CN111234492A - PLA/TPU supercritical foaming composite material and preparation method thereof - Google Patents
PLA/TPU supercritical foaming composite material and preparation method thereof Download PDFInfo
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C08J2483/04—Polysiloxanes
Abstract
The invention discloses a PLA/TPU supercritical foaming composite material and a preparation method thereof, wherein the PLA/TPU supercritical foaming composite material is prepared from the following raw materials in parts by weight: 300-370 parts of polylactic acid, 130-155 parts of polyether polyurethane, 40-48 parts of organic silicon modified polyurethane, 20-27 parts of hydroxyl silicone oil, 14-18 parts of maleic anhydride grafted polyethylene, 15-25 parts of glass fiber, 7-10 parts of nucleating agent, 6-8 parts of chain extender and 5-8 parts of cross-linking agent. The PLA/TPU supercritical foaming composite material has high tensile strength and good mechanical property; the rebound rate is high, and the rebound performance is excellent; the density is low, the foaming multiplying power is high, the size (diameter) of the foam holes is moderate, the foam holes are uniform, and the foaming effect is good; the composite material has comprehensive mechanical properties such as ultralight property, good elasticity and the like; in addition, the degradable environment-friendly material is degradable.
Description
Technical Field
The invention relates to the technical field of foaming materials, in particular to a PLA/TPU supercritical foaming composite material and a preparation method thereof
Background
Polylactic acid (PLA) is a biodegradable polymer prepared by chemical synthesis from renewable plant resources, and various prepared films, fibers and other products can be widely applied to the fields of clothing, textile, non-woven fabrics, packaging, agriculture, forestry, medical and health products, daily necessities and the like. PLA has excellent biocompatibility and biodegradability, and the final degradation products are carbon dioxide and water, so that the environment cannot be polluted. Preparing a polylactic acid foaming material by a method of melting, mixing and mould pressing for foaming; the polylactic acid foaming material can also be prepared by supercritical carbon dioxide.
The polylactic acid foaming material can replace petroleum-based foaming plastic and is applied to the fields of packaging and consumer goods. PLA belongs to a crystalline polymer, has a slow crystallization rate, poor heat resistance and low melt strength, cannot maintain the cell morphology during foaming, is prone to collapse and merge of cells, and is prone to cause molecular chain breakage due to processing instability (such as thermal degradation, oxidation, hydrolysis and the like) to further reduce the melt strength, which are not beneficial to foaming.
The national intellectual property office 2019.11.22 discloses an invention patent with the patent name "CN 110483962A" as "a high-strength polylactic acid foamed plastic", and the invention provides a high-strength polylactic acid foamed plastic which comprises (by mass percent): 38-46% of polylactic acid, 1.2-3% of chain extender, 6-8% of plasticizer, 2-3% of azodicarbonamide, 1.6-2.2% of sodium bicarbonate, 0.1-3.2% of zinc oxide, 6-8% of talcum powder, 8-12% of nano aluminum dioxide, 9-14% of atactic polypropylene and the balance of deionized water, and the invention also discloses a preparation method of the high-strength polylactic acid foamed plastic, which comprises the following preparation steps: s1: weighing and proportioning; s2: dehydrating polylactic acid; s3: modifying and mixing; s4: extruding and granulating; s5: cooling and shaping; according to the patent, the polylactic acid is filled with the nano aluminum dioxide, and the plastic has good mechanical properties by utilizing the chemical bond effect between the polylactic acid and the nano aluminum dioxide.
TPU is known by the name thermoplastic polyurethane elastomer. The halogen-free flame-retardant TPU can be widely applied to the fields of daily necessities, sports goods, toys, decorative materials and the like, and can also replace soft PVC to meet the environmental protection requirements of more and more fields. The elastomer is a high polymer material with the glass transition temperature lower than the room temperature, the elongation at break of more than 50 percent and good recoverability after the external force is removed. The polyurethane elastomer is a special class of elastomers, and has a wide hardness range and a wide performance range, so that the polyurethane elastomer is a high polymer material between rubber and plastic. It can be plasticized by heating, and has no or little cross-linking in chemical structure, and its molecules are basically linear, but have some physical cross-linking. Such polyurethanes are known as TPUs.
Supercritical fluid foaming, one type of physical foaming, is gradually being widely used due to its clean, environmentally friendly characteristics. However, in the preparation process of the supercritical fluid compression foaming, the supercritical fluid of the polymer is soaked and saturated for a long time, and the production efficiency is low.
However, the polylactic acid foam materials used at present have the following problems:
1. poor elasticity of polylactic acid foam material
2. The polylactic acid foaming material has low tensile strength and poor mechanical property;
3. the foaming effect is poor, so that the problems of uneven foam holes, low foaming multiplying power and the like are caused;
4. the heat resistance and other comprehensive use performances are poor, and the use is influenced.
Disclosure of Invention
Based on the above situation, the present invention aims to provide a PLA/TPU supercritical foamed composite material and a preparation method thereof, which can effectively solve the above problems.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a PLA/TPU supercritical foaming composite material is prepared from the following raw materials in parts by weight:
300-370 parts of polylactic acid,
130-155 parts of polyether polyurethane,
40-48 parts of organic silicon modified polyurethane,
20-27 parts of hydroxyl silicone oil,
14-18 parts of maleic anhydride grafted polyethylene,
15-25 parts of glass fiber,
7-10 parts of nucleating agent,
6-8 parts of chain extender,
5-8 parts of a cross-linking agent.
Preferably, the PLA/TPU supercritical foaming composite material is prepared from the following raw materials in parts by weight:
335 parts of polylactic acid,
143 parts of polyether polyurethane,
44 parts of organic silicon modified polyurethane,
23.5 parts of hydroxyl silicone oil,
16 parts of maleic anhydride grafted polyethylene,
20 portions of glass fiber,
8.8 portions of nucleating agent,
7 parts of chain extender,
7 parts of a crosslinking agent.
Preferably, the nucleating agent is a mixture of the nucleating agent TMC-328 and zinc acrylate.
Preferably, the mass ratio of the nucleating agent TMC-328 to the zinc acrylate in the mixture of the nucleating agent TMC-328 and the zinc acrylate is 1: (0.35-0.42).
Preferably, the chain extender is a mixture of a polyurethane chain extender MCDEA and 4-hydroxyethyloxyethyl-1-hydroxyethylbenzene diether.
Preferably, the mass ratio of the polyurethane chain extender MCDEA to the 4-hydroxyethyl oxyethyl-1-hydroxyethyl benzene diether in the mixture of the polyurethane chain extender MCDEA and the 4-hydroxyethyl oxyethyl-1-hydroxyethyl benzene diether is 1: (1.65-1.85).
Preferably, the crosslinking agent is an organic peroxide crosslinking agent.
Preferably, the organic peroxide crosslinking agent is di-tert-butyl hydroperoxide.
Preferably, the organosilicon modified polyurethane is an organosilicon modified polyurethane elastomer synthesized by a prepolymer method by using 2, 4-toluene diisocyanate, tetrahydrofuran propylene oxide copolymerized ether polyol, 3 '-dichloro-4, 4' -diaminodiphenylmethane and organosilicon diol as raw materials.
The invention also provides a preparation method of the PLA/TPU supercritical foaming composite material, which comprises the following steps:
1) weighing the following components in parts by weight: polylactic acid, polyether polyurethane, organic silicon modified polyurethane, hydroxyl silicone oil, maleic anhydride grafted polyethylene, glass fiber, a nucleating agent, a chain extender and a cross-linking agent;
2) mixing polylactic acid, polyether polyurethane, organic silicon modified polyurethane, hydroxyl silicone oil, maleic anhydride grafted polyethylene and a chain extender, feeding the mixture into an internal mixer, and internally mixing for 70-90 min under the environment of N2 and at the temperature of 135-140 ℃;
3) then adding glass fiber, nucleating agent and cross-linking agent, and banburying and blending at 125-130 ℃ until all components are uniformly mixed to obtain a banburying blend;
4) and (2) placing the banburying blend in a sealed pressure-resistant mold, rapidly heating the mold to 138-145 ℃, then introducing supercritical CO2 fluid into the mold, controlling the pressure in the mold to be 15-18 MPa, and rapidly relieving pressure when carbon dioxide gas is saturated in the banburying blend to obtain the PLA/TPU supercritical foaming composite material.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the PLA/TPU supercritical foaming composite material is prepared by selecting raw materials, optimizing the content of each raw material, and selecting polylactic acid, polyether polyurethane, organic silicon modified polyurethane, hydroxyl silicone oil, maleic anhydride grafted polyethylene, glass fiber, a nucleating agent, a chain extender and a cross-linking agent in proper proportion, so that the advantages of the PLA/TPU supercritical foaming composite material are fully exerted, the PLA/TPU supercritical foaming composite material is mutually supplemented and promoted, the quality of the PLA/TPU supercritical foaming composite material is improved, and the prepared PLA/TPU supercritical foaming composite material has high tensile strength and good mechanical property; the rebound rate is high, and the rebound performance is excellent; the density is low, the foaming multiplying power is high, the size (diameter) of the foam holes is moderate, the foam holes are uniform, and the foaming effect is good; has the comprehensive mechanical properties of ultra-light weight, good elasticity and the like. In addition, the degradable environment-friendly material is degradable.
In the raw materials of the PLA/TPU supercritical foaming composite material, polylactic acid is used as a main raw material, the PLA/TPU supercritical foaming composite material has degradability and is environment-friendly, but the foaming performance and the mechanical property need to be improved.
The raw materials of the PLA/TPU supercritical foaming composite material are added with polyether polyurethane in a proper proportion, so that the PLA/TPU supercritical foaming composite material has good compatibility with polylactic acid, is matched with other components (especially organic silicon modified polyurethane) to play a good synergistic effect, greatly improves the resilience performance of the PLA/TPU supercritical foaming composite material, obviously improves the mechanical strength and has good comprehensive mechanical property; meanwhile, the processing fluidity can be improved, and the processing is facilitated.
The raw materials of the PLA/TPU supercritical foaming composite material are added with organosilicon modified polyurethane in a proper proportion, and the organosilicon modified polyurethane is preferably an organosilicon modified polyurethane elastomer synthesized by adopting a prepolymer method and taking 2, 4-toluene diisocyanate, tetrahydrofuran propylene oxide copolymerized polyether polyol, 3 '-dichloro-4, 4' -diaminodiphenylmethane and organosilicon diol as raw materials. The special organic silicon modified polyurethane is adopted, has good compatibility with other components, can improve the tensile strength and the tearing strength of the PLA/TPU supercritical foaming composite material, also contains a silicon-containing group chain segment which is carbon dioxide-philic, has affinity to carbon dioxide, can promote the diffusion rate of the carbon dioxide in the composite material, and forms a uniform continuous phase structure due to the good compatibility of the raw material components when supercritical foaming is carried out, so that the carbon dioxide can be rapidly diffused, the foaming effect is good, and the foaming efficiency is high; the foam holes are uniform, small and compact, and poor appearance performance, mechanical performance and the like caused by poor foaming effect, small or large size, non-uniformity and the like of the foam holes are avoided.
The raw materials of the PLA/TPU supercritical foaming composite material are added with nucleating agent with proper proportion, and the nucleating agent is preferably a mixture of the nucleating agent TMC-328 and zinc acrylate. The nucleating agent TMC-328 is more suitable for nucleating of PLA supercritical foaming, and meanwhile, zinc acrylate with a proper proportion is added as an auxiliary nucleating agent, and can be matched with the nucleating agent TMC-328 to play a good synergistic effect, so that the size of foam holes is greatly reduced, the density of the foam holes is improved, the foam holes are more uniform, and a closed-cell structure is better formed, thereby ensuring that the PLA/TPU supercritical foaming composite material has a good foaming effect.
The PLA/TPU supercritical foaming composite material is prepared by adding a chain extender in a proper proportion into raw materials, wherein the chain extender is preferably a mixture of a polyurethane chain extender MCDEA and 4-hydroxyethyl oxyethyl-1-hydroxyethyl benzene diether. The chain extender mainly reacts with PLA to widen the chain of the PLA, and simultaneously reacts with a small amount of polyether polyurethane, organic silicon modified polyurethane and the like to increase the number of side chains of a molecular chain; the polyurethane chain extender MCDEA mainly reacts with polyether polyurethane, organic silicon modified polyurethane and hydroxyl silicone oil, the polyurethane chain extender MCDEA and 4-hydroxyethyl oxyethyl-1-hydroxyethyl benzene diether are matched with each other to play a good synergistic effect, a microporous channel is formed between matrix materials (polylactic acid, polyether polyurethane, organic silicon modified polyurethane and the like), rapid diffusion of carbon dioxide is facilitated, and the foaming capacity of the material is remarkably improved.
The raw materials of the PLA/TPU supercritical foaming composite material are added with a proper proportion of a cross-linking agent, wherein the cross-linking agent is preferably an organic peroxide cross-linking agent, and the organic peroxide cross-linking agent is further preferably di-tert-butyl hydroperoxide. The cross-linking agent enables polylactic acid, polyether polyurethane, organic silicon modified polyurethane and the like to be subjected to composite cross-linking (vulcanization) better to form a three-dimensional network structure, ensures that the foamed material has high rebound rate, reduces permanent deformation, and further improves the comprehensive mechanical property of the PLA/TPU supercritical foamed composite material.
The PLA/TPU supercritical foaming composite material is added with glass fiber in a proper proportion to play a role in reinforcement.
The raw materials of the PLA/TPU supercritical foaming composite material are added with maleic anhydride grafted polyethylene in a proper proportion, and the PLA/TPU supercritical foaming composite material is mainly used for improving the dispersion compatibility of glass fibers in the raw material system and improving the processing fluidity of the raw material system.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the following description of the preferred embodiments of the present invention is provided in connection with specific examples, which should not be construed as limiting the present patent.
The test methods or test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials, unless otherwise indicated, are conventionally obtained commercially or prepared by conventional methods.
Example 1:
a PLA/TPU supercritical foaming composite material is prepared from the following raw materials in parts by weight:
300-370 parts of polylactic acid,
130-155 parts of polyether polyurethane,
40-48 parts of organic silicon modified polyurethane,
20-27 parts of hydroxyl silicone oil,
14-18 parts of maleic anhydride grafted polyethylene,
15-25 parts of glass fiber,
7-10 parts of nucleating agent,
6-8 parts of chain extender,
5-8 parts of a cross-linking agent.
In this embodiment, the PLA/TPU supercritical foamed composite is preferably, but not limited to, made from raw materials comprising, by weight:
335 parts of polylactic acid,
143 parts of polyether polyurethane,
44 parts of organic silicon modified polyurethane,
23.5 parts of hydroxyl silicone oil,
16 parts of maleic anhydride grafted polyethylene,
20 portions of glass fiber,
8.8 portions of nucleating agent,
7 parts of chain extender,
7 parts of a crosslinking agent.
In the present embodiment, the nucleating agent is preferably, but not limited to, a mixture of the nucleating agent TMC-328 and zinc acrylate.
In this embodiment, the mass ratio of the nucleating agent TMC-328 to the zinc acrylate in the mixture of the nucleating agent TMC-328 and the zinc acrylate is preferably, but not limited to, 1: (0.35-0.42).
In this example, the chain extender is preferably, but not limited to, a mixture of the polyurethane chain extender MCDEA and 4-hydroxyethyloxyethyl-1-hydroxyethylbenzene diether.
In this example, the mass ratio of the polyurethane chain extender MCDEA and 4-hydroxyethyloxyethyl-1-hydroxyethylbenzene diether in the mixture of the polyurethane chain extender MCDEA and 4-hydroxyethyloxyethyl-1-hydroxyethylbenzene diether is preferably, but not limited to, 1: (1.65-1.85).
In the present embodiment, the crosslinking agent is preferably, but not limited to, an organic peroxide crosslinking agent.
In this embodiment, the organic peroxide crosslinking agent is preferably, but not limited to, di-t-butyl hydroperoxide.
In this embodiment, the silicone-modified polyurethane is preferably, but not limited to, a silicone-modified polyurethane elastomer synthesized by using 2, 4-toluene diisocyanate, tetrahydrofuran propylene oxide co-polyether polyol, 3 '-dichloro-4, 4' -diaminodiphenylmethane and silicone glycol as raw materials, and preferably, but not limited to, a prepolymer method.
The embodiment also provides a preparation method of the PLA/TPU supercritical foaming composite material, which comprises the following steps:
1) weighing the following components in parts by weight: polylactic acid, polyether polyurethane, organic silicon modified polyurethane, hydroxyl silicone oil, maleic anhydride grafted polyethylene, glass fiber, a nucleating agent, a chain extender and a cross-linking agent;
2) mixing polylactic acid, polyether polyurethane, organosilicon modified polyurethane, hydroxyl silicone oil, maleic anhydride grafted polyethylene and a chain extender, feeding the mixture into an internal mixer, and firstly adding N2Banburying for 70-90 min at 135-140 ℃ in the environment;
3) then adding glass fiber, nucleating agent and cross-linking agent, and banburying and blending at 125-130 ℃ until all components are uniformly mixed to obtain a banburying blend;
4) placing the banburying blend in a sealed pressure-resistant mold, rapidly heating the mold to 138-145 ℃, and introducing supercritical CO into the mold2And controlling the pressure in the die to be 15-18 MPa, and quickly relieving pressure when carbon dioxide gas is saturated in the banburying blend to obtain the PLA/TPU supercritical foaming composite material.
Example 2:
a PLA/TPU supercritical foaming composite material is prepared from the following raw materials in parts by weight:
300 portions of polylactic acid,
130 portions of polyether polyurethane,
40 parts of organic silicon modified polyurethane,
20 parts of hydroxyl silicone oil,
14 parts of maleic anhydride grafted polyethylene,
15 portions of glass fiber,
7 portions of nucleating agent,
6 parts of chain extender,
5 parts of a crosslinking agent.
In this embodiment, the nucleating agent is a mixture of the nucleating agent TMC-328 and zinc acrylate.
In the embodiment, the mass ratio of the nucleating agent TMC-328 to the zinc acrylate in the mixture of the nucleating agent TMC-328 and the zinc acrylate is 1: 0.35.
in this example, the chain extender is a mixture of the polyurethane chain extender MCDEA and 4-hydroxyethyloxyethyl-1-hydroxyethylbenzene diether.
In this example, the mass ratio of the polyurethane chain extender MCDEA and 4-hydroxyethyloxyethyl-1-hydroxyethylbenzene diether in the mixture of the polyurethane chain extender MCDEA and 4-hydroxyethyloxyethyl-1-hydroxyethylbenzene diether was 1: 1.65.
in this embodiment, the crosslinking agent is an organic peroxide crosslinking agent.
In this example, the organic peroxide crosslinking agent was di-t-butyl hydroperoxide.
In this embodiment, the organosilicon modified polyurethane is an organosilicon modified polyurethane elastomer synthesized by a prepolymer method using 2, 4-toluene diisocyanate, tetrahydrofuran propylene oxide copolymerized ether polyol, 3 '-dichloro-4, 4' -diaminodiphenylmethane and organosilicon diol as raw materials.
In this embodiment, the preparation method of the PLA/TPU supercritical foamed composite material includes the following steps:
1) weighing the following components in parts by weight: polylactic acid, polyether polyurethane, organic silicon modified polyurethane, hydroxyl silicone oil, maleic anhydride grafted polyethylene, glass fiber, a nucleating agent, a chain extender and a cross-linking agent;
2) mixing polylactic acid, polyether polyurethane, organosilicon modified polyurethane, hydroxyl silicone oil, maleic anhydride grafted polyethylene and a chain extender, feeding the mixture into an internal mixer, and firstly adding N2Banburying for 70min at 135 deg.C in the environment;
3) then adding glass fiber, nucleating agent and cross-linking agent, and banburying and blending at 125 ℃ until all components are uniformly mixed to prepare a banburying blend;
4) placing the banburying blend in a sealed pressure-resistant mold, rapidly heating the mold to 138 ℃, and introducing supercritical CO into the mold2And controlling the pressure in the die to be 15MPa, and quickly relieving pressure when carbon dioxide gas is saturated in the banburying blend to obtain the PLA/TPU supercritical foaming composite material.
Example 3:
a PLA/TPU supercritical foaming composite material is prepared from the following raw materials in parts by weight:
370 portions of polylactic acid,
155 portions of polyether polyurethane,
48 parts of organic silicon modified polyurethane,
27 parts of hydroxyl silicone oil,
18 parts of maleic anhydride grafted polyethylene,
25 portions of glass fiber,
10 portions of nucleating agent,
8 parts of chain extender,
8 parts of a crosslinking agent.
In this embodiment, the nucleating agent is a mixture of the nucleating agent TMC-328 and zinc acrylate.
In the embodiment, the mass ratio of the nucleating agent TMC-328 to the zinc acrylate in the mixture of the nucleating agent TMC-328 and the zinc acrylate is 1: 0.42.
in this example, the chain extender is a mixture of the polyurethane chain extender MCDEA and 4-hydroxyethyloxyethyl-1-hydroxyethylbenzene diether.
In this example, the mass ratio of the polyurethane chain extender MCDEA and 4-hydroxyethyloxyethyl-1-hydroxyethylbenzene diether in the mixture of the polyurethane chain extender MCDEA and 4-hydroxyethyloxyethyl-1-hydroxyethylbenzene diether was 1: 1.85.
in this embodiment, the crosslinking agent is an organic peroxide crosslinking agent.
In this example, the organic peroxide crosslinking agent was di-t-butyl hydroperoxide.
In this embodiment, the organosilicon modified polyurethane is an organosilicon modified polyurethane elastomer synthesized by a prepolymer method using 2, 4-toluene diisocyanate, tetrahydrofuran propylene oxide copolymerized ether polyol, 3 '-dichloro-4, 4' -diaminodiphenylmethane and organosilicon diol as raw materials.
In this embodiment, the preparation method of the PLA/TPU supercritical foamed composite material includes the following steps:
1) weighing the following components in parts by weight: polylactic acid, polyether polyurethane, organic silicon modified polyurethane, hydroxyl silicone oil, maleic anhydride grafted polyethylene, glass fiber, a nucleating agent, a chain extender and a cross-linking agent;
2) mixing polylactic acid, polyether polyurethane, organosilicon modified polyurethane, hydroxyl silicone oil, maleic anhydride grafted polyethylene and a chain extender, feeding the mixture into an internal mixer, and firstly adding N2Banburying for 90min at 140 deg.C in the environment;
3) then adding glass fiber, nucleating agent and cross-linking agent, and banburying and blending at 130 ℃ until all components are uniformly mixed to prepare a banburying blend;
4) placing the banburying blend in a sealed pressure-resistant mold, rapidly heating the mold to 145 ℃, and introducing supercritical CO into the mold2And controlling the pressure in the die to be 18MPa, and quickly relieving pressure when carbon dioxide gas is saturated in the banburying blend to obtain the PLA/TPU supercritical foaming composite material.
Example 4:
a PLA/TPU supercritical foaming composite material is prepared from the following raw materials in parts by weight:
335 parts of polylactic acid,
143 parts of polyether polyurethane,
44 parts of organic silicon modified polyurethane,
23.5 parts of hydroxyl silicone oil,
16 parts of maleic anhydride grafted polyethylene,
20 portions of glass fiber,
8.8 portions of nucleating agent,
7 parts of chain extender,
7 parts of a crosslinking agent.
In this embodiment, the nucleating agent is a mixture of the nucleating agent TMC-328 and zinc acrylate.
In the embodiment, the mass ratio of the nucleating agent TMC-328 to the zinc acrylate in the mixture of the nucleating agent TMC-328 and the zinc acrylate is 1: 0.38.
in this example, the chain extender is a mixture of the polyurethane chain extender MCDEA and 4-hydroxyethyloxyethyl-1-hydroxyethylbenzene diether.
In this example, the mass ratio of the polyurethane chain extender MCDEA and 4-hydroxyethyloxyethyl-1-hydroxyethylbenzene diether in the mixture of the polyurethane chain extender MCDEA and 4-hydroxyethyloxyethyl-1-hydroxyethylbenzene diether was 1: 1.75.
in this embodiment, the crosslinking agent is an organic peroxide crosslinking agent.
In this example, the organic peroxide crosslinking agent was di-t-butyl hydroperoxide.
In this embodiment, the organosilicon modified polyurethane is an organosilicon modified polyurethane elastomer synthesized by a prepolymer method using 2, 4-toluene diisocyanate, tetrahydrofuran propylene oxide copolymerized ether polyol, 3 '-dichloro-4, 4' -diaminodiphenylmethane and organosilicon diol as raw materials.
In this embodiment, the preparation method of the PLA/TPU supercritical foamed composite material includes the following steps:
1) weighing the following components in parts by weight: polylactic acid, polyether polyurethane, organic silicon modified polyurethane, hydroxyl silicone oil, maleic anhydride grafted polyethylene, glass fiber, a nucleating agent, a chain extender and a cross-linking agent;
2) mixing polylactic acid, polyether polyurethane, organosilicon modified polyurethane, hydroxyl silicone oil, maleic anhydride grafted polyethylene and a chain extender, feeding the mixture into an internal mixer, and firstly adding N2Banburying for 80min at 138 deg.C in the environment;
3) then adding glass fiber, nucleating agent and cross-linking agent, and banburying and blending at the temperature of 128 ℃ until all components are uniformly mixed to prepare a banburying blend;
4) placing the banburying blend in a sealed pressure-resistant mold, rapidly heating the mold to 143 ℃, and introducing supercritical CO into the mold2And controlling the pressure in the die to be 16.5MPa, and quickly relieving pressure when carbon dioxide gas is saturated in the banburying blend to obtain the PLA/TPU supercritical foaming composite material.
Comparative example:
the patent application of the invention is Chinese patent application with the publication number of CN110483962A and the patent name of high-strength polylactic acid foamed plastic.
The following tests were carried out on the PLA/TPU supercritical foamed composite materials obtained in examples 2 to 4 of the present invention and comparative examples, and the test results are shown in Table 1.
TABLE 1
As can be seen from the analysis of the above table, the PLA/TPU supercritical foaming composite material of the invention has high tensile strength and good mechanical properties; the rebound rate is high, and the rebound performance is excellent; the density is low, the foaming multiplying power is high, the size (diameter) of the foam holes is moderate, the foam holes are uniform, and the foaming effect is good; has the comprehensive mechanical properties of ultra-light weight, good elasticity and the like.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (10)
1. A PLA/TPU supercritical foaming composite material is characterized by being prepared from the following raw materials in parts by weight:
300-370 parts of polylactic acid,
130-155 parts of polyether polyurethane,
40-48 parts of organic silicon modified polyurethane,
20-27 parts of hydroxyl silicone oil,
14-18 parts of maleic anhydride grafted polyethylene,
15-25 parts of glass fiber,
7-10 parts of nucleating agent,
6-8 parts of chain extender,
5-8 parts of a cross-linking agent.
2. The PLA/TPU supercritical foamed composite according to claim 1, characterized in that the PLA/TPU supercritical foamed composite is made from raw materials comprising, in parts by weight:
335 parts of polylactic acid,
143 parts of polyether polyurethane,
44 parts of organic silicon modified polyurethane,
23.5 parts of hydroxyl silicone oil,
16 parts of maleic anhydride grafted polyethylene,
20 portions of glass fiber,
8.8 portions of nucleating agent,
7 parts of chain extender,
7 parts of a crosslinking agent.
3. The PLA/TPU supercritical foamed composite according to claim 1, characterized in that the nucleating agent is a mixture of nucleating agent TMC-328 and zinc acrylate.
4. The PLA/TPU supercritical foamed composite according to claim 3, characterized in that the mass ratio of nucleating agent TMC-328 to zinc acrylate in the mixture of nucleating agent TMC-328 and zinc acrylate is 1: (0.35-0.42).
5. The PLA/TPU supercritical foamed composite according to claim 1, characterized in that the chain extender is a mixture of the polyurethane chain extender MCDEA and 4-hydroxyethyloxyethyl-1-hydroxyethylbenzene diether.
6. The PLA/TPU supercritical foamed composite according to claim 5, characterized in that the mass ratio of the polyurethane chain extender MCDEA and 4-hydroxyethyloxyethyl-1-hydroxyethylbenzene diether in the mixture of the polyurethane chain extender MCDEA and 4-hydroxyethyloxyethyl-1-hydroxyethylbenzene diether is 1: (1.65-1.85).
7. The PLA/TPU supercritical foamed composite according to claim 1, characterized in that the crosslinking agent is an organic peroxide crosslinking agent.
8. The PLA/TPU supercritical foamed composite according to claim 7, characterized in that the organic peroxide crosslinking agent is di-tert-butyl hydroperoxide.
9. The PLA/TPU supercritical foaming composite material of claim 1, wherein the organosilicon modified polyurethane is an organosilicon modified polyurethane elastomer synthesized by a prepolymer method from 2, 4-toluene diisocyanate, tetrahydrofuran propylene oxide co-polyether polyol, 3 '-dichloro-4, 4' -diaminodiphenylmethane and organosilicon diol.
10. A method for preparing a PLA/TPU supercritical foamed composite material according to any of claims 1-9, comprising the steps of:
1) weighing the following components in parts by weight: polylactic acid, polyether polyurethane, organic silicon modified polyurethane, hydroxyl silicone oil, maleic anhydride grafted polyethylene, glass fiber, a nucleating agent, a chain extender and a cross-linking agent;
2) mixing polylactic acid, polyether polyurethane, organosilicon modified polyurethane, hydroxyl silicone oil, maleic anhydride grafted polyethylene and a chain extender, feeding the mixture into an internal mixer, and firstly adding N2The sealing is carried out under the conditions of environment and temperature of 135-140 DEG CRefining for 70-90 min;
3) then adding glass fiber, nucleating agent and cross-linking agent, and banburying and blending at 125-130 ℃ until all components are uniformly mixed to obtain a banburying blend;
placing the banburying blend in a sealed pressure-resistant mold, rapidly heating the mold to 138-145 ℃, and introducing supercritical CO into the mold2And controlling the pressure in the die to be 15-18 MPa, and quickly relieving pressure when carbon dioxide gas is saturated in the banburying blend to obtain the PLA/TPU supercritical foaming composite material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114181499A (en) * | 2020-09-15 | 2022-03-15 | 华润化学材料科技股份有限公司 | Micro-foaming polyester and preparation method and application thereof |
| CN114425269A (en) * | 2022-01-26 | 2022-05-03 | 武汉纺织大学 | Efficient oil-water separation composite foam based on surface engineering and preparation method thereof |
| WO2023035325A1 (en) * | 2021-09-11 | 2023-03-16 | 福建鸿星尔克体育用品有限公司 | Method for preparing ultra-light sole equipped with hydrogen explosion structure, sole and sneaker |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104371292A (en) * | 2014-12-01 | 2015-02-25 | 贵州省材料产业技术研究院 | High-tenacity high-thermostability polylactic acid material and preparation method thereof |
| CN105038164A (en) * | 2015-08-18 | 2015-11-11 | 华南理工大学 | Polylactide-based blended material, preparation method thereof and method for preparing foam material from polylactide-based blended material |
| CN106146875A (en) * | 2016-07-11 | 2016-11-23 | 浙江新恒泰新材料有限公司 | A kind of high magnification thermoplastic polyurethane microporous foam sheet material and production method thereof |
| CN108003584A (en) * | 2017-12-25 | 2018-05-08 | 上海德亿化工有限公司 | A kind of degradable PLA expanded materials and preparation method thereof |
| CN108178913A (en) * | 2017-12-12 | 2018-06-19 | 东莞市雄林新材料科技股份有限公司 | A kind of automobile TPU expanded materials with noise reduction function and preparation method thereof |
| CN109608843A (en) * | 2018-12-20 | 2019-04-12 | 桂林电器科学研究院有限公司 | A kind of activeness and quietness modified polylactic acid material and preparation method thereof |
| CN110791088A (en) * | 2019-11-12 | 2020-02-14 | 福建安达福新材料科技有限公司 | PA/TPU supercritical foaming composite material and preparation method thereof |
-
2020
- 2020-04-02 CN CN202010256552.4A patent/CN111234492A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104371292A (en) * | 2014-12-01 | 2015-02-25 | 贵州省材料产业技术研究院 | High-tenacity high-thermostability polylactic acid material and preparation method thereof |
| CN105038164A (en) * | 2015-08-18 | 2015-11-11 | 华南理工大学 | Polylactide-based blended material, preparation method thereof and method for preparing foam material from polylactide-based blended material |
| CN106146875A (en) * | 2016-07-11 | 2016-11-23 | 浙江新恒泰新材料有限公司 | A kind of high magnification thermoplastic polyurethane microporous foam sheet material and production method thereof |
| CN108178913A (en) * | 2017-12-12 | 2018-06-19 | 东莞市雄林新材料科技股份有限公司 | A kind of automobile TPU expanded materials with noise reduction function and preparation method thereof |
| CN108003584A (en) * | 2017-12-25 | 2018-05-08 | 上海德亿化工有限公司 | A kind of degradable PLA expanded materials and preparation method thereof |
| CN109608843A (en) * | 2018-12-20 | 2019-04-12 | 桂林电器科学研究院有限公司 | A kind of activeness and quietness modified polylactic acid material and preparation method thereof |
| CN110791088A (en) * | 2019-11-12 | 2020-02-14 | 福建安达福新材料科技有限公司 | PA/TPU supercritical foaming composite material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 李鲜英: "有机硅改性共聚醚型聚氨酯弹性体的制备与性能研究", 《聚氨酯工业》 * |
| 耿悦: "PLA/TPU复合体系微孔发泡性能的研究", 《塑料科技》 * |
| 黄爽: "有机硅改性聚氨酯增韧聚乳酸的研究", 《塑料科技》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114181499A (en) * | 2020-09-15 | 2022-03-15 | 华润化学材料科技股份有限公司 | Micro-foaming polyester and preparation method and application thereof |
| CN114181499B (en) * | 2020-09-15 | 2023-07-14 | 常州华润高性能复合材料有限公司 | Micro-foaming polyester and preparation method and application thereof |
| WO2023035325A1 (en) * | 2021-09-11 | 2023-03-16 | 福建鸿星尔克体育用品有限公司 | Method for preparing ultra-light sole equipped with hydrogen explosion structure, sole and sneaker |
| CN114425269A (en) * | 2022-01-26 | 2022-05-03 | 武汉纺织大学 | Efficient oil-water separation composite foam based on surface engineering and preparation method thereof |
| CN114425269B (en) * | 2022-01-26 | 2023-12-22 | 武汉纺织大学 | High-efficiency oil-water separation composite foam based on surface engineering and preparation method thereof |
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