CN108467574B - Transparent flame-retardant master batch, PET (polyethylene terephthalate) film and preparation method - Google Patents
Transparent flame-retardant master batch, PET (polyethylene terephthalate) film and preparation method Download PDFInfo
- Publication number
- CN108467574B CN108467574B CN201810166844.1A CN201810166844A CN108467574B CN 108467574 B CN108467574 B CN 108467574B CN 201810166844 A CN201810166844 A CN 201810166844A CN 108467574 B CN108467574 B CN 108467574B
- Authority
- CN
- China
- Prior art keywords
- retardant
- flame
- master batch
- transparent
- parts
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use 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; Derivatives of such polymers
- C08J2433/04—Characterised by the use 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; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use 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; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2433/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
-
- 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
- C08K3/02—Elements
- C08K2003/026—Phosphorus
-
- 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
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention relates to the technical field of master batches, in particular to a transparent flame-retardant master batch, a PET (polyethylene terephthalate) film and a preparation method thereof. According to the invention, the microcrystalline cellulose used as a carbon source is used for coating the red phosphorus used as an acid source, so that the compatibility of the red phosphorus and an organic polymer can be well improved, the flame-retardant microspheres can be fully dispersed in the optical polyester resin, and the microcrystalline cellulose has a porous property, can be used as the carbon source to easily form an expanded carbon layer, and can enlarge the effective range of isolated flame retardance; in addition, the invention adopts high-permeability optical polyester resin, and can effectively improve the transparency of the master batch.
Description
Technical Field
The invention relates to the technical field of master batches, and particularly relates to a transparent flame-retardant master batch, a PET (polyethylene terephthalate) film and a preparation method of the transparent flame-retardant master batch.
Background
The PET polyester film has wide application in many fields due to dimensional stability and high transparency, and has a large market. In order to increase the added value of products, many enterprises are also developing and producing special PET films, such as color PET polyester films, matte PET polyester films, twisted PET polyester films, high-transparency PET polyester films, antistatic PET polyester films, and the like. These special films have higher added value than the common polyester films and also have a large market.
Flame retardant PET films are also a special type of film. The main means for preparing the flame-retardant PET film at present is blending modification, and the flame-retardant function is realized by adding a flame retardant into polyester resin, but the flame-retardant PET film has the problem that the flame retardance, the light transmittance and the mechanical property cannot be simultaneously realized.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide the transparent flame-retardant master batch for blending modified PET resin, and the prepared PET film has flame retardance, light transmittance and mechanical property; the invention also aims to provide the transparent flame-retardant PET film and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
a transparent flame-retardant master batch comprises the following raw materials in parts by weight:
the flame-retardant microspheres are core-shell structure microspheres, the core of the flame-retardant microspheres is nano red phosphorus, the shell of the flame-retardant microspheres is microcrystalline cellulose, and the synergistic flame retardant is metal hydroxide.
The flame retardant mechanism of the transparent flame retardant master batch of the invention is as follows: under the condition of high temperature, the synergistic flame retardant releases bound water and generates temperature-resistant flame-retardant metal oxide, and the red phosphorus absorbs the bound water and other water vapor to form oxygen-containing phosphoric acid, so that microcrystalline cellulose coated with the red phosphorus is carbonized to form a protective carbon layer, and the aim of isolating and retarding flame is fulfilled. The invention has the advantages that: the microcrystalline cellulose used as a carbon source is used for coating the red phosphorus used as an acid source, so that the compatibility of the red phosphorus and an organic polymer can be well improved, the flame-retardant microspheres can be fully dispersed in the optical polyester resin, and the microcrystalline cellulose has porous property, is easy to form an expanded carbon layer as the carbon source, and increases the effective range of isolated flame retardance; in addition, the invention adopts high-permeability optical-grade polyester resin, the transparency of the master batch can be effectively improved, and the optical-grade polyester resin is preferably polyester resin with the light transmittance of more than 90%.
The preparation method of the flame-retardant microsphere comprises the following steps:
A. dissolving microcrystalline cellulose in a chlorinated 1-methyl 3-butylimidazolium salt ionic liquid at a mass ratio of 4-10:100 at 70-90 ℃ to form a microcrystalline cellulose solution;
B. b, adding nano red phosphorus into the microcrystalline cellulose solution obtained in the step A, and uniformly stirring to obtain a suspension, wherein the nano red phosphorus accounts for 2-6wt% of the suspension;
C. and C, performing electrostatic spraying on the suspension obtained in the step B to obtain the flame-retardant microspheres.
The invention utilizes the cellulose regeneration principle to coat the nano red phosphorus, can effectively cover the red phosphorus, and avoids the red phosphorus from coloring the PET film, and the microcrystalline cellulose can be crosslinked with the branched chain in the polyester resin, thereby forming a stable fiber network in the polyester resin and greatly improving the mechanical property of the polyester resin.
Wherein the particle size of the nano red phosphorus is 40-60nm, the particle size of the flame-retardant microsphere is 12.1-24.6 mu m, and the BET specific surface area is 27-63m2(ii) in terms of/g. By controlling the particle size of the nano red phosphorus, the dispersibility of the nano red phosphorus in the flame-retardant microspheres can be improved, and by controlling the particle size and the specific surface area of the flame-retardant microspheres, the reactivity of the flame-retardant microspheres and the polyester resin can be improved, and the compatibility of the flame-retardant microspheres and the polyester resin can be improved, so that the flame retardance and the mechanical property of the master batch are improved.
Wherein in the step C, the spraying voltage of electrostatic spraying is 20-40kV, and the spraying temperature is 20-30 ℃.
Wherein the optical-grade polyester resin is at least one of polycarbonate, polymethyl methacrylate and polyethylene terephthalate.
The synergistic flame retardant is nano magnesium hydroxide and/or nano aluminum hydroxide, and preferably consists of the nano magnesium hydroxide and the nano aluminum hydroxide in a weight ratio of 1-2: 1. The invention is beneficial to improving the flame retardance of the transparent flame-retardant master batch and the dispersity of the transparent flame-retardant master batch in the PET film by controlling the composition of the synergistic flame retardant.
The dispersing agent is at least one of modified ethylene bis fatty acid amide, pentaerythritol stearate and calcium stearate, and preferably, the dispersing agent is prepared from the modified ethylene bis fatty acid amide, the pentaerythritol stearate and the calcium stearate according to the weight ratio of 1-3:1-3: 1-3. The compound dispersing agent can effectively provide the dispersibility of the transparent flame-retardant master batch on the PET film.
The preparation method of the transparent flame-retardant master batch comprises the following steps: and mixing, melting, extruding and granulating the raw materials.
The invention also provides a transparent flame-retardant PET film which comprises the following raw materials in parts by weight:
100 parts of PET resin
20-40 parts of transparent flame-retardant master batch
0.1-10 parts of other auxiliary agents;
the transparent flame-retardant master batch is the transparent flame-retardant master batch.
Wherein the rest auxiliary agent is at least one of antioxidant, ultraviolet absorbent, colorant, antistatic agent, lubricant and compatilizer.
The transparent flame-retardant PET film has transparency, flame retardance and mechanical property, the flame retardance and the mechanical property are caused by the properties of the transparent flame-retardant microspheres, and the transparency is caused by the light transmission of PET and optical-grade polyester resin, and compared with other types of flame-retardant PET films, the transparent flame-retardant PET film has less dosage of lightproof flame-retardant substances.
The invention also provides a preparation method of the transparent flame-retardant PET film, which comprises the following steps: and (3) melting and mixing the PET resin, the transparent flame-retardant master batch and the rest of auxiliary agents, and stretching to form a film to obtain the transparent flame-retardant PET film.
The invention has the beneficial effects that: the microcrystalline cellulose used as a carbon source is used for coating the red phosphorus used as an acid source, so that the compatibility of the red phosphorus and an organic polymer can be well improved, the flame-retardant microspheres can be fully dispersed in the optical polyester resin, and the microcrystalline cellulose has porous property, is easy to form an expanded carbon layer as the carbon source, and increases the effective range of isolated flame retardance; in addition, the invention adopts high-permeability optical polyester resin, and can effectively improve the transparency of the master batch.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
A transparent flame-retardant master batch comprises the following raw materials in parts by weight:
the flame-retardant microspheres are core-shell structure microspheres, the core of the flame-retardant microspheres is nano red phosphorus, and the shell of the flame-retardant microspheres is microcrystalline cellulose.
The preparation method of the flame-retardant microsphere comprises the following steps:
A. dissolving microcrystalline cellulose in chlorinated 1-methyl 3-butylimidazolium salt ionic liquid according to the mass ratio of 7:100 at the temperature of 80 ℃ to form a microcrystalline cellulose solution;
B. b, adding nano red phosphorus into the microcrystalline cellulose solution obtained in the step A, and uniformly stirring to obtain a suspension, wherein the nano red phosphorus accounts for 4 wt% of the suspension;
C. and C, performing electrostatic spraying on the suspension obtained in the step B to obtain the flame-retardant microspheres.
Wherein the particle size of the nano red phosphorus is 50nm, the particle size of the flame-retardant microsphere is 18.7 mu m, and the BET specific surface area is 44.1m2/g。
Wherein, in the step C, the spraying voltage of electrostatic spraying is 30kV, and the spraying temperature is 25 ℃.
Wherein the optical-grade polyester resin is polyethylene terephthalate.
The synergistic flame retardant consists of nano magnesium hydroxide and nano aluminum hydroxide according to the weight ratio of 3: 2.
The dispersing agent is prepared from modified ethylene bis-fatty acid amide, pentaerythritol stearate and calcium stearate according to the weight ratio of 1:1: 1.
The preparation method of the transparent flame-retardant master batch comprises the following steps: and mixing, melting, extruding and granulating the raw materials.
The invention also provides a transparent flame-retardant PET film which comprises the following raw materials in parts by weight:
100 parts of PET resin
30 portions of transparent flame-retardant master batch
2 parts of other auxiliary agents;
the transparent flame-retardant master batch is the transparent flame-retardant master batch.
Wherein the rest auxiliary agents are antioxidants.
The invention also provides a preparation method of the transparent flame-retardant PET film, which comprises the following steps: and (3) melting and mixing the PET resin, the transparent flame-retardant master batch and the rest of auxiliary agents, and stretching to form a film to obtain the transparent flame-retardant PET film.
Example 2
A transparent flame-retardant master batch comprises the following raw materials in parts by weight:
the flame-retardant microspheres are core-shell structure microspheres, the core of the flame-retardant microspheres is nano red phosphorus, and the shell of the flame-retardant microspheres is microcrystalline cellulose.
The preparation method of the flame-retardant microsphere comprises the following steps:
A. dissolving microcrystalline cellulose in chlorinated 1-methyl 3-butylimidazolium salt ionic liquid according to the mass ratio of 4:100 at the temperature of 70 ℃ to form a microcrystalline cellulose solution;
B. b, adding nano red phosphorus into the microcrystalline cellulose solution obtained in the step A, and uniformly stirring to obtain a suspension, wherein the nano red phosphorus accounts for 2 wt% of the suspension;
C. and C, performing electrostatic spraying on the suspension obtained in the step B to obtain the flame-retardant microspheres.
Wherein the particle size of the nano red phosphorus is 40nm, the particle size of the flame retardant microsphere is 12.7 mu m, and the BET specific surface area is30.5m2/g。
Wherein, in the step C, the spraying voltage of electrostatic spraying is 30kV, and the spraying temperature is 25 ℃.
Wherein the optical grade polyester resin is polycarbonate.
The synergistic flame retardant consists of nano magnesium hydroxide and nano aluminum hydroxide according to the weight ratio of 1: 1.
The dispersing agent is prepared from modified ethylene bis-fatty acid amide, pentaerythritol stearate and calcium stearate according to the weight ratio of 3:1: 1.
The preparation method of the transparent flame-retardant master batch comprises the following steps: and mixing, melting, extruding and granulating the raw materials.
The invention also provides a transparent flame-retardant PET film which comprises the following raw materials in parts by weight:
100 parts of PET resin
20 portions of transparent flame-retardant master batch
0.1 part of other auxiliary agents;
the transparent flame-retardant master batch is the transparent flame-retardant master batch.
Wherein the rest auxiliary agents are ultraviolet absorbers.
The invention also provides a preparation method of the transparent flame-retardant PET film, which comprises the following steps: and (3) melting and mixing the PET resin, the transparent flame-retardant master batch and the rest of auxiliary agents, and stretching to form a film to obtain the transparent flame-retardant PET film.
Example 3
A transparent flame-retardant master batch comprises the following raw materials in parts by weight:
the flame-retardant microspheres are core-shell structure microspheres, the core of the flame-retardant microspheres is nano red phosphorus, and the shell of the flame-retardant microspheres is microcrystalline cellulose.
The preparation method of the flame-retardant microsphere comprises the following steps:
A. dissolving microcrystalline cellulose in chlorinated 1-methyl 3-butylimidazolium salt ionic liquid according to the mass ratio of 10:100 at the temperature of 90 ℃ to form a microcrystalline cellulose solution;
B. b, adding nano red phosphorus into the microcrystalline cellulose solution obtained in the step A, and uniformly stirring to obtain a suspension, wherein the nano red phosphorus accounts for 6wt% of the suspension;
C. and C, performing electrostatic spraying on the suspension obtained in the step B to obtain the flame-retardant microspheres.
Wherein the particle size of the nano red phosphorus is 60nm, the particle size of the flame-retardant microsphere is 22.5 mu m, and the BET specific surface area is 60.1m2/g。
Wherein, in the step C, the spraying voltage of electrostatic spraying is 40kV, and the spraying temperature is 30 ℃.
Wherein the optical-grade polyester resin is polymethyl methacrylate.
The synergistic flame retardant consists of nano magnesium hydroxide and nano aluminum hydroxide according to the weight ratio of 2: 1.
The dispersing agent is at least one of modified ethylene bis fatty acid amide, pentaerythritol stearate and calcium stearate, and preferably, the dispersing agent is prepared from the modified ethylene bis fatty acid amide, the pentaerythritol stearate and the calcium stearate according to the weight ratio of 1:1: 3.
The preparation method of the transparent flame-retardant master batch comprises the following steps: and mixing, melting, extruding and granulating the raw materials.
The invention also provides a transparent flame-retardant PET film which comprises the following raw materials in parts by weight:
100 parts of PET resin
40 parts of transparent flame-retardant master batch
10 parts of other auxiliary agents;
the transparent flame-retardant master batch is the transparent flame-retardant master batch.
Wherein the rest auxiliary agents are a mixture of an antioxidant, an ultraviolet absorber, a coloring agent, an antistatic agent, a lubricant and a compatilizer.
The invention also provides a preparation method of the transparent flame-retardant PET film, which comprises the following steps: and (3) melting and mixing the PET resin, the transparent flame-retardant master batch and the rest of auxiliary agents, and stretching to form a film to obtain the transparent flame-retardant PET film.
Example 4
A transparent flame-retardant master batch comprises the following raw materials in parts by weight:
the flame-retardant microspheres are core-shell structure microspheres, the core of the flame-retardant microspheres is nano red phosphorus, and the shell of the flame-retardant microspheres is microcrystalline cellulose.
The preparation method of the flame-retardant microsphere comprises the following steps:
A. dissolving microcrystalline cellulose in chlorinated 1-methyl 3-butylimidazolium salt ionic liquid according to the mass ratio of 6:100 at the temperature of 75 ℃ to form a microcrystalline cellulose solution;
B. b, adding nano red phosphorus into the microcrystalline cellulose solution obtained in the step A, and uniformly stirring to obtain a suspension, wherein the nano red phosphorus accounts for 3 wt% of the suspension;
C. and C, performing electrostatic spraying on the suspension obtained in the step B to obtain the flame-retardant microspheres.
Wherein the particle size of the nano red phosphorus is 44nm, the particle size of the flame-retardant microsphere is 16.1 mu m, and the BET specific surface area is 33.7m2/g。
In the step C, the spraying voltage of electrostatic spraying is 25kV, and the spraying temperature is 22 ℃.
Wherein the optical-grade polyester resin is prepared from polycarbonate, polymethyl methacrylate and polyethylene terephthalate according to the weight ratio of 1:1: 1.
Wherein the synergistic flame retardant is nano magnesium hydroxide.
Wherein the dispersant is modified ethylene bis fatty acid amide.
The preparation method of the transparent flame-retardant master batch comprises the following steps: and mixing, melting, extruding and granulating the raw materials.
The invention also provides a transparent flame-retardant PET film which comprises the following raw materials in parts by weight:
100 parts of PET resin
25 parts of transparent flame-retardant master batch
2 parts of other auxiliary agents;
the transparent flame-retardant master batch is the transparent flame-retardant master batch.
Wherein, the rest auxiliary agents are antistatic agents.
The invention also provides a preparation method of the transparent flame-retardant PET film, which comprises the following steps: and (3) melting and mixing the PET resin, the transparent flame-retardant master batch and the rest of auxiliary agents, and stretching to form a film to obtain the transparent flame-retardant PET film.
Example 5
A transparent flame-retardant master batch comprises the following raw materials in parts by weight:
the flame-retardant microspheres are core-shell structure microspheres, the core of the flame-retardant microspheres is nano red phosphorus, and the shell of the flame-retardant microspheres is microcrystalline cellulose.
The preparation method of the flame-retardant microsphere comprises the following steps:
A. dissolving microcrystalline cellulose in chlorinated 1-methyl 3-butylimidazolium salt ionic liquid according to the mass ratio of 8:100 at the temperature of 85 ℃ to form microcrystalline cellulose solution;
B. b, adding nano red phosphorus into the microcrystalline cellulose solution obtained in the step A, and uniformly stirring to obtain a suspension, wherein the nano red phosphorus accounts for 5 wt% of the suspension;
C. and C, performing electrostatic spraying on the suspension obtained in the step B to obtain the flame-retardant microspheres.
Wherein the particle size of the nano red phosphorus is 55nm, the particle size of the flame-retardant microsphere is 19.6 mu m, and the BET specific surface area is 49.9m2/g。
Wherein, in the step C, the spraying voltage of electrostatic spraying is 35kV, and the spraying temperature is 27 ℃.
Wherein the optical-grade polyester resin is polyethylene terephthalate.
Wherein the synergistic flame retardant is nano aluminum hydroxide.
Wherein the dispersant is pentaerythritol stearate.
The preparation method of the transparent flame-retardant master batch comprises the following steps: and mixing, melting, extruding and granulating the raw materials.
The invention also provides a transparent flame-retardant PET film which comprises the following raw materials in parts by weight:
100 parts of PET resin
35 portions of transparent flame-retardant master batch
3 parts of other auxiliary agents;
the transparent flame-retardant master batch is the transparent flame-retardant master batch.
Wherein the rest auxiliary agents are antioxidants.
The invention also provides a preparation method of the transparent flame-retardant PET film, which comprises the following steps: and (3) melting and mixing the PET resin, the transparent flame-retardant master batch and the rest of auxiliary agents, and stretching to form a film to obtain the transparent flame-retardant PET film.
Comparative example 1
And the PET film was stretched to form a film with the PET resin used in examples 1 to 5 (i.e., before the transparent flame-retardant master batch was added).
The films of examples 1 to 5 and comparative example 1 were formed to a thickness of 200 μm, and then subjected to tensile strength, elongation at break, and light transmittance tests of ASTM standards, and national oxygen index and U L-94 vertical burning tests, with the results as follows:
as can be seen from the above table, although the light transmittance of the PET film modified by the transparent flame-retardant master batch is slightly reduced, the flame retardance and the mechanical properties such as tensile strength and elongation at break are greatly improved, and the PET film prepared by the invention has excellent flame retardance, mechanical property and transparency and has a huge application prospect.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (6)
1. A transparent flame-retardant master batch is characterized in that: the feed comprises the following raw materials in parts by weight:
40-60 parts of optical-grade polyester resin
10-30 parts of flame-retardant microspheres
1-7 parts of synergistic flame retardant
1-3 parts of a dispersant;
the flame-retardant microspheres are core-shell structure microspheres, the core of the flame-retardant microspheres is nano red phosphorus, the shell of the flame-retardant microspheres is microcrystalline cellulose, and the synergistic flame retardant is metal hydroxide;
the optical-grade polyester resin is at least one of polycarbonate, polymethyl methacrylate and polyethylene terephthalate;
the preparation method of the flame-retardant microsphere comprises the following steps:
A. dissolving microcrystalline cellulose in a chlorinated 1-methyl 3-butylimidazolium salt ionic liquid at a mass ratio of 4-10:100 at 70-90 ℃ to form a microcrystalline cellulose solution;
B. b, adding nano red phosphorus into the microcrystalline cellulose solution obtained in the step A, and uniformly stirring to obtain a suspension, wherein the nano red phosphorus accounts for 2-6wt% of the suspension;
C. c, performing electrostatic spraying on the suspension obtained in the step B to obtain the flame-retardant microspheres;
the particle size of the nano red phosphorus is 40-60nm, the particle size of the flame-retardant microsphere is 12.1-24.6 mu m, and the BET specific surface area is 27-63m2/g；
In the step C, the spraying voltage of electrostatic spraying is 20-40kV, and the spraying temperature is 20-30 ℃.
2. The transparent flame-retardant master batch according to claim 1, characterized in that: the synergistic flame retardant is nano magnesium hydroxide and/or nano aluminum hydroxide.
3. The transparent flame-retardant master batch according to claim 1, characterized in that: the dispersing agent is at least one of modified ethylene bis fatty acid amide, pentaerythritol stearate and calcium stearate.
4. A transparent flame-retardant PET film is characterized in that: the composite material comprises the following raw materials in parts by weight:
100 parts of PET resin
20-40 parts of transparent flame-retardant master batch
0.1-10 parts of other auxiliary agents;
wherein the transparent flame-retardant master batch is the transparent flame-retardant master batch of any one of claims 1 to 3.
5. The transparent flame-retardant PET film according to claim 4, wherein: the other auxiliary agent is at least one of antioxidant, ultraviolet absorbent, colorant, antistatic agent, lubricant and compatilizer.
6. The method for preparing a transparent flame-retardant PET film according to claim 4 or 5, which is characterized in that: and (3) melting and mixing the PET resin, the transparent flame-retardant master batch and the rest of auxiliary agents, and stretching to form a film to obtain the transparent flame-retardant PET film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810166844.1A CN108467574B (en) | 2018-02-28 | 2018-02-28 | Transparent flame-retardant master batch, PET (polyethylene terephthalate) film and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810166844.1A CN108467574B (en) | 2018-02-28 | 2018-02-28 | Transparent flame-retardant master batch, PET (polyethylene terephthalate) film and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108467574A CN108467574A (en) | 2018-08-31 |
| CN108467574B true CN108467574B (en) | 2020-07-10 |
Family
ID=63265002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810166844.1A Active CN108467574B (en) | 2018-02-28 | 2018-02-28 | Transparent flame-retardant master batch, PET (polyethylene terephthalate) film and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108467574B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109575324B (en) * | 2018-11-28 | 2021-06-22 | 宁波力达得为高分子科技有限公司 | Chemically modified transparent flame-retardant PET master batch and manufacturing method and application thereof |
| CN110183904B (en) * | 2019-06-13 | 2022-09-30 | 广东顺德洋紫薇化工有限公司 | Flame-retardant ink, preparation method thereof and flame-retardant film |
| CN110433740B (en) * | 2019-06-25 | 2021-12-07 | 浙江工业大学 | Preparation method of thermal expansibility microsphere wrapping ionic liquid |
| CN110628195A (en) * | 2019-08-14 | 2019-12-31 | 湖南登科材料科技有限公司 | Preparation method of flame-retardant plastic master batch |
| CN112831863B (en) * | 2021-03-09 | 2023-01-24 | 高州市铭顺劳保制品有限公司 | Flame-retardant polyester fiber and preparation process thereof |
| CN116144220B (en) * | 2023-02-07 | 2024-01-02 | 北京石油化工学院 | Low-density solid flame-retardant buoyancy material and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101139805A (en) * | 2007-08-15 | 2008-03-12 | 清华大学 | High-voltage static atomizing preparing technique for nano-grade cellulosic material |
| CN101456962A (en) * | 2008-12-29 | 2009-06-17 | 黄华昌 | High-content red phosphorus flame-retardant master batch |
| CN104419133A (en) * | 2013-09-05 | 2015-03-18 | 青岛欣展塑胶有限公司 | High-flame-retardancy and environment-friendly PBT/PET alloy with high CTI value |
| CN104845099A (en) * | 2014-12-07 | 2015-08-19 | 青岛佳亿阳工贸有限公司 | Red phosphor masterbatch flame-retardant modified PET/PTT alloy material |
| CN104845235A (en) * | 2014-12-17 | 2015-08-19 | 王妮娜 | Red phosphorus masterbatch for PTT flame retardant modification |
| CN104861585A (en) * | 2014-10-18 | 2015-08-26 | 青岛欣展塑胶有限公司 | Red phosphorus master batch modified composition based on PTT polyesters |
| CN104861451A (en) * | 2014-10-11 | 2015-08-26 | 青岛欣展塑胶有限公司 | Environmental protection flame retardation master batch used for PTT polyesters and preparation method therefor |
| CN104861512A (en) * | 2014-10-14 | 2015-08-26 | 青岛欣展塑胶有限公司 | PTT high-efficiency toughening flame retardation master batch |
| CN106220936A (en) * | 2016-08-19 | 2016-12-14 | 广州市银塑阻燃材料有限公司 | A kind of high CTI microcapsule coated red phosphorus combustion inhibitor master batch and preparation method thereof |
| CN107603020A (en) * | 2017-10-23 | 2018-01-19 | 成都新柯力化工科技有限公司 | A kind of method that anti-flaming function masterbatch is prepared by gel method |
-
2018
- 2018-02-28 CN CN201810166844.1A patent/CN108467574B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101139805A (en) * | 2007-08-15 | 2008-03-12 | 清华大学 | High-voltage static atomizing preparing technique for nano-grade cellulosic material |
| CN101456962A (en) * | 2008-12-29 | 2009-06-17 | 黄华昌 | High-content red phosphorus flame-retardant master batch |
| CN104419133A (en) * | 2013-09-05 | 2015-03-18 | 青岛欣展塑胶有限公司 | High-flame-retardancy and environment-friendly PBT/PET alloy with high CTI value |
| CN104861451A (en) * | 2014-10-11 | 2015-08-26 | 青岛欣展塑胶有限公司 | Environmental protection flame retardation master batch used for PTT polyesters and preparation method therefor |
| CN104861512A (en) * | 2014-10-14 | 2015-08-26 | 青岛欣展塑胶有限公司 | PTT high-efficiency toughening flame retardation master batch |
| CN104861585A (en) * | 2014-10-18 | 2015-08-26 | 青岛欣展塑胶有限公司 | Red phosphorus master batch modified composition based on PTT polyesters |
| CN104845099A (en) * | 2014-12-07 | 2015-08-19 | 青岛佳亿阳工贸有限公司 | Red phosphor masterbatch flame-retardant modified PET/PTT alloy material |
| CN104845235A (en) * | 2014-12-17 | 2015-08-19 | 王妮娜 | Red phosphorus masterbatch for PTT flame retardant modification |
| CN106220936A (en) * | 2016-08-19 | 2016-12-14 | 广州市银塑阻燃材料有限公司 | A kind of high CTI microcapsule coated red phosphorus combustion inhibitor master batch and preparation method thereof |
| CN107603020A (en) * | 2017-10-23 | 2018-01-19 | 成都新柯力化工科技有限公司 | A kind of method that anti-flaming function masterbatch is prepared by gel method |
Non-Patent Citations (1)
| Title |
|---|
| "纤维素制备微球材料的研究进展";曾丹林等;《材料报导A：综述篇》;20151231;第29卷(第9期);第68-72页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108467574A (en) | 2018-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108467574B (en) | Transparent flame-retardant master batch, PET (polyethylene terephthalate) film and preparation method | |
| CN111533991A (en) | Polypropylene melt-blown material master batch, polypropylene melt-blown material and preparation methods of polypropylene melt-blown material master batch and polypropylene melt-blown material | |
| US5409980A (en) | Flame retardant compositions | |
| CN109021386A (en) | A kind of corrosion proof cable material and preparation method thereof | |
| CN101792586A (en) | High light-flux anti-glare polycarbonate and method for preparing same | |
| CN111978699B (en) | High-shading thin-wall flame-retardant PC material and preparation method and application thereof | |
| CN110591335B (en) | High-flame-retardance low-smoke-toxicity weather-resistant cable sheath material and preparation method thereof | |
| CN112321983B (en) | Sheath rubber material for 105 ℃ CMP (chemical mechanical polishing) level security cable and preparation method thereof | |
| CN116574338B (en) | High weather-resistant chlorinated polyethylene cable sheath material | |
| CN110577708A (en) | Modified floating bead/graphene oxide flame-retardant runway particle material | |
| CN104356538B (en) | Flame-retardant smoke-eliminating polyvinyl chloride wire and cable material | |
| CN108440919B (en) | Antistatic master batch, PET film and preparation method | |
| CN108486681A (en) | Sunlight fabric fiber for architectural shading | |
| CN111690197B (en) | Melamine-containing direct intercalation g-C 3 N 4 Flame-retardant cable material and preparation method thereof | |
| CN108486682B (en) | High-flame-retardance high-mechanical-strength sunlight fabric fiber and preparation method thereof | |
| CN112029157B (en) | Anti-dripping composite intumescent flame retardant and preparation method and application thereof | |
| CN114854133A (en) | Halogen-free flame-retardant long glass fiber reinforced polypropylene composite material and preparation method thereof | |
| CN113667070A (en) | Low-smoke halogen-free flame-retardant cable compatilizer, maleic anhydride grafted modified polyolefin and preparation method thereof | |
| CN112778628B (en) | Outdoor aging-resistant environment-friendly flame-retardant polypropylene composite material and preparation method thereof | |
| CN111748165B (en) | High-strength flame-retardant cable material | |
| CN114702729B (en) | High polymer material additive and application thereof in high polymer functional plastic | |
| CN114230860B (en) | Flame-retardant decabromodiphenyl ethane compound and preparation method thereof | |
| CN111849063B (en) | Flame-retardant photodiffusion polypropylene composition and flame-retardant photodiffusion polypropylene | |
| CN117362804B (en) | Environment-friendly cable sheath material and cable | |
| CN114133680B (en) | PVC material and preparation method and application thereof for wires or cables |
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 | ||
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 523000 Room 101, building 1, No. 2, Jinsheng Road, Zhangmutou town, Dongguan City, Guangdong Province Patentee after: DONGGUAN JISHUO INDUSTRIAL Co.,Ltd. Address before: 523000 building a, Zhangluo second industrial zone, Zhangmutou town, Dongguan City, Guangdong Province Patentee before: DONGGUAN JISHUO INDUSTRIAL Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 523000 Room 101, building 1, No. 2, Jinsheng Road, Zhangmutou town, Dongguan City, Guangdong Province Patentee after: Guangdong Jishuo New Materials Co.,Ltd. Address before: 523000 Room 101, building 1, No. 2, Jinsheng Road, Zhangmutou town, Dongguan City, Guangdong Province Patentee before: DONGGUAN JISHUO INDUSTRIAL Co.,Ltd. |