CN117447825A - High-strength high-toughness plastic buckle for automobile safety belt - Google Patents
High-strength high-toughness plastic buckle for automobile safety belt Download PDFInfo
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- CN117447825A CN117447825A CN202311575712.1A CN202311575712A CN117447825A CN 117447825 A CN117447825 A CN 117447825A CN 202311575712 A CN202311575712 A CN 202311575712A CN 117447825 A CN117447825 A CN 117447825A
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- 239000004033 plastic Substances 0.000 title claims abstract description 52
- 239000000835 fiber Substances 0.000 claims abstract description 89
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical class N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000000463 material Substances 0.000 claims abstract description 23
- 239000012745 toughening agent Substances 0.000 claims abstract description 22
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 17
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 17
- 239000000314 lubricant Substances 0.000 claims abstract description 17
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 17
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 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 abstract description 14
- 239000003063 flame retardant Substances 0.000 claims abstract description 14
- YAAQEISEHDUIFO-UHFFFAOYSA-N C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 Chemical compound C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 YAAQEISEHDUIFO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920002877 acrylic styrene acrylonitrile Polymers 0.000 claims abstract description 12
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 39
- 239000011259 mixed solution Substances 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 37
- 238000010438 heat treatment Methods 0.000 claims description 25
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 24
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000004321 preservation Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- 238000005303 weighing Methods 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 241000790917 Dioxys <bee> Species 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 238000006011 modification reaction Methods 0.000 claims description 12
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 230000005484 gravity Effects 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 9
- 229920000877 Melamine resin Polymers 0.000 claims description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 5
- 238000001746 injection moulding Methods 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
- 229920000388 Polyphosphate Polymers 0.000 claims description 3
- 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 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001205 polyphosphate Substances 0.000 claims description 3
- 235000011176 polyphosphates Nutrition 0.000 claims description 3
- 238000005576 amination reaction Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 3
- 229920000515 polycarbonate Polymers 0.000 abstract description 2
- 239000004417 polycarbonate Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- OYWRDHBGMCXGFY-UHFFFAOYSA-N 1,2,3-triazinane Chemical compound C1CNNNC1 OYWRDHBGMCXGFY-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009661 fatigue test Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000012360 testing method 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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention relates to a high-strength high-toughness automobile safety belt plastic buckle, which comprises the following material components in parts by weight: 50-80 parts of polycarbonate resin, 12-24 parts of acrylonitrile-styrene-acrylate copolymer, 5-10 parts of modified silicon nitride fiber, 3-8 parts of flame retardant, 3-6 parts of toughening agent, 1-3 parts of lubricant, 0.1-0.4 part of anti-dripping agent and 0.5-1 part of antioxidant. The invention prepares the plastic buckle for the automobile safety belt, adopts the composite modified material of the polycarbonate, and has the advantages of high strength, high toughness, high thermal stability, high wear resistance and the like.
Description
Technical Field
The invention relates to the field of automobile accessories, in particular to a high-strength high-toughness plastic buckle for an automobile safety belt.
Background
The automobile safety belt limiting buckle is a buckle structure which is arranged on an automobile safety belt and is used for adjusting and positioning, and is usually made of plastic, the automobile safety belt is a necessary safety guarantee measure when people take an automobile, and when people with different body types use the safety belt, the length of the safety belt needs to be properly adjusted, if the safety belt is too tight, the riding is uncomfortable, and if the safety belt is too loose, the safety protection effect cannot be achieved; the safety belt can be adjusted and limited to a proper length by utilizing the limit buckle of the automobile safety belt.
For more convenient use and enhanced hand feeling experience, most of existing automobile safety belt buckles adopt some high-strength plastic products, but due to the fact that the use frequency of the automobile safety belt buckles is high, many of the existing plastic products cannot fully meet requirements, such as breakage caused by insufficient strength or insufficient toughness, permanent deformation is easily generated due to creep after long-time use, normal assembly of the buckle is not caused, and the use experience of people is greatly reduced under the conditions, and large potential safety hazards are caused. Therefore, there is a need in the automotive market for an automotive safety belt plastic buckle with high strength, strong toughness, good corrosion resistance, good creep resistance, and good heat resistance to improve the safety of the automotive safety belt.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a high-strength high-toughness plastic buckle for an automobile safety belt.
The aim of the invention is realized by adopting the following technical scheme:
the high-strength high-toughness plastic buckle for the automobile safety belt comprises the following material components in parts by weight:
50-80 parts of polycarbonate resin, 12-24 parts of acrylonitrile-styrene-acrylate copolymer, 5-10 parts of modified silicon nitride fiber, 3-8 parts of flame retardant, 3-6 parts of toughening agent, 1-3 parts of lubricant, 0.1-0.4 part of anti-dripping agent and 0.5-1 part of antioxidant.
Preferably, the polycarbonate resin has a brand of Qimei PC-6600 and a specific gravity of 1.2g/cm 3 The melt index was 10g/10min (300 ℃ C., 1.2 kg).
Preferably, the acrylonitrile-styrene-acrylate copolymer is Qimei PW-978B with a specific gravity of 1.07g/cm 3 The melt index was 13g/10min (220 ℃,10 kg).
Preferably, the preparation method of the modified silicon nitride fiber comprises the following steps:
s1, surface treatment of silicon nitride fibers:
weighing silicon nitride fiber and 3-aminopropyl trimethoxy silane, mixing in deionized water, stirring at 70-80deg.C for 6-10h, removing liquid after treatment, washing with water for three times, and drying in an oven to obtain aminated silicon nitride fiber;
wherein the mass ratio of the silicon nitride fiber to the 3-aminopropyl trimethoxy silane to the deionized water is 1:0.1-0.4:10;
s2, synthesizing a prepolymerization modification reaction solution:
weighing trioxymethylene, dissolving in N-methylpyrrolidone, adding a small amount of deionized water, uniformly mixing, and stirring at 70-80 ℃ for half an hour to obtain a mixed solution A;
wherein, the mass ratio of the trioxymethylene to the deionized water to the N-methyl pyrrolidone is 0.3-0.6:0.1-0.3:2-5;
mixing aminated silicon nitride fiber and 4,4' - (1, 4-benzene dioxy) diphenylamine in N-methyl pyrrolidone, and uniformly dispersing by ultrasonic at room temperature to obtain a mixed solution B;
wherein the mass ratio of the aminated silicon nitride fiber to the 4,4' - (1, 4-benzene dioxy) diphenylamine to the N-methyl pyrrolidone is 1:0.2-0.4:4-10;
heating the mixed solution B to 55-65 ℃, slowly adding the mixed solution A, finishing the addition within half an hour, and then continuously stirring and reacting for half an hour to obtain a prepolymerization modified reaction solution;
wherein the mass ratio of the mixed solution A to the mixed solution B is 1:1;
s3, synthesizing modified silicon nitride fibers:
and (3) placing the prepolymerization modification reaction liquid in an oven, heating to 100 ℃, carrying out heat preservation treatment for half an hour, heating to 180 ℃, carrying out heat preservation treatment for half an hour, heating to 220 ℃, carrying out heat preservation treatment for 1-2 hours, naturally cooling to normal temperature, washing with acetone for three times, and drying again to obtain the modified silicon nitride fiber.
Preferably, the length of the silicon nitride fiber is 10+ -2 mm, the diameter of the silicon nitride fiber is 5+ -1 μm, and the density of the silicon nitride fiber is 2.45g/cm 3 。
Preferably, the flame retardant is a nitrogen-based flame retardant, including one of Melamine Cyanurate (MCA), melamine polyphosphate (MPP), and Melamine (MA).
Preferably, the toughening agent is a silicon based toughening agent, including one of MR-502, M-577, M-722.
Preferably, the lubricant is at least one of ethylene bis-stearamide, calcium stearate, zinc stearate and polytetrafluoroethylene wax.
Preferably, the anti-dripping agent is polytetrafluoroethylene, and the molecular weight is 35-55 ten thousand.
Preferably, the antioxidant comprises one or more of antioxidant 1076, antioxidant 1010, antioxidant 168 in combination.
Preferably, the preparation method of the plastic buckle of the automobile safety belt comprises the following steps:
firstly, weighing polycarbonate resin, acrylonitrile-styrene-acrylic ester copolymer, a toughening agent, a lubricant, an anti-dripping agent and an antioxidant which are calculated in parts by weight, and uniformly mixing in a mixing mill;
transferring the mixed raw materials in the mixing mill into a double-screw extruder, gradually adding modified silicon nitride fibers through a feeding port, and then melting, extruding and granulating through the extruder to obtain plastic master batches;
and thirdly, injection molding the obtained plastic master batch in a mold to obtain the plastic buckle of the automobile safety belt.
Preferably, the mixing speed of the mixer in the first step is 200-500r/min and the mixing time is 10-20min.
Preferably, the temperatures of the zones of the twin-screw extruder of the second step comprise, in order: 245-255 ℃, 255-260 ℃, 260-270 ℃, 265-275 ℃, 260-265 ℃, 255-265 ℃ and the screw rotating speed of 300-400r/min.
Preferably, the temperature of the injection molding in the third step is 275-285 ℃, the pressure is 70-110MPa, and the mold temperature is 60-80 ℃.
The beneficial effects of the invention are as follows:
1. the invention prepares the plastic buckle for the automobile safety belt, adopts the composite modified material of the polycarbonate, and has the advantages of high strength, high toughness, high thermal stability, high wear resistance and the like.
2. Among the components of the buckle material, the main material is polycarbonate resin, and has the advantages of high strength, high weather resistance and good high temperature resistance; the acrylonitrile-styrene-acrylate copolymer and the toughening agent can be compounded to improve the toughness and the processability of the material; the modified silicon nitride fiber is the silicon nitride fiber subjected to surface modification treatment, so that the compatibility is better, and the material performance can be enhanced to a greater extent; in addition, a flame retardant, a lubricant and an antioxidant are added to further improve the performance of the material.
3. Although the common silicon nitride fiber has high strength and better high temperature resistance performance, the silicon nitride fiber has brittle property, and has poor surface activity and poor compatibility with organic matters, so that the silicon nitride fiber can not exert the advantages when used as an additive of a material, and even can influence the self performance of the material. According to the invention, the silicon nitride fiber with the surface coated with the polyhexamethylene triazine is prepared by carrying out surface modification on the silicon nitride fiber, and has very good performance in materials.
4. The preparation method of the modified silicon nitride fiber comprises the steps of firstly carrying out surface amino activation treatment on the modified silicon nitride fiber, then mixing the modified silicon nitride fiber with 4,4' - (1, 4-benzene dioxy) diphenylamine, gradually coating the surface to generate pre-poly hexahydrotriazine under the action of formaldehyde, and then carrying out heating and curing to obtain the polyhexamethylene triazine composite modified silicon nitride fiber. In the process, the surface of the silicon nitride fiber is subjected to amination treatment, so that not only is the dispersibility improved, but also the reaction can be participated, and the obtained product has more excellent performance than the product obtained by directly soaking the silicon nitride fiber in the prepolymer for resolidification.
Detailed Description
The technical scheme of the invention is described below through specific examples. It is to be understood that the mention of one or more method steps of the present invention does not exclude the presence of other method steps before and after the combination step or that other method steps may be interposed between these explicitly mentioned steps; it should also be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Moreover, unless otherwise indicated, the numbering of the method steps is merely a convenient tool for identifying the method steps and is not intended to limit the order of arrangement of the method steps or to limit the scope of the invention in which the invention may be practiced, as such changes or modifications in their relative relationships may be regarded as within the scope of the invention without substantial modification to the technical matter.
In order to better understand the above technical solution, exemplary embodiments of the present invention are described in more detail below. While exemplary embodiments of the invention are shown, it should be understood that the invention may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
The invention is further described with reference to the following examples.
Example 1
The high-strength high-toughness plastic buckle for the automobile safety belt comprises the following material components in parts by weight:
65 parts of polycarbonate resin, 18 parts of acrylonitrile-styrene-acrylate copolymer, 8 parts of modified silicon nitride fiber, 5 parts of flame retardant, 4 parts of toughening agent, 2 parts of lubricant, 0.2 part of anti-dripping agent and 0.8 part of antioxidant.
The polycarbonate resin has the brand of Qimei PC-6600 and the specific gravity of 1.2g/cm 3 The melt index was 10g/10min (300 ℃ C., 1.2 kg). The acrylonitrile-styrene-acrylate copolymer has the brand name Qimei PW-978B and a specific gravity of 1.07g/cm 3 The melt index was 13g/10min (220 ℃,10 kg).
The flame retardant is Melamine Cyanurate (MCA). The toughening agent is a silicon toughening agent MR-502. The lubricant is ethylene bis stearamide. The anti-dripping agent is polytetrafluoroethylene, and the molecular weight is 45 ten thousand. The antioxidant is antioxidant 1076.
The preparation method of the modified silicon nitride fiber comprises the following steps:
s1, surface treatment of silicon nitride fibers:
weighing silicon nitride fiber and 3-aminopropyl trimethoxy silane, mixing in deionized water at 75deg.CStirring for 8 hours, removing liquid after the treatment is finished, washing for three times, and drying in an oven to obtain the aminated silicon nitride fiber; the length of the silicon nitride fiber is 10+ -2 mm, the diameter of the silicon nitride fiber is 5+ -1 μm, and the density of the silicon nitride fiber is 2.45g/cm 3 The mass ratio of the silicon nitride fiber to the 3-aminopropyl trimethoxy silane to the deionized water is 1:0.1-0.4:10;
s2, synthesizing a prepolymerization modification reaction solution:
weighing trioxymethylene, dissolving in N-methylpyrrolidone, adding a small amount of deionized water, uniformly mixing, and stirring at 70-80 ℃ for half an hour to obtain a mixed solution A; the mass ratio of the trioxymethylene to the deionized water to the N-methylpyrrolidone is 0.4:0.2:3;
mixing aminated silicon nitride fiber and 4,4' - (1, 4-benzene dioxy) diphenylamine in N-methyl pyrrolidone, and uniformly dispersing by ultrasonic at room temperature to obtain a mixed solution B; the mass ratio of the aminated silicon nitride fiber to the 4,4' - (1, 4-benzene dioxy) diphenylamine to the N-methyl pyrrolidone is 1:0.3:6;
heating the mixed solution B to 60 ℃, slowly adding the mixed solution A, and after the mixed solution A is added in half an hour, continuously stirring and reacting for half an hour to obtain a prepolymerization modified reaction solution; the mass ratio of the mixed solution A to the mixed solution B is 1:1;
s3, synthesizing modified silicon nitride fibers:
and (3) placing the prepolymerization modification reaction liquid in an oven, heating to 100 ℃, carrying out heat preservation treatment for half an hour, heating to 180 ℃, carrying out heat preservation treatment for half an hour, heating to 220 ℃, carrying out heat preservation treatment for 2 hours, naturally cooling to normal temperature, washing with acetone for three times, and drying again to obtain the modified silicon nitride fiber.
The preparation method of the plastic buckle of the automobile safety belt comprises the following steps:
firstly, weighing polycarbonate resin, acrylonitrile-styrene-acrylic ester copolymer, a toughening agent, a lubricant, an anti-dripping agent and an antioxidant which are calculated in parts by weight, and uniformly mixing in a mixing mill at a mixing speed of 300r/min for 15min;
transferring the mixed raw materials in the mixing mill into a double-screw extruder, gradually adding modified silicon nitride fibers through a feeding port, and then melting, extruding and granulating through the extruder, wherein the temperatures of all the areas sequentially comprise: 250 ℃, 255 ℃, 260 ℃, 270 ℃, 265 ℃ and 260 ℃ and the rotating speed of the screw is 350r/min to obtain plastic master batch;
and thirdly, injection molding the obtained plastic master batch in a mold at the temperature of 280 ℃ and the pressure of 80MPa, wherein the mold temperature is 70 ℃, so as to obtain the plastic buckle of the automobile safety belt.
Example 2
The high-strength high-toughness plastic buckle for the automobile safety belt comprises the following material components in parts by weight:
50 parts of polycarbonate resin, 12 parts of acrylonitrile-styrene-acrylate copolymer, 5 parts of modified silicon nitride fiber, 3 parts of flame retardant, 3 parts of toughening agent, 1 part of lubricant, 0.1 part of anti-dripping agent and 0.5 part of antioxidant.
The polycarbonate resin has the brand of Qimei PC-6600 and the specific gravity of 1.2g/cm 3 The melt index was 10g/10min (300 ℃ C., 1.2 kg). The acrylonitrile-styrene-acrylate copolymer has the brand name Qimei PW-978B and a specific gravity of 1.07g/cm 3 The melt index was 13g/10min (220 ℃,10 kg).
The flame retardant is melamine polyphosphate (MPP). The toughening agent is a silicon toughening agent M-577. The lubricant is calcium stearate. The anti-dripping agent is polytetrafluoroethylene, and the molecular weight is 35 ten thousand. The antioxidant is antioxidant 1010.
The preparation method of the modified silicon nitride fiber comprises the following steps:
s1, surface treatment of silicon nitride fibers:
weighing silicon nitride fiber and 3-aminopropyl trimethoxy silane, mixing in deionized water, stirring at 70 ℃ for 6 hours, removing liquid after treatment, washing for three times, and drying in an oven to obtain aminated silicon nitride fiber; the length of the silicon nitride fiber is 10+ -2 mm, the diameter of the silicon nitride fiber is 5+ -1 μm, and the density of the silicon nitride fiber is 2.45g/cm 3 The mass ratio of the silicon nitride fiber to the 3-aminopropyl trimethoxysilane to the deionized water is 1:0.1:10;
s2, synthesizing a prepolymerization modification reaction solution:
weighing trioxymethylene, dissolving in N-methylpyrrolidone, adding a small amount of deionized water, uniformly mixing, and stirring at 70 ℃ for half an hour to obtain a mixed solution A; the mass ratio of the trioxymethylene to the deionized water to the N-methylpyrrolidone is 0.3:0.1:2;
mixing aminated silicon nitride fiber and 4,4' - (1, 4-benzene dioxy) diphenylamine in N-methyl pyrrolidone, and uniformly dispersing by ultrasonic at room temperature to obtain a mixed solution B; the mass ratio of the aminated silicon nitride fiber to the 4,4' - (1, 4-benzene dioxy) diphenylamine to the N-methyl pyrrolidone is 1:0.2:4;
heating the mixed solution B to 55 ℃, slowly adding the mixed solution A, and after the mixed solution A is added in half an hour, continuously stirring and reacting for half an hour to obtain a prepolymerization modified reaction solution; the mass ratio of the mixed solution A to the mixed solution B is 1:1;
s3, synthesizing modified silicon nitride fibers:
and (3) placing the prepolymerization modification reaction liquid in an oven, heating to 100 ℃, carrying out heat preservation treatment for half an hour, heating to 180 ℃, carrying out heat preservation treatment for half an hour, heating to 220 ℃, carrying out heat preservation treatment for 1 hour, naturally cooling to normal temperature, washing with acetone for three times, and drying again to obtain the modified silicon nitride fiber.
The preparation method of the plastic buckle of the automobile safety belt comprises the following steps:
firstly, weighing polycarbonate resin, acrylonitrile-styrene-acrylic ester copolymer, a toughening agent, a lubricant, an anti-dripping agent and an antioxidant which are calculated in parts by weight, and uniformly mixing in a mixing mill at the mixing speed of 200r/min for 10min;
transferring the mixed raw materials in the mixing mill into a double-screw extruder, gradually adding modified silicon nitride fibers through a feeding port, and then melting, extruding and granulating through the extruder, wherein the temperatures of all the areas sequentially comprise: 245 ℃, 255 ℃, 260 ℃, 265 ℃, 260 ℃ and 255 ℃ and the screw rotation speed of 300r/min to obtain plastic master batch;
thirdly, the obtained plastic master batch is injection molded in a mold, the temperature is 275 ℃, the pressure is 70MPa, the mold temperature is 60 ℃, and the plastic buckle of the automobile safety belt is obtained.
Example 3
The high-strength high-toughness plastic buckle for the automobile safety belt comprises the following material components in parts by weight:
80 parts of polycarbonate resin, 24 parts of acrylonitrile-styrene-acrylate copolymer, 10 parts of modified silicon nitride fiber, 8 parts of flame retardant, 6 parts of toughening agent, 3 parts of lubricant, 0.4 part of anti-dripping agent and 1 part of antioxidant.
The polycarbonate resin has the brand of Qimei PC-6600 and the specific gravity of 1.2g/cm 3 The melt index was 10g/10min (300 ℃ C., 1.2 kg). The acrylonitrile-styrene-acrylate copolymer has the brand name Qimei PW-978B and a specific gravity of 1.07g/cm 3 The melt index was 13g/10min (220 ℃,10 kg).
The flame retardant is Melamine (MA). The toughening agent is a silicon toughening agent M-722. The lubricant is polytetrafluoroethylene wax. The anti-dripping agent is polytetrafluoroethylene and has a molecular weight of 55 ten thousand. The antioxidant is antioxidant 168.
The preparation method of the modified silicon nitride fiber comprises the following steps:
s1, surface treatment of silicon nitride fibers:
weighing silicon nitride fiber and 3-aminopropyl trimethoxy silane, mixing in deionized water, stirring at 80 ℃ for 10 hours, removing liquid after treatment, washing for three times, and drying in an oven to obtain aminated silicon nitride fiber; the length of the silicon nitride fiber is 10+ -2 mm, the diameter of the silicon nitride fiber is 5+ -1 μm, and the density of the silicon nitride fiber is 2.45g/cm 3 The mass ratio of the silicon nitride fiber to the 3-aminopropyl trimethoxysilane to the deionized water is 1:0.4:10;
s2, synthesizing a prepolymerization modification reaction solution:
weighing trioxymethylene, dissolving in N-methylpyrrolidone, adding a small amount of deionized water, uniformly mixing, and stirring at 80 ℃ for half an hour to obtain a mixed solution A; the mass ratio of the trioxymethylene to the deionized water to the N-methylpyrrolidone is 0.6:0.3:5;
mixing aminated silicon nitride fiber and 4,4' - (1, 4-benzene dioxy) diphenylamine in N-methyl pyrrolidone, and uniformly dispersing by ultrasonic at room temperature to obtain a mixed solution B; the mass ratio of the aminated silicon nitride fiber to the 4,4' - (1, 4-benzene dioxy) diphenylamine to the N-methyl pyrrolidone is 1:0.4:10;
heating the mixed solution B to 65 ℃, slowly adding the mixed solution A, and after the mixed solution A is added in half an hour, continuously stirring and reacting for half an hour to obtain a prepolymerization modified reaction solution; the mass ratio of the mixed solution A to the mixed solution B is 1:1;
s3, synthesizing modified silicon nitride fibers:
and (3) placing the prepolymerization modification reaction liquid in an oven, heating to 100 ℃, carrying out heat preservation treatment for half an hour, heating to 180 ℃, carrying out heat preservation treatment for half an hour, heating to 220 ℃, carrying out heat preservation treatment for 2 hours, naturally cooling to normal temperature, washing with acetone for three times, and drying again to obtain the modified silicon nitride fiber.
The preparation method of the plastic buckle of the automobile safety belt comprises the following steps:
firstly, weighing polycarbonate resin, acrylonitrile-styrene-acrylic ester copolymer, a toughening agent, a lubricant, an anti-dripping agent and an antioxidant which are calculated in parts by weight, and uniformly mixing in a mixing mill at a mixing speed of 500r/min for 20min;
transferring the mixed raw materials in the mixing mill into a double-screw extruder, gradually adding modified silicon nitride fibers through a feeding port, and then melting, extruding and granulating through the extruder, wherein the temperatures of all the areas sequentially comprise: 255 ℃, 260 ℃, 270 ℃, 275 ℃, 265 ℃ and the screw rotation speed of 400r/min to obtain plastic master batch;
thirdly, the obtained plastic master batch is injection molded in a mold, the temperature is 285 ℃, the pressure is 110MPa, the mold temperature is 80 ℃, and the automobile safety belt plastic buckle is obtained.
Comparative example 1
Compared with the embodiment 1, the plastic buckle of the automobile safety belt is different in that: the modified silicon nitride fiber is replaced by silicon nitride fiber, the length of the silicon nitride fiber is 10+/-2 mm, the diameter of the silicon nitride fiber is 5+/-1 mu m, and the density of the silicon nitride fiber is 2.45g/cm 3 。
Comparative example 2
Compared with the embodiment 1, the plastic buckle of the automobile safety belt is different in that: the modified silicon nitride fiber was replaced with an aminated silicon nitride fiber, and the preparation process was the same as in example 1.
Comparative example 3
Compared with the embodiment 1, the plastic buckle of the automobile safety belt is different in that: the preparation process of the modified silicon nitride fiber is different.
The preparation process of the modified silicon nitride fiber comprises the following steps:
s1, synthesizing a prepolymerization modification reaction solution:
weighing trioxymethylene, dissolving in N-methylpyrrolidone, adding a small amount of deionized water, uniformly mixing, and stirring at 70-80 ℃ for half an hour to obtain a mixed solution A; the mass ratio of the trioxymethylene to the deionized water to the N-methylpyrrolidone is 0.4:0.2:3; dissolving 4,4' - (1, 4-benzene dioxy) diphenylamine in N-methyl pyrrolidone, and uniformly dispersing the mixture by ultrasonic at room temperature to obtain a mixed solution B; the mass ratio of the 4,4' - (1, 4-benzene dioxy) diphenylamine to the N-methylpyrrolidone is 0.3:6;
heating the mixed solution B to 60 ℃, slowly adding the mixed solution A, and after the mixed solution A is added in half an hour, continuously stirring and reacting for half an hour to obtain a prepolymerization modified reaction solution; the mass ratio of the mixed solution A to the mixed solution B is 1:1;
s2, synthesizing modified silicon nitride fibers:
adding silicon nitride fibers into the prepolymerization modification reaction liquid, uniformly mixing the silicon nitride fibers and the prepolymerization modification reaction liquid according to the mass ratio of 1:10, then placing the mixture in an oven, heating to 100 ℃, carrying out heat preservation treatment for half an hour, heating to 180 ℃, carrying out heat preservation treatment for half an hour, heating to 220 ℃, carrying out heat preservation treatment for 2 hours, naturally cooling to normal temperature, washing with acetone for three times, and drying again to obtain the modified silicon nitride fibers.
The performance of the automobile safety belt plastic buckle materials prepared in the example 1 and the comparative examples 1-3 is detected, and the tensile strength standard is GB/T1040; notched impact strength standard IOS 7391-2; creep resistance is to age the material at 180 ℃ for 10min, then restore to normal temperature, and detect the strain after 8h of treatment under 12MPa by an electromagnetic fatigue test; the results of the measurements are then shown in Table 1.
Table 1 results of performance testing of plastic snap materials
| Example 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Tensile Strength (MPa) | 132.2 | 116.8 | 121.5 | 127.6 |
| Heat distortion temperature (DEG C) | 163 | 141 | 143 | 155 |
| Hardness (HRA) | 98 | 86 | 89 | 93 |
| Notched impact Strength (kJ/m) 2 ) | 78.5 | 63.2 | 67.7 | 72.3 |
| Creep strain resistance (%) | 0.02 | 0.29 | 0.15 | 0.08 |
As can be seen from table 1, the tensile strength, heat resistance, hardness, impact strength and creep resistance of the plastic fastening material of the example 1 of the present invention are much higher than those of the other comparative examples, which indicates that the plastic fastening material of the example 1 of the present invention has the advantages of high strength, high toughness, high thermal stability and high abrasion resistance.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms should not be understood as necessarily being directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Further, one skilled in the art can engage and combine the different embodiments or examples described in this specification.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (10)
1. The high-strength high-toughness plastic buckle for the automobile safety belt is characterized by comprising the following material components in parts by weight:
50-80 parts of polycarbonate resin, 12-24 parts of acrylonitrile-styrene-acrylate copolymer, 5-10 parts of modified silicon nitride fiber, 3-8 parts of flame retardant, 3-6 parts of toughening agent, 1-3 parts of lubricant, 0.1-0.4 part of anti-dripping agent and 0.5-1 part of antioxidant.
2. The high-strength high-toughness plastic buckle for automobile safety belt according to claim 1, wherein the polycarbonate resin is characterized by the brand of Qimei PC-6600 and the specific gravity of 1.2g/cm 3 The melt index was 10g/10min (300 ℃ C., 1.2 kg).
3. The high strength, high toughness plastic buckle for automotive safety belt according to claim 1, wherein said acrylonitrile-styrene-acrylate copolymer is identified by the brand name of qi mei PW-978B, and has a specific gravity of 1.07g/cm 3 The melt index was 13g/10min (220 ℃,10 kg).
4. The high-strength high-toughness automobile safety belt plastic buckle according to claim 1, wherein the preparation method of the modified silicon nitride fiber comprises the following steps:
s1, carrying out amination treatment on the surface of silicon nitride fiber by using 3-aminopropyl trimethoxy silane;
s2, weighing trioxymethylene, dissolving in N-methylpyrrolidone, adding a small amount of deionized water, uniformly mixing, and stirring at 70-80 ℃ for half an hour to obtain a mixed solution A; mixing aminated silicon nitride fiber and 4,4' - (1, 4-benzene dioxy) diphenylamine in N-methyl pyrrolidone, and uniformly dispersing by ultrasonic at room temperature to obtain a mixed solution B; heating the mixed solution B to 55-65 ℃, slowly adding the mixed solution A, finishing the addition within half an hour, and then continuously stirring and reacting for half an hour to obtain a prepolymerization modified reaction solution;
and S3, placing the prepolymerization modification reaction solution in an oven, heating to 100 ℃, carrying out heat preservation treatment for half an hour, heating to 180 ℃, carrying out heat preservation treatment for half an hour, heating to 220 ℃, carrying out heat preservation treatment for 1-2 hours, naturally cooling to normal temperature, washing with acetone for three times, and drying again to obtain the modified silicon nitride fiber.
5. The high strength, high toughness automotive seat belt plastic buckle according to claim 1, wherein the flame retardant is a nitrogen based flame retardant comprising one of Melamine Cyanurate (MCA), melamine polyphosphate (MPP), melamine (MA).
6. The high strength, high toughness automotive seat belt plastic buckle according to claim 1, wherein the toughening agent is a silicon based toughening agent comprising one of MR-502, M-577, M-722.
7. The high strength, high toughness plastic car seat belt buckle according to claim 1, wherein said lubricant is at least one of ethylene bis-stearamide, calcium stearate, zinc stearate, polytetrafluoroethylene wax.
8. The high-strength high-toughness automobile safety belt plastic buckle according to claim 1, wherein the anti-dripping agent is polytetrafluoroethylene and has a molecular weight of 35-55 ten thousand.
9. The high strength, high toughness automotive seat belt plastic buckle according to claim 1, wherein said antioxidant comprises one or more combinations of antioxidant 1076, antioxidant 1010, antioxidant 168.
10. The high-strength and high-toughness plastic buckle for automobile safety belts according to claim 1, wherein the preparation method of the plastic buckle for automobile safety belts comprises the following steps:
firstly, weighing polycarbonate resin, acrylonitrile-styrene-acrylic ester copolymer, a toughening agent, a lubricant, an anti-dripping agent and an antioxidant which are calculated in parts by weight, and uniformly mixing in a mixing mill;
transferring the mixed raw materials in the mixing mill into a double-screw extruder, gradually adding modified silicon nitride fibers through a feeding port, and then melting, extruding and granulating through the extruder to obtain plastic master batches;
and thirdly, injection molding the obtained plastic master batch in a mold to obtain the plastic buckle of the automobile safety belt.
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| CN102399424A (en) * | 2010-09-08 | 2012-04-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Polycarbonate/acrylonitrile-styrene-acrylate copolymer alloy material and preparation method thereof |
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| US20150376442A1 (en) * | 2014-06-27 | 2015-12-31 | International Business Machines Corporation | Soluble, processable polyhemiaminals and polyhexahydrotriazines |
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