CN110776733B - In-situ reaction compatibilization halogen-free flame-retardant nylon 6 and preparation method thereof - Google Patents
In-situ reaction compatibilization halogen-free flame-retardant nylon 6 and preparation method thereof Download PDFInfo
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- 229920002292 Nylon 6 Polymers 0.000 title claims abstract description 102
- 239000003063 flame retardant Substances 0.000 title claims abstract description 75
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- 238000011065 in-situ storage Methods 0.000 title claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 26
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- 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 abstract description 35
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 claims abstract description 31
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 14
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- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
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- 238000005469 granulation Methods 0.000 claims abstract description 5
- 230000003179 granulation Effects 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims abstract description 5
- 230000008018 melting Effects 0.000 claims abstract description 5
- 238000012545 processing Methods 0.000 claims description 10
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 10
- 239000002131 composite material Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 0 CCCC(C(C)C(N*)=O)C(O)=O Chemical compound CCCC(C(C)C(N*)=O)C(O)=O 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- AORTZIIKTZPIQU-UHFFFAOYSA-N CCCCC(C(C)C(O1)=O)C1=O Chemical compound CCCCC(C(C)C(O1)=O)C1=O AORTZIIKTZPIQU-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- XXDFPKUDKBJJNI-UHFFFAOYSA-N O=C(N(C1OC1)C(N1C2OC2)=O)N(C2OC2)C1=O Chemical compound O=C(N(C1OC1)C(N1C2OC2)=O)N(C2OC2)C1=O XXDFPKUDKBJJNI-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- REBHQKBZDKXDMN-UHFFFAOYSA-M [PH2]([O-])=O.C(C)[Al+]CC Chemical compound [PH2]([O-])=O.C(C)[Al+]CC REBHQKBZDKXDMN-UHFFFAOYSA-M 0.000 description 1
- LXWPJAGZRHTAOO-UHFFFAOYSA-N [Sb].[Br] Chemical compound [Sb].[Br] LXWPJAGZRHTAOO-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- OXVFDZYQLGRLCD-UHFFFAOYSA-N hydroxypioglitazone Chemical compound N1=CC(C(O)C)=CC=C1CCOC(C=C1)=CC=C1CC1C(=O)NC(=O)S1 OXVFDZYQLGRLCD-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
The invention discloses an in-situ reaction compatibilization halogen-free flame-retardant nylon 6 and a preparation method thereof. The halogen-free flame-retardant nylon 6 comprises the following components: nylon 6, aluminum diethylphosphinate coated by melamine cyanurate, triglycidyl isocyanurate and ethylene-maleic anhydride block copolymer. The in-situ reaction compatibilization preparation method of the halogen-free flame-retardant nylon 6 comprises the following steps: 1) mixing nylon 6, an ethylene-maleic anhydride block copolymer and melamine cyanurate-coated aluminum diethylphosphinate according to a ratio to obtain a mixture; 2) and putting the mixture into a main feeding port of a double-screw extruder, putting triglycidyl isocyanurate into a side feeding port of the double-screw extruder, and carrying out melting, extrusion and granulation to obtain the composite material. The nylon 6 prepared by the in-situ reaction compatibilization method has the advantages of excellent flame retardant property, good mechanical property and thermal deformation property, simple preparation raw materials and production process, low cost and very wide application prospect.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to halogen-free flame retardant nylon 6 compatibilized by in-situ reaction and a preparation method thereof.
Background
Nylon 6(PA6) has excellent comprehensive performance, is synthetic resin widely applied to engineering plastics, and is mainly applied to the fields of automobiles, electronics and electricity. However, unmodified PA6 has the defects of low heat distortion temperature, poor flame retardant property and the like. The heat distortion temperature of the PA6 can be raised by introducing the glass fibers, but the flame retardance of the PA6 is further reduced by the 'wick' effect of the glass fibers, and the introduction of a large amount of glass fibers enables the surface of a PA6 product to be prone to generate flaws, so that the appearance consistency of the PA6 product is influenced. Although the flame retardant can be added to improve the flame retardant property of PA6, because the melt viscosity of PA6 is low and molten drops are easily generated during combustion, a large amount of flame retardant needs to be added, but the compatibility between PA6 and the flame retardant is poor, so that the mechanical property of flame retardant PA6 is obviously reduced compared with that of pure PA 6.
In the prior art, CN104086991A discloses that nano silicon dioxide and treated basic magnesium sulfate whisker are used as a flame retardant to improve the flame retardant property and mechanical property of PA6, but the flame retardant property of PA6 is not obviously improved, and the obtained PA6 composite material only reaches UL-94V1 grade. CN108148401A discloses a polyamide PA6 composite material, but this solution uses a traditional bromine-antimony fire retardant system, and the composite material has a risk of generating harmful dioxin during combustion. CN107201028A discloses an environment-friendly PA6 material, the flame retardant grade reaches UL-94V0 grade, the material has better flame retardant property, but the maximum tensile strength of the composite material is only 51.26MPa, and the material is obviously reduced compared with a pure PA6 material. Therefore, how to simultaneously improve the mechanical property, the heat distortion temperature and the flame retardance of the PA6 without introducing glass fibers is a technical problem to be solved by researchers in the field.
Disclosure of Invention
In order to overcome the problems of mechanical property, thermal deformation temperature and flame retardance of nylon 6 in the prior art, the invention aims to provide in-situ reaction compatibilization halogen-free flame retardant nylon 6 and a preparation method thereof.
The invention concept of the invention is as follows: by adopting an in-situ reaction compatibilization method, PA6, melamine cyanurate coated aluminum diethylphosphinate, triglycidyl isocyanurate (TGIC) and an Ethylene-maleic anhydride block copolymer (Ethylene-b-MAH) are blended, an epoxy group in the TGIC reacts with a terminal carboxyl group of PA6 in situ in a twin-screw extruder to generate a macromolecular graft PA6-g-TGIC, and a triazine ring structure of the TGIC is similar to and compatible with a triazine ring structure of the melamine cyanurate coated aluminum diethylphosphinate, so that the compatibility of PA6 and flame retardant melamine cyanurate coated aluminum diethylphosphinate is improved, on the other hand, a large amount of maleic anhydride groups in the Ethylene-b-MAH react with terminal amine groups of PA6 to generate branched macromolecular PA6-MAH-b-Ethylene, the melt viscosity of PA6 is greatly improved, the melt viscosity of PA6 is inhibited during combustion, and the mechanical property and the thermal deformation temperature of the halogen-free flame-retardant nylon 6 are improved, so that the problems in the prior art are solved, and the halogen-free flame-retardant PA6 with excellent flame-retardant property and better mechanical property and thermal deformation property is prepared.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides an in-situ reaction compatibilization halogen-free flame-retardant nylon 6, and the halogen-free flame-retardant nylon 6 comprises the following components in parts by mass: 80-90 parts of nylon 6, 10-15 parts of melamine cyanurate-coated aluminum diethylphosphinate, 1-3 parts of triglycidyl isocyanurate and 0.5-2 parts of ethylene-maleic anhydride block copolymer. The halogen-free flame-retardant nylon 6 is prepared by a preparation method of in-situ reaction compatibilization.
Preferably, the halogen-free flame retardant nylon 6 comprises 85-90 parts by mass of nylon 6.
In the halogen-free flame-retardant nylon 6, the nylon 6 can be selected from any commercially available nylon 6 material, and belongs to common raw materials in the field.
In the halogen-free flame-retardant nylon 6, the structural formula of aluminum diethylphosphinate in aluminum diethylphosphinate coated by melamine cyanurate is shown as a formula (I):
in the present invention, the purpose of selecting melamine cyanurate coated aluminum diethylphosphinate as a flame retardant is described as follows: PA6 is a crystalline polymer with very low melt viscosity, therefore it is very easy to generate molten drops during burning test, and the absorbent cotton is ignited, and the expected flame retardant effect can not be achieved. If the melamine cyanurate is used as the PA6 flame retardant, the melamine cyanurate does not contain an acid source based on the necessary conditions of an intumescent flame retardant acid source, a gas source and a carbon source, so that the catalytic carbon formation effect is not obvious, a large amount of molten drops are still generated during the flame retardant test, and the expected flame retardant effect cannot be achieved. If the aluminum diethylphosphinate is independently used as the flame retardant, the aluminum diethylphosphinate belongs to low molecular salts and has poor compatibility with PA6 macromolecules, so that the halogen-free flame-retardant PA6 prepared by independently adding the aluminum diethylphosphinate as the flame retardant has poor mechanical properties. The PA6 and triglycidyl isocyanurate react to generate macromolecule PA6 containing triazine ring, the melamine cyanurate also has a triazine ring structure, and diethyl aluminum phosphinate coated by the melamine cyanurate is used as a flame retardant, so that the compatibility of the melamine cyanurate with the macromolecule PA6 containing triazine ring is greatly improved according to the similar compatibility principle, and the mechanical property is improved.
Preferably, in the halogen-free flame-retardant nylon 6, the coating amount of the melamine cyanurate in the melamine cyanurate-coated aluminum diethylphosphinate is 1.5 to 2.5 percent of the mass of the aluminum diethylphosphinate. The coating amount of the melamine cyanurate is preferably 1.5 to 2.5 percent. If the coating amount is too large, the flame retardant effect is adversely affected by the conflict between Melamine Cyanurate (MCA) which promotes the dripping during the combustion of PA6 and diethyl aluminum hypophosphite which inhibits the dripping of PA 6.
In the halogen-free flame-retardant nylon 6, the structural formula of triglycidyl isocyanurate (TGIC) is shown as the formula (II):
in the halogen-free flame-retardant nylon 6, the structural formula of the Ethylene-maleic anhydride block copolymer (Ethylene-b-MAH) is shown as the formula (III):
In the halogen-free flame-retardant nylon 6, the weight average molecular weight M of the ethylene-maleic anhydride block copolymerwPreferably 5 to 7 ten thousand, and more preferably 6 ten thousand.
The invention provides a method for preparing the halogen-free flame-retardant nylon 6 by in-situ reaction compatibilization, which comprises the following steps:
1) mixing nylon 6, an ethylene-maleic anhydride block copolymer and melamine cyanurate-coated aluminum diethylphosphinate according to a ratio to obtain a mixture;
2) and putting the mixture into a main feeding port of a double-screw extruder, putting triglycidyl isocyanurate into a side feeding port of the double-screw extruder, and carrying out melting, extrusion and granulation to obtain the halogen-free flame-retardant nylon 6.
Preferably, in the in-situ reactive compatibilization preparation method, the nylon 6 and the ethylene-maleic anhydride block copolymer are respectively dried before use.
Preferably, in the in-situ reaction compatibilization preparation method, the nylon 6 and the ethylene-maleic anhydride segmented copolymer are respectively dried before use, specifically, the nylon 6 and the ethylene-maleic anhydride segmented copolymer are dried in vacuum at the drying temperature of 100 ℃ for 3-5 hours, and then are sealed and cooled to room temperature; most preferably, the drying treatment is vacuum drying at a drying temperature of 100 ℃ for 4 hours, and then sealing and cooling to room temperature.
Preferably, in step 2) of the in-situ reactive compatibilization preparation method, the twin-screw extruder is a parallel co-rotating twin-screw extruder.
Preferably, in step 2) of the in-situ reaction compatibilization preparation method, the double-screw extruder is provided with 10 sections of barrels, and a side feeding port is arranged at the 5 th section of barrel.
Preferably, in the step 2) of the in-situ reaction compatibilization preparation method, the processing rotating speed of the double-screw extruder is 100 r/min-220 r/min; more preferably, the processing rotating speed of the double-screw extruder is 100 r/min-102 r/min.
Preferably, in step 2) of the in-situ reactive compatibilization preparation method, the barrel processing temperature of the twin-screw extruder is as follows: the temperature of a first area (a 1 st section of cylinder) is 140-200 ℃; the temperature of the second area to the ninth area (2 nd to 9 th sections of the cylinder) is 210 ℃ to 230 ℃; the temperature of the ten areas (the 10 th section of the cylinder) is 200-220 ℃; further preferably, the barrel processing temperature of the twin-screw extruder is as follows: the temperature of the first zone is 148-152 ℃; the temperature of the second area to the ninth area is 218 ℃ to 222 ℃; the temperature of the ten areas is 208-212 ℃.
Preferably, in the step 2) of the in-situ reactive compatibilization preparation method, the length-diameter ratio of the double-screw extruder is (44-48): 1.
preferably, in the step 2) of the in-situ reaction compatibilization preparation method, the processing vacuum degree of the double-screw extruder is more than or equal to-0.06 MPa.
The invention has the beneficial effects that:
the nylon 6 prepared by the in-situ reaction compatibilization method has the advantages of excellent flame retardant property, good mechanical property and thermal deformation property, simple preparation raw materials and production process, low cost and very wide application prospect.
Specifically, the advantages of the present invention over the prior art are as follows:
the invention adopts aluminum diethylphosphinate, TGIC and Ethylene-b-MAH coated by melamine cyanurate to carry out flame retardant modification on PA6, and has the advantages of simple components, less flame retardant consumption, simple production process and lower production cost.
The halogen-free flame retardant PA6 material adopts the cooperation of aluminum diethylphosphinate coated by melamine cyanurate, TGIC and Ethylene-b-MAH, not only obviously improves the dripping property of PA6 during combustion, but also obviously reduces the mechanical property of the halogen-free flame retardant PA6 due to the formation of branched macromolecules and obviously improves the thermal deformation temperature.
Drawings
FIG. 1 is a schematic diagram of the preparation of halogen-free flame retardant nylon 6 by in-situ reactive compatibilization.
Detailed Description
FIG. 1 is a schematic diagram of the preparation of halogen-free flame-retardant nylon 6 by in-situ reaction compatibilization. The present invention will be described in further detail with reference to fig. 1 by way of specific examples. The starting materials, reagents or apparatus used in the examples and comparative examples were obtained from conventional commercial sources unless otherwise specified. Unless otherwise indicated, the testing or testing methods are conventional in the art.
The raw materials used in the examples/comparative examples of the present invention were as follows:
nylon 6(PA6) was purchased from Japan, Inc., brand 1013B;
the melamine cyanurate-coated aluminum diethylphosphinate is purchased from Puseofur chemical Co., Ltd., Qingyuan, and the coating amount of the melamine cyanurate is 2% of the amount of the aluminum diethylphosphinate;
triglycidyl isocyanurate (TGIC) is purchased from guangzhou cattle chemical ltd;
ethylene-maleic anhydride block copolymers (Ethylene-b-MAH) were purchased from Vertellus chemical, Van. Del., under the designation E-60P.
Example 1
The in-situ reaction compatibilized halogen-free flame-retardant PA6 is prepared by mixing the following raw materials in parts by mass: PA 690 parts, melamine cyanurate coated aluminum diethylphosphinate 10 parts, TGIC 2 parts, and Ethylene-b-MAH 1 parts.
The preparation method of the in-situ reaction compatibilized halogen-free flame-retardant PA6 comprises the following steps:
(1) the PA6 and the Ethylene-b-MAH are respectively put into a vacuum oven for drying treatment at the drying temperature of 100 ℃ for 4 hours, and then the PA6 and the Ethylene-b-MAH are sealed and cooled to the room temperature.
(2) Uniformly mixing the dried PA6 and Ethylene-b-MAH with aluminum diethylphosphinate coated by melamine cyanurate according to a proportion for later use.
(3) The processing is carried out by using a parallel co-rotating double-screw extruder, the parallel co-rotating double-screw extruder is provided with 10 sections of cylinder bodies, the 5 th section of cylinder body is provided with a material filling port (a side feeding port), and the length-diameter ratio is 44: 1. And (3) putting the mixed material obtained in the step (2) into a main feeding port of a parallel co-rotating twin-screw extruder, adding TGIC at a side feeding port of the extruder in proportion, and carrying out melting, extrusion and granulation. The processing technology is as follows: the rotating speed of the parallel co-rotating twin-screw extruder is 101r/min, and the temperature control range of each barrel is as follows: the temperature of the first area is 150 ℃, the temperature of the second area to the ninth area is 220 ℃, and the temperature of the tenth area is 210 ℃; the vacuum degree during processing is-0.06 MPa.
Example 2
The in-situ reaction compatibilized halogen-free flame-retardant PA6 is prepared by mixing the following raw materials in parts by mass: PA 690 parts, melamine cyanurate coated aluminum diethylphosphinate 10 parts, TGIC 3 parts, and Ethylene-b-MAH 2 parts.
The preparation method of the in-situ reaction compatibilized halogen-free flame-retardant PA6 is the same as that of the example 1.
Example 3
The in-situ reaction compatibilized halogen-free flame-retardant PA6 is prepared by mixing the following raw materials in parts by mass: PA 685 parts, melamine cyanurate-coated aluminum diethylphosphinate 10 parts, TGIC 3 parts, and Ethylene-b-MAH 2 parts.
The preparation method of the in-situ reaction compatibilized halogen-free flame-retardant PA6 is the same as that of the example 1.
Example 4
The in-situ reaction compatibilized halogen-free flame-retardant PA6 is prepared by mixing the following raw materials in parts by mass: PA 685 parts, melamine cyanurate-coated aluminum diethylphosphinate 15 parts, TGIC 1 parts, and Ethylene-b-MAH 0.5 parts.
The preparation method of the in-situ reaction compatibilized halogen-free flame-retardant PA6 is the same as that of the example 1.
Comparative example 1
In this example, 100 parts by mass of PA6 were taken directly as a comparison.
Comparative example 2
In the embodiment, the flame-retardant PA6 material is prepared by only adopting PA6 and aluminum diethylphosphinate coated by melamine cyanurate, and is prepared by mixing the following raw materials in parts by mass: PA 685 parts, melamine cyanurate coated aluminum diethylphosphinate 15 parts.
The flame retardant PA6 material of this example was prepared in the same manner as in example 1, except that the starting materials used were added in the same manner as in the composition of this example.
The raw material composition ratios of examples 1 to 4 and comparative examples 1 to 2 are shown in Table 1.
TABLE 1 Nylon Material composition of examples and comparative examples
The nylon materials of examples 1-4 and comparative examples 1-2 were subjected to performance tests, and the test results are shown in table 2. The test methods corresponding to the test items in table 2 are as follows:
tensile strength: testing according to ASTM D638-08 standard, wherein the tensile rate is 50 mm/min;
flexural strength and flexural modulus: the thickness of the sample strip is 3.2mm according to the test of ASTM-D790-07;
heat distortion temperature: testing according to ASTM D648-07 standard, and carrying light load at 0.45 MPa;
notched impact strength: the thickness of the sample strip is 3.2mm according to the test of ASTM D256-06 standard;
flame retardant rating: UL-94, 1.6 mm.
Table 2 test results of nylon materials of examples and comparative examples
As shown in Table 2, the addition of a small amount of TGIC and Ethylene-b-MAH can obviously reduce the dosage of the flame retardant, and the mechanical property and the thermal deformation temperature of the halogen-free flame retardant PA6 are improved, so that the halogen-free flame retardant PA6 is suitable for places with high requirements on the mechanical property and the flame retardant property, and has a wide application prospect.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A halogen-free flame-retardant nylon 6 is characterized in that: the paint comprises the following components in parts by mass: 80-90 parts of nylon 6, 10-15 parts of melamine cyanurate-coated aluminum diethylphosphinate, 1-3 parts of triglycidyl isocyanurate and 0.5-2 parts of an ethylene-maleic anhydride block copolymer;
the halogen-free flame-retardant nylon 6 is prepared by adopting an in-situ reaction compatibilization method, and comprises the following steps:
1) mixing nylon 6, an ethylene-maleic anhydride block copolymer and melamine cyanurate-coated aluminum diethylphosphinate according to a ratio to obtain a mixture;
2) and putting the mixture into a main feeding port of a double-screw extruder, putting triglycidyl isocyanurate into a side feeding port of the double-screw extruder, and carrying out melting, extrusion and granulation to obtain the halogen-free flame-retardant nylon 6.
2. The halogen-free flame retardant nylon 6 according to claim 1, characterized in that: in the process of coating the aluminum diethylphosphinate by the melamine cyanurate, the coating amount of the melamine cyanurate is 1.5-2.5% of the mass of the aluminum diethylphosphinate.
3. A method for preparing the halogen-free flame-retardant nylon 6 of claim 1 or 2 by in-situ reactive compatibilization, which is characterized by comprising the following steps: the method comprises the following steps:
1) mixing nylon 6, an ethylene-maleic anhydride block copolymer and melamine cyanurate-coated aluminum diethylphosphinate according to a ratio to obtain a mixture;
2) and putting the mixture into a main feeding port of a double-screw extruder, putting triglycidyl isocyanurate into a side feeding port of the double-screw extruder, and carrying out melting, extrusion and granulation to obtain the halogen-free flame-retardant nylon 6.
4. The method of claim 3, wherein: the nylon 6 and the ethylene-maleic anhydride block copolymer are respectively dried before use.
5. The method of claim 4, wherein: the drying treatment is vacuum drying at the drying temperature of 100 ℃ for 3-5 hours, and then sealing and cooling to the room temperature.
6. The method of claim 3, wherein: in the step 2), the double-screw extruder is a parallel co-rotating double-screw extruder.
7. The method of claim 6, wherein: in the step 2), the double-screw extruder is provided with 10 sections of cylinder bodies, and a side feeding port is arranged at the 5 th section of cylinder body.
8. The method of claim 7, wherein: in the step 2), the processing rotating speed of the double-screw extruder is 100 r/min-220 r/min.
9. The method of claim 7, wherein: in the step 2), the processing temperature of the cylinder body of the double-screw extruder is as follows: the temperature of the first area is 140-200 ℃; the temperature of the second area to the ninth area is 210 ℃ to 230 ℃; the temperature of the ten zones is 200-220 ℃.
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| CN107216650A (en) * | 2017-06-02 | 2017-09-29 | 中山康诺德新材料有限公司 | A kind of long glass fiber reinforced halogen-free reinforced nylon compound and preparation method thereof |
| CN107828208A (en) * | 2017-11-08 | 2018-03-23 | 无锡中科苏惠自动化技术有限公司 | A kind of high-performance refractory composites of automation equipment and preparation method thereof |
| CN107903496A (en) * | 2017-11-28 | 2018-04-13 | 广东顺德同程新材料科技有限公司 | A kind of anti-flaming polypropylene material with low smell and pin flame performance and preparation method thereof |
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| CN107216650A (en) * | 2017-06-02 | 2017-09-29 | 中山康诺德新材料有限公司 | A kind of long glass fiber reinforced halogen-free reinforced nylon compound and preparation method thereof |
| CN107828208A (en) * | 2017-11-08 | 2018-03-23 | 无锡中科苏惠自动化技术有限公司 | A kind of high-performance refractory composites of automation equipment and preparation method thereof |
| CN107903496A (en) * | 2017-11-28 | 2018-04-13 | 广东顺德同程新材料科技有限公司 | A kind of anti-flaming polypropylene material with low smell and pin flame performance and preparation method thereof |
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