CN112375332A - Environment-friendly flame-retardant laser etching material and preparation method thereof - Google Patents
Environment-friendly flame-retardant laser etching material and preparation method thereof Download PDFInfo
- Publication number
- CN112375332A CN112375332A CN202011335492.1A CN202011335492A CN112375332A CN 112375332 A CN112375332 A CN 112375332A CN 202011335492 A CN202011335492 A CN 202011335492A CN 112375332 A CN112375332 A CN 112375332A
- Authority
- CN
- China
- Prior art keywords
- parts
- laser etching
- environment
- flame retardant
- retardant
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- 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
- C08K2201/011—Nanostructured additives
-
- 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
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- 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)
Abstract
The invention relates to an environment-friendly flame-retardant laser etching material and a preparation method thereof, wherein the environment-friendly flame-retardant laser etching material comprises the following components in parts by weight: 40-80 parts of transparent ABS resin, 20-60 parts of PBT resin, 1-10 parts of antistatic color master batch, 1-3 parts of compatilizer, 6-12 parts of laser engraving agent, 1-6 parts of flame retardant, 1-4 parts of lubricant, 0.2-0.6 part of light stabilizer and 0.5-2 parts of antioxidant. A finished product processed by the environment-friendly flame-retardant laser etching material prepared by the invention has better concave-convex touch hand feeling, the processing procedure is environment-friendly, the process flow is simple, the laser etching material can be more stably applied, and the flame-retardant laser etching material has stronger flame retardance, is safer for human bodies, and meets the market demand.
Description
Technical Field
The invention relates to the field of environment-friendly flame retardance, and particularly relates to an environment-friendly flame-retardant laser etching material and a preparation method thereof.
Background
ABS resin obtained by acrylonitrile, butadiene and styrene through ternary polymerization is widely applied to the electronic and electrical industry due to excellent comprehensive performance, and the ABS laser etching material occupies a large share in laser etching products. Laser engraving (laser marking) has been successfully applied to computer keyboards, lamp switch covers, automobile interior buttons and door handles, instrument panels, rigid containers and container covers, electrical connections, capacitors. The ABS laser engraving material realizes that the ABS does not need the traditional printing process, and is a new energy-saving and environment-friendly technology in the electronic and electrical industry.
With the improvement of the living standard of people, people are pursuing the comfort of living environment increasingly, the attention on environmental protection is also gradually promoted, and the safety and environmental protection performance of daily products are required to be higher. Although the ABS resin has excellent properties such as no toxicity, no odor, low water absorption, etc., it has a very low oxygen index, is a flammable substance, burns quickly on fire, and generates a large amount of harmful and toxic fumes, so it needs to be used in combination with a flame retardant. The commonly used flame retardant is prepared by compounding a brominated flame retardant with antimony trioxide, although the flame retardant effect is good, the halogen flame retardant causes great pollution when used, and polluting gas is generated in the production process, so that the flame retardant laser engraving material which can meet daily use and is halogen-free and environment-friendly is urgently needed in the market at present.
Disclosure of Invention
Aiming at the problems, the invention provides an environment-friendly flame-retardant laser etching material and a preparation method thereof, which can simultaneously meet the requirements of daily use and halogen-free environment protection.
The invention is realized by the following technical scheme:
the invention aims to provide an environment-friendly flame-retardant laser etching material which comprises the following components in parts by weight:
40-80 parts of transparent ABS resin, 20-60 parts of PBT resin, 1-10 parts of antistatic color master batch, 1-3 parts of compatilizer, 6-12 parts of laser engraving agent, 1-6 parts of flame retardant, 1-4 parts of lubricant, 0.2-0.6 part of light stabilizer and 0.5-2 parts of antioxidant.
Preferably, the environment-friendly flame-retardant laser etching material comprises the following components in parts by weight:
50-70 parts of transparent ABS resin, 20-40 parts of PBT resin, 3-7 parts of antistatic color master batch, 1-3 parts of compatilizer, 6-12 parts of laser engraving agent, 1-6 parts of flame retardant, 1-4 parts of lubricant, 0.2-0.6 part of light stabilizer and 0.5-2 parts of antioxidant.
Preferably, the transparent ABS resin is a methyl methacrylate-acrylonitrile-butadiene-styrene resin.
Preferably, the PBT resin is a semi-crystalline thermoplastic polyester with the viscosity of 0.8-1.2 dl/g.
Preferably, the compatibilizer is one or more of maleic anhydride grafted acrylonitrile-butadiene-styrene, acrylonitrile-styrene-glycidyl methacrylate, and styrene maleic anhydride copolymer.
Preferably, the laser etching agent is a mixture of an organic metal compound and nano silicon dioxide; wherein the mass ratio of the organic metal compound to the nano silicon dioxide is 2-4: 1.
Preferably, in the laser etching agent, the organic metal compound is an organic copper compound and/or an organic zinc compound.
Preferably, the flame retardant is a pyridine phosphorus composite flame retardant; the preparation method of the pyridine-phosphorus composite flame retardant comprises the following steps:
s1, weighing 2-pyridinecarboxamide, adding the 2-pyridinecarboxamide into absolute ethyl alcohol, and stirring the mixture uniformly to obtain a 2-pyridinecarboxamide solution; weighing phenylacetaldehyde, adding the phenylacetaldehyde into absolute ethyl alcohol, and stirring the mixture uniformly to obtain a phenylacetaldehyde solution;
wherein in the 2-pyridinecarboxamide solution, the mass ratio of the 2-pyridinecarboxamide to the absolute ethyl alcohol is 1: 5-12; in the phenylacetaldehyde solution, the mass ratio of phenylacetaldehyde to absolute ethyl alcohol is 1: 6-14;
s2, pouring the 2-pyridine carboxamide solution into a reaction container, introducing inert gas as protective gas, dropwise adding the phenylacetaldehyde solution into the 2-pyridine carboxamide solution while stirring at room temperature, continuously stirring and reacting for 1-2 hours after completely dropwise adding, and then performing rotary evaporation to dryness to obtain a powdery pyridine imine product;
wherein the mass ratio of the 2-pyridine carboxamide solution to the phenylacetaldehyde solution is 2-3: 1; the phenylacetaldehyde solution needs to be subjected to dropwise addition reaction within 1 hour after the preparation is finished, and the dropwise addition speed is 1-2 drops/second; the stirring speed is 200-500 rpm;
s3, weighing tetrabutyl phosphorus hydroxide, adding the tetrabutyl phosphorus hydroxide into the absolute ethyl alcohol, stirring at room temperature until the tetrabutyl phosphorus hydroxide is uniform, introducing inert gas serving as protective gas, adding the pyridine imine product, stirring and reacting at 70-80 ℃ in a water bath for 6-10 hours, cooling to room temperature, removing the protective gas, performing rotary evaporation to dryness, washing with a saturated sodium carbonate solution for three times, washing with purified water for three times, and performing vacuum drying to obtain the pyridine-phosphorus composite flame retardant;
wherein the mass ratio of tetrabutyl phosphorus hydroxide, the pyridine imine product and absolute ethyl alcohol is 1: 2.2-3.4: 10-15.
Preferably, the lubricant is pentaerythritol stearate and/or ethylene bis stearamide.
Preferably, the light stabilizer is a mixture of 2-hydroxy-4-methoxybenzophenone and a hindered amine.
Preferably, the antioxidant is a hindered phenol compound and/or a phosphite compound.
The invention also aims to provide a preparation method of the environment-friendly flame-retardant laser etching material, which comprises the following steps:
step 1, weighing transparent ABS resin, PBT resin, antistatic color master batch, compatilizer, laser etching agent, flame retardant, lubricant, light stabilizer and antioxidant according to the amount for later use;
step 2, adding the transparent ABS resin and the PBT resin into a mixing stirrer to be uniformly mixed to obtain mixed resin;
step 3, sequentially adding the antistatic color master batch, the compatilizer, the laser etching agent, the flame retardant, the lubricant, the light stabilizer and the antioxidant into a mixing stirrer containing the mixed resin, and continuously mixing until the mixture is uniform to obtain a mixed product;
and 4, adding the mixed product into a double-screw extruder for melt extrusion and granulation to obtain the environment-friendly flame-retardant laser etching material.
The invention has the beneficial effects that:
1. the environment-friendly flame-retardant laser etching material is prepared by using transparent ABS resin, PBT resin and various auxiliaries; the ABS resin has the characteristics of strong impact resistance, scratch resistance, dimensional stability and the like, and simultaneously has the characteristics of moisture resistance, corrosion resistance, easiness in processing and the like, and the weather resistance, the oil resistance and the solvent resistance of the PBT resin can be further improved after the PBT resin is mixed with the PBT resin.
2. The invention prepares a halogen-free environment-friendly pyridine phosphorus composite flame retardant, and in view of the defects of large volatility, poor heat resistance and particularly poor compatibility of the conventional phosphorus flame retardant, the mechanical property of the resin is usually reduced after the conventional phosphorus flame retardant is combined with the resin. Therefore, the invention selects tetrabutyl phosphorus hydroxide as a phosphorus base material and 2-pyridinecarboxamide and phenylacetaldehyde as structural auxiliary materials to prepare the halogen-free flame retardant with small volatility, high heat resistance and excellent compatibility through screening. The preparation method comprises the steps of firstly reacting 2-pyridinecarboxamide with phenylacetaldehyde to prepare a Schiff base product containing imine groups, and then combining the Schiff base product with tetrabutyl phosphorus hydroxide to react to form the final phosphorus flame retardant. The addition of pyridine Schiff bases can improve the compatibility of tetrabutyl phosphorus hydroxide and resin, and can play a role in further agglomeration and flame retardance in the process of flame retardance, so that the properties of the resin are not reduced.
3. The laser carving powder is prepared by mixing the organic metal compound and the nano silicon dioxide, and the mixed use of the organic metal and the inorganic silicon dioxide can ensure that the laser marking or code printing on the surface of the plastic is smoother, thereby greatly improving the definition of the laser marking of the plastic material; the antistatic color master batch is added, so that the antistatic property of the material can be further enhanced while the dye is carried out, and the material is easier to color; in addition, the laser etching material is added with a compatilizer, a laser etching agent, a flame retardant, a lubricant, a light stabilizer and an antioxidant, and is used for further enhancing the performance of the laser etching material.
4. According to the preparation method, the resin is mixed firstly, the mixture is subjected to banburying uniformly and then various auxiliary agents are added, and a process of mixing a stirrer firstly and then a double-screw extruder is used, so that the stirring and dispersing are more uniform, the bonding or grafting efficiency of various materials is higher, the finished product is more stable, and the laser engraving effect is more remarkable.
A finished product processed by the environment-friendly flame-retardant laser etching material prepared by the invention has better concave-convex touch hand feeling, the processing procedure is environment-friendly, the process flow is simple, the laser etching material can be more stably applied, and the flame-retardant laser etching material has stronger flame retardance, is safer for human bodies, and meets the market demand.
Detailed Description
The invention is further described with reference to the following examples.
Example 1
The environment-friendly flame-retardant laser etching material comprises the following components in parts by weight:
60 parts of transparent ABS resin, 30 parts of PBT resin, 6 parts of antistatic color master batch, 2 parts of compatilizer, 9 parts of radium carving agent, 3 parts of flame retardant, 2.5 parts of lubricant, 0.4 part of light stabilizer and 1 part of antioxidant.
The transparent ABS resin is methyl methacrylate-acrylonitrile-butadiene-styrene resin.
The PBT resin is a semi-crystalline thermoplastic polyester with the viscosity of 0.8-1.2 dl/g.
The compatilizer is styrene maleic anhydride copolymer.
The laser etching agent is a mixture consisting of an organic metal compound and nano silicon dioxide; wherein the mass ratio of the organic metal compound to the nano silicon dioxide is 2-4: 1.
In the laser etching agent, the organic metal compound is an organic copper compound.
The flame retardant is a pyridine phosphorus composite flame retardant; the preparation method of the pyridine-phosphorus composite flame retardant comprises the following steps:
s1, weighing 2-pyridinecarboxamide, adding the 2-pyridinecarboxamide into absolute ethyl alcohol, and stirring the mixture uniformly to obtain a 2-pyridinecarboxamide solution; weighing phenylacetaldehyde, adding the phenylacetaldehyde into absolute ethyl alcohol, and stirring the mixture uniformly to obtain a phenylacetaldehyde solution;
wherein in the 2-pyridinecarboxamide solution, the mass ratio of the 2-pyridinecarboxamide to the absolute ethyl alcohol is 1: 5-12; in the phenylacetaldehyde solution, the mass ratio of phenylacetaldehyde to absolute ethyl alcohol is 1: 6-14;
s2, pouring the 2-pyridine carboxamide solution into a reaction container, introducing inert gas as protective gas, dropwise adding the phenylacetaldehyde solution into the 2-pyridine carboxamide solution while stirring at room temperature, continuously stirring and reacting for 1-2 hours after completely dropwise adding, and then performing rotary evaporation to dryness to obtain a powdery pyridine imine product;
wherein the mass ratio of the 2-pyridine carboxamide solution to the phenylacetaldehyde solution is 2-3: 1; the phenylacetaldehyde solution needs to be subjected to dropwise addition reaction within 1 hour after the preparation is finished, and the dropwise addition speed is 1-2 drops/second; the stirring speed is 200-500 rpm;
s3, weighing tetrabutyl phosphorus hydroxide, adding the tetrabutyl phosphorus hydroxide into the absolute ethyl alcohol, stirring at room temperature until the tetrabutyl phosphorus hydroxide is uniform, introducing inert gas serving as protective gas, adding the pyridine imine product, stirring and reacting at 70-80 ℃ in a water bath for 6-10 hours, cooling to room temperature, removing the protective gas, performing rotary evaporation to dryness, washing with a saturated sodium carbonate solution for three times, washing with purified water for three times, and performing vacuum drying to obtain the pyridine-phosphorus composite flame retardant;
wherein the mass ratio of tetrabutyl phosphorus hydroxide, the pyridine imine product and absolute ethyl alcohol is 1: 2.2-3.4: 10-15.
The lubricant is pentaerythritol stearate.
The light stabilizer is a mixture of 2-hydroxy-4-methoxybenzophenone and hindered amine.
The antioxidant is a hindered phenol compound.
The preparation method of the environment-friendly flame-retardant laser etching material comprises the following steps:
step 1, weighing transparent ABS resin, PBT resin, antistatic color master batch, compatilizer, laser etching agent, flame retardant, lubricant, light stabilizer and antioxidant according to the amount for later use;
step 2, adding the transparent ABS resin and the PBT resin into a mixing stirrer to be uniformly mixed to obtain mixed resin;
step 3, sequentially adding the antistatic color master batch, the compatilizer, the laser etching agent, the flame retardant, the lubricant, the light stabilizer and the antioxidant into a mixing stirrer containing the mixed resin, and continuously mixing until the mixture is uniform to obtain a mixed product;
and 4, adding the mixed product into a double-screw extruder for melt extrusion and granulation to obtain the environment-friendly flame-retardant laser etching material.
Example 2
The environment-friendly flame-retardant laser etching material comprises the following components in parts by weight:
40 parts of transparent ABS resin, 20 parts of PBT resin, 1 part of antistatic color master batch, 1 part of compatilizer, 6 parts of radium carving agent, 1 part of flame retardant, 1 part of lubricant, 0.2 part of light stabilizer and 0.5 part of antioxidant.
The transparent ABS resin is methyl methacrylate-acrylonitrile-butadiene-styrene resin.
The PBT resin is a semi-crystalline thermoplastic polyester with the viscosity of 0.8-1.2 dl/g.
The compatilizer is maleic anhydride grafted acrylonitrile-butadiene-styrene.
The laser etching agent is a mixture consisting of an organic metal compound and nano silicon dioxide; wherein the mass ratio of the organic metal compound to the nano silicon dioxide is 2-4: 1.
In the laser etching agent, the organic metal compound is an organic zinc compound.
The flame retardant is a pyridine phosphorus composite flame retardant; the preparation method of the pyridine-phosphorus composite flame retardant comprises the following steps:
s1, weighing 2-pyridinecarboxamide, adding the 2-pyridinecarboxamide into absolute ethyl alcohol, and stirring the mixture uniformly to obtain a 2-pyridinecarboxamide solution; weighing phenylacetaldehyde, adding the phenylacetaldehyde into absolute ethyl alcohol, and stirring the mixture uniformly to obtain a phenylacetaldehyde solution;
wherein in the 2-pyridinecarboxamide solution, the mass ratio of the 2-pyridinecarboxamide to the absolute ethyl alcohol is 1: 5-12; in the phenylacetaldehyde solution, the mass ratio of phenylacetaldehyde to absolute ethyl alcohol is 1: 6-14;
s2, pouring the 2-pyridine carboxamide solution into a reaction container, introducing inert gas as protective gas, dropwise adding the phenylacetaldehyde solution into the 2-pyridine carboxamide solution while stirring at room temperature, continuously stirring and reacting for 1-2 hours after completely dropwise adding, and then performing rotary evaporation to dryness to obtain a powdery pyridine imine product;
wherein the mass ratio of the 2-pyridine carboxamide solution to the phenylacetaldehyde solution is 2-3: 1; the phenylacetaldehyde solution needs to be subjected to dropwise addition reaction within 1 hour after the preparation is finished, and the dropwise addition speed is 1-2 drops/second; the stirring speed is 200-500 rpm;
s3, weighing tetrabutyl phosphorus hydroxide, adding the tetrabutyl phosphorus hydroxide into the absolute ethyl alcohol, stirring at room temperature until the tetrabutyl phosphorus hydroxide is uniform, introducing inert gas serving as protective gas, adding the pyridine imine product, stirring and reacting at 70-80 ℃ in a water bath for 6-10 hours, cooling to room temperature, removing the protective gas, performing rotary evaporation to dryness, washing with a saturated sodium carbonate solution for three times, washing with purified water for three times, and performing vacuum drying to obtain the pyridine-phosphorus composite flame retardant;
wherein the mass ratio of tetrabutyl phosphorus hydroxide, the pyridine imine product and absolute ethyl alcohol is 1: 2.2-3.4: 10-15.
The lubricant is ethylene bis stearamide.
The light stabilizer is a mixture of 2-hydroxy-4-methoxybenzophenone and hindered amine.
The antioxidant is a phosphite ester compound.
The preparation method of the environment-friendly flame-retardant laser etching material comprises the following steps:
step 1, weighing transparent ABS resin, PBT resin, antistatic color master batch, compatilizer, laser etching agent, flame retardant, lubricant, light stabilizer and antioxidant according to the amount for later use;
step 2, adding the transparent ABS resin and the PBT resin into a mixing stirrer to be uniformly mixed to obtain mixed resin;
step 3, sequentially adding the antistatic color master batch, the compatilizer, the laser etching agent, the flame retardant, the lubricant, the light stabilizer and the antioxidant into a mixing stirrer containing the mixed resin, and continuously mixing until the mixture is uniform to obtain a mixed product;
and 4, adding the mixed product into a double-screw extruder for melt extrusion and granulation to obtain the environment-friendly flame-retardant laser etching material.
Example 3
The environment-friendly flame-retardant laser etching material comprises the following components in parts by weight:
80 parts of transparent ABS resin, 60 parts of PBT resin, 10 parts of antistatic color master batch, 3 parts of compatilizer, 12 parts of radium carving agent, 6 parts of flame retardant, 4 parts of lubricant, 0.6 part of light stabilizer and 2 parts of antioxidant.
The transparent ABS resin is methyl methacrylate-acrylonitrile-butadiene-styrene resin.
The PBT resin is a semi-crystalline thermoplastic polyester with the viscosity of 0.8-1.2 dl/g.
The compatilizer is acrylonitrile-styrene-glycidyl methacrylate.
The laser etching agent is a mixture consisting of an organic metal compound and nano silicon dioxide; wherein the mass ratio of the organic metal compound to the nano silicon dioxide is 2-4: 1.
In the laser etching agent, the organic metal compound is an organic copper compound.
The flame retardant is a pyridine phosphorus composite flame retardant; the preparation method of the pyridine-phosphorus composite flame retardant comprises the following steps:
s1, weighing 2-pyridinecarboxamide, adding the 2-pyridinecarboxamide into absolute ethyl alcohol, and stirring the mixture uniformly to obtain a 2-pyridinecarboxamide solution; weighing phenylacetaldehyde, adding the phenylacetaldehyde into absolute ethyl alcohol, and stirring the mixture uniformly to obtain a phenylacetaldehyde solution;
wherein in the 2-pyridinecarboxamide solution, the mass ratio of the 2-pyridinecarboxamide to the absolute ethyl alcohol is 1: 5-12; in the phenylacetaldehyde solution, the mass ratio of phenylacetaldehyde to absolute ethyl alcohol is 1: 6-14;
s2, pouring the 2-pyridine carboxamide solution into a reaction container, introducing inert gas as protective gas, dropwise adding the phenylacetaldehyde solution into the 2-pyridine carboxamide solution while stirring at room temperature, continuously stirring and reacting for 1-2 hours after completely dropwise adding, and then performing rotary evaporation to dryness to obtain a powdery pyridine imine product;
wherein the mass ratio of the 2-pyridine carboxamide solution to the phenylacetaldehyde solution is 2-3: 1; the phenylacetaldehyde solution needs to be subjected to dropwise addition reaction within 1 hour after the preparation is finished, and the dropwise addition speed is 1-2 drops/second; the stirring speed is 200-500 rpm;
s3, weighing tetrabutyl phosphorus hydroxide, adding the tetrabutyl phosphorus hydroxide into the absolute ethyl alcohol, stirring at room temperature until the tetrabutyl phosphorus hydroxide is uniform, introducing inert gas serving as protective gas, adding the pyridine imine product, stirring and reacting at 70-80 ℃ in a water bath for 6-10 hours, cooling to room temperature, removing the protective gas, performing rotary evaporation to dryness, washing with a saturated sodium carbonate solution for three times, washing with purified water for three times, and performing vacuum drying to obtain the pyridine-phosphorus composite flame retardant;
wherein the mass ratio of tetrabutyl phosphorus hydroxide, the pyridine imine product and absolute ethyl alcohol is 1: 2.2-3.4: 10-15.
The lubricant is pentaerythritol stearate.
The light stabilizer is a mixture of 2-hydroxy-4-methoxybenzophenone and hindered amine.
The antioxidant is a hindered phenol compound.
The preparation method of the environment-friendly flame-retardant laser etching material comprises the following steps:
step 1, weighing transparent ABS resin, PBT resin, antistatic color master batch, compatilizer, laser etching agent, flame retardant, lubricant, light stabilizer and antioxidant according to the amount for later use;
step 2, adding the transparent ABS resin and the PBT resin into a mixing stirrer to be uniformly mixed to obtain mixed resin;
step 3, sequentially adding the antistatic color master batch, the compatilizer, the laser etching agent, the flame retardant, the lubricant, the light stabilizer and the antioxidant into a mixing stirrer containing the mixed resin, and continuously mixing until the mixture is uniform to obtain a mixed product;
and 4, adding the mixed product into a double-screw extruder for melt extrusion and granulation to obtain the environment-friendly flame-retardant laser etching material.
Comparative example
The laser etching material comprises the following components in parts by weight:
60 parts of transparent ABS resin, 30 parts of PBT resin, 6 parts of antistatic color master batch, 2 parts of compatilizer, 9 parts of radium carving agent, 2.5 parts of lubricant, 0.4 part of light stabilizer and 1 part of antioxidant.
The transparent ABS resin is methyl methacrylate-acrylonitrile-butadiene-styrene resin.
The PBT resin is a semi-crystalline thermoplastic polyester with the viscosity of 0.8-1.2 dl/g.
The compatilizer is styrene maleic anhydride copolymer.
The laser etching agent is a mixture consisting of an organic metal compound and nano silicon dioxide; wherein the mass ratio of the organic metal compound to the nano silicon dioxide is 2-4: 1.
In the laser etching agent, the organic metal compound is an organic copper compound.
The lubricant is pentaerythritol stearate.
The light stabilizer is a mixture of 2-hydroxy-4-methoxybenzophenone and hindered amine.
The antioxidant is a hindered phenol compound.
The preparation method of the laser etching material comprises the following steps:
step 1, weighing transparent ABS resin, PBT resin, antistatic color master batch, compatilizer, laser etching agent, flame retardant, lubricant, light stabilizer and antioxidant according to the amount for later use;
step 2, adding the transparent ABS resin and the PBT resin into a mixing stirrer to be uniformly mixed to obtain mixed resin;
step 3, sequentially adding the antistatic color master batch, the compatilizer, the laser etching agent, the flame retardant, the lubricant, the light stabilizer and the antioxidant into a mixing stirrer containing the mixed resin, and continuously mixing until the mixture is uniform to obtain a mixed product;
and 4, adding the mixed product into a double-screw extruder for melt extrusion and granulation to obtain the laser carving material.
In order to more clearly illustrate the invention, the performance of the laser etching materials prepared in the examples 1 to 3 of the invention and the comparative example was tested and compared, and the results are shown in table 1.
Wherein the tensile strength, elongation at break, heat distortion temperature, bending strength and oxygen index are all detected by ASTM method; the scratch resistance is detected by a pencil scratch method;
TABLE 1 Performance testing of laser engravings
| Example 1 | Example 2 | Example 3 | Comparative example | |
| Tensile strength/MPa | 50.3 | 48.1 | 51.5 | 48.6 |
| Elongation at break/% | 38 | 39 | 37 | 39 |
| Heat distortion temperature/. degree.C | 126 | 120 | 128 | 112 |
| Flexural Strength/MPa | 67.5 | 66.2 | 67.8 | 67.4 |
| Scratch resistance/MPa | 4H | 4H | 4H | 4H |
| Oxygen index/% | 32.4 | 30.6 | 33.1 | 21.2 |
As can be seen from Table 1, the laser etching materials prepared in the embodiments 1-3 of the invention have no great difference in tensile strength, elongation at break, bending strength and scratch resistance from the comparative examples, have a certain improvement in thermal deformation temperature and a great improvement in oxygen index, and the results show that the environment-friendly flame-retardant laser etching material prepared by the invention has excellent flame retardant property, almost has no influence on the mechanical property of the material, and further improves the thermal deformation temperature of the material.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The environment-friendly flame-retardant laser etching material is characterized by comprising the following components in parts by weight:
40-80 parts of transparent ABS resin, 20-60 parts of PBT resin, 1-10 parts of antistatic color master batch, 1-3 parts of compatilizer, 6-12 parts of laser engraving agent, 1-6 parts of flame retardant, 1-4 parts of lubricant, 0.2-0.6 part of light stabilizer and 0.5-2 parts of antioxidant.
2. The environment-friendly flame-retardant laser etching material as claimed in claim 1, which is characterized by comprising the following components in parts by weight:
50-70 parts of transparent ABS resin, 20-40 parts of PBT resin, 3-7 parts of antistatic color master batch, 1-3 parts of compatilizer, 6-12 parts of laser engraving agent, 1-6 parts of flame retardant, 1-4 parts of lubricant, 0.2-0.6 part of light stabilizer and 0.5-2 parts of antioxidant.
3. The environment-friendly flame retardant laser engraving material as claimed in claim 1, wherein the transparent ABS resin is a methyl methacrylate-acrylonitrile-butadiene-styrene resin; the PBT resin is a semi-crystalline thermoplastic polyester with the viscosity of 0.8-1.2 dl/g.
4. The environment-friendly flame retardant laser engraving material as claimed in claim 1, wherein the compatilizer is one or more of maleic anhydride grafted acrylonitrile-butadiene-styrene, acrylonitrile-styrene-glycidyl methacrylate and styrene maleic anhydride copolymer.
5. The environment-friendly flame retardant laser etching material as claimed in claim 1, wherein the laser etching agent is a mixture of an organic metal compound and nano silicon dioxide; wherein the mass ratio of the organic metal compound to the nano silicon dioxide is 2-4: 1; the organic metal compound is an organic copper compound and/or an organic zinc compound.
6. The environment-friendly flame-retardant laser etching material as claimed in claim 1, wherein the flame retardant is a pyridine-phosphorus composite flame retardant; the preparation method of the pyridine-phosphorus composite flame retardant comprises the following steps:
s1, weighing 2-pyridinecarboxamide, adding the 2-pyridinecarboxamide into absolute ethyl alcohol, and stirring the mixture uniformly to obtain a 2-pyridinecarboxamide solution; weighing phenylacetaldehyde, adding the phenylacetaldehyde into absolute ethyl alcohol, and stirring the mixture uniformly to obtain a phenylacetaldehyde solution;
wherein in the 2-pyridinecarboxamide solution, the mass ratio of the 2-pyridinecarboxamide to the absolute ethyl alcohol is 1: 5-12; in the phenylacetaldehyde solution, the mass ratio of phenylacetaldehyde to absolute ethyl alcohol is 1: 6-14;
s2, pouring the 2-pyridine carboxamide solution into a reaction container, introducing inert gas as protective gas, dropwise adding the phenylacetaldehyde solution into the 2-pyridine carboxamide solution while stirring at room temperature, continuously stirring and reacting for 1-2 hours after completely dropwise adding, and then performing rotary evaporation to dryness to obtain a powdery pyridine imine product;
wherein the mass ratio of the 2-pyridine carboxamide solution to the phenylacetaldehyde solution is 2-3: 1; the phenylacetaldehyde solution needs to be subjected to dropwise addition reaction within 1 hour after the preparation is finished, and the dropwise addition speed is 1-2 drops/second; the stirring speed is 200-500 rpm;
s3, weighing tetrabutyl phosphorus hydroxide, adding the tetrabutyl phosphorus hydroxide into the absolute ethyl alcohol, stirring at room temperature until the tetrabutyl phosphorus hydroxide is uniform, introducing inert gas serving as protective gas, adding the pyridine imine product, stirring and reacting at 70-80 ℃ in a water bath for 6-10 hours, cooling to room temperature, removing the protective gas, performing rotary evaporation to dryness, washing with a saturated sodium carbonate solution for three times, washing with purified water for three times, and performing vacuum drying to obtain the pyridine-phosphorus composite flame retardant;
wherein the mass ratio of tetrabutyl phosphorus hydroxide, the pyridine imine product and absolute ethyl alcohol is 1: 2.2-3.4: 10-15.
7. The environment-friendly flame retardant laser etching material as claimed in claim 1, wherein the lubricant is pentaerythritol stearate and/or ethylene bis stearamide.
8. The environment-friendly flame retardant laser etching material as claimed in claim 1, wherein the light stabilizer is a mixture of 2-hydroxy-4-methoxybenzophenone and hindered amine.
9. The environment-friendly flame retardant laser etching material as claimed in claim 1, wherein the antioxidant is a hindered phenol compound and/or a phosphite compound.
10. The preparation method of the environment-friendly flame-retardant laser etching material as claimed in any one of claims 1 to 9, which is characterized by comprising the following steps:
step 1, weighing transparent ABS resin, PBT resin, antistatic color master batch, compatilizer, laser etching agent, flame retardant, lubricant, light stabilizer and antioxidant according to the amount for later use;
step 2, adding the transparent ABS resin and the PBT resin into a mixing stirrer to be uniformly mixed to obtain mixed resin;
step 3, sequentially adding the antistatic color master batch, the compatilizer, the laser etching agent, the flame retardant, the lubricant, the light stabilizer and the antioxidant into a mixing stirrer containing the mixed resin, and continuously mixing until the mixture is uniform to obtain a mixed product;
and 4, adding the mixed product into a double-screw extruder for melt extrusion and granulation to obtain the environment-friendly flame-retardant laser etching material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011335492.1A CN112375332A (en) | 2020-11-24 | 2020-11-24 | Environment-friendly flame-retardant laser etching material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011335492.1A CN112375332A (en) | 2020-11-24 | 2020-11-24 | Environment-friendly flame-retardant laser etching material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112375332A true CN112375332A (en) | 2021-02-19 |
Family
ID=74588066
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011335492.1A Withdrawn CN112375332A (en) | 2020-11-24 | 2020-11-24 | Environment-friendly flame-retardant laser etching material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112375332A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113736247A (en) * | 2021-09-24 | 2021-12-03 | 东莞市众一新材料科技有限公司 | Polyamide composite material capable of being laser etched and preparation method thereof |
| CN116903990A (en) * | 2023-08-31 | 2023-10-20 | 江苏汉光实业股份有限公司 | Modified ABS composite plastic particle and preparation method thereof |
-
2020
- 2020-11-24 CN CN202011335492.1A patent/CN112375332A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113736247A (en) * | 2021-09-24 | 2021-12-03 | 东莞市众一新材料科技有限公司 | Polyamide composite material capable of being laser etched and preparation method thereof |
| CN116903990A (en) * | 2023-08-31 | 2023-10-20 | 江苏汉光实业股份有限公司 | Modified ABS composite plastic particle and preparation method thereof |
| CN116903990B (en) * | 2023-08-31 | 2024-01-30 | 江苏汉光实业股份有限公司 | Modified ABS composite plastic particle and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE69907251T2 (en) | FLAME RETARDANT RESIN COMPOSITION | |
| CN102617997B (en) | Glass fiber-reinforced PBT/PET (Polybutylece Terephthalate/Polyethyleneglycol Terephthalate) composite material and preparation method thereof | |
| CN112375332A (en) | Environment-friendly flame-retardant laser etching material and preparation method thereof | |
| CN110951163B (en) | High-surface-tension low-density polypropylene composite material and preparation method thereof | |
| CN100564450C (en) | A kind of flame retardant resistance and shock-resistance thermoplastic resin excellent constituent | |
| CN106905674B (en) | A kind of Flame-retardant PET and PC composite material and preparation method | |
| CN110283441B (en) | Mesoporous molecular sieve compound laser direct forming material and application thereof | |
| CN108912642B (en) | Antistatic, low-smoke, halogen-free and flame-retardant PC/ABS alloy material and preparation process thereof | |
| CN112679932B (en) | Antibacterial high-ball-pressure-temperature halogen-free flame-retardant PC/ABS composite material and preparation method thereof | |
| CN110885545B (en) | Weather-resistant flame-retardant PC/PBT alloy and preparation method thereof | |
| CN115584114B (en) | Polycarbonate alloy composition and preparation method and application thereof | |
| CN109796740B (en) | Stain-resistant PC/PET alloy and preparation method thereof | |
| CN114854133B (en) | Halogen-free flame-retardant long glass fiber reinforced polypropylene composite material and preparation method thereof | |
| CN115651383A (en) | Polycarbonate alloy material and preparation method and application thereof | |
| CN103665743B (en) | A kind of automotive upholstery color inhibition PC/ABS Alloy And Preparation Method | |
| CN110467813A (en) | A kind of silicon systems halogen-free flameproof biology base nylon and preparation method thereof | |
| JP2020100714A (en) | Fiber-reinforced thermoplastic resin composition and molded body obtained therefrom | |
| CN115678237A (en) | Slow-burning polycarbonate composite material and preparation method and application thereof | |
| CN112111142A (en) | Low-smoke-density flame-retardant PC/ABS alloy material and preparation method thereof | |
| CN112679933A (en) | Environment-friendly flame-retardant transparent polyester material | |
| CN117777621A (en) | Modified PVC plastic particle | |
| JP2003226758A (en) | Method for producing colored flame-retardant resin composition | |
| CN108530850A (en) | A kind of fire retardant PBT with no halogen/ASA alloys and preparation method thereof | |
| CN114854130B (en) | High-impact-resistance halogen-free flame-retardant polypropylene composite material and preparation method thereof | |
| CN110894331B (en) | Environment-friendly low-smoke flame-retardant HIPS material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20210219 |