CN114933799B - Low-odor 5 VA-grade halogen-free flame-retardant nylon 6 composite material and preparation method thereof - Google Patents
Low-odor 5 VA-grade halogen-free flame-retardant nylon 6 composite material and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 143
- 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 title claims abstract description 123
- 229920002292 Nylon 6 Polymers 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 11
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 34
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 28
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 21
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000002781 deodorant agent Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 12
- 239000000314 lubricant Substances 0.000 claims abstract description 11
- 239000012745 toughening agent Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 229910021536 Zeolite Inorganic materials 0.000 claims description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 9
- 239000010457 zeolite Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 150000007970 thio esters Chemical class 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 229920001903 high density polyethylene Polymers 0.000 claims description 3
- 239000004700 high-density polyethylene Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 6
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 13
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 229910052901 montmorillonite Inorganic materials 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- -1 flame-retardant compound Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 2
- 229920006052 Chinlon® Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229940045916 polymetaphosphate Drugs 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K2003/026—Phosphorus
-
- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a low-odor 5 VA-grade halogen-free flame-retardant nylon 6 composite material and a preparation method thereof, wherein the halogen-free flame-retardant nylon 6 composite material is prepared from the following raw materials in parts by weight: the flame retardant nylon 6 composite material comprises, by weight, 40-60 parts of PA6, 2-5 parts of a toughening agent, 25-35 parts of a compound flame retardant, 8-12 parts of a flame retardant synergist, 0.3-0.5 part of an antioxidant, 0.5-1.5 parts of a lubricant, 0.5-1 part of a deodorant and 0.1-0.3 part of an anti-dripping agent, wherein the compound flame retardant is a red phosphorus flame retardant master batch and an MCA flame retardant, and the two components are synergistic with each other, so that the halogen-free flame retardant nylon 6 composite material has excellent flame retardant property; the flame retardant synergist is superfine barium sulfate, has better flame retardance and excellent chemical inertia, ensures that the halogen-free flame retardant nylon 6 composite material has better stability and flame retardance, ensures that the flame retardant grade of the halogen-free flame retardant nylon 6 composite material reaches 5VA grade, ensures that the odor grade of the halogen-free flame retardant nylon 6 composite material reaches within 3.0 and 3.0, and ensures that the halogen-free flame retardant nylon 6 composite material is more suitable for producing low-odor electronic and electric appliance parts and automobile parts.
Description
Technical Field
The invention relates to a halogen-free flame-retardant nylon 6 composite material and a preparation method thereof, in particular to a low-odor 5 VA-level halogen-free flame-retardant nylon 6 composite material and a preparation method thereof.
Background
With the increasing requirements of people on flame retardant effect, odor grade and the like of plastic products, the traditional plastic products are difficult to meet the demands of consumers. The patent document with the publication number of CN109233264A discloses a halogen-free flame-retardant glass fiber reinforced nylon composite material and a preparation method thereof, wherein the halogen-free flame-retardant compound agent in the composite material is prepared by compounding red phosphorus flame-retardant master batch, melamine cyanurate and organic nano montmorillonite according to the mass ratio of 5:1:1-5:3:3. Wherein when the mass ratio of the red phosphorus flame-retardant master batch to the melamine cyanurate to the organic nano montmorillonite is 15:5:5, the flame-retardant grade of the composite material is best and reaches the V-0 grade. The flame retardant grades are gradually increased from HB, V-2, V-1, V-0 and 5VB to 5VA, and for some plastics with the flame retardant grade of 5VA, the flame retardant grade of the halogen-free flame retardant compound agent is still insufficient.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a low-odor 5 VA-level halogen-free flame-retardant nylon 6 composite material with good flame retardant effect and a preparation method thereof.
The technical scheme adopted for solving the technical problems is as follows:
a low-odor 5 VA-grade halogen-free flame-retardant nylon 6 composite material is prepared from the following raw materials in parts by weight: 40 to 60 parts of PA6, 2 to 5 parts of toughening agent, 25 to 35 parts of compound flame retardant, 8 to 12 parts of flame retardant synergist, 0.3 to 0.5 part of antioxidant, 0.5 to 1.5 parts of lubricant, 0.5 to 1 part of deodorant and 0.1 to 0.3 part of anti-dripping agent.
The compound flame retardant is red phosphorus flame retardant master batch and MCA flame retardant.
The flame retardant synergist is superfine barium sulfate.
The weight part ratio of the red phosphorus flame-retardant master batch to the superfine barium sulfate is 7:2.5-7:3.5.
The weight part ratio of the red phosphorus flame retardant master batch to the MCA flame retardant is 7:2.5-7:3.5.
The melt index of the PA6 is 2.5-5 g/10min.
The toughening agent is one or more of HDPE, maleic anhydride grafted POE and maleic anhydride grafted PE.
The antioxidant is one or two of hindered phenol antioxidants and thioester antioxidants.
The lubricant is one or more of silicone master batch, zinc stearate and stearic acid.
The deodorant is zeolite deodorant.
The anti-dripping agent is coated PTFE.
The method for preparing the low-odor 5 VA-grade halogen-free flame-retardant nylon 6 composite material is characterized by comprising the following steps of:
step one: and (3) drying the PA6, the toughening agent, the compound flame retardant, the flame retardant synergist, the antioxidant, the lubricant, the deodorant and the anti-dripping agent, and then putting into a high-speed stirrer for stirring at the rotating speed of 400-800 rpm to obtain the mixture.
Step two: and (3) putting the mixture into a double-screw extruder for extrusion, and then cooling, granulating and drying to obtain the halogen-free flame-retardant nylon 6 composite material.
The beneficial effects of the invention are as follows:
the invention provides a low-odor 5 VA-grade halogen-free flame-retardant nylon 6 composite material and a preparation method thereof, wherein red phosphorus flame-retardant master batch and an MCA flame retardant are compounded to be used as a compound flame retardant, and the two are mutually synergistic, so that the halogen-free flame-retardant nylon 6 composite material has excellent flame retardant property; the superfine barium sulfate is adopted as a flame retardant synergist, so that the flame retardant has better flame retardance and excellent chemical inertness, the halogen-free flame retardant nylon 6 composite material has better stability and flame retardance, and the flame retardant grade of the halogen-free flame retardant nylon 6 composite material reaches the grade of 5 VA.
In addition, the zeolite deodorant is added in the invention, so that the odor grade of the halogen-free flame-retardant nylon 6 composite material is within 3.0 and 3.0, and the halogen-free flame-retardant nylon 6 composite material is more suitable for producing low-odor electronic and electric parts and automobile parts.
Detailed Description
The parts not particularly emphasized in the following examples are all at normal temperature and pressure.
A low-odor 5 VA-grade halogen-free flame-retardant nylon 6 composite material is prepared from the following raw materials in parts by weight: 40 to 60 parts of PA6, 2 to 5 parts of toughening agent, 25 to 35 parts of compound flame retardant, 8 to 12 parts of flame retardant synergist, 0.3 to 0.5 part of antioxidant, 0.5 to 1.5 parts of lubricant, 0.5 to 1 part of deodorant and 0.1 to 0.3 part of anti-dripping agent.
The compound flame retardant is red phosphorus flame retardant master batch and MCA flame retardant.
The flame retardant synergist is superfine barium sulfate.
The weight part ratio of the red phosphorus flame-retardant master batch to the superfine barium sulfate is 7:2.5-7:3.5.
The weight part ratio of the red phosphorus flame retardant master batch to the MCA flame retardant is 7:2.5-7:3.5.
The melt index of the PA6 is 2.5-5 g/10min, so that the overall toughness strength of the product is enhanced.
The toughening agent is one or more of HDPE, maleic anhydride grafted POE and maleic anhydride grafted PE, so that the overall toughness strength of the product is enhanced, and meanwhile, under the cooperation of the melt index of PA6 of 2.5-5 g/10min, the toughness strength of the product reaches the requirement.
The antioxidant is one or two of hindered phenol antioxidants and thioester antioxidants.
The lubricant is one or more of silicone master batch, zinc stearate and stearic acid.
The deodorant is zeolite deodorant.
The anti-dripping agent is coated PTFE.
The method for preparing the low-odor 5 VA-grade halogen-free flame-retardant nylon 6 composite material is characterized by comprising the following steps of:
step one: and (3) drying the PA6, the toughening agent, the compound flame retardant, the flame retardant synergist, the antioxidant, the lubricant, the deodorant and the anti-dripping agent at the temperature of 80-100 ℃ for 1-2 hours, and then putting the mixture into a high-speed stirrer for stirring for 6-10 minutes at the rotating speed of 400-800 rpm to obtain the mixture.
Step two: and (3) putting the mixture into a double-screw extruder for extrusion, and then cooling, granulating and drying to obtain the halogen-free flame-retardant nylon 6 composite material.
The temperature zone of the double-screw extruder is set between 200 ℃ and 245 ℃, the feeding rotating speed is 12-24 revolutions per minute, and the rotating speed of the main machine is 450-600 revolutions per minute.
The embodiment provides a low-odor 5 VA-level halogen-free flame-retardant nylon 6 composite material and a preparation method thereof, wherein red phosphorus flame-retardant master batch and MCA flame retardant are compounded to be used as a compound flame retardant, and the two are mutually synergistic, so that the halogen-free flame-retardant nylon 6 composite material has excellent flame retardant property; the superfine barium sulfate is adopted as a flame retardant synergist, so that the flame retardant has better flame retardance and excellent chemical inertness, the halogen-free flame retardant nylon 6 composite material has better stability and flame retardance, and the flame retardant grade of the halogen-free flame retardant nylon 6 composite material reaches the grade of 5 VA.
In addition, the zeolite deodorant is added in the embodiment, so that the odor grade of the halogen-free flame-retardant nylon 6 composite material is within 3.0 and 3.0, and the halogen-free flame-retardant nylon 6 composite material is more suitable for producing low-odor electronic and electric parts and automobile parts.
The raw materials of examples 1 to 3 were respectively prepared according to table 1, and a low-odor 5 VA-grade halogen-free flame retardant nylon 6 composite material was prepared. The preparation method comprises the following steps: the raw materials of each example were dried at 90℃for 2 hours, and then put into a high-speed stirrer to be stirred for 10 minutes at 600 rpm, to obtain a mixture. Step two: putting the mixture into a double-screw extruder for extrusion, setting 11 temperature areas of the double-screw extruder to be 200 ℃, 245 ℃, 240 ℃, 230 ℃, 240 ℃, 245 ℃, and 15 revolutions per minute of feeding speed and 450 revolutions per minute of host machine, and then cooling, granulating and drying to obtain the halogen-free flame retardant nylon 6 composite material. The mechanical properties and odor grade (VDA 270-1992) of the finished product obtained by the prepared composite material according to the national standard test of the sample strip are 3,80 ℃/2h.
The raw materials of comparative examples 1 to 5 were prepared according to Table 2, and the finished products of comparative examples 1 to 5 were prepared by the preparation method of examples 1 to 3, respectively, and the prepared composite materials were subjected to 3,80 ℃for 2 hours according to the mechanical properties and odor grades (VDA 270-1992) of the finished products obtained by the national standard test of the sample bars.
Wherein, in examples 1 to 3, in comparative examples, PA6 was M2800, which is produced by Guangdong New Enmeida chinlon Co., ltd; the red phosphorus flame-retardant master batch adopts HNH, which is produced by Qingyuan city, a fire-retardant material Co., ltd; the MCA flame retardant is XS-MC-15, manufactured by Zhejiang Xudian flame retardant Co., ltd; the superfine barium sulfate is produced by the chemical industry Co.Ltd in the Shunde district of the Buddha city; the toughening agent is maleic anhydride grafted POE and maleic anhydride grafted PE, wherein the maleic anhydride grafted POE is produced by Korea chemical Co., ltd, the maleic anhydride grafted PE is produced by MC226, and the photo new material technology Co., ltd; the antioxidants are hindered phenol antioxidants 1098 and thioester antioxidants 412S, which are all commercially available; the lubricant is silicone master batch and zinc stearate, the silicone master batch is LYSI-01V, which is produced by Chengdu Siricke technology Co., ltd, and the zinc stearate is AV300, which is produced by Dongguan Hanweixin material technology Co., ltd; the zeolite deodorant is ST-15, which is produced by Starbeda chemical materials Co., ltd; the coated PTFE adopts SN3208; the organic nano montmorillonite is manufactured by DK2, zhejiang Feng Hong New Material Co., ltd.
| Raw materials | Example 1 | Example 2 | Example 3 |
| PA6 | 56 | 56 | 56 |
| Flame-retardant master batch of red phosphorus | 21 | 21 | 21 |
| MCA flame retardant | 7.5 | 9 | 10.5 |
| Superfine barium sulfate | 7.5 | 9 | 10.5 |
| Organic nano montmorillonite | - | - | - |
| Maleic anhydride grafted POE | 2.5 | 2.5 | 2.5 |
| Maleic anhydride grafted PE | 1 | 1 | 1 |
| Hindered phenol antioxidant | 0.1 | 0.1 | 0.1 |
| Thio-ester antioxidant | 0.2 | 0.2 | 0.2 |
| Silicone master batch | 0.5 | 0.5 | 1 |
| Zinc stearate | 0.2 | 0.2 | 0.2 |
| Zeolite deodorant | 0.5 | 0.5 | 0.5 |
| Coated PTFE | 0.2 | 0.2 | 0.2 |
TABLE 1
TABLE 2
Table 3 shows the performance data after the test of examples 1 to 3
As can be seen from table 3, the ratio of red phosphorus flame retardant masterbatch, MCA flame retardant and ultra-fine barium sulfate is 7:2.5: 2.5-7:3.5:3.5, the prepared composite material reaches the flame retardant grade of 5VA, and has excellent flame retardant property; the added zeolite deodorant ensures that the odor grade of the composite material is within 3.0, and is suitable for producing low-odor electronic and electric parts and automobile parts.
Table 4 shows the performance data of comparative examples 1 to 5 after the test
As can be seen from Table 4, the difference between comparative example 1 and example 2 is that the comparative example 1 is free from adding MCA flame retardant, only red phosphorus flame retardant master batch and superfine barium sulfate are adopted, the flame retardant performance of the test result is not up to 5VA grade, which shows that the flame retardant effect of the flame retardant after the single flame retardant is not compounded is good, the MCA flame retardant is decomposed to generate moisture when forming a carbon foam layer, the hydrogenated product generated by the red phosphorus flame retardant master batch during reaction is rapidly hydrated into phosphoric acid, the phosphoric acid is condensed to produce a polymetaphosphate glassy covering, the flame retardant effect of the red phosphorus is fully exerted, the presence of the MCA flame retardant promotes the formation of a charring layer during combustion, the charring layer can not only block the entry of heat and oxygen, but also block the entry of micromolecular combustible gas generated by pyrolysis into gas phase, in addition, the phosphorus compound and nitride react to generate a crosslinked coating containing P-N bonds in the system, which is also helpful for improving the flame retardance of the material.
The difference between comparative example 2 and example 2 is that only red phosphorus flame retardant master batch and MCA flame retardant are adopted in comparative example 2, and the flame retardant effect is certain, but no superfine barium sulfate is added, so that the flame retardant effect of the product cannot reach the 5VA grade, and the superfine barium sulfate has better flame retardance and excellent chemical inertness besides the filler effect, so that the product has better stability, better flame retardant effect and higher flame retardant grade.
Comparative example 3 is a mixture ratio 10 of red phosphorus flame retardant master batch, MCA flame retardant and organic nano montmorillonite of the patent in the background art: 2:2 is applied to the invention, the flame retardant grade reaches V-1 grade in the patent of the background technology, and the better grade of 5VA cannot be reached in the comparative example 3; comparative example 4 is prepared by applying the mixture ratio of 15:5:5 of red phosphorus flame retardant master batch, MCA flame retardant and organic nano montmorillonite of the prior art to the invention, wherein the flame retardant grade is V-0 grade in the prior art, and the better grade of 5VA cannot be achieved after the flame retardant is applied to comparative example 4; comparative example 5 is prepared from red phosphorus flame retardant masterbatch, MCA flame retardant and organic nano montmorillonite according to the optimal ratio of 21:9:9 in the invention, but the flame retardant can not reach the 5VA grade. Thus, although the organic nano montmorillonite is also a filler, the synergistic effect of the organic nano montmorillonite on the flame retardant effect is not good, and even if the organic nano montmorillonite is added in the same amount as the superfine barium sulfate, the product cannot achieve the flame retardant effect of 5VA grade.
In addition, the zeolite deodorant enables the odor grade of the product to be within 3.0 and 3.0, so that the product is more suitable for producing low-odor electronic and electric parts and automobile parts.
The above embodiments do not limit the protection scope of the invention, and those skilled in the art can make equivalent modifications and variations without departing from the whole inventive concept, and they still fall within the scope of the invention.
Claims (7)
1. The low-odor 5 VA-grade halogen-free flame-retardant nylon 6 composite material is characterized by being prepared from the following raw materials in parts by weight: 40-60 parts of PA6, 2-5 parts of toughening agent, 25-35 parts of compound flame retardant, 8-12 parts of flame retardant synergist, 0.3-0.5 part of antioxidant, 0.5-1.5 parts of lubricant, 0.5-1 part of deodorant and 0.1-0.3 part of anti-dripping agent; the odor removing agent is zeolite odor removing agent, and the compound flame retardant is red phosphorus flame retardant master batch and MCA flame retardant; the flame retardant synergist is superfine barium sulfate, the weight part ratio of the red phosphorus flame retardant master batch to the superfine barium sulfate is 7:2.5-7:3.5, and the weight part ratio of the MCA flame retardant to the superfine barium sulfate is 1:1.
2. The low-odor 5 VA-grade halogen-free flame retardant nylon 6 composite material of claim 1, wherein the PA6 has a melt index of 2.5-5 g/10min.
3. The low-odor 5 VA-class halogen-free flame retardant nylon 6 composite of claim 1, wherein the toughening agent is one or more of HDPE, maleic anhydride grafted POE, maleic anhydride grafted PE.
4. The low-odor 5 VA-grade halogen-free flame retardant nylon 6 composite material of claim 1, wherein the antioxidant is one or two of hindered phenol antioxidants and thioester antioxidants.
5. The low-odor 5 VA-class halogen-free flame retardant nylon 6 composite of claim 1, wherein the lubricant is one or more of silicone masterbatch, zinc stearate, stearic acid.
6. The low odor 5VA class halogen free flame retardant nylon 6 composite of claim 1 wherein said anti-drip agent is coated PTFE.
7. A method for preparing the low odor 5 VA-class halogen-free flame retardant nylon 6 composite according to any one of claims 1 to 6, characterized by comprising the steps of:
step one: drying the PA6, the toughening agent, the compound flame retardant, the flame retardant synergist, the antioxidant, the lubricant, the deodorant and the anti-dripping agent, and then putting the dried materials into a high-speed stirrer for stirring at the rotating speed of 400-800 rpm to obtain a mixture;
step two: and (3) putting the mixture into a double-screw extruder for extrusion, and then cooling, granulating and drying to obtain the halogen-free flame-retardant nylon 6 composite material.
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