CN111100445A - Polyamide composition and preparation method and application thereof - Google Patents
Polyamide composition and preparation method and application thereof Download PDFInfo
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- CN111100445A CN111100445A CN201811250965.0A CN201811250965A CN111100445A CN 111100445 A CN111100445 A CN 111100445A CN 201811250965 A CN201811250965 A CN 201811250965A CN 111100445 A CN111100445 A CN 111100445A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- 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
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
Abstract
The invention belongs to the field of polymers, and discloses a polyamide composition, and a preparation method and application thereof. The polyamide composition comprises: 1-30 wt% of polyamide A, wherein the polyamide A is a linear chain structure, and the total content of long chain branch structures and short chain branch structures of the polyamide A is less than 0.005 wt%; 70-99 wt% of a polyamide B, said polyamide B having a branched structure of long chain branches; the relative viscosity of the polyamide A and the relative viscosity of the polyamide B are respectively and independently 2.8-3.9, and the difference between the relative viscosities of the polyamide A and the polyamide B is less than 0.2. The polyamide composition provided by the invention has higher melt strength, good melt stability and excellent foaming performance, when the polyamide composition is used for foaming, the foaming multiplying power is high, the density is small, and the obtained foaming material has the advantages of complete foam holes, good stability, smooth appearance, high closed cell rate and the like, and can meet the application of foaming.
Description
Technical Field
The invention belongs to the field of polymers, and particularly relates to a polyamide composition, and a preparation method and foaming application thereof.
Background
Polyamide 6 has good comprehensive properties including mechanical properties, heat resistance, wear resistance, chemical resistance and self-lubricity, has low friction coefficient, certain flame retardance and easy processing, and has very wide application fields mainly including the fields of synthetic fibers, films, engineering plastics and the like. When the foamed polyamide 6 is used for automobiles, the weight of a finished piece can be obviously reduced on the premise of ensuring the basic performance of the material, the automobile is favorably lightened, and the foamed polyamide 6 has a wide market application prospect. However, since polyamide 6 is a linear chain structure containing amide repeating units, a low melt strength is generally exhibited during melt processing, and it is difficult to resist severe stress applied during cell growth, resulting in collapse and breakage of cells, and thus, how to increase the melt strength of polyamide 6 is an urgent problem to be solved.
Research shows that polyamide 6 nanometer composite material can be used to improve the foaming performance of polyamide 6, but the processing process is complex, most of the polyamide 6 nanometer composite material is cross-linked polymer, the environmental protection performance is poor, and the polyamide 6 nanometer composite material cannot be recycled. CN105601977A discloses a method of introducing chain extender to increase the melt strength of polyamide 6, but the monomer used is actually polymerization tackifying for increasing the relative viscosity of polyamide 6, and is not introduced with long-chain branched structure, so the amount of chain extender needed is large, and the improvement effect is limited.
To date, many challenges still face for improving the melt strength of polyamide 6 for foaming, one of which is the problem of low strength in the melt state, so that cells cannot grow effectively and collapse, wrinkle and the like occur. Therefore, it is urgently required to develop a method capable of improving the melt strength and stability of polyamide.
Disclosure of Invention
The invention aims to overcome the defects that the existing polyamide 6 has poor melt stability and is difficult to be used for preparing foaming materials, and provides a polyamide composition which has high relative viscosity, good melt stability and excellent foaming performance, a preparation method and foaming application thereof.
Specifically, the present invention provides a polyamide composition comprising:
1-30 wt% of polyamide A, wherein the polyamide A is a linear chain structure, and the total content of long chain branch structures and short chain branch structures of the polyamide A is less than 0.005 wt%; the linear chain structure means that the main chain is a straight chain containing amide repeating units and does not contain a side group or a side chain with an amide group;
70-99 wt% of polyamide B, wherein the polyamide B contains a long-chain branched structure, and the content of the long-chain branched structure of the polyamide B is 0.005-0.6 wt%; the long-chain branched structure refers to a side chain with the number of amide repeating units more than 10 in the molecular structure of the linear polyamide;
the relative viscosity of the polyamide A and the relative viscosity of the polyamide B are respectively and independently 2.8-3.9, and the difference between the relative viscosities of the polyamide A and the polyamide B is less than 0.2.
The invention also provides a preparation method of the polyamide composition, which comprises the step of uniformly mixing the components in the polyamide composition.
In addition, the invention also provides application of the polyamide composition in tank foaming, extrusion foaming or mould pressing foaming.
According to the polyamide composition provided by the invention, the polyamide A with a linear chain structure and the polyamide B with a long-chain branched structure are matched according to a specific using amount so as to ensure that the finally obtained polyamide composition has higher melt strength and good melt stability.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The present invention provides a polyamide composition comprising:
1-30 wt% of polyamide A, wherein the polyamide A is a linear chain structure, and the total content of long chain branch structures and short chain branch structures of the polyamide A is less than 0.005 wt%; the linear chain structure means that the main chain is a straight chain containing amide repeating units and does not contain a side group or a side chain with an amide group;
70-99 wt% of polyamide B, wherein the polyamide B contains a long-chain branched structure, and the content of the long-chain branched structure of the polyamide B is 0.005-0.6 wt%; the long-chain branched structure refers to a side chain with the number of amide repeating units more than 10 in the molecular structure of the linear polyamide;
the relative viscosity of the polyamide A and the relative viscosity of the polyamide B are respectively and independently 2.8-3.9, and the difference between the relative viscosities of the polyamide A and the polyamide B is less than 0.2.
The term "long chain branching" means that the polyamide backbone contains a number of amide groups greater than 10 in the branched structure. The term "short chain branching" means that the polyamide has a number of amide groups ranging from 1 to 6 in the branched structure of the polyamide main chain. The content of long and short chain branches is the average of the following parameters of all polymer chains: the number of amide groups in the long-branched structure and the short-branched structure on one polymer chain is divided by the number of amide groups in the main chain.
According to the invention, the bio-based multifunctional branching monomer is introduced on the polyamide resin, and a long-chain branched structure is introduced from a molecular chain structure, so that the entanglement interaction force of the molecular chain can be improved, and the melt strength and melt stability of the polyamide can be effectively improved.
In the present invention, the relative viscosities of the polyamide A and the polyamide B were measured using an Ubbelohde viscometer, specifically, the relative viscosities were determined based on the ratio of the flow-out time of the sample to the flow-out time of the solvent used, wherein the solvent used was a 96 wt% sulfuric acid aqueous solution, and the test temperature was 25 ℃.
According to the present invention, the main chains of the polyamide a and the polyamide B contain repeating amide bond groups, and the monomer for forming the repeating amide bond groups may be at least one of a dibasic acid and a diamine (e.g., adipic acid and hexamethylenediamine), or a monoamino monocarboxylic acid and a lactam, oligomer, and anhydride of the monoamino monocarboxylic acid. The monoamino monocarboxylic acid may be at least one of omega-aminopentanoic acid, omega-aminocaproic acid, omega-aminoheptanoic acid, and omega-aminoundecanoic acid, for example.
The branching point in the long chain branched structure of the polyamide B is derived from a comonomer C having a functionality of 3 or more, in principle any compound having three or more functional groups capable of reacting with other groups to form amide groups can be used, these functional groups can be amine, carboxyl or precursor groups, correspondingly the monomer C is at least one of a compound having an amine and/or carboxyl functionality of 3 or more, preferably a polyacid (tribasic or tribasic), a polyamine (tribasic or tribasic), a compound containing at least two amine groups and at least one carboxyl group, and a compound containing at least one amine group and at least two carboxyl groups, wherein the polyacid can be at least one of trimesic acid, [2,2':6',2 "-terpyridine ] -4,4', 4" -tricarboxylic acid, 1, 2-diaminopropane-N, N' -tetraacetic acid, 3,5,3',5' -biphenyltetracarboxylic acid, etc. the polyamine can be at least one of a triamine, and/or a trialkylamine (preferably a polyamine containing at least one amino group such as a diamine, preferably a diamine, such as melamine, a diamine, and/or a diamine, such as a diamine, preferably a diamine, wherein the polyamine (preferably contains at least one amino group, such as 0.005, 0.01, 0.0.05, and more preferably at least one amino group, and more preferably at least one amino acid).
The relative viscosity of the polyamide B is basically the same as that of the polyamide A, the polymerization process can be carried out by adopting the known process for preparing the polyamide 6, and a multifunctional branching monomer C is introduced in the polymerization process, so that the reaction rate can be accelerated.
The content of the long-chain branched structure of the polyamide B is preferably 0.01 to 0.3 wt%, more preferably 0.01 to 0.2 wt%, most preferably 0.05 to 0.2 wt%.
The relative viscosity of the polyamide A and the polyamide B is preferably from 3.0 to 3.8 independently of one another.
According to the invention, the polyamide composition may further contain an antioxidant in an amount of 0.1 to 2 parts by weight per 100 parts by weight of the polyamide A. The antioxidant may be, for example, a phenol antioxidant, a phosphite antioxidant, or the like. In addition, the polyamide composition may also contain other conventional processing aids.
The preparation method of the polyamide composition provided by the invention comprises the step of uniformly mixing the components in the polyamide composition.
The preparation method of the polyamide composition provided by the invention can also comprise the step of carrying out extrusion granulation on the obtained mixed product by adopting a double-screw extrusion granulator.
According to a particular embodiment of the invention, the process for the preparation of the polyamide composition comprises:
(1) drying polyamide A and polyamide B in a vacuum oven at 80 ℃ for 10 hours, and premixing the two resins in proportion to obtain a premix;
(2) adding known antioxidant system such as phenol antioxidant, phosphite antioxidant, etc. into the premix to obtain mixture;
(3) and adding the mixture into a double-screw extruder for extrusion granulation to obtain polyamide composition granules.
In addition, the invention also provides application of the polyamide composition in tank foaming, extrusion foaming or mould pressing foaming. Wherein, the kettle pressure foaming is that the foaming agent is used for impregnating resin particles in a high-pressure kettle, the foaming agent is quickly released and foamed to prepare foamed particles with the particle size of 2-4mm, and then the foamed particles are heated and formed in a mould for the second time, and the product has the advantages of high foaming ratio (15-45 times) and capability of obtaining products with complex shapes. The extrusion foaming is performed by feeding polyamide composition pellets into an extruder, and if necessary, melting and kneading the pellets with carbon dioxide, a hydrocarbon or chemical blowing agent, and a crosslinking agent under heat and pressure, followed by extrusion foaming. The plate is placed into a mould press for mould pressing foaming, a foaming agent such as carbon dioxide is introduced, the temperature and the pressure are raised, the foaming agent is soaked and saturated in the plate, then the pressure and the temperature are quickly released and reduced, and the foamed plate is prepared and can be processed by using a common hot press.
The present invention is further illustrated by the following examples. It is to be understood, however, that these examples are for the purpose of illustration and explanation only and are not intended to limit the present invention.
Example 1
The polyamide composition is prepared by drying polyamide A (linear chain structure, long-branched chain structure and short-branched chain structure with total content less than 0.005 wt%, relative viscosity of 3.5, melting point of 220 ℃ and obtained by homopolymerization of omega-aminocaproic acid) and polyamide B (containing long-branched chain structure with content of long-branched chain structure of 0.06 wt%, relative viscosity of 3.6, melting point of 220 ℃, main chain and branched chain of omega-aminocaproic acid homopolymerization chain, branching point derived from lysine and content of lysine derived units of 0.05 wt%) in a vacuum oven at 80 ℃ for 10h, adding 2 wt% of polyamide A, 98 wt% of polyamide B and antioxidant (the antioxidant is 0.2 wt% of polyamide A) into a high-speed mixer for premixing, adding the premix into a double-screw extruder for extrusion and granulation. The polyamide composition is foamed by a kettle type foaming method, wherein a foaming agent is carbon dioxide, the foaming temperature is 150-.
Example 2
The polyamide composition is prepared by drying polyamide A (linear chain structure, long-chain structure and short-chain structure content is less than 0.005 wt%, relative viscosity is 3.1, melting point is 260 ℃, and the polyamide B is obtained by condensation polymerization of adipic acid and hexamethylene diamine) and polyamide B (containing long-chain branched structure, long-chain branched structure content is 0.1 wt%, relative viscosity is 3.2, melting point is 260 ℃, main chain and branched chain are adipic acid and hexamethylene diamine condensed chain, branching point is derived from isophthalic acid aniline, and content of isophthalic acid aniline derived unit is 0.1 wt%) in a vacuum oven at 80 ℃ for 10h, adding 15 wt% of polyamide A and 85 wt% of polyamide B and antioxidant (the content of antioxidant is 1 wt% of polyamide A) into a high-speed mixer for premixing, adding the premix into a double-screw extruder for extrusion granulation to obtain the polyamide composition. The polyamide composition is foamed by a kettle type foaming method, wherein a foaming agent is carbon dioxide, the foaming temperature is 150-.
Example 3
Polyamide composition, polyamide A (linear chain structure, long chain structure and short chain structure content less than 0.005 wt%, relative viscosity 3.2, melting point 185 ℃, obtained by homopolymerization of omega-amino undecanoic acid) and polyamide B (containing long chain branched structure, long chain branched structure content 0.1 wt%, relative viscosity 3.2, melting point 185 ℃, main chain and branched chain omega-amino undecanoic acid homopolymerization chain, branching point derived from aspartic acid and aspartic acid derived unit content 0.1 wt%) are dried in a vacuum oven at 80 ℃ for 10h, 30 wt% of polyamide A and 70 wt% of polyamide B and antioxidant (antioxidant content is 0.5 wt% of polyamide A) are added into a high-speed mixer for premixing, and the premix is added into a double-screw extruder for extrusion granulation to obtain the polyamide composition. The polyamide composition is foamed by a kettle type foaming method, wherein a foaming agent is carbon dioxide, the foaming temperature is 150-.
Comparative example 1
Expanded beads were prepared by following the procedure of example 1 except that the amount of polyamide A was 98% by weight and the amount of polyamide B was 2% by weight, to obtain expanded beads, the expansion effect of which is shown in Table 1.
TABLE 1
| Item | Density (g/ml) | Closed cell content (%) | Whether the beads are smooth or not | Whether the cell shape is complete |
| Example 1 | 0.0586 | 89.8 | Is that | Is that |
| Example 2 | 0.1620 | 84.6 | Is that | Is that |
| Example 3 | 0.1050 | 83.4 | Is that | Is that |
| Comparative example 1 | 0.3758 | 75.5 | Whether or not | Whether or not |
From the results in table 1, it can be seen that when the polyamide composition provided by the present invention is used for foaming, the obtained foamed material has the characteristics of complete cells, smooth appearance and high closed cell rate, and can completely meet the application of foaming.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. A polyamide composition, characterized in that the polyamide composition comprises:
1-30 wt% of polyamide A, wherein the polyamide A is a linear chain structure, and the total content of long chain branch structures and short chain branch structures of the polyamide A is less than 0.005 wt%; the linear chain structure means that the main chain is a straight chain containing amide repeating units and does not contain a side group or a side chain with an amide group;
70-99 wt% of polyamide B, wherein the polyamide B contains a long-chain branched structure, and the content of the long-chain branched structure of the polyamide B is 0.005-0.6 wt%; the long-chain branched structure refers to a side chain with the number of amide repeating units more than 10 in the molecular structure of the linear polyamide;
the relative viscosity of the polyamide A and the relative viscosity of the polyamide B are respectively and independently 2.8-3.9, and the difference between the relative viscosities of the polyamide A and the polyamide B is less than 0.2.
2. The polyamide composition according to claim 1, wherein the polyamide A and the polyamide B have repeating amide bond groups in their main chains, and the monomers for forming the repeating amide bond groups are at least one of a dibasic acid and a diamine, or a monoamino monocarboxylic acid selected from at least one of omega-aminopentanoic acid, omega-aminocaproic acid, omega-aminoheptanoic acid, and omega-aminoundecanoic acid, and a lactam, oligomer, and an anhydride of the monoamino monocarboxylic acid and the monoamino monocarboxylic acid.
3. The polyamide composition according to claim 1, wherein the branch points in the long-chain branched structure of the polyamide B are derived from a comonomer C, which is at least one of a compound having an amine and/or carboxyl functionality of 3 or more, preferably a polyacid, a polyamine, a compound containing at least two amine groups and at least one carboxyl group, and a compound containing at least one amine group and at least two carboxyl groups, more preferably at least one selected from trimesic acid, [2,2':6',2 "-terpyridine ] -4,4', 4" -tricarboxylic acid, 1, 2-diaminopropane-N, N' -tetraacetic acid, 3,5,3',5' -biphenyltetracarboxylic acid, melamine, tris (2-aminoethyl) amine, polyalkylenetriamine, dialkylenetriamine, α, omega-amino acids, and anilide dicarboxylate.
4. Polyamide composition according to claim 3, wherein the comonomer C is present in an amount of from 0.005 to 0.6% by weight, preferably from 0.01 to 0.2% by weight, more preferably from 0.05 to 0.08% by weight.
5. Polyamide composition according to any one of claims 1 to 4, wherein the polyamide B has a content of long-chain branched structures ranging from 0.01 to 0.3% by weight, preferably ranging from 0.01 to 0.2% by weight and more preferably ranging from 0.05 to 0.2% by weight.
6. The polyamide composition of any one of claims 1-4 wherein the relative viscosity of polyamide A and polyamide B is each independently from 3.0 to 3.8.
7. The polyamide composition according to any one of claims 1 to 4, wherein the polyamide composition further comprises 0.1 to 2 parts by weight of an antioxidant per 100 parts by weight of the polyamide A.
8. Process for the preparation of a polyamide composition according to any one of claims 1 to 7, characterized in that it comprises mixing the components of the polyamide composition homogeneously.
9. The production method according to claim 8, further comprising subjecting the resulting mixed product to extrusion granulation using a twin-screw extrusion granulator.
10. Use of a polyamide composition according to any one of claims 1 to 7 in kettle foaming, extrusion foaming or compression molding foaming.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1193400A (en) * | 1975-11-12 | 1985-09-10 | Ronald A. Zelonka | Formable polyamide compositions |
| CN1671763A (en) * | 2002-06-21 | 2005-09-21 | 罗狄亚聚酰胺中间体公司 | Expansible polyamide composition and polyamide foam derived therefrom |
| CN101796111A (en) * | 2007-02-23 | 2010-08-04 | 罗地亚管理公司 | microcellular polyamide articles |
| CN102421833A (en) * | 2009-05-15 | 2012-04-18 | 罗地亚经营管理公司 | Method for preparing polyamide foam and foam capable of being produced by said method |
| CN105601977A (en) * | 2016-01-13 | 2016-05-25 | 华东理工大学 | Modified polyamide-6 microcellular foam material and preparation method thereof |
-
2018
- 2018-10-25 CN CN201811250965.0A patent/CN111100445B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1193400A (en) * | 1975-11-12 | 1985-09-10 | Ronald A. Zelonka | Formable polyamide compositions |
| CN1671763A (en) * | 2002-06-21 | 2005-09-21 | 罗狄亚聚酰胺中间体公司 | Expansible polyamide composition and polyamide foam derived therefrom |
| CN101796111A (en) * | 2007-02-23 | 2010-08-04 | 罗地亚管理公司 | microcellular polyamide articles |
| CN102421833A (en) * | 2009-05-15 | 2012-04-18 | 罗地亚经营管理公司 | Method for preparing polyamide foam and foam capable of being produced by said method |
| CN105601977A (en) * | 2016-01-13 | 2016-05-25 | 华东理工大学 | Modified polyamide-6 microcellular foam material and preparation method thereof |
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