CN114891324B - Flame-retardant modified material with cross-linked grid structure, and preparation method and application thereof - Google Patents
Flame-retardant modified material with cross-linked grid structure, and preparation method and application thereof Download PDFInfo
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- 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
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- 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
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- C08K2003/026—Phosphorus
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
The invention discloses a flame-retardant modified material with a cross-linked grid structure, a preparation method and application thereof, wherein the flame-retardant modified material is prepared from the following components in parts by weight: 70-90 parts of polybutylene adipate terephthalate, 10-30 parts of polylactic acid, 0.1-0.5 part of initiator, 5-15 parts of flame retardant, 0.1-1 part of nucleating agent, 0.5-2 parts of anti-hydrolysis agent and 2-6 parts of compatilizer. In the PBAT/PLA composite system prepared by the invention, due to the PBAT flexible chain and the PLA rigid chain, a specific cross-linked grid structure can be formed based on original sites in the PBAT/PLA system by adding the initiator and the flame retardant in the process of twin-screw melt blending extrusion, and the structure can have firm mechanical structure and better flame retardant effect.
Description
Technical Field
The invention relates to the field of biodegradable polymer materials, in particular to a flame-retardant modified material with a cross-linked grid structure prepared based on a bio-based degradable polybutylene adipate terephthalate (PBAT) and polylactic acid (PLA) composite system and application thereof.
Background
The biodegradable foam material has remarkable advantages, and polylactic acid (PLA), poly adipic acid-butylene terephthalate (PBAT) and the like belong to one of the degradation materials which are very active in the research of the current biodegradable plastics and have good market application prospects. PBAT belongs to a thermoplastic biodegradable material, is a copolymer of butanediol adipate and butanediol terephthalate, and has good ductility and elongation at break as well as good heat resistance and impact resistance. PLA is a completely biodegradable thermoplastic polymer, has good mechanical properties, transparency and biocompatibility, and is widely applied to the biomedical industry. PLA also has high tensile strength, compression modulus, but PLA also has several disadvantages. PLA with optical activity has higher crystallinity, long degradation period, large brittleness, hard quality and poorer toughness. Therefore, the PBAT and the PLA are subjected to composite modification by adding the auxiliary agent, and a product with better performance is obtained. Can be widely used in the fields of packaging materials, disposable daily necessities, heat insulation materials and the like, and is an important way for solving the problem of white pollution of plastics.
The 3D printing technology, which is one of the rapid prototyping technologies, is also called additive manufacturing, and is a form of constructing an object by using an adhesive material such as powdered metal or plastic based on a digital model file and by printing layer by layer. However, the 3D printing technology still has the problems of poor molding, serious shrinkage and the like at present due to the limitation of material performance. It finds application primarily in guidelines and tools in surgery, and for making anatomical replicas for learning purposes. Furthermore, the personalized orthosis, prosthesis or implant can be printed based on a 3D scan or a tomographic model. Customization also works in the fields of art and jewelry, consumer goods or sports where unique works with complex designs can be printed. Another field of application is construction and architecture. Additive manufacturing on the one hand helps building and optimizing models, and on the other hand it offers the possibility to create buildings and elements with new designs, high complexity, greater functional integration and less waste. The high design freedom and the possibility of complex geometries are also used for the design of new lightweight components, which are widely used in the aerospace industry.
PBAT/PLA has a low limiting oxygen index, is flammable, and easily forms a large amount of drops when burned, limiting its application in various fields, and thus it is necessary to modify it for flame retardancy. The flame retardant is added by an economical and common method in industry, and is mainly divided into a halogen-containing flame retardant and a halogen-free flame retardant.
The halogen-containing flame retardant is a halogen-containing polymer or a flame-retardant mixture combined with the halogen-containing flame retardant, has good flame-retardant effect, low price, good stability, small addition amount and good compatibility with synthetic resin materials, and can maintain the original physical and chemical properties of flame retardant products. Mainly comprising antimony trioxide and decabromodiphenyl ether, namely a commonly-called bromine antimony-grade flame retardant. The halogen-free flame retardant is a high-performance phosphorus-nitrogen organic flame retardant which is subjected to special surface treatment, is easy to disperse in plastic materials, does not precipitate and has a good flame retardant effect. Mainly comprises triazine triketone compounds and triazine triamine compounds, and the material manufactured by the halogen-free flame retardant has small smoke amount during combustion and does not generate corrosive and toxic gas. At present, materials widely used for manufacturing halogen-containing flame retardants generate a large amount of smoke and toxic corrosive hydrogen halide gas when heated, and cause secondary damage. Therefore, the invention provides a flame-retardant modified material with a cross-linked grid structure, which is prepared based on a bio-based degradable polybutylene adipate terephthalate (PBAT) and polylactic acid (PLA) composite system, and an application thereof.
Disclosure of Invention
The invention aims to: the invention aims to solve the technical problem of providing a flame-retardant modified material with a cross-linked grid structure aiming at the defects of the prior art.
The invention also aims to solve the technical problem of providing a preparation method of the flame-retardant modified material with the cross-linked grid structure.
The technical problem to be solved by the invention is to provide the application of the flame-retardant modified material with the cross-linked grid structure.
The invention idea is as follows: the flexibility of the PBAT is good, resulting in a low melt strength, and the addition of PLA considerably improves the melt strength. Meanwhile, based on a PBAT/PLA blending system in the extrusion granulation process, a specific cross-linked grid structure is formed by adding an initiator and a flame retardant to react, so that the composite material has a firm mechanical structure and a better flame retardant effect. Therefore, the invention provides a flame-retardant modified material with a cross-linked grid structure prepared based on a bio-based degradable polybutylene adipate terephthalate (PBAT) and polylactic acid (PLA) composite system and application thereof.
In order to solve the technical problem, the invention discloses a flame-retardant modified material with a cross-linked grid structure, which is prepared from the following components in parts by weight: 70-90 parts of polybutylene adipate terephthalate (PBAT), 10-30 parts of polylactic acid (PLA), 0.1-0.5 part of initiator, 5-15 parts of flame retardant, 0.1-1 part of nucleating agent, 0.5-2 parts of hydrolysis resistant agent and 2-6 parts of compatilizer.
Wherein the PBAT includes but is not limited to a brand number of Jinhui Luong high-tech Co., ltd
Product of PBAT, based on +>
PBAT products, and TH801T products manufactured by Fuyanghesu technologies GmbH; preferably, based on BASF, germany>
Product of PBAT, designation C2200.
Wherein the PLA includes but is not limited to a product of Dunn of Darlco, thailand under the trademark LX-175, a product of Natureworks, USA under the trademark 2003D, and a product of polylactic acid, inc., fengyilai, anhui under the trademark FY204; preferably, the PLA product of Biengong of Darlococo Thailand is LX-175.
Wherein the initiator is any one or combination of more of dicumyl peroxide, azobisisobutyronitrile and benzoyl peroxide.
Wherein the flame retardant is a halogen-free flame retardant; the halogen-free flame retardant is a high-performance phosphorus-oxygen organic flame retardant, comprises any one or combination of a plurality of red phosphorus flame retardant, ammonium polyphosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and phosphate, and has the advantages of small smoke generation amount during combustion and no generation of corrosive and toxic gas.
Wherein, the nucleating agent is any one or the combination of more of talcum powder, calcium carbonate, silicon dioxide, alum and calcium oxide.
Wherein, the anti-hydrolysis agent is carbodiimide, and is a low-toxicity, safe and environment-friendly hydrolysis agent.
Wherein the compatilizer is any one or a combination of more of maleic anhydride grafted polybutylene adipate terephthalate, methacrylic condensed ester grafted polybutylene adipate terephthalate, epoxy compatilizers, oxazoline compatilizers and isocyanate compatilizers.
In order to solve the second technical problem, the invention discloses a preparation method of the flame-retardant modified material, which comprises the following steps: drying polybutylene adipate terephthalate (PBAT) and polylactic acid (PLA) in a drying oven at 60-75 ℃ for 2-4 hours for later use; according to the formula ratio, putting polybutylene adipate terephthalate, polylactic acid, nucleating agent, anti-hydrolysis agent and compatilizer into a high-speed mixer, dispersing and stirring for 5-10 minutes, and discharging for later use; and extruding the mixed material in a double-screw extruder, melting and mixing, adding an initiator and a flame retardant while extruding, and simultaneously extruding, cooling and granulating to obtain the flame retardant.
The mixed material of the polybutylene adipate-terephthalate, the polylactic acid, the nucleating agent, the hydrolysis resistant agent and the compatilizer is prepared by firstly stirring the polybutylene adipate-terephthalate and the polylactic acid in a high-speed mixer for 5-10 minutes, then adding the nucleating agent, the hydrolysis resistant agent and the compatilizer and stirring for 5-10 minutes.
Wherein the high-speed mixer has a use rotating speed of 300-3000 r/min, preferably 1200 r/min.
Wherein the extrusion temperature of the double-screw extruder is 150-190 ℃, and the screw rotating speed is 30-100 r/min.
Wherein, the rotating speed of the granulator is 1000-2000 r/min, preferably 1500 r/min.
In order to solve the third technical problem, the invention discloses an application of the flame-retardant modified material in 3D printing.
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) In the PBAT/PLA composite system prepared by the invention, due to the PBAT flexible chain and the PLA rigid chain, a specific cross-linked grid structure can be formed based on original sites in the PBAT/PLA system by adding the initiator and the flame retardant in the process of twin-screw melt blending extrusion, and the structure can have firm mechanical structure and better flame retardant effect (figure 1).
(2) The invention improves the limiting oxygen index of PBAT and PLA by adding the halogen-free flame retardant, and prepares the bio-based degradable PBAT/PLA composite flame-retardant material with good flame-retardant performance and small harm to the environment.
(3) The flame-retardant modified material with a cross-linked grid structure is prepared based on a bio-based degradable polybutylene adipate terephthalate (PBAT) and polylactic acid (PLA) composite system, so that the mechanical property of the flame-retardant modified material is greatly improved, the problem of contractibility caused by the material can be greatly reduced by applying the flame-retardant modified material in the current advanced 3D printing technology, and the forming problem of the 3D printing technology is solved.
Drawings
The foregoing and/or other advantages of the invention will become more apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 is a diagram of the mechanism of the crosslinking reaction of PBAT/PLA/DCP (dicumyl peroxide).
Detailed Description
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
(1) Will be provided with
PBAT-C2200 is dried for 3 to 5 hours at 65 to 70 ℃, and PLA-LX175 is dried for 3 to 5 hours at 65 to 75 ℃ for standby;
(2) Drying, and collecting
PBAT-C2200 (70 parts by weight) and PLA-LX175 (30 parts by weight) are added into a high-speed mixer to be stirred for 5 to 10 minutes, and then the nucleating agent is weighed: talcum powder-TMC 300 (0.5 part by weight), hydrolysis resistant agent: polymeric carbodiimide (0.3 parts by weight), a compatibilizer: maleic anhydride grafted polybutylene adipate terephthalate (3 parts by weight) is sequentially added into a high-speed mixer to be stirred for 3-5 minutes, and the mixture is discharged for standby;
(3) Adding the mixture obtained in the step (2) into a double-screw extruder, extruding and adding an initiator: dicumyl peroxide (0.1 part by weight), a halogen-free flame retardant: cooling ammonium polyphosphate (5 parts by weight) and granulating to obtain the product;
wherein the rotating speed of the high-speed mixer is 1200 r/min; the temperatures of all zones of the double-screw extruder are 160 ℃,180 ℃,180 ℃,185 ℃,185 ℃,190 ℃,190 ℃,185 ℃,190 ℃, 220 ℃ of a die head and 75 revolutions per minute from the first zone to the ninth zone; the pelletizer speed was 1200 rpm.
The oxygen index of the obtained bio-based degradable PBAT/PLA composite flame-retardant material is 39.5%, and the shrinkage rate is 29%.
Example 2
(1) Will be provided with
PBAT-C2200 is dried for 3 to 5 hours at 65 to 70 ℃, and PLA-LX175 is dried for 3 to 5 hours at 65 to 75 ℃ for standby;
(2) Drying, and collecting
PBAT-C2200 (80 parts by weight) and PLA-LX175 (20 parts by weight) are added into a high-speed mixer to be stirred for 5 to 10 minutes, and then the nucleating agent is weighed: talcum powder-TMC 300 (1 part by weight), hydrolysis-resistant agent: polymeric carbodiimide (0.3 parts by weight), a compatibilizer: adding 3 parts by weight of methacrylic condensed ester grafted polybutylene adipate terephthalate into a high-speed mixer in sequence, stirring for 3-5 minutes, and discharging for later use;
(3) Adding the mixture obtained in the step (2) into a double-screw extruder while extruding, and adding an initiator: benzoyl peroxide (0.1 part by weight), halogen-free flame retardant: cooling the red phosphorus flame retardant (5 parts by weight), and granulating to obtain the product;
wherein the rotating speed of the high-speed mixer is 1200 r/min; the temperature of each zone of the double-screw extruder is 150 ℃,180 ℃,180 ℃,185 ℃,185 ℃,190 ℃,190 ℃,185 ℃,190 ℃, 220 ℃ of a die head and 75 revolutions per minute from the first zone to the ninth zone; the pelletizer speed was 1200 rpm.
The oxygen index of the obtained bio-based degradable PBAT/PLA composite flame-retardant material is 38.0%, and the shrinkage rate is 30%.
Example 3
(1) Will be provided with
PBAT-C2200 is dried for 3 to 5 hours at 65 to 70 ℃, and PLA-LX175 is dried for 3 to 5 hours at 65 to 75 ℃ for standby;
(2) Drying, and collecting
PBAT-C2200 (80 parts by weight) and PLA-LX175 (20 parts by weight) are added into a high-speed mixer to be stirred for 5 to 10 minutes, and then the nucleating agent is weighed: talcum powder-TMC 300 (0.5 part by weight), hydrolysis-resistant agent: polymeric carbodiimide (0.6 parts by weight), compatibilizer: epoxy compatibilizer: ADR-4468 (2 parts by weight) is sequentially added into a high-speed mixer to be stirred for 3-5 minutes, and then the mixture is discharged for standby;
(3) Adding the mixture obtained in the step (2) into a double-screw extruder while extruding, and adding an initiator: adding dicumyl peroxide (0.5 part by weight) into a halogen-free flame retardant: cooling the red phosphorus flame retardant (15 parts by weight), and granulating to obtain the product;
wherein the rotating speed of the high-speed mixer is 1200 r/min; the temperature of each zone of the double-screw extruder is 150 ℃,180 ℃,180 ℃,185 ℃,185 ℃,190 ℃,190 ℃,185 ℃,190 ℃, 220 ℃ of a die head and 75 revolutions per minute from the first zone to the ninth zone; the pelletizer speed was 1200 rpm.
The oxygen index of the obtained bio-based degradable PBAT/PLA composite flame retardant material is 42.5%, and the shrinkage rate is 15%.
Example 4
(1) Will be provided with
PBAT-C2200 is dried for 3 to 5 hours at 65 to 70 ℃, and PLA-LX175 is dried for 3 to 5 hours at 65 to 75 ℃ for standby;
(2) Drying, and collecting
PBAT-C2200 (90 parts by weight) and PLA-LX175 (10 parts by weight) are added into a high-speed mixer to be stirred for 5 to 10 minutes, and then the nucleating agent is weighed: talcum powder-TMC 300 (1 part by weight), hydrolysis-resistant agent: polymeric carbodiimide (0.6 parts by weight), compatibilizer: sequentially adding 3 parts of 2-oxazoline (by weight) into a high-speed mixer, stirring for 4-8 minutes, and discharging for later use;
(3) Adding the mixture obtained in the step (2) into a double-screw extruder, extruding and adding an initiator: adding 0.5 part of benzoyl peroxide into a halogen-free flame retardant: cooling and dicing the red phosphorus flame retardant (15 parts by weight) to obtain the product;
wherein the rotating speed of the high-speed mixer is 1200 r/min; the temperature of each zone of the double-screw extruder is 150 ℃,180 ℃,180 ℃,185 ℃,185 ℃,190 ℃,190 ℃,185 ℃,190 ℃, 220 ℃ of a die head and 75 revolutions per minute from the first zone to the ninth zone; the pelletizer speed was 1200 rpm.
The oxygen index of the obtained bio-based degradable PBAT/PLA composite flame retardant material is 40.7%, and the shrinkage rate is 20%.
Example 5
(1) Will be provided with
PBAT-C2200 is dried for 3 to 5 hours at 65 to 70 ℃, and PLA-LX175 is dried for 3 to 5 hours at 65 to 75 ℃ for standby;
(2) Drying, and collecting
PBATC2200 (80 parts by weight) and PLA-LX175 (20 parts by weight) are added into a high-speed mixer to be stirred for 10 to 15 minutes, and then the nucleating agent is weighed: silicon dioxide (0.5 part by weight), hydrolysis resistant agent: polymeric carbodiimide (0.3 parts by weight), a compatibilizer: 2-oxazoline (weight)3 portions) and sequentially adding the mixture into a high-speed mixer to stir for 4 to 8 minutes, and discharging for later use;
(3) Adding the mixture obtained in the step (2) into a double-screw extruder, extruding and adding an initiator: adding dicumyl peroxide (0.3 part by weight) into a halogen-free flame retardant: cooling the red phosphorus flame retardant (15 parts by weight) and granulating to obtain the product;
wherein the rotating speed of the high-speed mixer is 1200 r/min; the temperature of each zone of the double-screw extruder is 150 ℃,180 ℃,180 ℃,185 ℃,185 ℃,190 ℃,190 ℃,185 ℃,190 ℃, 220 ℃ of a die head and 75 revolutions per minute from the first zone to the ninth zone; the pelletizer speed was 1200 rpm.
The oxygen index of the obtained bio-based degradable PBAT/PLA composite flame-retardant material is 40%, and the shrinkage rate is 22%.
Example 6
(1) Will be provided with
PBAT-C2200 is dried for 3 to 5 hours at 65 to 70 ℃, and PLA-LX175 is dried for 3 to 5 hours at 65 to 75 ℃ for standby;
(2) Drying, and collecting
PBAT-C2200 (80 parts by weight) and PLA-LX175 (20 parts by weight) are added into a high-speed mixer to be stirred for 10-15 minutes, and then the nucleating agent is weighed: silicon dioxide (0.5 part by weight), hydrolysis resistant agent: polymeric carbodiimide (0.3 parts by weight), a compatibilizer: sequentially adding 3 parts of 2-oxazoline (by weight) into a high-speed mixer, stirring for 4-8 minutes, and discharging for later use;
(3) Adding the mixture obtained in the step (2) into a double-screw extruder, extruding and adding an initiator: adding 0.3 part of benzoyl peroxide into a halogen-free flame retardant: cooling the red phosphorus flame retardant (15 parts by weight), and granulating to obtain the product;
wherein the rotating speed of the high-speed mixer is 1200 r/min; the temperature of each zone of the double-screw extruder is 150 ℃,180 ℃,180 ℃,185 ℃,185 ℃,190 ℃,190 ℃,185 ℃,190 ℃, 220 ℃ of a die head and 75 revolutions per minute from the first zone to the ninth zone; the granulator speed was 1200 rpm.
The oxygen index of the obtained bio-based degradable PBAT/PLA composite flame-retardant material is 39.8%, and the shrinkage rate is 28%.
In the specific embodiment, the mechanical property of PBAT/PLA is improved by adding the auxiliary filler, the melt strength and the limited oxygen index are both improved by 38-45%, and a better flame retardant effect is achieved. The shrinkage rate is 15-30%, and the problem of shrinkage molding is improved.
Comparative example 1
The preparation process of the flame-retardant modified material with the cross-linked grid structure prepared by the composite system of the bio-based degradable polybutylene adipate terephthalate (PBAT) and the polylactic acid (PLA) in the comparative example is the same as that in example 1, except that no initiator is added. The oxygen index of the obtained bio-based degradable PBAT/PLA composite flame retardant material is 35% and is lower than that of example 1, the shrinkage rate is 35%, and the flame retardant effect is poor and the shrinkage is severe.
Comparative example 2
The preparation process of the flame-retardant modified material with the cross-linked grid structure prepared by the composite system of the bio-based degradable polybutylene adipate terephthalate (PBAT) and the polylactic acid (PLA) in the comparative example is the same as that in example 1, except that no flame retardant is added. The oxygen index of the obtained bio-based degradable PBAT/PLA composite flame retardant material is 22 percent and is lower than that of the embodiment 2, and the shrinkage rate is 33 percent.
Comparative example 3
The preparation process of the flame-retardant modified material with the cross-linked grid structure prepared by the composite system of the bio-based degradable polybutylene adipate terephthalate (PBAT) and the polylactic acid (PLA) in the comparative example is the same as that in example 1, except that no PLA is added. The oxygen index of the obtained bio-based degradable PBAT flame-retardant material is 30%, and the shrinkage rate is 45%. Poor flame-retardant effect and severe molding shrinkage.
Comparative example 4
The preparation process of the flame-retardant modified material with a cross-linked grid structure, which is prepared by a bio-based degradable polybutylene adipate terephthalate (PBAT) and polylactic acid (PLA) composite system in the comparative example, is the same as that of example 1, except that no PBAT is added. The oxygen index of the obtained bio-based degradable PBAT/PLA composite flame-retardant material is 28%, and the shrinkage rate is 40%. The flame retardant effect is reduced and the molding shrinkage is severe.
Comparative example 5
The preparation process of the flame-retardant modified material with the cross-linked grid structure prepared by the bio-based degradable polybutylene adipate terephthalate (PBAT) and polylactic acid (PLA) composite system in the comparative example is the same as that in example 1, except that the initiator and the flame retardant are mixed in a high-speed mixer together with other auxiliary materials in step 2, and the mixture is directly added into a double-screw extruder for extrusion, cooling and grain cutting after being mixed. The oxygen index of the obtained bio-based degradable PBAT/PLA composite flame-retardant material is 30%, and the shrinkage rate is 35%. The flame retardant effect is reduced and the molding shrinkage is severe.
Disadvantages of mixing: the initiator and the flame retardant are directly mixed with other auxiliary materials to cause other reactions, so that the crosslinking reaction of the initiator and the flame retardant with a PBAT/PLA system is greatly reduced, a crosslinking structure cannot be generated, and the flame retardant toughening effect is poor.
Comparative example 6
The preparation process of the flame-retardant modified material with the cross-linked grid structure prepared by the bio-based degradable polybutylene adipate terephthalate (PBAT) and polylactic acid (PLA) composite system in the comparative example is the same as that in example 1, except that the halogen-free flame retardant is replaced by the halogen-containing flame retardant antimony trioxide. The oxygen index of the obtained bio-based degradable PBAT/PLA composite flame retardant material is 26%, and the shrinkage rate is 45%. The flame retardant effect is reduced and the molding shrinkage is severe.
After the surface treatment, the halogen-free flame retardant series has good dispersibility and compatibility in a PBAT/PLA system, and more in-situ points and DCP form a more stable cross-linking structure in the system, so as to achieve better flame retardant effect and more excellent forming effect.
The invention provides a method and a concept for preparing a flame-retardant modified material with a cross-linked grid structure based on a bio-based degradable polybutylene adipate terephthalate (PBAT) and polylactic acid (PLA) composite system, and a method for applying the same, and the method for implementing the technical scheme are many, and the above description is only a preferred embodiment of the present invention, and it should be noted that, for a person having ordinary skill in the art, a plurality of improvements and embellishments can be made without departing from the principle of the present invention, and the improvements and embellishments should also be regarded as the scope of the present invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (8)
1. The flame-retardant modified material is characterized by being prepared from the following components in parts by weight: 70-90 parts of polybutylene adipate terephthalate, 10-30 parts of polylactic acid, 0.1-0.5 part of initiator, 5-15 parts of flame retardant, 0.1-1 part of nucleating agent, 0.5-2 parts of anti-hydrolysis agent and 2-6 parts of compatilizer;
the initiator is any one or combination of more of dicumyl peroxide and benzoyl peroxide;
the flame retardant is a halogen-free flame retardant, and the halogen-free flame retardant comprises any one or a combination of several of a red phosphorus flame retardant, ammonium polyphosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and phosphate;
the flame-retardant modified material is prepared by the following method, according to the formula ratio, a mixed material of polybutylene adipate-terephthalate, polylactic acid, a nucleating agent, a hydrolysis resistant agent and a compatilizer is extruded by a double-screw extruder, and is melted and mixed, and an initiator and a flame retardant are added while the mixture is extruded.
2. The flame-retardant modified material of claim 1, wherein the nucleating agent is any one or a combination of talc, calcium carbonate, silicon dioxide, alum and calcium oxide.
3. The flame retardant modified material of claim 1, wherein the hydrolysis resistant agent is carbodiimide.
4. The flame-retardant modified material of claim 1, wherein the compatibilizer is one or a combination of maleic anhydride grafted polybutylene adipate terephthalate, methacrylic acetal grafted polybutylene adipate terephthalate, epoxy compatilizers, oxazoline compatilizers and isocyanate compatilizers.
5. The preparation method of the flame-retardant modified material as claimed in any one of claims 1 to 4, which is characterized by comprising the following steps: according to the formula ratio, the mixed materials of polybutylene adipate terephthalate, polylactic acid, nucleating agent, hydrolysis resistant agent and compatilizer are extruded out of a double-screw extruder, and are melted and mixed, and initiator and flame retardant are added during extrusion.
6. The preparation method of the flame-retardant modified material according to claim 5, wherein the mixture of the polybutylene adipate terephthalate, the polylactic acid, the nucleating agent, the hydrolysis resistant agent and the compatilizer is prepared by stirring the polybutylene adipate terephthalate and the polylactic acid in a high-speed mixer for 5 to 10 minutes, adding the nucleating agent, the hydrolysis resistant agent and the compatilizer, and stirring for 5 to 10 minutes.
7. The preparation method of the flame-retardant modified material as claimed in claim 5, wherein the extrusion temperature of the twin-screw extruder is 150 to 190 ℃, and the screw rotation speed is 30 to 100 revolutions per minute.
8. Use of the flame retardant modified material of any one of claims 1 to 4 in 3D printing.
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