CN111574827B - Halogen-free flame-retardant PA6 and preparation method thereof - Google Patents
Halogen-free flame-retardant PA6 and preparation method thereof Download PDFInfo
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- CN111574827B CN111574827B CN202010388109.2A CN202010388109A CN111574827B CN 111574827 B CN111574827 B CN 111574827B CN 202010388109 A CN202010388109 A CN 202010388109A CN 111574827 B CN111574827 B CN 111574827B
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- C08L2201/02—Flame or fire retardant/resistant
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- C08L2201/22—Halogen free composition
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Abstract
The invention relates to a halogen-free flame-retardant PA6 composite material, which comprises 66-90 wt% of PA6 base material, 9-25 wt% of compound halogen-free flame retardant, 0.1-2.0 wt% of main antioxidant, 0.2-4.0 wt% of auxiliary antioxidant and 0.7-3.0 wt% of lubricant; the compound halogen-free flame retardant consists of hypophosphite-cyclotetrasiloxane double-base synergistic compound and a nitrogen flame retardant. The hypophosphite-cyclotetrasiloxane diradical cooperation is adopted, so that the flame retardant has excellent char forming performance and excellent flame retardant effect, the addition amount of the halogen-free flame retardant can be greatly reduced, the compatibility problem of the flame retardant and a matrix is improved, and the mechanical property of the matrix can be enhanced due to the existence of the Si-containing crosslinking structure in the siloxane group, so that the adverse effect caused by the addition of the flame retardant is further counteracted; the halogen-free flame-retardant PA6 composite material has the advantages of high flame-retardant efficiency, no halogen, low smoke, low toxicity, dripping resistance, excellent processability and wide application.
Description
Technical Field
The invention relates to halogen-free flame-retardant PA6, and belongs to the technical field of flame-retardant PA6 composite materials obtained by adding specific flame-retardant components into PA 6.
Background
Polyamide 6 (PA 6) is widely used in the fields of electronics, electricity, instruments, traffic, construction, and the like because of its excellent physical and mechanical properties, oil resistance, abrasion resistance, self-lubricity, and the like. Because the PA6 is easy to burn and hard to form carbon, and drops continuously during burning, the flame is easy to spread to cause fire, therefore, in order to meet the requirement of the product on the flame retardant property of the polymer material, the PA6 needs to be subjected to effective flame retardant modification. The addition of flame retardants to PA6 is a common method of altering the flammability of PA 6.
The flame retardants currently used in PA6 mainly include two main types, namely halogen-based flame retardants and halogen-free flame retardants. Although the halogen flame retardant plays a very important role in flame retardation of PA6, the halogen flame retardant has a large smoke amount in the combustion process, releases toxic (such as dioxin and the like) and corrosive gases, and causes great harm to the environment and human bodies, and the European Union starts to implement the ROHS directive in 2006, and people gradually give up using the halogen flame retardant. Halogen-free has the advantages of high efficiency, low smoke, low toxicity, small addition amount, no molten drop and the like, and is receiving more and more attention. Most halogen-free flame retardants, however, contain only one flame retardant element, such as phosphorus (P), silicon (Si), nitrogen (N), boron (B), and the like. However, only a small amount of single-component flame retardant can meet the requirement of the flame-retardant matrix PA 6. The flame retardant containing a plurality of elements can improve the flame retardant efficiency through the synergistic effect among different elements such as P-N, P-Si, N-Si and the like. Recently, a theory of dual-group synergistic flame retardancy has been proposed and widely used. Two types of flame-retardant groups are introduced into the same molecule through chemical bonds, and the flame retardant with higher flame-retardant efficiency is obtained by utilizing the synergistic flame-retardant effect between the groups. This form of flame retardant group has been shown in the prior literature and published materials to play a key role in increasing efficiency, and intramolecular groups exhibit superior flame retardant efficiency over those intermolecular groups.
At present, most researches use a flame retardant containing a single flame retardant group to be added into PA6, but the addition amount is often large to meet the flame retardant requirement. Therefore, the problems of poor compatibility of the flame retardant and a matrix, uneven mixing and the like can occur, and the mechanical property of the material is greatly influenced. Therefore, hypophosphite and siloxane are combined in one molecular unit through chemical bonds to form the hypophosphite-cyclotetrasiloxane double-base flame retardant, so that the flame retardant efficiency can be improved, meanwhile, the influence of the added flame retardant on the mechanical property is reduced due to the introduction of siloxane flexible groups, and the high-performance flame retardant PA6 material with excellent comprehensive performance is obtained.
Disclosure of Invention
Aiming at the problems existing at present, the invention provides a novel PA6 halogen-free flame-retardant composite material taking hypophosphite-cyclotetrasiloxane double-base synergistic compound as a flame retardant, which has the characteristics of high flame-retardant efficiency, compact formed carbon layer and low combustion toxicity, and can reduce the influence of adding the flame retardant on the mechanical property.
The invention provides a compound halogen-free flame retardant consisting of hypophosphite-cyclotetrasiloxane double-base synergistic compound and a nitrogen flame retardant; wherein the mass ratio of the hypophosphite-cyclotetrasiloxane bistatic compound to the nitrogen flame retardant is 2.
The invention provides halogen-free flame retardant PA6 which is characterized by comprising 66-90% of PA6 base material, 9-25% of compound halogen-free flame retardant, 0.1-2.0% of main antioxidant, 0.2-4.0% of auxiliary antioxidant and 0.7-3.0% of lubricant by mass percent.
The chemical structural formula of the hypophosphite-cyclotetrasiloxane double-base synergistic compound is as follows:
the hypophosphite-cyclotetrasiloxane double-based compound is one or a mixture of more of an aluminum hypophosphite-cyclotetrasiloxane double-based compound, zinc hypophosphite-cyclotetrasiloxane double-based compound, nickel hypophosphite-cyclotetrasiloxane double-based compound and lanthanum hypophosphite-cyclotetrasiloxane double-based compound;
the nitrogen flame retardant is selected from one or a mixture of more of melamine cyanurate, melamine polyphosphate, melamine pyrophosphate and ammonium polyphosphate;
the main antioxidant is one or a mixture of an antioxidant 1010 and an antioxidant 1076;
the auxiliary antioxidant is one or a mixture of antioxidant 168 or antioxidant 1098;
the lubricant is any one or a mixture of more of white oil, polyethylene wax and solid paraffin;
the halogen-free flame-retardant PA6 composite material provided by the invention has the following advantages:
(1) The hypophosphite-cyclotetrasiloxane double-base synergistic compound halogen-free flame retardant provided by the invention has high thermal decomposition temperature and higher carbon residue yield at high temperature, and is very suitable for the processing and flame retardant requirements of some high-processing-temperature polymer materials;
(2) The hypophosphite-cyclotetrasiloxane diyl synergistic compound halogen-free flame retardant contains siloxane groups. These Si-containing cross-linked structures can enhance the mechanical properties of the matrix to further offset the adverse effects due to the addition of flame retardants;
(3) The hypophosphite-cyclotetrasiloxane double-base synergistic compound halogen-free flame retardant provided by the invention has two flame retardant groups, and the flame retardant groups in the two molecules can generate mutual synergistic action in a gas phase and a condensed phase in a combustion process, so that the flame retardant has excellent char formation property and excellent flame retardant effect, the addition amount of the halogen-free flame retardant can be greatly reduced, the compatibility problem of the flame retardant and a matrix is improved, the adverse effect on the mechanical property of the matrix is further reduced, and the production and the use are very convenient;
(4) According to the halogen-free flame-retardant PA6 provided by the invention, due to the reasonable introduction of hypophosphite and cyclotetrasiloxane and the optimized addition proportion of the flame retardant, the inflammability of the PA6 is overcome, the PA6 has anti-dripping property in the combustion process, and the fire safety of the material is improved;
the hypophosphite-cyclotetrasiloxane bistatic synergistic compound provided by the invention is particularly suitable for halogen-free flame retardance of high-processing-temperature polymer materials as a halogen-free environment-friendly flame retardant system.
Drawings
FIG. 1 is a TGA and DTG graph of a hypophosphite-cyclotetrasiloxane diradical synergistic compound in a nitrogen atmosphere;
FIG. 2 is a graph of Heat Release Rate (HRR) -t for pure PA6 and halogen-free flame retardant PA6 composite prepared according to the present invention;
FIG. 3 is a graph of smoke release rate (THR) -t for pure PA6 and halogen-free flame retardant PA6 composites prepared according to the present invention.
Detailed Description
Table 1 is a diagram of the mass ratio of various substances in different examples of the present invention, and the present invention is further described below with reference to specific examples.
Example 1
In the embodiment, 8.00 wt% of a compound halogen-free flame retardant (a mixture of aluminum hypophosphite and cyclotetrasiloxane in a mass ratio of 2.6 to 3 of melamine cyanurate), 0.15 wt% of a main antioxidant 1010, 0.3 wt% of an auxiliary antioxidant 1098, 1.55 wt% of a lubricant polyethylene wax and 90 wt% of PA6 are compounded, then the mixture is uniformly mixed in a high-speed mixer, vacuum-dried at 100 ℃, crushed by a crusher, melted and extruded in a double-screw extruder, cooled and granulated to obtain the halogen-free flame-retardant PA6 composite material. And measured for data such as limiting oxygen index LOI, vertical burn UL-94 rating, and tensile and notched impact strengths, as shown in Table 2.
TABLE 1
TABLE 2
Example 2
In the embodiment, 8.00 wt% of halogen-free flame retardant (aluminum hypophosphite-cyclotetrasiloxane double-base compound and melamine cyanurate in a mass ratio of 3. And measured for data such as limiting oxygen index LOI, vertical burning UL-94 rating, and tensile strength and notched impact strength, as shown in Table 2.
Example 3
In the embodiment, 12.00 wt% of a compound halogen-free flame retardant (the mass ratio of the nickel hypophosphite-cyclotetrasiloxane double-base compound to the ammonium polyphosphate is 4. And measured for data such as limiting oxygen index LOI, vertical burn UL-94 rating, and tensile and notched impact strengths, as shown in Table 2.
Example 4
In the embodiment, 22.00 wt% of a compound halogen-free flame retardant (the mass ratio of lanthanum hypophosphite-cyclotetrasiloxane double-base compound to melamine pyrophosphate is 5. And measured for data such as limiting oxygen index LOI, vertical burning UL-94 rating, and tensile strength and notched impact strength, as shown in Table 2.
Example 5
In the embodiment, 17.00 wt% of a compound halogen-free flame retardant (a mixture of an aluminum hypophosphite-cyclotetrasiloxane bistatic compound and a zinc hypophosphite-cyclotetrasiloxane bistatic compound, and a mixture of melamine pyrophosphate and melamine polyphosphate in a mass ratio of 3). And measured for data such as limiting oxygen index LOI, vertical burning UL-94 rating, and tensile strength and notched impact strength, as shown in Table 2.
Claims (6)
1. A halogen-free flame retardant PA6 is characterized by comprising 66-90% of PA6 base material, 9-25% of compound halogen-free flame retardant, 0.1-2.0% of main antioxidant, 0.2-4.0% of auxiliary antioxidant and 0.7-3.0% of lubricant by mass percentage; the compound halogen-free flame retardant consists of hypophosphite-cyclotetrasiloxane double-base synergistic compound and a nitrogen flame retardant; the mass ratio of the hypophosphite-cyclotetrasiloxane bistyl synergistic compound to the nitrogen flame retardant is 2; the chemical structural formula of the hypophosphite-cyclotetrasiloxane double-base synergistic compound is as follows:
2. the halogen-free flame retardant PA6 as claimed in claim 1, wherein the hypophosphite-cyclotetrasiloxane bis-based compound is selected from one or more of a compound of an aluminum hypophosphite-cyclotetrasiloxane bis-based compound, a zinc hypophosphite-cyclotetrasiloxane bis-based compound, a nickel hypophosphite-cyclotetrasiloxane bis-based compound, and a lanthanum hypophosphite-cyclotetrasiloxane bis-based compound.
3. The halogen-free flame retardant PA6 according to claim 1, wherein the nitrogen-based flame retardant is one or more selected from melamine cyanurate, melamine polyphosphate, melamine pyrophosphate and ammonium polyphosphate.
4. The halogen-free flame retardant PA6 as claimed in claim 1, wherein the primary antioxidant is one or a combination of antioxidant 1010 and antioxidant 1076.
5. The halogen-free flame retardant PA6 as claimed in claim 1, wherein the secondary antioxidant is one or a combination of antioxidant 168 and antioxidant 1098.
6. The halogen-free flame retardant PA6 of claim 1, wherein the lubricant is one or more of white oil, polyethylene wax and paraffin wax.
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| CN109608878A (en) * | 2018-12-13 | 2019-04-12 | 上海长伟锦磁工程塑料有限公司 | A kind of halogen-free flameproof enhancing PA/POK alloy material of wet and heat ageing resistant |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100838451B1 (en) * | 2005-12-30 | 2008-06-16 | 제일모직주식회사 | Flame retardant polycarbonate resin composition having good impact, high heat resistance |
| US8703853B2 (en) * | 2012-06-21 | 2014-04-22 | Robert Valentine Kasowski | Flame retardant and composition containing it |
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| CN106633918A (en) * | 2017-01-13 | 2017-05-10 | 山东船舶技术研究院 | High-strength high-heat-resistance flame-retardant silicone rubber material and preparation method thereof |
| CN109608878A (en) * | 2018-12-13 | 2019-04-12 | 上海长伟锦磁工程塑料有限公司 | A kind of halogen-free flameproof enhancing PA/POK alloy material of wet and heat ageing resistant |
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| "Phosphorus-containing silica gel-coated ammonium polyphosphate: Preparation, characterization, and its effect on the flame retardancy of rigid polyurethane foam";Chen Yajun等;《J. APPL. POLYM. SCI.》;20181231;46334（1-11） * |
| "Preparation and Characteristics of an Environmentally Friendly Hyperbranched Flame-Retardant Polyurethane Hybrid Containing Nitrogen, Phosphorus, and Silicon";Chen Chin-Hsing等;《Polymers》;20190419;第11卷(第4期);720 * |
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