CN112745664A - Rapid-forming halogen-free flame-retardant PA6 composite material and preparation method thereof - Google Patents
Rapid-forming halogen-free flame-retardant PA6 composite material and preparation method thereof Download PDFInfo
- Publication number
- CN112745664A CN112745664A CN201911298010.7A CN201911298010A CN112745664A CN 112745664 A CN112745664 A CN 112745664A CN 201911298010 A CN201911298010 A CN 201911298010A CN 112745664 A CN112745664 A CN 112745664A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- preparation
- composite material
- halogen
- percent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to a rapid-forming halogen-free flame-retardant PA6 composite material and a preparation method thereof, wherein the rapid-forming halogen-free flame-retardant PA6 composite material comprises the following raw materials in percentage by mass: PA6 resin: 65-80 percent; phosphorus-nitrogen composite flame retardant: 15 to 25 percent; synergistic flame retardant: 3 to 5 percent; nucleating agent: 0.5-2%; antioxidant: 0.5-1%; lubricant: 1 to 2 percent. The rapid-forming halogen-free flame-retardant PA6 composite material prepared by the invention does not contain halogen, meets the requirements of green and environment protection, has the characteristics of rapid forming, shortening of injection molding cycle and the like, is particularly suitable for injection molding of thin-wall plastic products, effectively shortens the molding cycle during injection molding of the material, improves the production efficiency, and simultaneously maintains the physical properties and the flame retardant property of the material.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a rapidly-formed halogen-free flame-retardant PA6 composite material and a preparation method thereof.
Background
The halogen-free flame retardant mainly comprises a phosphorus compound and a metal hydroxide compound, wherein the phosphorus compound and the metal hydroxide compound are nonvolatile during combustion, do not generate corrosive gas, are called as natural flame retardants, are widely applied to market movement, and in the prior art, the halogen-free flame retardant PA6 is developed and applied more frequently, but the conditions of long forming period or difficulty in injection molding and demolding generally exist at present, the research and development on rapid forming are relatively less, and the halogen-free flame retardant PA6 is rarely involved in published literature records. In the injection molding process of the conventional halogen-free flame-retardant PA6 material, the conditions of mold sticking, mold stripping top deformation and the like often occur, and in order to overcome the problem, the pressure maintaining and cooling time in the injection molding process only needs to be prolonged, so that the molding period is prolonged, and the production efficiency is reduced.
Disclosure of Invention
The invention aims to solve the defects and provides a rapidly-formed halogen-free flame-retardant PA6 composite material and a preparation method thereof.
1. In order to overcome the defects in the background art, the technical scheme adopted by the invention for solving the technical problems is as follows: a quick-forming halogen-free flame-retardant PA6 composite material and a preparation method thereof are disclosed, wherein the composite material comprises the following raw materials by mass percent: PA6 resin: 65-80 percent; phosphorus-nitrogen composite flame retardant: 15 to 25 percent; synergistic flame retardant: 3 to 5 percent; nucleating agent: 0.5-2%; antioxidant: 0.5-1%; lubricant: 1-2%, and comprises the following steps:
(1) weighing the raw materials according to the weight percentage;
(2) adding the PA6 resin, the nucleating agent, the antioxidant and the lubricant into a first high-speed mixer, and mixing for 2-4min to obtain a PA6 resin mixture;
(3) adding the phosphorus-nitrogen composite flame retardant and the synergistic flame retardant into a second high-speed mixer to be mixed for 2-4min to obtain a flame retardant mixture;
(4) adjusting the temperature of the extruder to ensure that the temperature distribution from the feeding section to the head of the extruder is respectively as follows: 175-; the temperature of the die head of the extruder is 225-235 ℃;
(5) adding the PA6 resin mixture into the extruder from a first feeding port, and adding the flame retardant mixture into the extruder from a second feeding port;
(6) after the material is extruded, carrying out water cooling, blow drying, grain cutting and packaging;
(7) the pellets were dried in a forced air drying oven at a temperature of 120. + -. 5 ℃ for 4-6 hours and injection molded by an injection molding machine to prepare test specimens.
Preferably, the PA6 resin has a density of 1.13-1.16, a melting point of 220-225 ℃ and a relative viscosity of 2.4-2.8 dl/g.
Preferably, the phosphorus-nitrogen composite flame retardant is one or more of MCA, MPP and APP.
Preferably, the synergistic flame retardant is one or more than two of hydroxide or borate of magnesium.
Preferably, the nucleating agent is one or more than two of superfine talcum powder, gas-phase silicon dioxide, sodium benzoate and calcium arylsulfonate.
Preferably, the antioxidant is one or two of antioxidant 1098 and antioxidant 168.
Preferably, the lubricant is one or more of stearate and polyester type lubricant.
The invention has the beneficial effects that: the rapid-forming halogen-free flame-retardant PA6 composite material prepared by the invention does not contain halogen, meets the requirements of green and environment protection, has the characteristics of rapid forming, shortening of injection molding cycle and the like, is particularly suitable for injection molding of thin-wall plastic products, effectively shortens the molding cycle during injection molding of the material, improves the production efficiency, and simultaneously maintains the physical properties and the flame retardant property of the material.
Detailed Description
The following detailed description of the preferred embodiments of the present invention is provided to enable those skilled in the art to more readily understand the advantages and features of the present invention, and to clearly and unequivocally define the scope of the present invention.
Example 1
In the embodiment of the invention, the rapidly-formed halogen-free flame-retardant PA6 composite material comprises the following raw materials in percentage by mass:
PA6 resin: 76.9 percent;
MPP：15%；
MCA：3%；
zinc borate: 3 percent;
superfine talcum powder: 0.5 percent;
and (3) lubricant PETS: 1 percent;
antioxidant 1098: 0.3 percent;
antioxidant 168: 0.3 percent.
The preparation method of the rapid-forming halogen-free flame-retardant PA6 composite material comprises the following specific steps:
(1) weighing the raw materials according to the weight percentage;
(2) adding PA6 resin, superfine talcum powder, antioxidant 1098, antioxidant 168 and lubricant PETS into a first high-speed mixer, and mixing for 3min to obtain a PA6 resin mixture;
(3) adding MPP, MCA and zinc borate into a second high-speed mixer and mixing for 3min to obtain a flame retardant mixture;
(4) adjusting the temperature of the extruder to ensure that the temperature distribution from the feeding section to the head of the extruder is respectively as follows: 175-; the temperature of the die head of the extruder is 225-235 ℃; (ii) a
(5) Adding the PA6 resin mixture into the extruder from a first feeding port, and adding the flame retardant mixture into the extruder from a second feeding port;
(6) after the material is extruded, carrying out water cooling, blow drying, grain cutting and packaging;
(7) the pellets were dried in a forced air drying oven at a temperature of 120 ℃ for 6 hours and injection molded by an injection molding machine to prepare test specimens.
Example 2
In the embodiment of the invention, the rapidly-formed halogen-free flame-retardant PA6 composite material comprises the following raw materials in percentage by mass:
PA6 resin: 73.9 percent;
MPP：15%；
MCA：6%；
zinc borate: 3 percent;
superfine talcum powder: 0.5 percent;
and (3) lubricant PETS: 1 percent;
antioxidant 1098: 0.3 percent;
antioxidant 168: 0.3 percent.
The preparation method of the rapid-forming halogen-free flame-retardant PA6 composite material comprises the following specific steps:
(1) weighing the raw materials according to the weight percentage;
(2) adding PA6 resin, superfine talcum powder, antioxidant 1098, antioxidant 168 and lubricant PETS into a first high-speed mixer, and mixing for 3min to obtain a PA6 resin mixture;
(3) adding MPP, MCA and zinc borate into a second high-speed mixer and mixing for 3min to obtain a flame retardant mixture;
(4) adjusting the temperature of the extruder to ensure that the temperature distribution from the feeding section to the head of the extruder is respectively as follows: 175-; the temperature of the die head of the extruder is 225-235 ℃; (ii) a
(5) Adding the PA6 resin mixture into the extruder from a first feeding port, and adding the flame retardant mixture into the extruder from a second feeding port;
(6) after the material is extruded, carrying out water cooling, blow drying, grain cutting and packaging;
(7) the pellets were dried in a forced air drying oven at a temperature of 120 ℃ for 6 hours and injection molded by an injection molding machine to prepare test specimens.
Example 3
In the embodiment of the invention, the rapidly-formed halogen-free flame-retardant PA6 composite material comprises the following raw materials in percentage by mass:
PA6 resin: 68.4 percent;
MPP：16%；
MCA：9%；
zinc borate: 3 percent;
superfine talcum powder: 1 percent;
and (3) lubricant PETS: 1 percent;
antioxidant 1098: 0.3 percent;
antioxidant 168: 0.3 percent.
The preparation method of the rapid-forming halogen-free flame-retardant PA6 composite material comprises the following specific steps:
(1) weighing the raw materials according to the weight percentage;
(2) adding PA6 resin, superfine talcum powder, antioxidant 1098, antioxidant 168 and lubricant PETS into a first high-speed mixer, and mixing for 3min to obtain a PA6 resin mixture;
(3) adding MPP, MCA and zinc borate into a second high-speed mixer and mixing for 3min to obtain a flame retardant mixture;
(4) adjusting the temperature of the extruder to ensure that the temperature distribution from the feeding section to the head of the extruder is respectively as follows: 175-; the temperature of the die head of the extruder is 225-235 ℃; (ii) a
(5) Adding the PA6 resin mixture into the extruder from a first feeding port, and adding the flame retardant mixture into the extruder from a second feeding port;
(6) after the material is extruded, carrying out water cooling, blow drying, grain cutting and packaging;
(7) the pellets were dried in a forced air drying oven at a temperature of 120 ℃ for 6 hours and injection molded by an injection molding machine to prepare test specimens.
The test specimens prepared in example 1, example 2 and example 3 were subjected to performance tests, respectively, and the data obtained are shown in table 1:
table 1 results of performance testing of test bars prepared in example 1, example 2 and example 3
| Item | Example 1 | Example 2 | Example 3 |
| Tensile strength MPa | 72.5 | 68.2 | 65.5 |
| Bending strength MPa | 95.3 | 100.2 | 105.5 |
| Flexural modulus MPa | 2529 | 2475 | 2329 |
| Notched impact strength KJ/M2 | 6.53 | 5.85 | 5.05 |
| Flame retardant rating | V-2 | V-0 | V-0 |
| Dwell time S | 2 | 2 | 2 |
| Releasability from mold | Good effect | Good effect | Good effect |
The rapid-forming halogen-free flame-retardant PA6 material prepared by the invention does not contain halogen, meets the requirements of green environmental protection, has the characteristics of rapid forming, shortening of injection molding cycle and the like, is particularly suitable for injection molding of thin-wall plastic products, effectively shortens the molding cycle during the injection molding process, improves the production efficiency, simultaneously maintains the physical property and the flame retardant property of the material, and embodies the economy and the benefit.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (7)
1. A quick-forming halogen-free flame-retardant PA6 composite material and a preparation method thereof are disclosed, wherein the composite material comprises the following raw materials by mass percent: PA6 resin: 65-80 percent; phosphorus-nitrogen composite flame retardant: 15 to 25 percent; synergistic flame retardant: 3 to 5 percent; nucleating agent: 0.5-2%; antioxidant: 0.5-1%; lubricant: 1-2%, and comprises the following steps:
(1) weighing the raw materials according to the weight percentage;
(2) adding the PA6 resin, the nucleating agent, the antioxidant and the lubricant into a first high-speed mixer, and mixing for 2-4min to obtain a PA6 resin mixture;
(3) adding the phosphorus-nitrogen composite flame retardant and the synergistic flame retardant into a second high-speed mixer to be mixed for 2-4min to obtain a flame retardant mixture;
(4) adjusting the temperature of the extruder to ensure that the temperature distribution from the feeding section to the head of the extruder is respectively as follows: 175-; the temperature of the die head of the extruder is 225-235 ℃;
(5) adding the PA6 resin mixture into the extruder from a first feeding port, and adding the flame retardant mixture into the extruder from a second feeding port;
(6) after the material is extruded, carrying out water cooling, blow drying, grain cutting and packaging;
(7) the pellets were dried in a forced air drying oven at a temperature of 120. + -. 5 ℃ for 4-6 hours and injection molded by an injection molding machine to prepare test specimens.
2. The rapid prototyping halogen-free flame retardant PA6 composite material and the preparation method thereof as claimed in claim 1, wherein the preparation method comprises the following steps: the PA6 resin has the density of 1.13-1.16, the melting point of 220-225 ℃ and the relative viscosity of 2.4-2.8 dl/g.
3. The rapid prototyping halogen-free flame retardant PA6 composite material and the preparation method thereof as claimed in claim 1, wherein the preparation method comprises the following steps: the phosphorus-nitrogen composite flame retardant is one or more than two of MCA, MPP and APP.
4. The rapid prototyping halogen-free flame retardant PA6 composite material and the preparation method thereof as claimed in claim 1, wherein the preparation method comprises the following steps: the synergistic flame retardant is one or more than two of hydroxide or borate of magnesium.
5. The rapid prototyping halogen-free flame retardant PA6 composite material and the preparation method thereof as claimed in claim 1, wherein the preparation method comprises the following steps: the nucleating agent is one or more than two of superfine talcum powder, gas-phase silicon dioxide, sodium benzoate and calcium aryl sulfonate.
6. The rapid prototyping halogen-free flame retardant PA6 composite material and the preparation method thereof as claimed in claim 1, wherein the preparation method comprises the following steps: the antioxidant is one or two of antioxidant 1098 and antioxidant 168.
7. The rapid prototyping halogen-free flame retardant PA6 composite material and the preparation method thereof as claimed in claim 1, wherein the preparation method comprises the following steps: the lubricant is one or more than two of stearate and polyester type lubricant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911298010.7A CN112745664A (en) | 2019-12-17 | 2019-12-17 | Rapid-forming halogen-free flame-retardant PA6 composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911298010.7A CN112745664A (en) | 2019-12-17 | 2019-12-17 | Rapid-forming halogen-free flame-retardant PA6 composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112745664A true CN112745664A (en) | 2021-05-04 |
Family
ID=75645308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911298010.7A Pending CN112745664A (en) | 2019-12-17 | 2019-12-17 | Rapid-forming halogen-free flame-retardant PA6 composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112745664A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104004350A (en) * | 2014-06-20 | 2014-08-27 | 江苏兆鋆新材料股份有限公司 | Glass fiber reinforced halogen-free flame retardant polyamide 6 composite material and manufacturing method thereof |
| CN104559085A (en) * | 2014-12-26 | 2015-04-29 | 上海集飞新材料科技有限公司 | Non-enhanced type halogen-free flame retardant PBT (polybutylene terephthalate) composite material and preparation method thereof |
-
2019
- 2019-12-17 CN CN201911298010.7A patent/CN112745664A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104004350A (en) * | 2014-06-20 | 2014-08-27 | 江苏兆鋆新材料股份有限公司 | Glass fiber reinforced halogen-free flame retardant polyamide 6 composite material and manufacturing method thereof |
| CN104559085A (en) * | 2014-12-26 | 2015-04-29 | 上海集飞新材料科技有限公司 | Non-enhanced type halogen-free flame retardant PBT (polybutylene terephthalate) composite material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111073239A (en) | A kind of high temperature resistant polylactic acid injection molding imitation porcelain tableware and preparation method thereof | |
| CN103589069A (en) | High-shock resistance polypropylene/polybutylene composite material as well as preparation method and purposes thereof | |
| CN103160028A (en) | Modified polypropylene material, preparation method and applications thereof | |
| CN103030883A (en) | Polypropylene composite material capable of quick injection molding and preparation method thereof | |
| CN102924805A (en) | Stress-whitening-resisting glass fiber reinforced polypropylene composite and preparation method thereof | |
| CN105153659A (en) | Heat resistant polylactic acid composite material and preparation method thereof | |
| CN103059417A (en) | Filled polypropylene composite material applied to rapid forming component | |
| CN111073235A (en) | Fast-crystallization high-temperature-resistant polylactic acid composition and preparation method thereof | |
| CN107383584A (en) | High-rigidity high-modulus thin-wall injection molding polypropylene material and preparation method thereof | |
| CN107082960A (en) | A kind of flame retardant type high-gloss polypropylene composite and preparation method thereof | |
| CN103289207A (en) | Bending-resistant white polypropylene material and preparation method thereof | |
| CN111662507B (en) | Polypropylene material with high weld mark strength and preparation method thereof | |
| CN1995123B (en) | Polypropylene material and its preparing process | |
| CN110903650B (en) | High-crystallinity polyphenylene sulfide composite material easy to machine and mold and preparation method and application thereof | |
| CN103788480A (en) | Micro-foaming injection polypropylene composite for automotive interiors as well as preparation method and use of composite | |
| CN112745664A (en) | Rapid-forming halogen-free flame-retardant PA6 composite material and preparation method thereof | |
| CN106867246A (en) | It is a kind of to be applied to flame-retardant PA 66 mixed component of monofilament and preparation method thereof | |
| CN110229421B (en) | High-temperature-resistant injection molding polypropylene material and preparation method and application thereof | |
| CN112852133A (en) | Anti-droplet PLA/PVA composite material and preparation method thereof | |
| CN104559121A (en) | Modification production method of polycarbonate engineering plastic | |
| CN111040330A (en) | Enhanced PVC pipe and production method thereof | |
| CN103660306A (en) | Method for molding halogen-free flame-retardant thermoplastic polyester composition | |
| CN111057374A (en) | Low-flash rapid crystalline polyphenylene sulfide composite material | |
| CN114106530B (en) | High CTI value halogen-free flame-retardant reinforced PET modified engineering plastic and preparation method and application thereof | |
| CN111892766B (en) | PP material injection molding process and bottle cap prepared by same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210504 |
|
| WD01 | Invention patent application deemed withdrawn after publication |
