CN110791088A - PA/TPU supercritical foaming composite material and preparation method thereof - Google Patents
PA/TPU supercritical foaming composite material and preparation method thereof Download PDFInfo
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- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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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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Abstract
The invention discloses a PA/TPU supercritical foaming composite material and a preparation method thereof, wherein the PA/TPU supercritical foaming composite material is prepared from the following raw materials in parts by weight: 200-240 parts of polyamide, 160-180 parts of organosilicon modified polyurethane, 70-77 parts of maleic anhydride graft modifier, 45-52 parts of maleic anhydride grafted high-density polyethylene, 22-26 parts of glass fiber, 15-18 parts of cross-linking agent and 5-7 parts of nucleating agent. The PA/TPU supercritical foaming composite material has good foaming effect and moderate and uniform cell size, and ensures good appearance performance, mechanical property and the like; the tensile strength is high, the tear resistance is high, and the tear resistance is good; low density, light weight, high strength and other excellent mechanical performance and use performance.
Description
Technical Field
The invention relates to the field of foaming materials, in particular to a PA/TPU supercritical foaming composite material and a preparation method thereof.
Background
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.
Polyamide is commonly known as Nylon (Nylon), called Polyamide (PA for short), has a density of 1.15g/cm3, and is a general name of thermoplastic resins containing repeated amide groups- [ NHCO ] -in the molecular main chain, and comprises aliphatic PA, aliphatic-aromatic PA and aromatic PA. The aliphatic PA has many varieties, large yield and wide application, and the name is determined by the specific carbon atom number of the synthetic monomer. Invented by the american famous chemist caroth and his research group. Nylon is a term for polyamide fiber (nylon) and can be made into long fibers or short fibers. Nylon is a trade name for polyamide fiber, also known as Nylon (Nylon). The basic component of Polyamide (abbreviated as PA) is aliphatic Polyamide linked by amide bonds [ NHCO ] -.
The polymer foaming material is a polymer/gas composite material taking a polymer as a matrix, has the properties of light weight, high specific strength, heat preservation, buffering and the like, and has good application in many fields.
At present, the preparation of foaming materials is mainly divided into chemical foaming and physical foaming, wherein the chemical foaming generally uses azo foaming agents, harmful gas is generated in the foaming process, and chemical residues exist. Conventional stream foaming methods include foaming with butane, hydrofluoro-type blowing agents, and the like.
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 current foamed materials of PA or TPU still have the following problems:
1. the foaming effect is poor, the size of the foam hole is small or large and uneven, so that the appearance performance and the mechanical property are poor;
2. the mechanical properties such as tensile strength, tearing strength and the like and the service performance are poor.
Disclosure of Invention
Based on the above situation, the present invention aims to provide a PA/TPU supercritical foaming 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 PA/TPU supercritical foaming composite material is prepared from the following raw materials in parts by weight:
200 to 240 parts of polyamide,
160-180 parts of organic silicon modified polyurethane,
70-77 parts of maleic anhydride grafting modifier,
45-52 parts of maleic anhydride grafted high-density polyethylene,
22-26 parts of glass fiber,
15-18 parts of cross-linking agent,
5-7 parts of a nucleating agent;
the polyamide is a mixture comprising polyhexamethylene sebacamide and hexamethylene adipamide-hexamethylene terephthalamide copolyamide, wherein the mass ratio of the polyhexamethylene sebacamide to the hexamethylene adipamide-hexamethylene terephthalamide copolyamide is 1: (0.5 to 0.7);
the organic silicon modified polyurethane is an organic silicon modified polyurethane elastomer synthesized by a prepolymer method by taking 2, 4-toluene diisocyanate, tetrahydrofuran propylene oxide copolymerized ether polyol, 3 '-dichloro-4, 4' -diaminodiphenylmethane and organic silicon glycol as raw materials;
the maleic anhydride grafting modifier is prepared from the following components in a mass ratio of 1: and (2) reacting the epoxy group-containing polysiloxane with maleic anhydride grafted polyethylene to obtain the polyethylene grafted silicon group-containing copolymer.
Preferably, the PA/TPU supercritical foaming composite material is prepared from the following raw materials in parts by weight:
220 parts of polyamide,
170 parts of organic silicon modified polyurethane,
74 parts of maleic anhydride grafting modifier,
48 parts of maleic anhydride grafted high-density polyethylene,
24 portions of glass fiber,
17 portions of cross-linking agent,
6 parts of nucleating agent.
More preferably, the polyamide is a mixture comprising polyhexamethylene sebacamide and hexamethylene adipamide-terephthalamide copolyamides, wherein the mass ratio of polyhexamethylene sebacamide to hexamethylene adipamide-terephthalamide copolyamides is 1: 0.62.
more preferably, the maleic anhydride grafting modifier is prepared by mixing, by mass, 1: 2.4 reacting the polysiloxane containing epoxy group with maleic anhydride grafted polyethylene to obtain the polyethylene grafted silicon-containing group copolymer.
Preferably, the cross-linking agent is a mixture formed by mixing dicumyl peroxide and benzoyl peroxide.
More preferably, the mass ratio of dicumyl peroxide to benzoyl peroxide in the mixture formed by mixing dicumyl peroxide and benzoyl peroxide is 1: (0.55-0.65).
Preferably, the nucleating agent is nano zinc oxide.
The invention also provides a preparation method of the PA/TPU supercritical foaming composite material, which comprises the following steps:
A. weighing: respectively weighing polyamide, organic silicon modified polyurethane, maleic anhydride grafted modifier, maleic anhydride grafted high-density polyethylene, glass fiber, cross-linking agent and nucleating agent according to parts by weight;
B. banburying: mixing polyamide, organic silicon modified polyurethane, maleic anhydride grafted modifier, maleic anhydride grafted high-density polyethylene and glass fiber, feeding the mixture into an internal mixer, firstly carrying out internal mixing and blending for 12-15 min at the temperature of 115-120 ℃, then adding cross-linking agent and nucleating agent, and carrying out internal mixing and blending at the temperature of 130-135 ℃ until all components are uniformly mixed to prepare an internal mixing blend;
C. tabletting: pressing the banburying blend into a sheet by a tablet press, and cutting;
D. supercritical foaming: and D, placing the sheet prepared in the step C into an oven, preheating to a foaming temperature, then placing the preheated foaming sheet into a high-temperature mold, introducing carbon dioxide gas, and quickly releasing the carbon dioxide gas in the mold when the carbon dioxide gas is saturated in the sheet to quickly foam the sheet to obtain the PA/TPU supercritical foaming composite material.
Preferably, in the step D, the temperature of the high-temperature die is 155-165 ℃, and the pressure of carbon dioxide gas in the die is 14-16 MPa.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the PA/TPU supercritical foaming composite material disclosed by the invention is prepared by selecting raw materials, optimizing the content of each raw material, and selecting polyamide, organic silicon modified polyurethane, maleic anhydride grafting modifier, maleic anhydride grafting high-density polyethylene, glass fiber, cross-linking agent and nucleating agent in proper proportion, so that the respective advantages are fully exerted, the mutual complementation and the mutual promotion are realized, the quality stability of a product is improved, the prepared PA/TPU supercritical foaming composite material disclosed by the invention is good in foaming effect, moderate in cell size and uniform, and good appearance performance, mechanical property and the like are ensured; the tensile strength is high, the tear resistance is high, and the tear resistance is good; low density, light weight, high strength and other excellent mechanical performance and use performance.
In the raw materials of the PA/TPU supercritical foaming composite material, polyhexamethylene sebacamide and hexamethylene adipamide-hexamethylene terephthalamide copolyamide with a proper proportion are adopted to be matched, wherein the polyhexamethylene sebacamide has small relative density, easy molding and processing and high mechanical strength; the addition of the hexamethylene adipamide-hexamethylene terephthalamide copolyamide can improve the rigidity of the composite material and has good appearance and strength; and the PA/TPU supercritical foaming composite material is matched with other components to play a good synergistic effect, so that the PA/TPU supercritical foaming composite material disclosed by the invention has the advantage that the tensile strength and the tear strength are improved under the same foaming condition.
The raw materials of the PA/TPU supercritical foaming composite material disclosed by the invention adopt special organic silicon modified polyurethane, have good compatibility with other components, can improve the tensile strength and the tearing strength of the PA/TPU supercritical foaming composite material disclosed by the invention, also contain a silicon-containing group chain segment which is carbon dioxide-philic, has affinity for carbon dioxide, and can promote the diffusion rate of the carbon dioxide in the composite material, and when the PA/TPU supercritical foaming composite material is subjected to supercritical foaming, because the compatibility of each raw material component is good, a uniform continuous phase structure is formed, the carbon dioxide can be rapidly diffused, the foaming effect is ensured to be 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.
In the raw materials of the PA/TPU supercritical foaming composite material, a maleic anhydride grafting modifier is added in a proper proportion and is matched with other components to play a good synergistic effect, and the maleic anhydride grafting modifier is prepared by mixing the components in a mass ratio of 1: and (2) reacting the epoxy group-containing polysiloxane with maleic anhydride grafted polyethylene to obtain the polyethylene grafted silicon group-containing copolymer. Preferably, the maleic anhydride grafting modifier is prepared by mixing the components in a mass ratio of 1: 2.4 reacting the polysiloxane containing epoxy group with maleic anhydride grafted polyethylene to obtain the polyethylene grafted silicon-containing group copolymer. The polyethylene grafted silicon-containing group copolymer not only has a carbon dioxide-philic silicon-containing group chain segment, but also has a maleic anhydride grafted polyethylene chain segment which can be compatible with the polyamide, the organic silicon modified polyurethane and the maleic anhydride grafted high-density polyethylene composite matrix; the polyethylene grafted silicon-group-containing copolymer has affinity to carbon dioxide, has high carbon dioxide adsorption capacity, and has extremely fast diffusion rate in the carbon dioxide, so that when supercritical foaming is carried out, because each raw material component has good compatibility, a uniform continuous phase structure is formed, the carbon dioxide can be rapidly diffused into the polyethylene grafted silicon-group-containing copolymer and then diffused into the whole raw material system; the polyethylene grafted silicon-group-containing copolymer is used as a diffusion channel of carbon dioxide, so that the contact area of the polyethylene grafted silicon-group-containing copolymer with the polyamide, the organic silicon modified polyurethane, the maleic anhydride grafted modifier and the maleic anhydride grafted high-density polyethylene composite matrix is increased, the diffusion path is reduced, the saturation time is shortened, the production efficiency is improved, the good foaming effect is ensured, and the foaming efficiency is high; the foam holes are uniform, small and compact, and have excellent mechanical properties and service performance such as light weight, high strength and the like.
In the raw materials of the PA/TPU supercritical foaming composite material, the maleic anhydride grafted high-density polyethylene is added in a proper proportion and is matched with other components, so that a good synergistic effect is achieved, and the tensile strength and the tear strength of the PA/TPU supercritical foaming composite material are further improved.
The raw materials of the PA/TPU supercritical foaming composite material are added with the glass fiber in a proper proportion, and the glass fiber is uniformly dispersed in the raw material system of the PA/TPU supercritical foaming composite material and is matched with other components, so that a good synergistic effect is achieved, and the tensile strength and the tear strength of the PA/TPU supercritical foaming composite material are further improved.
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 PA/TPU supercritical foaming composite material is prepared from the following raw materials in parts by weight:
200 to 240 parts of polyamide,
160-180 parts of organic silicon modified polyurethane,
70-77 parts of maleic anhydride grafting modifier,
45-52 parts of maleic anhydride grafted high-density polyethylene,
22-26 parts of glass fiber,
15-18 parts of cross-linking agent,
5-7 parts of a nucleating agent;
the polyamide is a mixture comprising polyhexamethylene sebacamide and hexamethylene adipamide-hexamethylene terephthalamide copolyamide, wherein the mass ratio of the polyhexamethylene sebacamide to the hexamethylene adipamide-hexamethylene terephthalamide copolyamide is 1: (0.5 to 0.7);
the organic silicon modified polyurethane is an organic silicon modified polyurethane elastomer synthesized by a prepolymer method by taking 2, 4-toluene diisocyanate, tetrahydrofuran propylene oxide copolymerized ether polyol, 3 '-dichloro-4, 4' -diaminodiphenylmethane and organic silicon glycol as raw materials;
the maleic anhydride grafting modifier is prepared from the following components in a mass ratio of 1: and (2) reacting the epoxy group-containing polysiloxane with maleic anhydride grafted polyethylene to obtain the polyethylene grafted silicon group-containing copolymer.
Preferably, the PA/TPU supercritical foaming composite material is prepared from the following raw materials in parts by weight:
220 parts of polyamide,
170 parts of organic silicon modified polyurethane,
74 parts of maleic anhydride grafting modifier,
48 parts of maleic anhydride grafted high-density polyethylene,
24 portions of glass fiber,
17 portions of cross-linking agent,
6 parts of nucleating agent.
More preferably, the polyamide is a mixture comprising polyhexamethylene sebacamide and hexamethylene adipamide-terephthalamide copolyamides, wherein the mass ratio of polyhexamethylene sebacamide to hexamethylene adipamide-terephthalamide copolyamides is 1: 0.62.
more preferably, the maleic anhydride grafting modifier is prepared by mixing, by mass, 1: 2.4 reacting the polysiloxane containing epoxy group with maleic anhydride grafted polyethylene to obtain the polyethylene grafted silicon-containing group copolymer.
Preferably, the cross-linking agent is a mixture formed by mixing dicumyl peroxide and benzoyl peroxide.
More preferably, the mass ratio of dicumyl peroxide to benzoyl peroxide in the mixture formed by mixing dicumyl peroxide and benzoyl peroxide is 1: (0.55-0.65).
Preferably, the nucleating agent is nano zinc oxide.
The embodiment also provides a preparation method of the PA/TPU supercritical foaming composite material, which comprises the following steps:
A. weighing: respectively weighing polyamide, organic silicon modified polyurethane, maleic anhydride grafted modifier, maleic anhydride grafted high-density polyethylene, glass fiber, cross-linking agent and nucleating agent according to parts by weight;
B. banburying: mixing polyamide, organic silicon modified polyurethane, maleic anhydride grafted modifier, maleic anhydride grafted high-density polyethylene and glass fiber, feeding the mixture into an internal mixer, firstly carrying out internal mixing and blending for 12-15 min at the temperature of 115-120 ℃, then adding cross-linking agent and nucleating agent, and carrying out internal mixing and blending at the temperature of 130-135 ℃ until all components are uniformly mixed to prepare an internal mixing blend;
C. tabletting: pressing the banburying blend into a sheet by a tablet press, and cutting;
D. supercritical foaming: and D, placing the sheet prepared in the step C into an oven, preheating to a foaming temperature, then placing the preheated foaming sheet into a high-temperature mold, introducing carbon dioxide gas, and quickly releasing the carbon dioxide gas in the mold when the carbon dioxide gas is saturated in the sheet to quickly foam the sheet to obtain the PA/TPU supercritical foaming composite material.
Preferably, in the step D, the temperature of the high-temperature die is 155-165 ℃, and the pressure of carbon dioxide gas in the die is 14-16 MPa.
Example 2:
a PA/TPU supercritical foaming composite material is prepared from the following raw materials in parts by weight:
200 portions of polyamide,
160 parts of organic silicon modified polyurethane,
70 portions of maleic anhydride graft modifier,
45 parts of maleic anhydride grafted high-density polyethylene,
22 portions of glass fiber,
15 portions of cross-linking agent,
5 parts of a nucleating agent;
the polyamide is a mixture of polyhexamethylene sebacamide and hexamethylene adipamide-hexamethylene terephthalamide copolyamide, wherein the mass ratio of the polyhexamethylene sebacamide to the hexamethylene adipamide-hexamethylene terephthalamide copolyamide is 1: 0.5;
the organic silicon modified polyurethane is an organic silicon modified polyurethane elastomer synthesized by a prepolymer method by taking 2, 4-toluene diisocyanate, tetrahydrofuran propylene oxide copolymerized ether polyol, 3 '-dichloro-4, 4' -diaminodiphenylmethane and organic silicon glycol as raw materials;
the maleic anhydride grafting modifier is prepared from the following components in a mass ratio of 1: 2, reacting the polysiloxane containing epoxy groups with maleic anhydride grafted polyethylene to obtain the polyethylene grafted silicon-containing group copolymer.
In this embodiment, the crosslinking agent is a mixture of dicumyl peroxide and benzoyl peroxide.
In this embodiment, the mass ratio of dicumyl peroxide to benzoyl peroxide in the mixture of dicumyl peroxide and benzoyl peroxide is 1: 0.55.
in this embodiment, the nucleating agent is nano zinc oxide.
In this embodiment, the preparation method of the PA/TPU supercritical foaming composite material comprises the following steps:
A. weighing: respectively weighing polyamide, organic silicon modified polyurethane, maleic anhydride grafted modifier, maleic anhydride grafted high-density polyethylene, glass fiber, cross-linking agent and nucleating agent according to parts by weight;
B. banburying: mixing polyamide, organosilicon modified polyurethane, maleic anhydride grafted modifier, maleic anhydride grafted high-density polyethylene and glass fiber, feeding the mixture into an internal mixer, firstly carrying out internal mixing blending for 15min at the temperature of 115 ℃, then adding a cross-linking agent and a nucleating agent, and carrying out internal mixing blending at the temperature of 130 ℃ until all components are uniformly mixed to obtain an internal mixing blend;
C. tabletting: pressing the banburying blend into a sheet by a tablet press, and cutting;
D. supercritical foaming: and D, placing the sheet prepared in the step C into an oven, preheating to a foaming temperature, then placing the preheated foaming sheet into a high-temperature mold, introducing carbon dioxide gas, and quickly releasing the carbon dioxide gas in the mold when the carbon dioxide gas is saturated in the sheet to quickly foam the sheet to obtain the PA/TPU supercritical foaming composite material.
In this example, in step D, the temperature of the high temperature mold was 155 ℃ and the pressure of carbon dioxide gas in the mold was 16 MPa.
Example 3:
a PA/TPU supercritical foaming composite material is prepared from the following raw materials in parts by weight:
240 portions of polyamide,
180 parts of organic silicon modified polyurethane,
77 parts of maleic anhydride graft modifier,
52 parts of maleic anhydride grafted high-density polyethylene,
26 parts of glass fiber,
18 portions of cross-linking agent,
7 parts of a nucleating agent;
the polyamide is a mixture of polyhexamethylene sebacamide and hexamethylene adipamide-hexamethylene terephthalamide copolyamide, wherein the mass ratio of the polyhexamethylene sebacamide to the hexamethylene adipamide-hexamethylene terephthalamide copolyamide is 1: 0.7;
the organic silicon modified polyurethane is an organic silicon modified polyurethane elastomer synthesized by a prepolymer method by taking 2, 4-toluene diisocyanate, tetrahydrofuran propylene oxide copolymerized ether polyol, 3 '-dichloro-4, 4' -diaminodiphenylmethane and organic silicon glycol as raw materials;
the maleic anhydride grafting modifier is prepared from the following components in a mass ratio of 1: 3, reacting the polysiloxane containing epoxy groups with maleic anhydride grafted polyethylene to obtain the polyethylene grafted silicon-containing group copolymer.
In this embodiment, the crosslinking agent is a mixture of dicumyl peroxide and benzoyl peroxide.
In this embodiment, the mass ratio of dicumyl peroxide to benzoyl peroxide in the mixture of dicumyl peroxide and benzoyl peroxide is 1: 0.65.
in this embodiment, the nucleating agent is nano zinc oxide.
In this embodiment, the preparation method of the PA/TPU supercritical foaming composite material comprises the following steps:
A. weighing: respectively weighing polyamide, organic silicon modified polyurethane, maleic anhydride grafted modifier, maleic anhydride grafted high-density polyethylene, glass fiber, cross-linking agent and nucleating agent according to parts by weight;
B. banburying: mixing polyamide, organosilicon modified polyurethane, maleic anhydride grafted modifier, maleic anhydride grafted high-density polyethylene and glass fiber, feeding the mixture into an internal mixer, firstly carrying out internal mixing and blending for 12min at the temperature of 120 ℃, then adding a cross-linking agent and a nucleating agent, and carrying out internal mixing and blending at the temperature of 135 ℃ until all components are uniformly mixed to obtain an internal mixing blend;
C. tabletting: pressing the banburying blend into a sheet by a tablet press, and cutting;
D. supercritical foaming: and D, placing the sheet prepared in the step C into an oven, preheating to a foaming temperature, then placing the preheated foaming sheet into a high-temperature mold, introducing carbon dioxide gas, and quickly releasing the carbon dioxide gas in the mold when the carbon dioxide gas is saturated in the sheet to quickly foam the sheet to obtain the PA/TPU supercritical foaming composite material.
In this example, in step D, the temperature of the high temperature mold was 165 ℃ and the pressure of carbon dioxide gas in the mold was 14 MPa.
Example 4:
a PA/TPU supercritical foaming composite material is prepared from the following raw materials in parts by weight:
220 parts of polyamide,
170 parts of organic silicon modified polyurethane,
74 parts of maleic anhydride grafting modifier,
48 parts of maleic anhydride grafted high-density polyethylene,
24 portions of glass fiber,
17 portions of cross-linking agent,
6 parts of a nucleating agent;
the organic silicon modified polyurethane is an organic silicon modified polyurethane elastomer synthesized by a prepolymer method by taking 2, 4-toluene diisocyanate, tetrahydrofuran propylene oxide copolymerized ether polyol, 3 '-dichloro-4, 4' -diaminodiphenylmethane and organic silicon glycol as raw materials;
in this example, the polyamide is a mixture of polyhexamethylene sebacamide and hexamethylene adipamide-terephthalamide copolyamide, the mass ratio of polyhexamethylene sebacamide to hexamethylene adipamide-terephthalamide copolyamide being 1: 0.62.
in this example, the maleic anhydride graft modifier is prepared by mixing, by mass, 1: 2.4 reacting the polysiloxane containing epoxy group with maleic anhydride grafted polyethylene to obtain the polyethylene grafted silicon-containing group copolymer.
In this embodiment, the crosslinking agent is a mixture of dicumyl peroxide and benzoyl peroxide.
In this embodiment, the mass ratio of dicumyl peroxide to benzoyl peroxide in the mixture of dicumyl peroxide and benzoyl peroxide is 1: 0.6.
in this embodiment, the nucleating agent is nano zinc oxide.
In this embodiment, the preparation method of the PA/TPU supercritical foaming composite material comprises the following steps:
A. weighing: respectively weighing polyamide, organic silicon modified polyurethane, maleic anhydride grafted modifier, maleic anhydride grafted high-density polyethylene, glass fiber, cross-linking agent and nucleating agent according to parts by weight;
B. banburying: mixing polyamide, organosilicon modified polyurethane, maleic anhydride grafted modifier, maleic anhydride grafted high-density polyethylene and glass fiber, feeding the mixture into an internal mixer, firstly carrying out internal mixing blending for 14min at the temperature of 118 ℃, then adding a cross-linking agent and a nucleating agent, and carrying out internal mixing blending at the temperature of 132 ℃ until all components are uniformly mixed to obtain an internal mixing blend;
C. tabletting: pressing the banburying blend into a sheet by a tablet press, and cutting;
D. supercritical foaming: and D, placing the sheet prepared in the step C into an oven, preheating to a foaming temperature, then placing the preheated foaming sheet into a high-temperature mold, introducing carbon dioxide gas, and quickly releasing the carbon dioxide gas in the mold when the carbon dioxide gas is saturated in the sheet to quickly foam the sheet to obtain the PA/TPU supercritical foaming composite material.
In this example, in step D, the temperature of the high temperature mold is 160 ℃, and the pressure of the carbon dioxide gas in the mold is 15 MPa.
Comparative example 1:
the difference from example 4 is that the polyamide is polyhexamethylene sebacamide, no hexamethylene adipamide-hexamethylene terephthalamide copolyamide, and the rest is the same as example 4.
Comparative example 2:
the difference from example 4 is that the silicone-modified polyurethane was replaced with a conventional polyurethane, and the other was the same as example 4.
Comparative example 3:
the difference from example 4 is that there is no maleic anhydride graft modifier, and the other is the same as example 4.
Comparative example 4:
the difference from example 4 is that no maleic anhydride grafted high density polyethylene was used, and the other examples were the same as example 4.
Comparative example 5:
the difference from example 4 is that no glass fiber is present, and the other is the same as example 4.
The following performance tests were performed on the PA/TPU supercritical foamed composite materials obtained in examples 2 to 4 of the present invention and comparative examples 1 to 5, and the test results are shown in table 1:
TABLE 1
As can be seen from the table above, the PA/TPU supercritical foamed composite material has high tensile strength, high tear resistance and good tear resistance; low density, light weight, high strength and other excellent mechanical performance and use performance.
From the above table analysis, it can be seen that the proper ratio of polyhexamethylene sebacamide to hexamethylene adipamide-hexamethylene terephthalamide copolyamide is adopted for blending, wherein the polyhexamethylene sebacamide has small relative density, easy molding and processing and high mechanical strength; the addition of the hexamethylene adipamide-hexamethylene terephthalamide copolyamide can improve the rigidity of the composite material and has good appearance and strength; and the PA/TPU supercritical foaming composite material is matched with other components to play a good synergistic effect, so that the PA/TPU supercritical foaming composite material disclosed by the invention has the advantage that the tensile strength and the tear strength are improved under the same foaming condition.
From the analysis of the above table, it can be seen that the special organosilicon modified polyurethane has good compatibility with other components, can improve the tensile strength and tear strength of the PA/TPU supercritical foaming composite material of the present invention, further contains a silicon-containing group chain segment that is carbon dioxide-philic, has affinity for carbon dioxide, and can promote the diffusion rate of carbon dioxide in the PA/TPU supercritical foaming composite material, and when supercritical foaming is performed, because each raw material component has good compatibility, a uniform continuous phase structure is formed, carbon dioxide can diffuse rapidly, so that a good foaming effect is ensured, 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.
From the analysis of the above table, it can be seen that the addition of the maleic anhydride graft modifier in a proper proportion, which is mixed with other components to achieve a good synergistic effect, is performed by mixing the maleic anhydride graft modifier with the other components in a mass ratio of 1: and (2) reacting the epoxy group-containing polysiloxane with maleic anhydride grafted polyethylene to obtain the polyethylene grafted silicon group-containing copolymer. Preferably, the maleic anhydride grafting modifier is prepared by mixing the components in a mass ratio of 1: 2.4 reacting the polysiloxane containing epoxy group with maleic anhydride grafted polyethylene to obtain the polyethylene grafted silicon-containing group copolymer. The polyethylene grafted silicon-containing group copolymer not only has a carbon dioxide-philic silicon-containing group chain segment, but also has a maleic anhydride grafted polyethylene chain segment which can be compatible with the polyamide, the organic silicon modified polyurethane and the maleic anhydride grafted high-density polyethylene composite matrix; the polyethylene grafted silicon-group-containing copolymer has affinity to carbon dioxide, has high carbon dioxide adsorption capacity, and has extremely fast diffusion rate in the carbon dioxide, so that when supercritical foaming is carried out, because each raw material component has good compatibility, a uniform continuous phase structure is formed, the carbon dioxide can be rapidly diffused into the polyethylene grafted silicon-group-containing copolymer and then diffused into the whole raw material system; the polyethylene grafted silicon-group-containing copolymer is used as a diffusion channel of carbon dioxide, so that the contact area of the polyethylene grafted silicon-group-containing copolymer and the polyamide, organic silicon modified polyurethane and maleic anhydride grafted high-density polyethylene composite matrix is increased, the diffusion path is reduced, the saturation time is shortened, the production efficiency is improved, the good foaming effect is ensured, and the foaming efficiency is high; the foam holes are uniform, small and compact, and have excellent mechanical properties and service performance such as light weight, high strength and the like.
From the analysis of the above table, it can be seen that the addition of the maleic anhydride grafted high density polyethylene in a proper proportion, in cooperation with other components, has a good synergistic effect, and further improves the tensile strength and tear strength of the PA/TPU supercritical foamed composite material of the present invention.
From the analysis of the above table, it can be seen that the addition of the glass fiber in a proper proportion in the raw material system of the present invention is uniformly dispersed, and the glass fiber is matched with other components to play a good synergistic role, so as to further improve the tensile strength and tear strength of the PA/TPU supercritical foamed composite material of the present invention.
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 (9)
1. The PA/TPU supercritical foaming composite material is characterized by being prepared from the following raw materials in parts by weight:
200 to 240 parts of polyamide,
160-180 parts of organic silicon modified polyurethane,
70-77 parts of maleic anhydride grafting modifier,
45-52 parts of maleic anhydride grafted high-density polyethylene,
22-26 parts of glass fiber,
15-18 parts of cross-linking agent,
5-7 parts of a nucleating agent;
the polyamide is a mixture comprising polyhexamethylene sebacamide and hexamethylene adipamide-hexamethylene terephthalamide copolyamide, wherein the mass ratio of the polyhexamethylene sebacamide to the hexamethylene adipamide-hexamethylene terephthalamide copolyamide is 1: (0.5 to 0.7);
the organic silicon modified polyurethane is an organic silicon modified polyurethane elastomer synthesized by a prepolymer method by taking 2, 4-toluene diisocyanate, tetrahydrofuran propylene oxide copolymerized ether polyol, 3 '-dichloro-4, 4' -diaminodiphenylmethane and organic silicon glycol as raw materials;
the maleic anhydride grafting modifier is prepared from the following components in a mass ratio of 1: and (2) reacting the epoxy group-containing polysiloxane with maleic anhydride grafted polyethylene to obtain the polyethylene grafted silicon group-containing copolymer.
2. The PA/TPU supercritical foamed composite according to claim 1, wherein the PA/TPU supercritical foamed composite is made from raw materials comprising, by weight:
220 parts of polyamide,
170 parts of organic silicon modified polyurethane,
74 parts of maleic anhydride grafting modifier,
48 parts of maleic anhydride grafted high-density polyethylene,
24 portions of glass fiber,
17 portions of cross-linking agent,
6 parts of nucleating agent.
3. The PA/TPU supercritical foamed composite according to claim 2, characterized in that the polyamide is a mixture comprising polyhexamethylene sebacamide and hexamethylene adipamide-terephthalamide copolyamide with a mass ratio of polyhexamethylene sebacamide to hexamethylene adipamide-terephthalamide copolyamide of 1: 0.62.
4. the PA/TPU supercritical foamed composite according to claim 2, characterized in that the maleic anhydride graft modifier is a copolymer of the maleic anhydride graft modifier and the maleic anhydride graft modifier in a mass ratio of 1: 2.4 reacting the polysiloxane containing epoxy group with maleic anhydride grafted polyethylene to obtain the polyethylene grafted silicon-containing group copolymer.
5. The PA/TPU supercritical foamed composite of claim 1 where the cross-linking agent is a mixture of dicumyl peroxide and benzoyl peroxide.
6. The PA/TPU supercritical foamed composite according to claim 5, wherein the mixture of dicumyl peroxide and benzoyl peroxide has a ratio of dicumyl peroxide to benzoyl peroxide by mass of 1: (0.55-0.65).
7. The PA/TPU supercritical foamed composite of claim 1 where the nucleating agent is nano zinc oxide.
8. A process for the preparation of PA/TPU supercritical foamed composite according to any of claims 1 to 7, characterized in that it comprises the following steps:
A. weighing: respectively weighing polyamide, organic silicon modified polyurethane, maleic anhydride grafted modifier, maleic anhydride grafted high-density polyethylene, glass fiber, cross-linking agent and nucleating agent according to parts by weight;
B. banburying: mixing polyamide, organic silicon modified polyurethane, maleic anhydride grafted modifier, maleic anhydride grafted high-density polyethylene and glass fiber, feeding the mixture into an internal mixer, firstly carrying out internal mixing and blending for 12-15 min at the temperature of 115-120 ℃, then adding cross-linking agent and nucleating agent, and carrying out internal mixing and blending at the temperature of 130-135 ℃ until all components are uniformly mixed to prepare an internal mixing blend;
C. tabletting: pressing the banburying blend into a sheet by a tablet press, and cutting;
D. supercritical foaming: and D, placing the sheet prepared in the step C into an oven, preheating to a foaming temperature, then placing the preheated foaming sheet into a high-temperature mold, introducing carbon dioxide gas, and quickly releasing the carbon dioxide gas in the mold when the carbon dioxide gas is saturated in the sheet to quickly foam the sheet to obtain the PA/TPU supercritical foaming composite material.
9. The preparation method of the PA/TPU supercritical foamed composite material according to claim 8, wherein in step D, the temperature of the high-temperature mold is 155-165 ℃, and the pressure of carbon dioxide gas in the mold is 14-16 MPa.
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