting and blending the first polyamide, the second polyamide and the polyol to prepare a melt, adding the fiber reinforcement material into the melt, mixing, extruding and cooling to prepare the automobile water chamber material.
7. The method according to claim 6, wherein the first polyamide is prepared by: adding terephthalic acid-hexamethylene diamine 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 reaction temperature constant, maintaining the pressure, exhausting, reducing the pressure to normal pressure, starting vacuumizing after reacting for 0.3-0.7 hour under normal pressure, and discharging after keeping the negative pressure of-0.05-0.5 MPa for 0.5-1.5 hours to prepare the first polyamide.
8. The method of claim 6, wherein the second polyamide is prepared by: adding terephthalic acid-hexamethylene diamine 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 reaction temperature constant, maintaining the pressure, exhausting, reducing the pressure to normal pressure, and discharging to obtain the second polyamide.
9. The preparation method according to claim 6, wherein the apparatus used in the preparation method is a twin-screw extruder, the screw rotation speed of the twin-screw extruder is 250-350rpm, and the throughput is 100-150 kg/h.
10. Use of the automotive water chamber charge of any one of claims 1-5 in the manufacture 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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| CN102827471A (en) * | 2011-06-17 | 2012-12-19 | Ems专利股份公司 | Semiaromatic moulding masses and their applications |
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