CN113929999A - Laser-engravable halogen-free flame-retardant identification sleeve and preparation method thereof - Google Patents
Laser-engravable halogen-free flame-retardant identification sleeve and preparation method thereof Download PDFInfo
- Publication number
- CN113929999A CN113929999A CN202111134392.7A CN202111134392A CN113929999A CN 113929999 A CN113929999 A CN 113929999A CN 202111134392 A CN202111134392 A CN 202111134392A CN 113929999 A CN113929999 A CN 113929999A
- Authority
- CN
- China
- Prior art keywords
- parts
- laser
- halogen
- engravable
- free flame
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
- C08L15/005—Hydrogenated nitrile rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- 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
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2272—Ferric oxide (Fe2O3)
-
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a laser-engravable halogen-free flame-retardant identification sleeve and a preparation method thereof, and belongs to the technical field of sleeve preparation. According to the invention, the laser etching auxiliary agent is added into the base material, so that the laser absorption rate of a material system is improved, the damage threshold of laser to the material system is reduced, and the technical problems of unclear identification, poor durability, environmental friendliness and the like in the prior art are solved; the problems of high smoke density, high toxicity and the like of the halogen-containing flame retardant during combustion are solved by using the phosphorus-nitrogen halogen-free flame retardant, and the halogen-containing flame retardant has a wide application prospect.
Description
Technical Field
The invention relates to a laser-engravable halogen-free flame-retardant identification sleeve and a preparation method thereof, and belongs to the technical field of sleeve preparation.
Background
At present, the heat-shrinkable identification sleeve is widely applied to the identification field of cable lines of electronic appliances, locomotives, ships, aerospace and the like due to light weight, scratch resistance and the like. The marking sleeve which adopts the printing ink printing mode to obtain the marking pattern is easy to fade and even fall off along with the time lapse of the marking pattern in the organic solvent environment, and the marking effect is lost. In addition, the process for manufacturing the marking tube by the traditional ink printing process is complex and inflexible, raw material waste exists, and a large amount of organic solvent in the ink is harmful to human health and cannot meet the current green and environment-friendly requirement.
The common identification sleeve has poor halogen-containing and solvent-resistant properties, and is easy to generate identification pattern deformation and mechanical property attenuation caused by swelling in a solvent environment; the problems of high smoke density, high toxicity and the like during fire combustion are met.
Laser engraving refers to laser engraving, which is to etch traces by chemical and physical changes of surface substances caused by light energy of laser beams, or burn off partial substances by the light energy to display patterns and characters to be etched. The thermal shrinkage identification sleeve is made of a high polymer material, laser etching identification patterns are not clear due to the limitation of the base material, and the identification degree is low.
In view of the above defects, the designer actively makes research and innovation to create a laser-engravable halogen-free flame-retardant identification sleeve and a preparation method thereof, so that the sleeve has industrial utilization value.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a laser-engravable halogen-free flame-retardant identification sleeve and a preparation method thereof.
The invention discloses a laser-engravable halogen-free flame-retardant thermal shrinkage mark bushing which comprises the following materials:
30-100 parts of modified solvent-resistant plastic master batch;
30-50 parts of a compound flame retardant;
0.1-2 parts of a sensitizing crosslinking agent;
1-4 parts of laser etching auxiliary agent;
0.5-2 parts of an antioxidant;
0.5-2 parts of an anti-aging agent;
5-10 parts of an acid acceptor;
0.5-3 parts of a lubricant;
2-5 parts of a reinforcing agent;
the modified solvent-resistant plastic master batch is prepared by adding 5-10 parts of a macromolecular compatilizer into 30-50 parts of polyolefin resin, 30-50 parts of oil-resistant rubber and 30-50 parts of a thermoplastic elastomer for modification.
Further, the material comprises the following materials:
60 parts of modified solvent-resistant plastic master batch;
40 parts of ammonium polyphosphate;
0.15 part of trimethylolpropane trimethacrylate;
3 parts of a self-made flame-retardant laser auxiliary agent;
0.8 part of pentaerythritol ester;
1 part of N, N' -di (beta-naphthyl) p-phenylenediamine;
7 parts of zinc oxide;
1.5 parts of polyethylene wax;
4 parts of carbon black;
the modified solvent-resistant plastic master batch is prepared by adding 5-10 parts of a macromolecular compatilizer into 30-50 parts of polyolefin resin, 30-50 parts of oil-resistant rubber and 30-50 parts of a thermoplastic elastomer for modification.
Further, the polyolefin resin is polyethylene, ethylene vinyl acetate, ethylene octene copolymer; the oil-resistant rubber is acrylate rubber, ethylene acrylate rubber and hydrogenated nitrile rubber; the elastomer is polyester elastomer or polyamide elastomer.
Further, the high molecular compatilizer is one or two of ethylene-methyl acrylate copolymer, maleic anhydride grafted EVA resin and ethylene octene copolymer.
Further, the compound flame retardant is a mixture of ammonium polyphosphate, melamine cyanurate, melamine polyphosphate, antimony trioxide, zinc borate, magnesium hydroxide, aluminum hydroxide and aluminum diethylphosphinate.
Further, the sensitizer is trimethylolpropane trimethacrylate or triallyl isocyanurate.
Further, the laser etching auxiliary agent is one or a mixture of more of a self-made flame-retardant laser auxiliary agent, mica iron oxide wrapped by silicon dioxide and basic copper phosphate.
Further, the antioxidant is one or a mixture of two of pentaerythritol ester, dioctadecyl pentaerythritol phosphite and diethyl 3, 5-di-tert-butyl-4-hydroxybenzyl phosphate.
Furthermore, the anti-aging agent is one or a mixture of two of N, N '-di (beta-naphthyl) p-phenylenediamine, N-cyclohexyl-N' -phenyl p-phenylenediamine and 2,2, 4-trimethyl-1, 2-dihydro-quinoline polymer.
Further, the acid acceptor is one or a mixture of two of zinc oxide and magnesium oxide.
Further, the lubricant is one or a mixture of polyethylene wax, zinc stearate and silicone.
Further, the reinforcing agent is carbon black or white carbon black.
A preparation method of a laser-engravable halogen-free flame-retardant thermal shrinkage identification sleeve comprises the following specific preparation steps:
(1) according to the weight parts, 30-100 parts of modified solvent-resistant plastic master batch, 30-50 parts of compound flame retardant, 0.1-2 parts of sensitizing crosslinking agent, 1-4 parts of laser engraving auxiliary agent, 0.5-2 parts of antioxidant, 0.5-2 parts of anti-aging agent, 5-10 parts of acid absorbent, 0.5-3 parts of lubricant and 2-5 parts of reinforcing agent are subjected to blending and banburying for 10-20 min by an internal mixer, and then extruded by a conical double screw to be subjected to hot cutting, so that modified laser engraving master batch is obtained;
(2) extruding the modified laser etching master batch out of a tube blank through a single-screw extruder at the temperature of 130-200 ℃;
(3) carrying out irradiation crosslinking on the tube blank by an electron accelerator, wherein the irradiation dose is 50-200 kGy;
(4) expanding the irradiated and crosslinked pipe blank by 2-4 times through an expander at 130-180 ℃, and cooling and shaping;
(5) and (3) shaping the cooled and shaped expanded pipe blank by shaping equipment to obtain the laser-engravable halogen-free flame-retardant thermal-shrinkable label sleeve.
By the scheme, the invention at least has the following advantages:
(1) the laser energy reaches a certain material damage threshold, and laser carving identification patterns are not clear and have low identification degree due to low laser energy absorption rate of the high polymer base material; the laser etching auxiliary agent is sensitive to infrared or carbon dioxide laser, can absorb the energy of the laser and convert the energy into heat energy, and generates physical and chemical reactions such as heating, carbonization, evaporation and the like on a high polymer material, thereby leaving a permanent laser marking effect. According to the invention, the laser etching auxiliary agent is added into the base material, so that the laser absorption rate of a material system is improved, the damage threshold of laser to the material system is reduced, and the technical problems of unclear identification, poor durability, environmental friendliness and the like in the prior art are solved; the problems of high smoke density, high toxicity and the like of the halogen-containing flame retardant during combustion are solved by using the phosphorus-nitrogen halogen-free flame retardant;
(2) according to the method, the biotite rich in metal oxides is used as a raw material, the biotite is refined and disintegrated through mechanical crushing, the refining and disintegration process starts along the trend of internal pores, the refined biotite is favorable for having sharp edges and convex structures, and then the biotite is soaked by hydrochloric acid, so that part of metal oxides in biotite fragments are corroded and removed, the surface roughness of the biotite is improved, and the adsorption performance of the biotite is improved; immersing the pieces of the biotite with the roughened surface into a dopamine solution, forming a layer of polydopamine protective film by oxidation and self-polymerization under the action of dissolved oxygen of dopamine in water, attaching the polydopamine protective film to the surface of the pretreated biotite, mixing the pretreated biotite with an aluminum sulfate solution, effectively adsorbing and fixing aluminum ions on the surface of the pretreated biotite by utilizing the adsorbability of the pretreated biotite and the adsorption effect of a chelating polymer layer on the surface of the pretreated biotite, adding ammonia water, reacting the ammonia water with the aluminum ions to generate aluminum hydroxide, adsorbing once aluminum hydroxide crystal nuclei are formed, keeping the size of the aluminum hydroxide crystal nuclei at a nanometer level, improving the roughness of the surface of the biotite, and matching sharp edges and convex structures generated after the disintegration of the biotite to facilitate the winding and hanging of a high molecular chain segment of a sleeve raw material so as to form firm mechanical winding between the self-made flame-retardant laser additive and the high molecular material, increase compatibility between the two, and then improve sheathed tube mechanical properties, in addition, the biotite main component is metal oxide, excellent laser absorption performance has, can promote the laser absorption rate of material system, reduce laser to its damage threshold value, it is unclear to solve current sign, the poor not environmental protection of resistant permanence etc. technical problem, its surface adhesion's one deck aluminium hydroxide is when the sleeve pipe burning in addition, can dewater and absorb partly heat, reduce the whole heat of sleeve pipe, the vapor of formation fills in the hole and the surface of self-control fire-retardant laser auxiliary agent, play the further cooling effect, and the infiltration of the oxygen in the air can be separated to this layer of water film of formation, thereby avoid the burning, improve sheathed tube flame retardant efficiency.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
(1) Weighing biotite, putting the biotite into a mineral grinder, grinding the biotite into a mineral grinder, sieving the ground biotite with a 50-mesh sieve to obtain a biotite ground substance, putting the biotite ground substance into a reaction kettle, adding 3% by mass of hydrochloric acid into the reaction kettle to completely immerse the biotite ground substance, soaking the mixture for 20-30 min, discharging the mixture, filtering and separating the mixture to obtain filter residues, namely the pretreated biotite; according to the method, the biotite rich in metal oxides is used as a raw material, the biotite is refined and disintegrated through mechanical crushing, the refining and disintegration process starts along the trend of internal pores, the refined biotite is favorable for having sharp edges and convex structures, and then the biotite is soaked by hydrochloric acid, so that part of metal oxides in biotite fragments are corroded and removed, the surface roughness of the biotite is improved, and the adsorption performance of the biotite is improved;
(2) immersing the obtained pretreated biotite into a dopamine solution with the mass concentration of 0.5mg/L, placing the pretreated biotite on a shaking table, shaking, dipping for 1-2 hours, filtering and separating to obtain a filter cake, mixing the obtained filter cake and an aluminum acid solution with the mass fraction of 30% according to the mass ratio of 1:10, filling the mixture into a reaction kettle to obtain a mixture, adding ammonia water with the mass fraction of 15% and the mass amount of 2 times that of the mixture into the reaction kettle, stirring for reaction for 2-3 hours, filtering, separating to obtain filter residues, and naturally airing to obtain the self-made flame-retardant laser additive; the invention immerses the pieces of the black mica with roughened surfaces into a dopamine solution, forms a layer of poly dopamine protective film to be attached to the surface of the pretreated black mica by oxidation and auto-polymerization under the action of the dissolved oxygen of the dopamine in water, then mixes the pretreated black mica with an aluminum sulfate solution, effectively adsorbs and fixes aluminum ions on the surface of the pretreated black mica by utilizing the adsorbability of the pretreated black mica and the adsorption of a chelating polymer layer on the surface of the pretreated black mica, then adds ammonia water to react with the aluminum ions to generate aluminum hydroxide, and can be adsorbed once aluminum hydroxide crystal nuclei are formed, so that the size of the aluminum hydroxide crystal nuclei can be kept at a nanometer level, the roughness of the surface of the black mica can be improved, and the existence of the rough structure is matched with sharp edges and convex structures generated after the disintegration of the black mica, thereby being convenient for winding and hanging with a high molecular chain segment of a sleeve raw material, and forming firm mechanical winding between the self-made flame-retardant laser additive and the high molecular material, the compatibility between the two is improved, the mechanical performance of the sleeve is further improved, in addition, the main component of the biotite is metal oxide, the excellent laser absorption performance is realized, the laser absorption rate of a material system can be improved, the damage threshold of laser to the biotite is reduced, the technical problems that the existing mark is not clear, the permanence resistance is poor, the environment is not protected and the like are solved, in addition, a layer of aluminum hydroxide attached to the surface of the biotite can be dehydrated and absorb a part of heat when the sleeve is burnt, the integral heat of the sleeve is reduced, the formed water vapor is filled in pores and the surface of the self-made flame-retardant laser auxiliary agent to play a role of further cooling, and the formed water film can obstruct the infiltration of oxygen in the air, so that the burning is avoided, and the flame-retardant effect of the sleeve is improved;
(3) according to the weight parts, 30-100 parts of modified solvent-resistant plastic master batch, 30-50 parts of compound flame retardant, 0.1-2 parts of sensitizing crosslinking agent, 1-4 parts of laser engraving auxiliary agent, 0.5-2 parts of antioxidant, 0.5-2 parts of anti-aging agent, 5-10 parts of acid absorbent, 0.5-3 parts of lubricant and 2-5 parts of reinforcing agent are subjected to blending and banburying for 10-20 min by an internal mixer, and then extruded by a conical double screw to be subjected to hot cutting, so that modified laser engraving master batch is obtained;
(4) extruding the modified laser etching master batch out of a tube blank through a single-screw extruder at the temperature of 130-200 ℃;
(5) carrying out irradiation crosslinking on the tube blank by an electron accelerator, wherein the irradiation dose is 50-200 kGy;
(6) expanding the irradiated and crosslinked pipe blank by 2-4 times through an expander at 130-180 ℃, and cooling and shaping;
(7) and (3) shaping the cooled and shaped expanded pipe blank by shaping equipment to obtain the laser-engravable halogen-free flame-retardant thermal-shrinkable label sleeve.
The modified solvent-resistant plastic master batch is prepared by adding 5-10 parts of a macromolecular compatilizer into 30-50 parts of polyolefin resin, 30-50 parts of oil-resistant rubber and 30-50 parts of a thermoplastic elastomer for modification;
the polyolefin resin is a copolymer of polyethylene, ethylene vinyl acetate and ethylene octene; the oil-resistant rubber is acrylate rubber, ethylene acrylate rubber and hydrogenated nitrile rubber; the elastomer is polyester elastomer or polyamide elastomer.
The high molecular compatilizer is one or two of ethylene-methyl acrylate copolymer, maleic anhydride grafted EVA resin and ethylene octene copolymer.
One or a mixture of more than 2 of the compound flame retardants of ammonium polyphosphate, melamine cyanurate, melamine polyphosphate, antimony trioxide, zinc borate, magnesium hydroxide, aluminum diethylphosphinate and the like is compounded.
The sensitizer is trimethylolpropane trimethacrylate or triallyl isocyanurate.
The laser etching auxiliary agent is one or a mixture of more of a self-made flame-retardant laser auxiliary agent, mica iron oxide wrapped by silicon dioxide and basic copper phosphate.
The antioxidant is one or a mixture of two of pentaerythritol ester, dioctadecyl pentaerythritol phosphite and 3, 5-di-tert-butyl-4-hydroxybenzyl diethyl phosphate.
The anti-aging agent is one or a mixture of two of N, N '-di (beta-naphthyl) p-phenylenediamine, N-cyclohexyl-N' -phenyl p-phenylenediamine and 2,2, 4-trimethyl-1, 2-dihydro quinoline polymer.
The acid acceptor is one or a mixture of two of zinc oxide and magnesium oxide.
The lubricant is one or a mixture of polyethylene wax, zinc stearate and silicone.
The reinforcing agent is carbon black or white carbon black.
Example 1
According to the weight parts, 30 parts of modified solvent-resistant plastic master batch, 30 parts of ammonium polyphosphate, 0.1 part of trimethylolpropane trimethacrylate, 1 part of silica-coated mica iron oxide, 0.5 part of pentaerythritol ester, 0.5 part of N, N' -di (beta-naphthyl) p-phenylenediamine, 5 parts of zinc oxide, 0.5 part of polyethylene wax and 2 parts of carbon black are subjected to blending and banburying for 10min by a banbury mixer, and then extruded by a conical double screw and hot cut is carried out to obtain a modified radium carving master batch;
extruding the modified laser etching master batch out of a tube blank through a single-screw extruder at 150 ℃;
carrying out irradiation crosslinking on the tube blank by an electron accelerator, wherein the irradiation dose is 150 kGy;
expanding the pipe blank after irradiation crosslinking by 2 times through an expander at 150 ℃, and cooling and shaping;
and (3) shaping the cooled and shaped expanded pipe blank by shaping equipment to obtain the laser-engravable halogen-free flame-retardant thermal-shrinkable label sleeve.
Example 2
According to the weight parts, 30 parts of modified solvent-resistant plastic master batch, 30 parts of ammonium polyphosphate, 0.1 part of trimethylolpropane trimethacrylate, 1 part of self-made flame-retardant laser additive, 0.5 part of pentaerythritol ester, 0.5 part of N, N' -di (beta-naphthyl) p-phenylenediamine, 5 parts of zinc oxide, 0.5 part of polyethylene wax and 2 parts of carbon black are subjected to blending and banburying for 10min by a banbury mixer, and then extruded by a conical double screw and hot cut to obtain a modified laser carving master batch;
extruding the modified laser etching master batch out of a tube blank through a single-screw extruder at 150 ℃;
carrying out irradiation crosslinking on the tube blank by an electron accelerator, wherein the irradiation dose is 150 kGy;
expanding the pipe blank after irradiation crosslinking by 2 times through an expander at 150 ℃, and cooling and shaping;
and (3) shaping the cooled and shaped expanded pipe blank by shaping equipment to obtain the laser-engravable halogen-free flame-retardant thermal-shrinkable label sleeve.
Example 3
According to the weight parts, 30 parts of modified solvent-resistant plastic master batch, 30 parts of ammonium polyphosphate, 0.1 part of trimethylolpropane trimethacrylate, 1 part of basic copper phosphate, 0.5 part of pentaerythritol ester, 0.5 part of N, N' -di (beta-naphthyl) p-phenylenediamine, 5 parts of zinc oxide, 0.5 part of polyethylene wax and 2 parts of carbon black are subjected to blending and banburying for 10min by a banbury mixer, and then extruded by a conical double screw and hot cut is carried out to obtain a modified radium carving master batch;
extruding the modified laser etching master batch out of a tube blank through a single-screw extruder at 150 ℃;
carrying out irradiation crosslinking on the tube blank by an electron accelerator, wherein the irradiation dose is 150 kGy;
expanding the pipe blank after irradiation crosslinking by 2 times through an expander at 150 ℃, and cooling and shaping;
and (3) shaping the cooled and shaped expanded pipe blank by shaping equipment to obtain the laser-engravable halogen-free flame-retardant thermal-shrinkable label sleeve.
Example 4
According to the weight parts, 50 parts of modified solvent-resistant plastic master batch, 35 parts of ammonium polyphosphate, 0.12 part of trimethylolpropane trimethacrylate, 2 parts of self-made flame-retardant laser additive, 0.7 part of pentaerythritol ester, 0.7 part of N, N' -di (beta-naphthyl) p-phenylenediamine, 6 parts of zinc oxide, 1.0 part of polyethylene wax and 2.5 parts of carbon black are subjected to blending and banburying for 20min by a banbury mixer, and then extruded by a conical double screw to be hot-cut, so that modified laser carving master batch is obtained;
extruding the modified laser etching master batch out of a tube blank through a single-screw extruder at 150 ℃;
carrying out irradiation crosslinking on the tube blank by an electron accelerator, wherein the irradiation dose is 150 kGy;
expanding the pipe blank after irradiation crosslinking by 2 times through an expander at 150 ℃, and cooling and shaping;
and (3) shaping the cooled and shaped expanded pipe blank by shaping equipment to obtain the laser-engravable halogen-free flame-retardant thermal-shrinkable label sleeve.
Example 5
According to the weight parts, 60 parts of modified solvent-resistant plastic master batch, 40 parts of ammonium polyphosphate, 0.15 part of trimethylolpropane trimethacrylate, 3 parts of self-made flame-retardant laser additive, 0.8 part of pentaerythritol ester, 1 part of N, N' -di (beta-naphthyl) p-phenylenediamine, 7 parts of zinc oxide, 1.5 parts of polyethylene wax and 4 parts of carbon black are subjected to blending and banburying for 20min by an internal mixer, and then extruded by a conical double screw and hot cut to obtain modified laser engraving master batch;
extruding the modified laser etching master batch out of a tube blank through a single-screw extruder at 150 ℃;
carrying out irradiation crosslinking on the tube blank by an electron accelerator, wherein the irradiation dose is 150 kGy;
expanding the pipe blank after irradiation crosslinking by 2 times through an expander at 150 ℃, and cooling and shaping;
and (3) shaping the cooled and shaped expanded pipe blank by shaping equipment to obtain the laser-engravable halogen-free flame-retardant thermal-shrinkable label sleeve.
Example 6
According to the weight parts, 90 parts of modified solvent-resistant plastic master batch, 40 parts of ammonium polyphosphate, 0.18 part of trimethylolpropane trimethacrylate, 3 parts of self-made flame-retardant laser additive, 1.5 parts of pentaerythritol ester, 1.5 parts of N, N' -di (beta-naphthyl) p-phenylenediamine, 9 parts of zinc oxide, 2.5 parts of polyethylene wax and 4 parts of carbon black are subjected to blending and banburying by an internal mixer for 10-20 min, and then extruded by a conical double screw and hot cut to obtain a modified laser carving master batch;
extruding the modified laser etching master batch out of a tube blank through a single-screw extruder at 150 ℃;
carrying out irradiation crosslinking on the tube blank by an electron accelerator, wherein the irradiation dose is 150 kGy;
expanding the pipe blank after irradiation crosslinking by 2 times through an expander at 150 ℃, and cooling and shaping;
and (3) shaping the cooled and shaped expanded pipe blank by shaping equipment to obtain the laser-engravable halogen-free flame-retardant thermal-shrinkable label sleeve.
Example 7
According to the weight parts, 100 parts of modified solvent-resistant plastic master batch, 50 parts of ammonium polyphosphate, 2 parts of trimethylolpropane trimethacrylate, 4 parts of self-made flame-retardant laser additive, 2 parts of pentaerythritol ester, 2 parts of N, N' -di (beta-naphthyl) p-phenylenediamine, 10 parts of zinc oxide, 3 parts of polyethylene wax and 5 parts of carbon black are subjected to blending and banburying for 20min by a banbury mixer, and then extruded by a conical double screw and hot-cut to obtain a modified laser carving master batch;
extruding the modified laser etching master batch out of a tube blank through a single-screw extruder at 150 ℃;
carrying out irradiation crosslinking on the tube blank by an electron accelerator, wherein the irradiation dose is 150 kGy;
expanding the pipe blank after irradiation crosslinking by 2 times through an expander at 150 ℃, and cooling and shaping;
and (3) shaping the cooled and shaped expanded pipe blank by shaping equipment to obtain the laser-engravable halogen-free flame-retardant thermal-shrinkable label sleeve.
Comparative example
Comparative example 1: the same procedure as in example 3 of the present invention was followed except that the radium etching aid was not added and the remaining components and amounts were not changed, and the sleeve was also prepared.
Performance detection
The performance of the sleeves of examples 1 to 6 of the present invention and comparative example 1 were measured, and the specific measurement results are shown in table 1:
detection method
Laser etching performance detection: detecting a laser etching damage threshold value of the material under pulse laser with a pulse width of 10 ns;
and (3) detecting the flame retardant property: the flame retardant performance, toxicity, smoke density and the like of the sleeve are detected by adopting a method of 'UL 94 flame retardant test method and standard' and 'EN 45545-2R 22/R23 material and fireproof requirements of elements', the detection result is characterized by flame retardant grades, and the flame retardant grades are divided into V0, V1 and V2, wherein the V0 grade has the best flame retardant performance, and the V2 has the worst flame retardant performance;
and (3) detecting the tensile strength: testing by using a testing method of ASTM D638;
and (3) detecting the notch impact strength: testing by using a test method of ASTM D790;
TABLE 1 Performance test results
Data analysis
Firstly, experimental data of examples 1 to 3 of the invention are compared, wherein the laser damage threshold of the sleeve in the example 3 is the lowest, the flame retardance is good, the mechanical strength is high, and the difference of the examples 1 to 3 lies in the difference of laser assistants, so that the self-made flame retardant laser assistant has better using effect compared with other laser assistants, the invention is also proved that the blackmica fragments with roughened surfaces are immersed into dopamine solution, a layer of polydopamine protective film formed by oxidation and self-polymerization is formed under the action of dissolved oxygen of dopamine in water and attached to the surface of the pretreated blackmica, then the pretreated blackmica is mixed with aluminum sulfate solution, aluminum ions are effectively adsorbed and fixed on the surface of the pretreated blackmica by the adsorbability of the pretreated blackmica and the adsorbability of a chelating polymer layer on the surface of the pretreated blackmica, then ammonia water is added, and the aluminium ions react to generate aluminium hydroxide, and once the aluminum hydroxide crystal nucleus is formed, the aluminum hydroxide crystal nucleus can be adsorbed, the size of the aluminum hydroxide crystal nucleus is kept at a nanometer level, the surface roughness of the biotite can be improved, the existence of the rough structure is matched with a sharp corner angle and a convex structure which are generated after the biotite is disintegrated, the aluminum hydroxide crystal nucleus is convenient to wind and hang with a high-molecular chain segment of a sleeve raw material, firm mechanical winding is formed between the self-made flame-retardant laser auxiliary agent and the high-molecular material, the compatibility between the self-made flame-retardant laser auxiliary agent and the high-molecular material is increased, the mechanical performance of the sleeve is further improved, in addition, the main component of the biotite is metal oxide, the excellent laser absorption performance is realized, the laser absorption rate of a material system can be improved, the damage threshold value of laser to the material system is reduced, the technical problems that the existing mark is not clear, the durability is poor, the environment is not protected and the like are solved, in addition, a layer of aluminum hydroxide attached to the surface of the aluminum hydroxide can dehydrate and absorb a part of heat when the sleeve is burnt, the formed water vapor is filled in pores and the surface of the self-made flame-retardant laser auxiliary agent to play a role of further cooling, and the formed water film can block the infiltration of oxygen in the air, so that the combustion is avoided, and the flame-retardant effect of the sleeve is improved;
then, experimental data of examples 3-7 of the invention are compared, the difference of examples 3-7 lies in that the proportion of each raw material of the casing pipe is different, and each performance data of the casing pipe in examples 3-5 is in a rising trend, and is reduced from example 4, and the casing pipe performance reaches the best in example 3, so that the casing pipe formula of the invention has the best proportion, and the performance reaches an excellent level only under the proportion of example 3 of the invention;
comparing the comparison example 1 with the examples 1-3 of the invention, wherein the comparison example 1 is not added with the laser etching auxiliary agent, and other components and dosage are not changed, so that the sleeve is prepared in the same way, and finally, the laser etching performance of the sleeve is obviously reduced, and the mechanical performance and the flame retardant performance are also reduced, thereby laterally proving that the invention improves the laser absorption rate of a material system, reduces the damage threshold of laser to the sleeve, and solves the technical problems of unclear identification, poor durability, environmental friendliness and the like in the prior art by adding the laser etching auxiliary agent into the base material; the problems of high smoke density, high toxicity and the like of the halogen-containing flame retardant are solved by using the phosphorus-nitrogen halogen-free flame retardant.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The laser-engravable halogen-free flame-retardant thermal shrinkage identification sleeve is characterized by comprising the following materials:
30-100 parts of modified solvent-resistant plastic master batch;
30-50 parts of a compound flame retardant;
0.1-2 parts of a sensitizing crosslinking agent;
1-4 parts of laser etching auxiliary agent;
0.5-2 parts of an antioxidant;
0.5-2 parts of an anti-aging agent;
5-10 parts of an acid acceptor;
0.5-3 parts of a lubricant;
2-5 parts of a reinforcing agent;
the modified solvent-resistant plastic master batch is prepared by adding 5-10 parts of a macromolecular compatilizer into 30-50 parts of polyolefin resin, 30-50 parts of oil-resistant rubber and 30-50 parts of a thermoplastic elastomer for modification.
2. The laser engravable halogen-free flame retardant thermal shrinkage mark bushing according to claim 1, which is characterized by comprising the following materials:
60 parts of modified solvent-resistant plastic master batch;
40 parts of ammonium polyphosphate;
0.15 part of trimethylolpropane trimethacrylate;
3 parts of a self-made flame-retardant laser auxiliary agent;
0.8 part of pentaerythritol ester;
1 part of N, N' -di (beta-naphthyl) p-phenylenediamine;
7 parts of zinc oxide;
1.5 parts of polyethylene wax;
4 parts of carbon black;
the modified solvent-resistant plastic master batch is prepared by adding 5-10 parts of a macromolecular compatilizer into 30-50 parts of polyolefin resin, 30-50 parts of oil-resistant rubber and 30-50 parts of a thermoplastic elastomer for modification.
3. The laser engravable halogen free flame retardant thermal shrinkage label bushing according to claim 1, wherein the polyolefin resin is polyethylene, ethylene vinyl acetate, ethylene octene copolymer; the oil-resistant rubber is acrylate rubber, ethylene acrylate rubber and hydrogenated nitrile rubber; the elastomer is polyester elastomer or polyamide elastomer.
4. The laser engravable halogen-free flame retardant thermal shrinkage mark bushing according to claim 1, wherein the high molecular compatilizer is one or two of ethylene-methyl acrylate copolymer, maleic anhydride grafted EVA resin, and ethylene octene copolymer.
5. The laser engravable halogen-free flame retardant thermal shrinkage identification sleeve according to claim 1, wherein a plurality of mixtures of ammonium polyphosphate, melamine cyanurate, melamine polyphosphate, antimony trioxide, zinc borate, magnesium hydroxide, aluminum hydroxide and aluminum diethylphosphinate are compounded as the compounded flame retardants.
6. The laser engravable halogen free flame retardant thermal shrinkable label sleeve according to claim 1, wherein the sensitizer is trimethylolpropane trimethacrylate or triallyl isocyanurate.
7. The laser engravable halogen-free flame retardant thermal shrinkage mark bushing according to claim 1, wherein the laser engraving auxiliary agent is one or a mixture of more of a self-made flame retardant laser auxiliary agent, silica-coated mica iron oxide and basic copper phosphate.
8. The laser engravable halogen-free flame retardant thermal shrinkable label sleeve according to claim 1, wherein the antioxidant is one or a mixture of two of pentaerythritol ester, dioctadecyl pentaerythritol phosphite and diethyl 3, 5-di-tert-butyl-4-hydroxybenzyl phosphate.
9. The laser engravable halogen-free flame retardant thermal shrinkable label bushing according to claim 1, wherein the anti-aging agent is one or a mixture of two of N, N '-di (beta-naphthyl) p-phenylenediamine, N-cyclohexyl-N' -phenyl p-phenylenediamine and 2,2, 4-trimethyl-1, 2-dihydro-quinoline polymer;
the acid acceptor is one or a mixture of two of zinc oxide and magnesium oxide;
the lubricant is one or a mixture of polyethylene wax, zinc stearate and silicone;
the reinforcing agent is carbon black or white carbon black.
10. A preparation method of a laser-engravable halogen-free flame-retardant thermal shrinkage identification sleeve is characterized by comprising the following specific preparation steps:
(1) according to the weight parts, 30-100 parts of modified solvent-resistant plastic master batch, 30-50 parts of compound flame retardant, 0.1-2 parts of sensitizing crosslinking agent, 1-4 parts of laser engraving auxiliary agent, 0.5-2 parts of antioxidant, 0.5-2 parts of anti-aging agent, 5-10 parts of acid absorbent, 0.5-3 parts of lubricant and 2-5 parts of reinforcing agent are subjected to blending and banburying for 10-20 min by an internal mixer, and then extruded by a conical double screw to be subjected to hot cutting, so that modified laser engraving master batch is obtained;
(2) extruding the modified laser etching master batch out of a tube blank through a single-screw extruder at the temperature of 130-200 ℃;
(3) carrying out irradiation crosslinking on the tube blank by an electron accelerator, wherein the irradiation dose is 50-200 kGy;
(4) expanding the irradiated and crosslinked pipe blank by 2-4 times through an expander at 130-180 ℃, and cooling and shaping;
(5) and (3) shaping the cooled and shaped expanded pipe blank by shaping equipment to obtain the laser-engravable halogen-free flame-retardant thermal-shrinkable label sleeve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111134392.7A CN113929999B (en) | 2021-09-27 | 2021-09-27 | Laser-carving halogen-free flame-retardant identification sleeve and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111134392.7A CN113929999B (en) | 2021-09-27 | 2021-09-27 | Laser-carving halogen-free flame-retardant identification sleeve and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113929999A true CN113929999A (en) | 2022-01-14 |
| CN113929999B CN113929999B (en) | 2023-06-13 |
Family
ID=79276984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111134392.7A Active CN113929999B (en) | 2021-09-27 | 2021-09-27 | Laser-carving halogen-free flame-retardant identification sleeve and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113929999B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114539769A (en) * | 2022-03-09 | 2022-05-27 | 珠海万通特种工程塑料有限公司 | Low-density polyamide composition and application thereof |
| CN114685980A (en) * | 2022-03-09 | 2022-07-01 | 珠海万通特种工程塑料有限公司 | Polyamide composition and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051028A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Laser marked PETG poly(ethylene terephthlate-co-cyclohex-anedimethyllene terephthalate) composition and preparation method thereof |
| CN106633312A (en) * | 2016-12-30 | 2017-05-10 | 深圳市沃尔核材股份有限公司 | Oil-resistant high-temperature-resistant halogen-free flame retardant thermal shrinkage identification tube and production method thereof |
| CN108148256A (en) * | 2017-12-22 | 2018-06-12 | 广州宝之泰电子科技有限公司 | It is a kind of can laser printing high fire-retardance flame-retardant heat shrinkable label sleeve and preparation method thereof |
| CN109370166A (en) * | 2018-09-25 | 2019-02-22 | 上海锦湖日丽塑料有限公司 | A kind of polyester material and preparation method thereof of suitable laser carving |
| CN110079003A (en) * | 2019-03-27 | 2019-08-02 | 大连联合高分子材料有限公司 | A kind of rail traffic vehicles EN45545 type flame-retardant heat shrinkable label sleeve and preparation method thereof |
| CN112210160A (en) * | 2020-10-12 | 2021-01-12 | 大连联合高分子材料有限公司 | Laser marking halogen-free identification heat-shrinkable tube and manufacturing method thereof |
-
2021
- 2021-09-27 CN CN202111134392.7A patent/CN113929999B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051028A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Laser marked PETG poly(ethylene terephthlate-co-cyclohex-anedimethyllene terephthalate) composition and preparation method thereof |
| CN106633312A (en) * | 2016-12-30 | 2017-05-10 | 深圳市沃尔核材股份有限公司 | Oil-resistant high-temperature-resistant halogen-free flame retardant thermal shrinkage identification tube and production method thereof |
| CN108148256A (en) * | 2017-12-22 | 2018-06-12 | 广州宝之泰电子科技有限公司 | It is a kind of can laser printing high fire-retardance flame-retardant heat shrinkable label sleeve and preparation method thereof |
| CN109370166A (en) * | 2018-09-25 | 2019-02-22 | 上海锦湖日丽塑料有限公司 | A kind of polyester material and preparation method thereof of suitable laser carving |
| CN110079003A (en) * | 2019-03-27 | 2019-08-02 | 大连联合高分子材料有限公司 | A kind of rail traffic vehicles EN45545 type flame-retardant heat shrinkable label sleeve and preparation method thereof |
| CN112210160A (en) * | 2020-10-12 | 2021-01-12 | 大连联合高分子材料有限公司 | Laser marking halogen-free identification heat-shrinkable tube and manufacturing method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114539769A (en) * | 2022-03-09 | 2022-05-27 | 珠海万通特种工程塑料有限公司 | Low-density polyamide composition and application thereof |
| CN114685980A (en) * | 2022-03-09 | 2022-07-01 | 珠海万通特种工程塑料有限公司 | Polyamide composition and application thereof |
| CN114539769B (en) * | 2022-03-09 | 2023-10-20 | 珠海万通特种工程塑料有限公司 | Low-density polyamide composition and application thereof |
| CN114685980B (en) * | 2022-03-09 | 2023-10-20 | 珠海万通特种工程塑料有限公司 | Polyamide composition and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113929999B (en) | 2023-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113929999A (en) | Laser-engravable halogen-free flame-retardant identification sleeve and preparation method thereof | |
| KR100564953B1 (en) | Flame-retardant resin composition and its use | |
| Chiu et al. | Dynamic flame retardancy of polypropylene filled with ammonium polyphosphate, pentaerythritol and melamine additives | |
| CN111073248B (en) | Hydrolysis-resistant, illumination-resistant and low-temperature-resistant halogen-free flame-retardant polycarbonate composite material and preparation method thereof | |
| CN111662538A (en) | Low-smoke-density high-performance halogen-free flame-retardant reinforced PBT (polybutylene terephthalate) compound and preparation method thereof | |
| CN107286563A (en) | A kind of expansion type flame retardant and its preparation and application for ABS electric switch outer covers | |
| CN104479232A (en) | Low-smoke halogen-free flame retardant ethylene propylene rubber cable material at temperature of 125 DEG C and preparation method thereof | |
| US20110278039A1 (en) | Eco friendly crosslinked flame retardant composition for wire and cable | |
| CN105385122B (en) | Application of bridged DOPO-based compound, product thereof and preparation method of product | |
| CN113930044B (en) | Flame-retardant ABS composite material, preparation method and application thereof | |
| CN111748179A (en) | Low-smoke-density high-performance halogen-containing flame-retardant reinforced PBT (polybutylene terephthalate) compound and preparation method thereof | |
| JP6782067B2 (en) | Organic materials as fireproof and flame retardant synergists | |
| Wang et al. | Epoxy resin/tin ethylenediamine tetra‐methylene phosphonate composites with simultaneous improvement of flame retardancy and smoke suppression | |
| Zhao et al. | Mechanical performance and flame retardancy of polypropylene composites containing zeolite and multiwalled carbon nanotubes | |
| CN1179014C (en) | Fire resistant adhesion agent and circuit components using same | |
| CN105778281A (en) | High-glow-wire low-smoke flame-retardant polypropylene composite material and preparation method thereof | |
| CN101343401A (en) | Halogen-free glue solution, halogen-free flame-proof cover copper foil substrate using the glue solution and preparation method thereof | |
| CN111004441A (en) | Halogen-free flame-retardant high-glow-wire high-CTI (comparative tracking index) polypropylene material for unattended electric appliance and preparation method thereof | |
| CN111019294A (en) | Halogen-free resin composition, high-flame-retardant printed circuit board and display device | |
| JPH03100064A (en) | Flame-retardant thermoplastic compound and its manufacture | |
| Li et al. | Synthesis of phosphorous phenanthrene/L-tryptophan flame retardant for enhanced flame retardancy of epoxy resins | |
| CN107189353A (en) | A kind of epoxy resin copper-clad plate and preparation method thereof | |
| CN107501710B (en) | 150 ℃ heat-resistant cross-linked low-smoke halogen-free electronic wire material and manufacturing method thereof | |
| CN108690257B (en) | Heat-resistant halogen-free low-smoke flame-retardant non-crosslinked polyolefin composition for cables | |
| Cao et al. | Effects of treated waste silicon rubber on properties of poly (lactic acid)/ammonium polyphosphate composites |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |