CN111690251A - Degradable flame-retardant plastic film and production process thereof - Google Patents
Degradable flame-retardant plastic film and production process thereof Download PDFInfo
- Publication number
- CN111690251A CN111690251A CN202010561883.9A CN202010561883A CN111690251A CN 111690251 A CN111690251 A CN 111690251A CN 202010561883 A CN202010561883 A CN 202010561883A CN 111690251 A CN111690251 A CN 111690251A
- Authority
- CN
- China
- Prior art keywords
- plastic film
- flame retardant
- parts
- flame
- stirring
- 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
- 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
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/24—Incorporating phosphorus atoms into the molecule
-
- 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
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
-
- 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
- C08J2415/00—Characterised by the use of rubber derivatives
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
-
- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- 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
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/06—Polyurethanes from polyesters
-
- 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
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
Abstract
The invention discloses a degradable flame-retardant plastic film which comprises the following raw materials in parts by weight: 30-40 parts of polyurethane resin, 30-40 parts of polylactic acid, 12-18 parts of polybutylene succinate, 2-3 parts of flame retardant, 4-6 parts of modified halloysite nanotube, 0.8-1 part of antioxidant and 1-2 parts of lubricant; the invention also discloses a production process of the plastic film. The plastic film adopts polyurethane resin, polylactic acid and poly butylene succinate as film forming matrixes, so that the plastic film has the biodegradable characteristic; by adding the self-made flame retardant into the film raw material, the self-made flame retardant can be uniformly distributed in a high polymer matrix and can generate a chemical bonding effect with a polyurethane molecular chain, so that the migration and migration phenomena of the flame retardant are effectively avoided; the modified halloysite has a synergistic effect on the flame retardant, so that the flame retardant property of the film is further improved; the plastic film has excellent flame retardant property on the basis of having the biodegradable characteristic.
Description
Technical Field
The invention belongs to the field of plastic film processing, and particularly relates to a degradable flame-retardant plastic film and a production process thereof.
Background
The plastic film is light, thin, waterproof, high in strength and low in cost, is a good packaging and agricultural covering material, brings great convenience to the life of people due to the use of the plastic film, the using amount of the plastic film is increased, but the used waste plastic film is not easy to recover and degrade, and a large number of waste plastic bags become a serious problem of environmental pollution at present. In order to reduce the pollution of the plastic film to the environment, some environment-friendly green degradable plastic films are developed, and the degradable plastic films comprise film-grade plastics and components capable of initiating the plastics to be degraded, but the processing performance of the existing degradable plastic films is poor, and the degradation time is long.
The Chinese patent with the patent number of CN201410777429.1 discloses a degradable flame-retardant plastic film and a preparation method thereof, and the degradable flame-retardant plastic film comprises the following raw material components in parts by weight: 85 parts of polyethylene, 20-30 parts of polylactic acid, 65-80 parts of PBM degradable material, 10-15 parts of filler, 5-10 parts of pullulan, 2-4 parts of antioxidant, 1-1.5 parts of ultraviolet absorbent and 25-30 parts of nano flame-retardant compound. According to the application, the inorganic mineral materials are doped into the film raw materials, so that the plastic film has certain flame retardant property. However, the inorganic mineral filler is nano-scale inorganic particles, has the defects of easy agglomeration and poor compatibility with a polymer matrix, is difficult to disperse uniformly in the plastic film, and ensures that the flame retardant property of the plastic film still cannot meet the use requirement.
Disclosure of Invention
The invention aims to provide a degradable flame-retardant plastic film and a production process thereof, wherein the plastic film adopts polyurethane resin, polylactic acid and poly butylene succinate as film forming matrixes, so that the plastic film has the biodegradable characteristic and meets the environmental protection requirement; the self-made flame retardant is added into the film raw material, has good compatibility with a high polymer matrix and can be uniformly distributed in the high polymer matrix, and in addition, the flame retardant can also generate a chemical bonding effect with a polyurethane molecular chain, so that the bonding force of the flame retardant and the polymer matrix is improved, and the migration and migration phenomena of the flame retardant are effectively avoided; the modified halloysite has a synergistic effect on the flame retardant, so that the flame retardant property of the film is further improved; the obtained plastic film has excellent flame retardant property on the basis of having the biodegradable characteristic, and the application range of the plastic film is expanded.
The purpose of the invention can be realized by the following technical scheme:
a degradable flame-retardant plastic film comprises the following raw materials in parts by weight: 30-40 parts of polyurethane resin, 30-40 parts of polylactic acid, 12-18 parts of polybutylene succinate, 2-3 parts of flame retardant, 4-6 parts of modified halloysite nanotube, 0.8-1 part of antioxidant and 1-2 parts of lubricant.
Further, the antioxidant is antioxidant 300, antioxidant 1010 or antioxidant 1076.
Further, the lubricant is polyethylene wax or silicone oil.
Further, the flame retardant is prepared by the following method:
s1, adding carboxyl-terminated polybutadiene and toluene into a three-neck flask with a stirring device, heating to 90 ℃, stirring at a constant temperature for 15-20min, cooling, adding a formic acid aqueous solution when the temperature is reduced to 38-40 ℃, adding a hydrogen peroxide aqueous solution after the temperature is reduced to room temperature, and uniformly stirring at 150r/min at room temperature for reaction for 10-12 h;
s2, pouring the reaction liquid into a separating funnel, adding distilled water for multiple times for separating, removing unreacted formic acid and hydrogen peroxide until the pH value of the reaction liquid is 6.8-7.0, separating the reaction liquid by using absolute ethyl alcohol, separating a product and a toluene solvent, separating the product out, and fully drying to obtain an intermediate;
s3, adding the intermediate into xylene at 90-95 ℃, stirring to dissolve the intermediate, adding 2-carboxyethylphenylphosphinic acid powder, heating to 120 ℃ under stirring, continuously stirring and reacting for 10-12h at 120 ℃ under the constant temperature of 115 ℃ under stirring, removing the xylene through rotary evaporation after the reaction is finished, and drying the product in a vacuum drying oven at 60 ℃ for 5-6h to obtain the flame retardant.
Further, in step S1, the mass fraction of the formic acid aqueous solution is 6%, and the mass fraction of the hydrogen peroxide aqueous solution is 30%; the dosage ratio of the carboxyl-terminated polybutadiene, the toluene, the formic acid aqueous solution and the hydrogen peroxide aqueous solution is 1g:8-10mL:10-15mL:6-8 mL.
Further, the ratio of the amounts of the intermediate, xylene and 2-carboxyethylphenylphosphinic acid used in step S3 is 1g:40-50mL:0.6-0.9 g.
Further, the modified halloysite nanotube is prepared by the following method:
dispersing the halloysite nanotube in NaOH aqueous solution according to the solid-to-liquid ratio of 1g:50mL, uniformly stirring at room temperature at 200r/min for 22-24h, centrifugally separating the obtained slurry, washing the product with distilled water for multiple times until the pH value of the washing liquid is 7.0, and finally drying the product in an oven at 80 ℃ for 20-24h to obtain the modified halloysite nanotube.
A production process of a degradable flame-retardant plastic film comprises the following steps:
firstly, putting polyurethane, polylactic acid and poly butylene succinate into a vacuum drying oven at 40-45 ℃ for drying for 15-18 h;
secondly, putting the dried polyurethane, polylactic acid, polybutylene succinate, flame retardant, modified halloysite nanotube and lubricant into a high-speed mixer, stirring and mixing at 8000r/min for 25-30min, adding antioxidant, and continuously stirring for 7-10min to obtain a mixed material;
thirdly, adding the blend into a charging barrel of a double-screw extruder, and then performing melt extrusion, water cooling, grain cutting and drying to obtain blend particles, wherein the extrusion temperature is 160-175 ℃;
fourthly, extruding and blowing the blended particles by a slide chamber type single screw extruder provided with a film blowing machine head to obtain a plastic film; wherein the film blowing temperature is 155-170 ℃, the screw rotating speed is 38-40r/min, the traction speed is 7.0m/min, and the winding speed is 7.0 m/min.
The invention has the beneficial effects that:
in the preparation process of the flame retardant, carbon-carbon double bonds C ═ C on a molecular chain of carboxyl-terminated polybutadiene generate epoxy groups under the oxidation action of formic acid and hydrogen peroxide, and the epoxy groups and-COOH on 2-carboxyethylphenylphosphinic acid molecules undergo a ring-opening reaction, so that the 2-carboxyethylphenylphosphinic acid molecules are grafted on side chains of the carboxyl-terminated polybutadiene molecules to form a high-molecular flame retardant; the macromolecular flame retardant has good compatibility with a high polymer matrix (polyurethane, polylactic acid and the like), can be uniformly distributed in the high polymer matrix, and can better exert the flame retardant effect, a carboxyl-terminated polybutadiene molecular chain also contains-COOH, and carboxyl can react with-NH-groups on polyurethane molecules, so that the binding force of the flame retardant and the polymer matrix is improved, the migration and migration phenomena of the flame retardant can be effectively avoided, the flame retardant can continuously and stably exert the flame retardant effect, and the durability of the flame retardant effect is improved; the binding force between the flame retardant and a polymer matrix is further improved, and the migration resistance of the flame retardant is improved;
according to the invention, the modified halloysite nanotube is added into the film raw material, and the modified halloysite nanotube is adopted to compound the flame retardant, so that more-OH is formed on the surface of the halloysite nanotube after alkali treatment and modification, and the-OH on the surface can not only react with-COOH on the flame retardant molecule, but also react with-NH-on the polyurethane molecular chain, so that the uniform dispersion of the halloysite nanotube is promoted, and the interaction between the halloysite nanotube and the flame retardant and the interaction between the halloysite nanotube and the polymer matrix are improved; the halloysite nanotube contains Si-O bonds and Al-O bonds, and can form a barrier structure under a high-temperature condition, so that the halloysite nanotube can play a flame retardant role in a condensed phase; when the modified halloysite nanotube and the flame retardant are compounded for use, the silicon-phosphorus synergistic effect can further promote the carbon formation of a polymer matrix, and the modified halloysite nanotube and the flame retardant react to generate silicoaluminophosphate in the combustion process, and the silicoaluminophosphate is used as an acid catalyst, so that the formation of phosphoric acid can be promoted, and the oxidation, dehydration, crosslinking and carbonization processes can be enhanced, so that the surface of residual carbon is more compact, a compact carbon layer formed at high temperature is favorable for oxygen isolation and heat insulation, the generation amount of combustible gas is reduced, and the condensed phase flame retardant effect is achieved; the modified halloysite can achieve a synergistic effect on the flame retardant, so that the flame retardant property of the film is further improved;
the plastic film adopts polyurethane resin, polylactic acid and poly butylene succinate as film forming matrixes, so that the plastic film has the biodegradable characteristic and meets the environmental protection requirement; the self-made flame retardant is added into the film raw material, has good compatibility with a high polymer matrix and can be uniformly distributed in the high polymer matrix, and in addition, the flame retardant can also generate a chemical bonding effect with a polyurethane molecular chain, so that the bonding force of the flame retardant and the polymer matrix is improved, and the migration and migration phenomena of the flame retardant are effectively avoided; the modified halloysite has a synergistic effect on the flame retardant, so that the flame retardant property of the film is further improved; the obtained plastic film has excellent flame retardant property on the basis of having the biodegradable characteristic, and the application range of the plastic film is expanded.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A degradable flame-retardant plastic film comprises the following raw materials in parts by weight: 30-40 parts of polyurethane resin, 30-40 parts of polylactic acid, 12-18 parts of polybutylene succinate, 2-3 parts of flame retardant, 4-6 parts of modified halloysite nanotube, 0.8-1 part of antioxidant and 1-2 parts of lubricant;
wherein the polyurethane resin is polyester polyurethane;
the antioxidant is antioxidant 300, antioxidant 1010 or antioxidant 1076;
the lubricant is polyethylene wax or silicone oil;
the flame retardant is prepared by the following method:
s1, adding carboxyl-terminated polybutadiene and toluene into a three-neck flask with a stirring device, heating to 90 ℃, stirring at a constant temperature for 15-20min, cooling, adding a formic acid aqueous solution (the mass fraction of the formic acid aqueous solution is 6%) when the temperature is reduced to 38-40 ℃, adding a hydrogen peroxide aqueous solution (the mass fraction of the hydrogen peroxide aqueous solution is 30%) when the temperature is reduced to room temperature, and uniformly stirring at 150r/min at room temperature for reaction for 10-12 h;
wherein the dosage ratio of the carboxyl-terminated polybutadiene, the toluene, the formic acid aqueous solution and the hydrogen peroxide aqueous solution is 1g:8-10mL:10-15mL:6-8 mL;
s2, pouring the reaction liquid into a separating funnel, adding distilled water for multiple times for separating, removing unreacted formic acid and hydrogen peroxide until the pH value of the reaction liquid is 6.8-7.0, separating the reaction liquid by using absolute ethyl alcohol, separating a product and a toluene solvent, separating the product out, and fully drying to obtain an intermediate;
s3, adding the intermediate into xylene at 90-95 ℃, stirring to dissolve the intermediate, adding 2-carboxyethyl phenyl phosphinic acid powder, heating to 120 ℃ under stirring, continuously stirring and reacting for 10-12h at 120 ℃ under the constant temperature of 115 ℃ under stirring, removing the xylene through rotary evaporation after the reaction is finished, and drying the product in a vacuum drying box at 60 ℃ for 5-6h to obtain the flame retardant;
wherein the dosage ratio of the intermediate, the dimethylbenzene to the 2-carboxyethyl phenyl phosphinic acid is 1g to 40-50mL to 0.6-0.9 g;
generating an epoxy group by a carbon-carbon double bond C ═ C on a molecular chain of the carboxyl-terminated polybutadiene under the oxidation action of formic acid and hydrogen peroxide, and carrying out a ring-opening reaction on the epoxy group and-COOH on a 2-carboxyethylphenylphosphinic acid molecule to graft the 2-carboxyethylphenylphosphinic acid molecule on a side chain of the carboxyl-terminated polybutadiene molecule to form a high-molecular flame retardant; the macromolecular flame retardant has good compatibility with a high polymer matrix (polyurethane, polylactic acid and the like), can be uniformly distributed in the high polymer matrix, and can better exert the flame retardant effect, a carboxyl-terminated polybutadiene molecular chain also contains-COOH, and carboxyl can react with-NH-groups on polyurethane molecules, so that the binding force of the flame retardant and the polymer matrix is improved, the migration and migration phenomena of the flame retardant can be effectively avoided, the flame retardant can continuously and stably exert the flame retardant effect, and the durability of the flame retardant effect is improved; the binding force between the flame retardant and a polymer matrix is further improved, and the migration resistance of the flame retardant is improved;
the modified halloysite nanotube is prepared by the following method:
dispersing halloysite nanotubes in a NaOH aqueous solution (the mass fraction of the NaOH aqueous solution is 8%) according to a solid-to-liquid ratio of 1g:50mL, uniformly stirring at 200r/min at room temperature for 22-24h, performing centrifugal separation on the obtained slurry, washing the product with distilled water for multiple times until the pH value of the washing liquid is 7.0, and finally drying the product in an oven at 80 ℃ for 20-24h to obtain modified halloysite nanotubes;
after the halloysite nanotube is modified by alkali treatment, more-OH is formed on the surface, and the-OH on the surface can not only act with-COOH on a flame retardant molecule, but also act with-NH-on a polyurethane molecular chain, so that the uniform dispersion of the halloysite nanotube is promoted, and the interaction between the halloysite nanotube and the flame retardant and the interaction between the halloysite nanotube and a polymer matrix are improved; the halloysite nanotube contains Si-O bonds and Al-O bonds, and can form a barrier structure under a high-temperature condition, so that the halloysite nanotube can play a flame retardant role in a condensed phase; when the modified halloysite nanotube and the flame retardant are compounded for use, the silicon-phosphorus synergistic effect can further promote the carbon formation of a polymer matrix, and the modified halloysite nanotube and the flame retardant react to generate silicoaluminophosphate in the combustion process, and the silicoaluminophosphate is used as an acid catalyst, so that the formation of phosphoric acid can be promoted, and the oxidation, dehydration, crosslinking and carbonization processes can be enhanced, so that the surface of residual carbon is more compact, a compact carbon layer formed at high temperature is favorable for oxygen isolation and heat insulation, the generation amount of combustible gas is reduced, and the condensed phase flame retardant effect is achieved; the modified halloysite can achieve a synergistic effect on the flame retardant, so that the flame retardant property of the film is further improved;
the production process of the plastic film comprises the following steps:
firstly, putting polyurethane, polylactic acid and poly butylene succinate into a vacuum drying oven at 40-45 ℃ for drying for 15-18 h;
secondly, putting the dried polyurethane, polylactic acid, polybutylene succinate, flame retardant, modified halloysite nanotube and lubricant into a high-speed mixer, stirring and mixing at 8000r/min for 25-30min, adding antioxidant, and continuously stirring for 7-10min to obtain a mixed material;
thirdly, adding the blend into a charging barrel of a double-screw extruder, and then performing melt extrusion, water cooling, grain cutting and drying to obtain blend particles, wherein the extrusion temperature is 160-175 ℃;
fourthly, extruding and blowing the blended particles by a slide chamber type single screw extruder provided with a film blowing machine head to obtain a plastic film; wherein the film blowing temperature is 155-170 ℃, the screw rotating speed is 38-40r/min, the traction speed is 7.0m/min, and the winding speed is 7.0 m/min.
Example 1
A degradable flame-retardant plastic film comprises the following raw materials in parts by weight: 30 parts of polyurethane resin, 30 parts of polylactic acid, 12 parts of polybutylene succinate, 2 parts of a flame retardant, 4 parts of a modified halloysite nanotube, 0.8 part of an antioxidant and 1 part of a lubricant;
the plastic film is prepared by the following steps:
firstly, putting polyurethane, polylactic acid and poly butylene succinate into a vacuum drying oven at 40 ℃ for drying for 18 h;
secondly, putting the dried polyurethane, polylactic acid, polybutylene succinate, flame retardant, modified halloysite nanotube and lubricant into a high-speed mixer, stirring and mixing at 8000r/min for 25min, adding antioxidant, and continuously stirring for 7min to obtain a blend;
thirdly, adding the blend into a charging barrel of a double-screw extruder, and then performing melt extrusion, water cooling, grain cutting and drying to obtain blend particles, wherein the extrusion temperature is 160 ℃;
fourthly, extruding and blowing the blended particles by a slide chamber type single screw extruder provided with a film blowing machine head to obtain a plastic film; wherein the film blowing temperature is 155 ℃, the screw rotating speed is 38r/min, the traction speed is 7.0m/min, and the winding speed is 7.0 m/min.
Example 2
A degradable flame-retardant plastic film comprises the following raw materials in parts by weight: 35 parts of polyurethane resin, 35 parts of polylactic acid, 15 parts of polybutylene succinate, 2.5 parts of flame retardant, 4.5 parts of modified halloysite nanotube, 0.9 part of antioxidant and 1.5 parts of lubricant;
the plastic film is prepared by the following steps:
firstly, putting polyurethane, polylactic acid and poly butylene succinate into a vacuum drying oven at 43 ℃ for drying for 16 h;
secondly, putting the dried polyurethane, polylactic acid, polybutylene succinate, flame retardant, modified halloysite nanotube and lubricant into a high-speed mixer, stirring and mixing for 28min at 8000r/min, adding antioxidant, and continuously stirring for 8min to obtain a mixed material;
thirdly, adding the blend into a charging barrel of a double-screw extruder, and then performing melt extrusion, water cooling, grain cutting and drying to obtain blend particles, wherein the extrusion temperature is 168 ℃;
fourthly, extruding and blowing the blended particles by a slide chamber type single screw extruder provided with a film blowing machine head to obtain a plastic film; wherein the film blowing temperature is 162 ℃, the screw rotating speed is 39r/min, the traction speed is 7.0m/min, and the winding speed is 7.0 m/min.
Example 3
A degradable flame-retardant plastic film comprises the following raw materials in parts by weight: 40 parts of polyurethane resin, 40 parts of polylactic acid, 18 parts of polybutylene succinate, 3 parts of a flame retardant, 6 parts of a modified halloysite nanotube, 1 part of an antioxidant and 2 parts of a lubricant;
the plastic film is prepared by the following steps:
firstly, putting polyurethane, polylactic acid and poly butylene succinate into a vacuum drying oven at 40-45 ℃ for drying for 15-18 h;
secondly, putting the dried polyurethane, polylactic acid, polybutylene succinate, flame retardant, modified halloysite nanotube and lubricant into a high-speed mixer, stirring and mixing for 30min at 8000r/min, adding antioxidant, and continuously stirring for 10min to obtain a mixed material;
thirdly, adding the blend into a charging barrel of a double-screw extruder, and then performing melt extrusion, water cooling, grain cutting and drying to obtain blend particles, wherein the extrusion temperature is 175 ℃;
fourthly, extruding and blowing the blended particles by a slide chamber type single screw extruder provided with a film blowing machine head to obtain a plastic film; wherein the film blowing temperature is 170 ℃, the screw rotating speed is 40r/min, the traction speed is 7.0m/min, and the winding speed is 7.0 m/min.
Comparative example 1
The flame retardant in example 1 was replaced by 2-carboxyethylphenylphosphinic acid, and the remaining raw materials and preparation were unchanged.
Comparative example 2
The modified halloysite nanotubes from example 1 were exchanged for halloysite nanotubes without any treatment, the remaining raw materials and preparation were unchanged.
Comparative example 3
The modified halloysite nanotube material of example 1 was removed, and the remaining materials and preparation were unchanged.
Comparative example 4
A pure PLA film.
The films prepared in the above examples were subjected to the following performance tests: cutting the plastic films prepared in the examples 1-3 and the comparative example 4 into standard test sizes, and testing the mechanical properties of the films according to ASTM D882-2010, including tensile strength, elongation at break and tear strength; the plastic films prepared in examples 1 to 3 and comparative examples 1 to 4 were cut into a standard test size, and the limiting oxygen index LOI and the vertical burning rating of each film were tested; a soil burying test, in which the films prepared in examples 1 to 3 and comparative example 4 were cut into a standard test size, buried in soil having a depth of about 20cm in a natural environment, samples were taken out after 45 days, and degradation mass loss rates of the respective films were calculated; the test results are shown in the following table:
as can be seen from the above table, examples 1 to 3The obtained plastic film has tensile strength of 55.8-57.2MPa, elongation at break of 10.5-11.3%, and tear strength of 94.9-96.4 kN.m-1Compared with a pure PLA film, each performance index is slightly improved, which shows that the plastic film prepared by the invention can meet the use requirement; as can be seen from the above table, the LOI index of the plastic films prepared in examples 1-3 is 28.5-29.4%, and the vertical burning grades reach V-0 grade, which indicates that the plastic films prepared by the invention have excellent flame retardant property; compared with the comparative example 1, the self-made flame retardant is a macromolecular flame retardant, has good compatibility with a polymer matrix, can generate chemical action with a polyurethane matrix, and improves the bonding force between the flame retardant and the film matrix; compared with comparative example 2 and comparative example 3, the modified halloysite nanotube has the advantages that more-OH is introduced into the surface of the halloysite nanotube after modification treatment, so that the interaction force between the halloysite nanotube and a polymer matrix and a flame retardant can be improved, the modified halloysite nanotube and the flame retardant can play a synergistic effect, the formation of char and the compactness of a char layer are promoted, and the flame retardant property of a plastic film is further improved; as can be seen from the above table, the plastic film prepared by the invention has a degradation mass loss rate of 77.9-79.4% after being buried in soil for 45d, and compared with a pure PLA film, the plastic film prepared by the invention has good biodegradable property and meets the requirement of environmental protection.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (8)
1. The degradable flame-retardant plastic film is characterized by comprising the following raw materials in parts by weight: 30-40 parts of polyurethane resin, 30-40 parts of polylactic acid, 12-18 parts of polybutylene succinate, 2-3 parts of flame retardant, 4-6 parts of modified halloysite nanotube, 0.8-1 part of antioxidant and 1-2 parts of lubricant.
2. The degradable flame retardant plastic film of claim 1, wherein the antioxidant is antioxidant 300, antioxidant 1010 or antioxidant 1076.
3. The degradable flame-retardant plastic film according to claim 1, wherein said lubricant is polyethylene wax or silicone oil.
4. The degradable flame-retardant plastic film according to claim 1, wherein the flame retardant is prepared by the following method:
s1, adding carboxyl-terminated polybutadiene and toluene into a three-neck flask with a stirring device, heating to 90 ℃, stirring at a constant temperature for 15-20min, cooling, adding a formic acid aqueous solution when the temperature is reduced to 38-40 ℃, adding a hydrogen peroxide aqueous solution after the temperature is reduced to room temperature, and uniformly stirring at 150r/min at room temperature for reaction for 10-12 h;
s2, pouring the reaction liquid into a separating funnel, adding distilled water for multiple times for separating, removing unreacted formic acid and hydrogen peroxide until the pH value of the reaction liquid is 6.8-7.0, separating the reaction liquid by using absolute ethyl alcohol, separating a product and a toluene solvent, separating the product out, and fully drying to obtain an intermediate;
s3, adding the intermediate into xylene at 90-95 ℃, stirring to dissolve the intermediate, adding 2-carboxyethylphenylphosphinic acid powder, heating to 120 ℃ under stirring, continuously stirring and reacting for 10-12h at 120 ℃ under the constant temperature of 115 ℃ under stirring, removing the xylene through rotary evaporation after the reaction is finished, and drying the product in a vacuum drying oven at 60 ℃ for 5-6h to obtain the flame retardant.
5. The degradable flame-retardant plastic film according to claim 4, wherein the mass fraction of the formic acid aqueous solution in step S1 is 6%, and the mass fraction of the hydrogen peroxide aqueous solution is 30%; the dosage ratio of the carboxyl-terminated polybutadiene, the toluene, the formic acid aqueous solution and the hydrogen peroxide aqueous solution is 1g:8-10mL:10-15mL:6-8 mL.
6. The degradable flame-retardant plastic film according to claim 4, wherein the ratio of the amount of the intermediate, xylene and 2-carboxyethylphenylphosphinic acid used in step S3 is 1g:40-50mL:0.6-0.9 g.
7. The degradable flame-retardant plastic film according to claim 1, wherein the modified halloysite nanotubes are prepared by the following method:
dispersing the halloysite nanotube in NaOH aqueous solution according to the solid-to-liquid ratio of 1g:50mL, uniformly stirring at room temperature at 200r/min for 22-24h, centrifugally separating the obtained slurry, washing the product with distilled water for multiple times until the pH value of the washing liquid is 7.0, and finally drying the product in an oven at 80 ℃ for 20-24h to obtain the modified halloysite nanotube.
8. The production process of the degradable flame-retardant plastic film according to claim 1, characterized by comprising the following steps:
firstly, putting polyurethane, polylactic acid and poly butylene succinate into a vacuum drying oven at 40-45 ℃ for drying for 15-18 h;
secondly, putting the dried polyurethane, polylactic acid, polybutylene succinate, flame retardant, modified halloysite nanotube and lubricant into a high-speed mixer, stirring and mixing at 8000r/min for 25-30min, adding antioxidant, and continuously stirring for 7-10min to obtain a mixed material;
thirdly, adding the blend into a charging barrel of a double-screw extruder, and then performing melt extrusion, water cooling, grain cutting and drying to obtain blend particles, wherein the extrusion temperature is 160-175 ℃;
fourthly, extruding and blowing the blended particles by a slide chamber type single screw extruder provided with a film blowing machine head to obtain a plastic film; wherein the film blowing temperature is 155-170 ℃, the screw rotating speed is 38-40r/min, the traction speed is 7.0m/min, and the winding speed is 7.0 m/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010561883.9A CN111690251B (en) | 2020-06-18 | 2020-06-18 | Degradable flame-retardant plastic film and production process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010561883.9A CN111690251B (en) | 2020-06-18 | 2020-06-18 | Degradable flame-retardant plastic film and production process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111690251A true CN111690251A (en) | 2020-09-22 |
| CN111690251B CN111690251B (en) | 2022-03-04 |
Family
ID=72481854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010561883.9A Active CN111690251B (en) | 2020-06-18 | 2020-06-18 | Degradable flame-retardant plastic film and production process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111690251B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112608590A (en) * | 2020-12-02 | 2021-04-06 | 陈天兵 | Flame-retardant plastic film and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090326133A1 (en) * | 2007-05-23 | 2009-12-31 | Naturalnano Research, Inc. | Fire and flame retardant polymer composites |
| CN110511434A (en) * | 2019-08-30 | 2019-11-29 | 厦门大学 | A kind of preparation method and applications for mixing silver-colored halloysite nanotubes composite material of the cladding containing polyphosphazene |
| CN111100332A (en) * | 2019-12-02 | 2020-05-05 | 厦门大学 | Preparation method and application of dumbbell type fluorine-containing polyphosphazene modified halloysite nanotube |
-
2020
- 2020-06-18 CN CN202010561883.9A patent/CN111690251B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090326133A1 (en) * | 2007-05-23 | 2009-12-31 | Naturalnano Research, Inc. | Fire and flame retardant polymer composites |
| CN110511434A (en) * | 2019-08-30 | 2019-11-29 | 厦门大学 | A kind of preparation method and applications for mixing silver-colored halloysite nanotubes composite material of the cladding containing polyphosphazene |
| CN111100332A (en) * | 2019-12-02 | 2020-05-05 | 厦门大学 | Preparation method and application of dumbbell type fluorine-containing polyphosphazene modified halloysite nanotube |
Non-Patent Citations (3)
| Title |
|---|
| QINGFA WANG等: "Kinetics of Epoxidation of Hydroxyl-Terminated Polybutadiene with Hydrogen Peroxide under Phase Transfer Catalysis", 《IND. ENG. CHEM. RES.》 * |
| 冯飞等: "聚乳酸／聚氨酯弹性体共混复合材料结构与性能研究", 《塑料工业》 * |
| 舒友等: "聚乳酸增韧改性研究", 《塑料科技》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112608590A (en) * | 2020-12-02 | 2021-04-06 | 陈天兵 | Flame-retardant plastic film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111690251B (en) | 2022-03-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107022142A (en) | A kind of DOPO derivatives grafts siloxanes flame retarding reaction type cable material and preparation method thereof | |
| CN111117173B (en) | Environment-friendly beverage packaging bag and processing technology thereof | |
| CN110283415B (en) | Thermoplastic elastomer with both conductivity and flame retardance and preparation method thereof | |
| CN105255124A (en) | Modified carbon nanotube flame retardant reinforced polyester composite material and preparation method thereof | |
| CN102030963A (en) | Halogen-free fire-retardant thermoplastic elastomer material and preparation method thereof | |
| CN101255247A (en) | Boiling-free silicane cross-linking polyolefin composition | |
| CN111690251B (en) | Degradable flame-retardant plastic film and production process thereof | |
| CN103724786A (en) | Halogen-free intumescent flame retardant EVA special material and preparation method thereof | |
| CN104448524A (en) | Halogen-free flame-retardant cable material and preparation method thereof | |
| CN112852133B (en) | Anti-droplet PLA/PVA composite material and preparation method thereof | |
| Shu et al. | Preparation and properties of bio-based flame retardant polyvinyl alcohol | |
| Su et al. | Characterization of cross-linked alkaline lignin/poly (vinyl alcohol) film with a formaldehyde cross-linker | |
| CN113308024A (en) | Aluminum hypophosphite-polyphosphazene core-shell type flame retardant and preparation method thereof | |
| CN110423443B (en) | Biomass-based high-toughness flame-retardant plate | |
| CN102617969B (en) | Preparation method of thermoplastic konjac glucomannan/poly butylenes succinate blending material | |
| CN111574802A (en) | Preparation method of polypropylene plastic particles | |
| CN115216093A (en) | Environment-friendly degradable plastic bag and preparation method thereof | |
| CN113861643B (en) | High-barrier biodegradable material and preparation method and application thereof | |
| CN114106538A (en) | Fully-degradable plastic processing technology | |
| CN112194872B (en) | Composite material based on recycled plastic and preparation method thereof | |
| CN113372594A (en) | Degradable plastic mulching film based on PBAT and preparation method thereof | |
| CN116218195B (en) | High-flame-retardance modified polyurethane cable material and preparation method thereof | |
| CN112608590A (en) | Flame-retardant plastic film and preparation method thereof | |
| CN115216089B (en) | Halogen-free flame-retardant master batch, thin-wall halogen-free flame-retardant polypropylene and preparation methods thereof | |
| CN108659424A (en) | A kind of water dissolving type prilling process of modified polyvinylalcohol |
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 | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220214 Address after: 528300 Beishui Industrial Zone, Bai'an highway, Beishui village committee, Xingtan town, Shunde District, Foshan City, Guangdong Province Applicant after: Guangdong baotexin New Material Technology Co.,Ltd. Address before: 362200 No. 184, Huguang Road East, Huzhong village, Chendai Town, Jinjiang City, Quanzhou City, Fujian Province Applicant before: Jinjiang Xiangqian shoe material Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |