CN116694069A - High-heat-resistance nylon sealing ring and preparation method thereof - Google Patents
High-heat-resistance nylon sealing ring and preparation method thereof Download PDFInfo
- Publication number
- CN116694069A CN116694069A CN202310578987.4A CN202310578987A CN116694069A CN 116694069 A CN116694069 A CN 116694069A CN 202310578987 A CN202310578987 A CN 202310578987A CN 116694069 A CN116694069 A CN 116694069A
- Authority
- CN
- China
- Prior art keywords
- mixture
- nylon
- sealing ring
- silane coupling
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004677 Nylon Substances 0.000 title claims abstract description 104
- 229920001778 nylon Polymers 0.000 title claims abstract description 104
- 238000007789 sealing Methods 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 73
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 43
- 239000003063 flame retardant Substances 0.000 claims abstract description 27
- 150000004756 silanes Chemical class 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 239000000945 filler Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 6
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 claims description 31
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 31
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical group CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 claims description 27
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 26
- 125000005462 imide group Chemical group 0.000 claims description 17
- 229910019142 PO4 Inorganic materials 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 13
- 239000010452 phosphate Substances 0.000 claims description 13
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 claims description 11
- 125000004122 cyclic group Chemical group 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 229910052582 BN Inorganic materials 0.000 claims description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims 1
- 238000005303 weighing Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical group CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- -1 i.e. Polymers 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 208000013883 Blast injury Diseases 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
- C08K5/5455—Silicon-containing compounds containing nitrogen containing at least one group
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- 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
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
The application relates to the technical field of nylon battery sealing rings, and particularly discloses a high-heat-resistance nylon sealing ring and a preparation method thereof. The nylon sealing ring with high heat resistance is prepared from the following raw materials: PA612, 4 '-diamino-2, 2' -dimethylbiphenyl, modified silane coupling agents, antioxidants, flame retardants, and fillers; the preparation method comprises the following steps: s1: adding PA612 and filler into a stirrer, and mixing to obtain a mixture A; s2: adding the rest raw materials into a stirrer to obtain a mixture B, adding the mixture A into the mixture B, and continuously stirring until the mixture is uniformly stirred to obtain a mixture C; s3: pouring the mixture C into a feed hopper, and heating to 278-285 ℃ for preheating; s4: and (3) extruding the mixture C preheated in the step (S3) from a machine head through a double screw, and cooling and granulating to obtain the high heat-resistant nylon sealing ring material. The nylon sealing ring with high heat resistance has the characteristic of high heat resistance.
Description
Technical Field
The application relates to the technical field of nylon battery sealing rings, in particular to a high-heat-resistance nylon sealing ring and a preparation method thereof.
Background
Nylon, i.e., polyamide resin, is excellent not only in various mechanical properties but also in chemical resistance, good self-lubricating property and flexibility, and thus is widely used in various fields such as various automobile parts, electric tool housings, electronic commerce equipment parts, sports goods, and the like. In the field of battery sealing rings, nylon is generally used as a battery sealing ring material.
In the related art, the nylon battery sealing ring is not ideal in heat resistance as a battery sealing ring material, and when the temperature is above 80 ℃, the intermolecular interval is increased due to the fact that the random thermal motion of the intramolecular motion units (chain segments) in the nylon battery sealing ring exceeds the intermolecular cohesion, so that the nylon battery sealing ring has poor heat resistance. In addition, because nylon battery sealing washer is very easy to cause the type change under the high temperature to influence the product and use, to the battery sealing washer that precision requirement is very high, if high temperature resistant is not good, just produce deformation easily, in case produce deformation, will cause battery weeping, thereby arouse the explosion injury of battery and life and property safety problem.
Therefore, the inventors considered that the nylon battery seal ring has a defect of poor high temperature resistance against the above related art.
Disclosure of Invention
In order to overcome the defect of poor high temperature resistance of the nylon battery sealing ring, the application provides a high heat-resistant nylon sealing ring and a preparation method thereof.
The application provides a high heat-resistant nylon sealing ring and a preparation method thereof, which adopts the following technical scheme:
in a first aspect, the application provides a nylon sealing ring with high heat resistance, which adopts the following technical scheme:
the nylon sealing ring with high heat resistance is prepared from the following raw materials in parts by weight:
by adopting the technical scheme, the 4,4 '-diamino-2, 2' -dimethylbiphenyl is an important high-performance material monomer, has the performance characteristics of easy bonding, low linear expansion coefficient, easy molding and the like, is mainly applied to preparing materials with extremely low dielectric constant, extremely low surface free energy, extremely high mechanical strength and extremely high wear resistance, and the 4,4 '-diamino-2, 2' -dimethylbiphenyl has a conjugated structure containing benzene rings, has good heat resistance, and can greatly improve the heat resistance, the stability and the oxidation resistance stability of the nylon battery sealing ring;
experiments show that the high temperature resistance and stability of the nylon battery sealing ring can be effectively improved by matching the 4,4 '-diamino-2, 2' -dimethylbiphenyl with the PA612, so that the prepared nylon battery sealing ring can be applied to automobile parts; the compounded nylon battery sealing ring has high temperature resistance; in addition, as the combustion condition can occur under the condition that the battery is abused, a flame retardant can be added into the nylon battery sealing ring to improve the flame retardant property of the nylon battery sealing ring and the potential safety hazard; the silane coupling agent is used for modifying the filler so as to increase the compatibility of the filler and the nylon PA612, and the filler adopted by the application can be used for improving the high temperature resistance of the nylon battery sealing ring and is matched with 4,4 '-diamino-2, 2' -dimethylbiphenyl to further increase the high temperature resistance of the nylon battery sealing ring, so that the prepared nylon battery sealing ring has high heat resistance and good flame retardant property at high temperature.
Preferably, the ratio of the mass parts of the 4,4 '-diamino-2, 2' -dimethylbiphenyl and the PA612 is 1 (2-2.5).
By adopting the technical scheme, when the mass part ratio of the 4,4 '-diamino-2, 2' -dimethylbiphenyl and the PA612 is 1 (2-2.5), the high temperature resistance of the nylon battery sealing ring is better, and if the mass part ratio of the 4,4 '-diamino-2, 2' -dimethylbiphenyl and the PA612 is less than 1:2, the heat resistance of the nylon battery sealing ring is reduced; therefore, the specific proportion of the 4,4 '-diamino-2, 2' -dimethylbiphenyl and the PA612 is adopted, and the two can be matched with each other, so that the high temperature resistance of the nylon battery sealing ring can be effectively improved.
Preferably, the high heat-resistant nylon sealing ring further comprises biphenyl tetracarboxylic dianhydride and biphenyl tetracarboxylic dianhydride, and the mass part ratio of the biphenyl tetracarboxylic dianhydride to the biphenyl tetracarboxylic dianhydride is 3: (4-7).
By adopting the technical scheme, the biphenyl tetracarboxylic dianhydride is firstly introduced into the PA612 system, so that the regularity of a macromolecular chain can be structurally destroyed, the tensile property of a nylon battery sealing ring can be improved to a certain extent, and the heat resistance of the nylon battery sealing ring can be maintained; in addition, the biphenyl tetracarboxylic dianhydride can endow more rigid structures to the PA612, and the benzene ring density is high, so that the nylon battery sealing ring has a stable chemical structure and high heat resistance;
in addition, the addition of the biphenyl tetracarboxylic dianhydride can effectively improve ordered stacking of molecular chains in the PA612, is favorable for improving mechanical properties of the nylon battery sealing ring, can increase ordered continuous repeated intervals of molecules and enable the molecules to be stacked more tightly, enables the ordered degree of the molecular chains of the nylon battery sealing ring to be higher, and further improves the tensile strength of the nylon battery sealing ring; the mechanical property of the nylon battery sealing ring at high temperature can be maintained, and the influence of high temperature on the mechanical property of the nylon battery sealing ring is reduced; in the application, the biphenyl tetracarboxylic dianhydride and the biphenyl tetracarboxylic dianhydride are matched with each other in a specific proportion, which is beneficial to improving the tensile strength and the initial modulus of the nylon battery sealing ring at high temperature.
Preferably, the modified silane coupling agent is a silane coupling agent containing an imide ring.
Preferably, the preparation method of the modified silane coupling agent comprises the following steps:
adding phthalic anhydride and glacial acetic acid into a reactor, dissolving, adding allylamine, and then heating for reflux reaction to obtain a preparation;
adding the preparation and benzene into a reactor, replacing by argon, adding triethoxysilane, heating to react, and evaporating solvent to obtain the silane coupling agent containing imide ring.
By adopting the technical scheme, when the addition amount of the 4,4 '-diamino-2, 2' -dimethylbiphenyl is gradually increased, the bond length of the ortho-position C-N bond is increased due to the action of the lateral methyl in the molecular structure, the bond energy is weakened, and the bond energy is easier to decompose at high temperature, so that the thermal stability performance tends to be poor. However, due to the existence of the special imide ring in the molecular chain of the modified silane coupling agent, the trend of poor thermal stability of the modified silane coupling agent is reduced, so that the silane coupling agent containing the imide ring can effectively improve the heat resistance of the nylon battery sealing ring;
experiments show that the modified silane coupling agent can generate polycondensation between silanes at a lower temperature to form a three-dimensional network structure of siloxane bonds; the imide ring can be pyrolyzed only at the high temperature of more than 500 ℃, so that the modified silane coupling agent is ensured to have good application performance at the high temperature, and has good high temperature resistance and thermo-oxidative stability.
Preferably, the flame retardant comprises a combination of one or more of DDP and a phosphaphenanthrene-based cyclic phosphate.
By adopting the technical scheme, the nylon battery sealing ring is used at high temperature, so that the selected flame retardant also needs to be selected as a high-temperature-resistant flame retardant; the flame retardant adopted by the application is DDP, which has larger steric hindrance and good high temperature resistance; the phosphaphenanthrene cyclic phosphate is an organic phosphorus heterocyclic compound, has good high temperature resistance, has phosphorus-carbon bonds, and has better flame retardant property than general phosphate; the flame retardant selected by the application has high phosphorus content, certain oxidation resistance and good high temperature resistance, and can be used in a high-temperature environment.
Preferably, the filler comprises a combination of one or more of silicon carbide, boron nitride and silicon dioxide.
By adopting the technical scheme, materials such as silicon carbide, boron nitride and silicon dioxide have good high temperature resistance, the compatibility of the materials with PA612 is improved by the silane coupling agent, and the strength, the high temperature resistance and the thermal stability of the nylon battery sealing ring are effectively improved.
Preferably, the antioxidant is a combination of one or more of antioxidant 168 and antioxidant 1010.
In a second aspect, the application provides a preparation method of a nylon sealing ring with high heat resistance, which adopts the following technical scheme:
a preparation method of a nylon sealing ring with high heat resistance comprises the following steps:
s1: adding PA612 and 4,4 '-diamino-2, 2' -dimethylbiphenyl into a stirrer for mixing, and stirring until the mixture is uniformly mixed to obtain a mixture A;
s2: mixing a modified silane coupling agent, an antioxidant, a filler and a flame retardant in a stirrer, stirring until the mixture is uniformly mixed to obtain a mixture B, adding the mixture A into the mixture B, and continuously stirring until the mixture is uniformly mixed to obtain a mixture C;
s3: pouring the mixture C into a feed hopper, and heating to 278-285 ℃ for preheating;
s4: and (3) extruding the mixture C preheated in the step (S3) from a machine head through a double screw, and cooling and granulating to obtain the high heat-resistant nylon sealing ring material.
Preferably, in step S2, biphenyl tetracarboxylic dianhydride and biphenyl tetracarboxylic dianhydride are also added.
By adopting the technical scheme, the nylon battery sealing ring prepared by the method has higher mechanical strength and high heat resistance, so that the nylon battery sealing ring also has good mechanical properties at high temperature.
In summary, the application has the following beneficial effects:
1. the 4,4 '-diamino-2, 2' -dimethylbiphenyl is matched with the PA612, so that the high temperature resistance and the stability of the nylon battery sealing ring can be effectively improved, and the prepared nylon battery sealing ring can be applied to automobile parts; the compounded nylon battery sealing ring has high temperature resistance.
2. The specific proportion of the 4,4 '-diamino-2, 2' -dimethylbiphenyl and the PA612 is adopted, the two components can be matched with each other, and the high temperature resistance of the PA612 nylon battery sealing ring can be effectively improved.
3. The addition of the biphenyl tetracarboxylic dianhydride can effectively improve ordered stacking of molecular chains in the PA612, is beneficial to improving the mechanical property of the nylon battery sealing ring, and further improves the tensile strength of the nylon battery sealing ring; and the mechanical property of the nylon battery sealing ring at high temperature can be maintained, and the influence of high temperature on the mechanical property of the nylon battery sealing ring is reduced.
4. The existence of the specific imide ring in the molecular chain of the modified silane coupling agent reduces the trend of poor thermal stability, so that the silane coupling agent containing the imide ring can effectively improve the heat resistance of the nylon battery sealing ring.
Detailed Description
The present application will be described in further detail with reference to examples. The specific description is as follows: the following examples, in which the specific conditions are not specified, are conducted under conventional conditions or conditions recommended by the manufacturer, and the raw materials used in the following examples are commercially available from ordinary sources except for the specific descriptions.
Preparation example
Preparation example 1
The preparation method of the modified silane coupling agent comprises the following steps:
adding 0.1mol of phthalic anhydride and 200ml of glacial acetic acid into a three-port bottle, stirring and dissolving, adding 0.1mol of allylamine, reacting for 1h at room temperature, heating and refluxing for 4h, then cooling to room temperature, adding 200ml of water into the three-port bottle, cooling, precipitating white solid, and carrying out suction filtration and water washing recrystallization to obtain a preparation;
weighing 0.05mol of the preparation and 100ml of benzene, adding into a three-mouth bottle, stirring for dissolution, replacing by argon, adding 0.05mol of triethoxysilane, heating to 70 ℃ for reaction for 5 hours, cooling to room temperature, evaporating the solvent to obtain a light yellow liquid for reaction, and passing through a column to obtain the silane coupling agent containing imide rings.
Examples
Example 1
The embodiment discloses a preparation method of a high heat-resistant nylon sealing ring, which comprises the following steps:
s1: weighing 80 parts of PA612 and 40 parts of 4,4 '-diamino-2, 2' -dimethylbiphenyl according to parts by weight, adding into a stirrer for mixing, stirring for 30min at a rotating speed of 180r/min until the raw materials are uniformly mixed, and taking out to obtain a mixture A; s2: weighing 1.3 parts by weight of modified silane coupling agent, 1.0 part by weight of antioxidant 168, 6 parts by weight of filler silicon carbide and 6 parts by weight of flame retardant DDP, mixing in a stirrer, stirring for 2 hours at a rotating speed of 160r/min until the raw materials are uniformly mixed to obtain a mixture B, then adding the mixture A in the step S1 into the mixture B, and continuing stirring for 2 hours at a rotating speed of 200r/min until the mixture A and the mixture B are uniformly mixed to obtain a mixture C;
s3: introducing the mixture C in the step S2 into a feed hopper, and heating to 278 ℃ for preheating;
s4: extruding the mixture C preheated in the step S3 from a machine head through a double screw, setting the rotating speed of the screw to 160r/min, and cooling and granulating through a water tank to obtain the nylon sealing ring material with high heat resistance.
Wherein the modified silane coupling agent is the silane coupling agent containing imide ring prepared in preparation example 1.
Example 2
The embodiment discloses a preparation method of a high heat-resistant nylon sealing ring, which comprises the following steps:
s1: weighing 90 parts of PA612 and 45 parts of 4,4 '-diamino-2, 2' -dimethylbiphenyl according to parts by weight, adding into a stirrer for mixing, stirring for 60min at a rotating speed of 200r/min until the raw materials are uniformly mixed, and taking out to obtain a mixture A; s2: weighing 1.0 part of modified silane coupling agent, 0.9 part of antioxidant 1010, 5 parts of filler boron nitride and 4 parts of flame retardant phosphaphenanthrene cyclic phosphate, mixing in a stirrer, stirring for 2.5 hours at a rotating speed of 180r/min until the raw materials are uniformly mixed to obtain a mixture B, then adding the mixture A in the step S1 into the mixture B, and continuously stirring for 2.5 hours at a rotating speed of 200r/min until the mixture A and the mixture B are uniformly mixed to obtain a mixture C;
s3: introducing the mixture C in the step S2 into a feed hopper, and heating to 280 ℃ for preheating;
s4: extruding the mixture C preheated in the step S3 from a machine head through double screws, setting the rotating speed of the screws to be 180r/min, and cooling and granulating through a water tank to obtain the nylon sealing ring material with high heat resistance.
Wherein the modified silane coupling agent is the silane coupling agent containing imide ring prepared in preparation example 1.
Example 3
The embodiment discloses a preparation method of a high heat-resistant nylon sealing ring, which comprises the following steps:
s1: weighing 100 parts of PA612 and 50 parts of 4,4 '-diamino-2, 2' -dimethylbiphenyl according to parts by weight, adding into a stirrer for mixing, stirring for 80min at a rotating speed of 220r/min until the raw materials are uniformly mixed, and taking out to obtain a mixture A; s2: weighing 0.8 part of modified silane coupling agent, 0.8 part of antioxidant 1010, 4 parts of filler silicon dioxide and 2 parts of flame retardant phosphaphenanthrene cyclic phosphate, mixing in a stirrer, stirring for 3.0h at a rotating speed of 200r/min until the raw materials are uniformly mixed to obtain a mixture B, adding the mixture A in the step S1 into the mixture B, and continuously stirring for 3.0h at a rotating speed of 200r/min until the mixture A and the mixture B are uniformly mixed to obtain a mixture C;
s3: introducing the mixture C in the step S2 into a feed hopper, and heating to 285 ℃ for preheating;
s4: extruding the mixture C preheated in the step S3 from a machine head through double screws, setting the rotating speed of the screws to be 200r/min, and cooling and granulating through a water tank to obtain the nylon sealing ring material with high heat resistance.
Wherein the modified silane coupling agent is the silane coupling agent containing imide ring prepared in preparation example 1.
Example 4
The embodiment discloses a preparation method of a high heat-resistant nylon sealing ring, which comprises the following steps:
s1: weighing 100 parts of PA612 and 40 parts of 4,4 '-diamino-2, 2' -dimethylbiphenyl according to parts by weight, adding into a stirrer for mixing, stirring for 60min at a rotating speed of 200r/min until the raw materials are uniformly mixed, and taking out to obtain a mixture A; s2: weighing 1.0 part of modified silane coupling agent, 0.9 part of antioxidant 1010, 5 parts of filler antioxidant 1010 and 4 parts of flame retardant phosphaphenanthrene cyclic phosphate, mixing in a stirrer, stirring for 2.5 hours at a rotating speed of 180r/min until the raw materials are uniformly mixed to obtain a mixture B, then adding the mixture A in the step S1 into the mixture B, and continuously stirring for 2.5 hours at a rotating speed of 200r/min until the mixture A and the mixture B are uniformly mixed to obtain a mixture C;
s3: introducing the mixture C in the step S2 into a feed hopper, and heating to 280 ℃ for preheating;
s4: extruding the mixture C preheated in the step S3 from a machine head through double screws, setting the rotating speed of the screws to be 180r/min, and cooling and granulating through a water tank to obtain the nylon sealing ring material with high heat resistance.
Wherein the modified silane coupling agent is the silane coupling agent containing imide ring prepared in preparation example 1.
Example 5
The embodiment discloses a preparation method of a high heat-resistant nylon sealing ring, which comprises the following steps:
s1: weighing 80 parts of PA612 and 50 parts of 4,4 '-diamino-2, 2' -dimethylbiphenyl according to parts by weight, adding into a stirrer for mixing, stirring for 60min at a rotating speed of 200r/min until the raw materials are uniformly mixed, and taking out to obtain a mixture A; s2: weighing 1.0 part of modified silane coupling agent, 0.9 part of antioxidant 1010, 5 parts of filler antioxidant 1010 and 4 parts of flame retardant phosphaphenanthrene cyclic phosphate, mixing in a stirrer, stirring for 2.5 hours at a rotating speed of 180r/min until the raw materials are uniformly mixed to obtain a mixture B, then adding the mixture A in the step S1 into the mixture B, and continuously stirring for 2.5 hours at a rotating speed of 200r/min until the mixture A and the mixture B are uniformly mixed to obtain a mixture C;
s3: introducing the mixture C in the step S2 into a feed hopper, and heating to 280 ℃ for preheating;
s4: extruding the mixture C preheated in the step S3 from a machine head through double screws, setting the rotating speed of the screws to be 180r/min, and cooling and granulating through a water tank to obtain the nylon sealing ring material with high heat resistance.
Wherein the modified silane coupling agent is the silane coupling agent containing imide ring prepared in preparation example 1.
Example 6
This example differs from example 2 in that 6 parts by weight of biphenyl tetracarboxylic dianhydride and 8 parts by weight of biphenyl tetracarboxylic dianhydride are further added to step S2.
Example 7
This example differs from example 2 in that 6 parts by weight of biphenyl tetracarboxylic dianhydride and 10 parts by weight of biphenyl tetracarboxylic dianhydride are further added to step S2.
Example 8
This example differs from example 2 in that 6 parts by weight of biphenyl tetracarboxylic dianhydride and 14 parts by weight of biphenyl tetracarboxylic dianhydride are further added to step S2.
Comparative example
Comparative example 1
The difference from example 2 is that the modified silane coupling agent is replaced with an equivalent amount of the general silane coupling agent.
Comparative example 2
The difference from example 2 is that the phosphaphenanthrene cyclic phosphate flame retardant is replaced with an equivalent amount of a silicon-based flame retardant.
Table 1: component proportion table of high heat-resistant nylon seal ring in examples 1-8
Performance test the following performance tests were performed on the highly heat-resistant nylon seal rings prepared in examples 1 to 8 and comparative examples 1 to 2, and specific test data are shown in table 2:
according to the standard test method of tensile properties of ASTM-D638 plastics, the tensile strength (MPa) of the prepared nylon battery sealing ring is respectively detected, and the higher the tensile strength is, the better the mechanical strength of the nylon battery sealing ring is.
And (3) respectively detecting the notch impact strength test of the prepared nylon battery sealing ring according to the GB/T1043.1-2008 determination of impact properties of the plastic simply supported beam.
And (3) testing the thermal deformation temperature of the prepared nylon battery sealing ring according to the GB/T1634.1-2004 plastic load deformation temperature measurement.
Vertical combustion experiment: according to UL94 standard requirements, the UL94 test is a UL94 burn test prescribed by Underwriters Laboratories by placing it in a thermostatic chamber at 23 ℃ and 50% relative humidity for 48 hours using a spline (125mm X13mm X1.6mmm) for flame retardancy evaluation; the flame retardant test and evaluation results are (flame retardant rating increasing from HB scale to V-0 scale).
Table 2: test data for highly heat-resistant nylon seal rings prepared in examples 1 to 8 and comparative examples 1 to 2
As can be seen by combining examples 1-8 and combining Table 2, the nylon battery sealing ring prepared by the application has good heat resistance, and in addition, the prepared nylon battery sealing ring ensures good heat resistance, and simultaneously improves other mechanical properties, tensile strength, notch impact strength and flame retardance.
As can be seen from example 2 in Table 2 in combination with comparative examples 1 to 2, the conventional silane coupling agent was used in comparative example 1, and the heat-resistant temperature in comparative example 1 was 228℃as compared with that in example 2, since the silane coupling agent did not contain an imide ring. The reason is that when the addition amount of 4,4 '-diamino-2, 2' -dimethylbiphenyl is gradually increased, that is, when 4,4 '-diamino-2, 2' -dimethylbiphenyl and PA612 are beyond a certain proportion, the effect of the side methyl groups in the 4,4 '-diamino-2, 2' -dimethylbiphenyl molecule causes the bond length of the ortho-position c—n bond thereof to be increased, the bond energy thereof is weakened, and decomposition is more easy at high temperature, so there is a tendency that the thermal stability performance is deteriorated; the modified silane coupling agent added in the embodiment 2 contains an imide ring, so that the condition of poor thermal stability caused by 4,4 '-diamino-2, 2' -dimethylbiphenyl can be reduced, and the prepared nylon battery sealing ring has higher heat-resistant temperature.
The flame retardant added in comparative example 2 is a silicon-based flame retardant, which can impart flame retardant properties to the nylon battery seal ring, but compared with a phosphaphenanthrene-based cyclic phosphate, the phosphaphenanthrene-based cyclic phosphate has a phosphorus-carbon bond, the flame retardant properties are better than those of general phosphate, and the phosphaphenanthrene-based cyclic phosphate is an organic phosphorus-based heterocyclic compound, and has good high temperature resistance.
As can be seen from examples 1 to 4 in Table 2 in combination with example 5, in example 5, the addition ratio of 4,4 '-diamino-2, 2' -dimethylbiphenyl to PA612 was 1:1.6, and the content of 4,4 '-diamino-2, 2' -dimethylbiphenyl was large, the bond length of the C-N bond in the molecule was increased, the bond energy was decreased, the decomposition was more likely at high temperature, and the heat resistance temperature was decreased; the addition ratio of the 4,4 '-diamino-2, 2' -dimethylbiphenyl and the PA612 adopted in the examples 1-4 is 1 (2-2.5), and the prepared nylon battery sealing ring has good heat resistance and thermal stability under the specific ratio.
As can be seen from example 2 in Table 2 in combination with examples 6 to 8, biphenyl tetracarboxylic dianhydride and biphenyl tetracarboxylic dianhydride were added in examples 6 to 8, and the mass part ratio of biphenyl tetracarboxylic dianhydride and biphenyl tetracarboxylic dianhydride was 3: (4-7) the tensile strength and heat-resistant temperature of examples 6-8 were improved; in addition, as the biphenyl tetracarboxylic dianhydride can endow more rigid structures to the PA612, the benzene ring density is high, so that the nylon battery sealing ring has stable chemical structure and high heat resistance; and when the mass portion ratio of the biphenyl tetracarboxylic dianhydride to the biphenyl tetracarboxylic dianhydride is 3: and 7, the heat resistance of the nylon battery sealing ring prepared at the moment is better.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (10)
1. A nylon sealing ring with high heat resistance is characterized in that: the composite material is prepared from the following raw materials in parts by weight:
80-100 parts of PA612
40-50 parts of 4,4 '-diamino-2, 2' -dimethylbiphenyl
0.8-1.3 parts of modified silane coupling agent
Antioxidant 0.8-1.0 parts
2-6 parts of flame retardant
4-6 parts of filler.
2. The nylon seal of claim 1, wherein the nylon seal is highly heat resistant: the mass part ratio of the 4,4 '-diamino-2, 2' -dimethylbiphenyl to the PA612 is 1 (2-2.5).
3. The nylon seal of claim 1, wherein the nylon seal is highly heat resistant: the nylon sealing ring with high heat resistance also comprises biphenyl tetracarboxylic dianhydride and biphenyl tetracarboxylic dianhydride, and the mass part ratio of the biphenyl tetracarboxylic dianhydride to the biphenyl tetracarboxylic dianhydride is 3: (4-7).
4. The nylon seal of claim 1, wherein the nylon seal is highly heat resistant: the modified silane coupling agent is a silane coupling agent containing an imide ring.
5. The nylon seal of claim 1, wherein the nylon seal is highly heat resistant: the preparation method of the modified silane coupling agent comprises the following steps:
adding phthalic anhydride and glacial acetic acid into a reactor, dissolving, adding allylamine, and then heating for reflux reaction to obtain a preparation;
adding the preparation and benzene into a reactor, replacing by argon, adding triethoxysilane, heating to react, and evaporating solvent to obtain the silane coupling agent containing imide ring.
6. The nylon seal of claim 1, wherein the nylon seal is highly heat resistant: the flame retardant comprises one or more combinations of DDP and phosphaphenanthrene cyclic phosphate.
7. The nylon seal of claim 1, wherein the nylon seal is highly heat resistant: the filler comprises a combination of one or more of silicon carbide, boron nitride, and silicon dioxide.
8. The nylon seal of claim 1, wherein the nylon seal is highly heat resistant: the antioxidant is a combination of one or more of antioxidant 168 and antioxidant 1010.
9. The method for preparing the nylon sealing ring with high heat resistance as claimed in any one of claims 1 to 8, comprising the following steps:
s1: adding PA612 and 4,4 '-diamino-2, 2' -dimethylbiphenyl into a stirrer for mixing, and stirring until the mixture is uniformly mixed to obtain a mixture A;
s2: mixing a modified silane coupling agent, an antioxidant, a filler and a flame retardant in a stirrer, stirring until the mixture is uniformly mixed to obtain a mixture B, adding the mixture A into the mixture B, and continuously stirring until the mixture is uniformly mixed to obtain a mixture C;
s3: pouring the mixture C into a feed hopper, and heating to 278-285 ℃ for preheating;
s4: and (3) extruding the mixture C preheated in the step (S3) from a machine head through a double screw, and cooling and granulating to obtain the high heat-resistant nylon sealing ring material.
10. The method for preparing the nylon sealing ring with high heat resistance according to claim 9, wherein the method comprises the following steps: in step S2, biphenyl tetracarboxylic dianhydride and biphenyl tetracarboxylic dianhydride are also added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310578987.4A CN116694069A (en) | 2023-05-22 | 2023-05-22 | High-heat-resistance nylon sealing ring and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310578987.4A CN116694069A (en) | 2023-05-22 | 2023-05-22 | High-heat-resistance nylon sealing ring and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116694069A true CN116694069A (en) | 2023-09-05 |
Family
ID=87823040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310578987.4A Pending CN116694069A (en) | 2023-05-22 | 2023-05-22 | High-heat-resistance nylon sealing ring and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116694069A (en) |
-
2023
- 2023-05-22 CN CN202310578987.4A patent/CN116694069A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kiskan et al. | Polybenzoxazine‐based composites as high‐performance materials | |
| KR101948213B1 (en) | Thermoplastic polyimide as flow promoter and flame retardant synergist for filled polyamide compositions | |
| CN109438976B (en) | Copolymerized nylon product and preparation method thereof | |
| CN111004501A (en) | Modified bio-based nylon 56 material and preparation method and application thereof | |
| CN101712793A (en) | Low temperature resistant environment-friendly inflaming retarding PC/PET alloy and method for preparing same | |
| CN114790330A (en) | Flame-retardant polyamide glass fiber composition and preparation method thereof | |
| WO1999027017A1 (en) | Thermoplastic resin composition | |
| JP2016176060A (en) | Polyamide resin composition and molded part obtained by molding the same | |
| Forchetti Casarino et al. | Synthesis and characterization of polybenzoxazine/silica‐based hybrid nanostructures for flame retardancy applications | |
| Jun et al. | Synergistic effect of a novel charring agent and ammonium polyphosphate on the flame retardancy of acrylonitrile butadiene styrene | |
| CN104559174A (en) | Preparation method of unenhanced halogen-free flame retardant nylon 66 | |
| CN116694069A (en) | High-heat-resistance nylon sealing ring and preparation method thereof | |
| KR102477271B1 (en) | Thermosetting resin composition with high toughness and flame retardant | |
| CN112979951B (en) | Flame retardant, flame-retardant transparent polycarbonate resin and preparation method thereof | |
| CN112852154A (en) | High-temperature-resistant easy-to-process thermoplastic transparent polyimide resin material with low thermal expansion coefficient and preparation method thereof | |
| JP2005200636A (en) | Flame-retardant polyamide resin composition | |
| CN113429782A (en) | Transparent polyamide resin and preparation method thereof | |
| EP0294195A2 (en) | Polyimide resin composition | |
| KR101781509B1 (en) | Polyamide based polymer compositions comprising hyperbranched polymer having enhanced flowability and preparation method thereof | |
| CN103910993A (en) | Flame Retardant Polyamide Resin Composition And Molded Article Comprising The Same | |
| CN114106527B (en) | Anti-dripping halogen-free flame-retardant PBT-based composite material and preparation method thereof | |
| JP7136394B1 (en) | Polyarylene sulfide resin composition, molded article and method for producing the same | |
| CN114539731B (en) | Flame-retardant material and preparation method thereof | |
| JP2017082203A (en) | Plastic fastener composed of polyamide resin composition | |
| KR101600618B1 (en) | Eco-environmental flame retardant polyamide resin composition comprising clay |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |