CN115322366A - Polyamide 6-modified high-strength high-toughness copolyamide and preparation method thereof - Google Patents
Polyamide 6-modified high-strength high-toughness copolyamide and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 112
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- -1 carboxamide salt Chemical class 0.000 claims abstract description 80
- 238000000034 method Methods 0.000 claims abstract description 19
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- 239000000463 material Substances 0.000 claims description 36
- 150000003839 salts Chemical class 0.000 claims description 34
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- 238000010438 heat treatment Methods 0.000 claims description 23
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 claims description 22
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- 239000012752 auxiliary agent Substances 0.000 claims description 22
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- 239000002253 acid Substances 0.000 claims description 8
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- 150000007970 thio esters Chemical class 0.000 claims description 4
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 claims description 3
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 claims description 3
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 claims description 3
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 3
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 claims description 3
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- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 2
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 claims description 2
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- 239000000126 substance Substances 0.000 description 15
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
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- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
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- 230000000694 effects Effects 0.000 description 4
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
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- 230000008025 crystallization Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 2
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 description 2
- 238000012661 block copolymerization Methods 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
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- 238000002844 melting Methods 0.000 description 2
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- 229920000728 polyester Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000577 Nylon 6/66 Polymers 0.000 description 1
- 229920000007 Nylon MXD6 Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- TZYHIGCKINZLPD-UHFFFAOYSA-N azepan-2-one;hexane-1,6-diamine;hexanedioic acid Chemical compound NCCCCCCN.O=C1CCCCCN1.OC(=O)CCCCC(O)=O TZYHIGCKINZLPD-UHFFFAOYSA-N 0.000 description 1
- 229920006233 biaxially oriented polyamide Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
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- 239000007822 coupling agent Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
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- 238000011065 in-situ storage Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000010983 kinetics study Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229920001910 maleic anhydride grafted polyolefin Polymers 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
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- 238000000053 physical method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Abstract
The invention relates to polyamide 6 modified high-strength high-toughness copolyamide and a preparation method thereof, wherein the preparation method comprises the following steps: during the reaction process of preparing polyamide 6 from caprolactam, adding odd-numbered carboxamide salt before the reaction starts or in the initial stage of the reaction, and obtaining the polyamide 6 modified high-strength high-toughness copolyamide after the reaction is finished; the addition amount of the odd-numbered carboxamide salt accounts for 5 to 30 percent of the total molar amount of the caprolactam and the odd-numbered carboxamide salt; the molecular structural formula of the prepared product is as follows:
wherein p represents the number of odd-numbered polyamide structural units and q represents the number of polyamide 6 structural units; the polyamide 6 modified high-strength and high-toughness copolyamide has the tensile strength of 40-70 MPa and the elongation at break of 200-1000 percent; the method has simple process, and the product of the invention has toughness and strength.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to polyamide 6-modified high-strength high-toughness copolyamide and a preparation method thereof.
Background
The polyamide is also called nylon, and is a polymer containing amido bonds in a molecular main chain, and has excellent wear resistance, corrosion resistance, fatigue resistance and the like. As an important global polymer material, polyamide has been widely used in synthetic fibers, engineering plastics, packaging films, and the like. Of these, polyamide 6 occupies half of the polyamide market and is the most commonly used polyamide product. However, polyamide 6 has poor toughness and cannot be used directly in the fields of engineering plastics such as household appliances and automobile parts, and therefore, research on toughening of polyamide 6 is a problem to be solved at present.
Patent CN109749433B discloses a polyamide composition, which is composed of polyamide, toughening master batch, nucleating agent, coupling agent and glass fiber, wherein the toughening master batch mainly comprises polyamide 6 and toughening agent maleic anhydride grafted ethylene propylene diene monomer or maleic anhydride grafted polyolefin elastomer, and the polyamide composition has a good toughening effect. Patent CN112480659A discloses a preparation method of a toughened biaxially oriented polyamide film, which is characterized in that a biaxially oriented film material prepared by melting, plasticizing and extruding a blend of nylon 6 and nylon MXD6, a polyether block polyamide elastomer, an antioxidant, an opening agent and the like has good heat resistance and strong toughness. However, the addition of a heterogeneous system (i.e., a modifier such as a polyolefin/rubber elastomer or a polyether block polyamide) always has a problem of poor compatibility, and it is difficult to achieve both rigidity and toughness of the material, and the strength and modulus of the polyamide are greatly reduced.
When polyamide is modified with polyamide, physical and chemical modification can be divided.
Blending modification in a physical method has been widely used in the prior art. Patent CN107857996B discloses a polyamide blend, aliphatic odd-even polyamide and/or other aliphatic polyamide components are mixed and then the copolyamide and/or fiber is prepared by a melt blending method. However, the two polyamide components have strong hydrogen bond interaction, which leads to strong interface interaction, and the polyamide still has the problem of poor compatibility during blending preparation. And the melting points, the crystallization properties and the like of the two polyamides are greatly different, which brings trouble to the subsequent processing process, and the obtained blending product has poor quality stability.
In contrast, the chemical modification method is more stable and durable, and the modification effect is more obvious, wherein the copolymerization modification is a very important method. Patent CN107915846B discloses a polyamide copolymer, which is prepared by respectively polycondensing odd-even amide salt and even-even amide salt to prepare prepolymer, and then mixing the prepolymers to carry out a polymerization reaction to obtain the polyamide copolymer. However, the preparation process is complicated, and the salt needs to be prepared into the prepolymer first and then reacted, so that the operation complexity is greatly improved, and the preparation cost is increased, thereby increasing the difficulty of industrial or large-scale preparation. In addition, the coupling polyamide has high hydrogen bond density, the molecular chain is greatly limited by the hydrogen bond, and the amide toughening modification effect is not obvious.
Therefore, the research on the polyamide 6 modified high-strength high-toughness copolyamide and the preparation method thereof has very important significance for solving the problem that the toughness and the strength cannot be simultaneously considered in the prior art.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a polyamide 6 modified high-strength high-toughness copolyamide and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a polyamide 6 modified high-strength high-toughness copolyamide has a molecular structural formula as follows:
wherein m ranges from 3 to 12, n ranges from 1 to 10, one of m and n is an odd number, the other is an even number, i =5, p represents the number of odd-numbered carbon polyamide structural units, q represents the number of polyamide 6 structural units, p is q = 0.05-0.3;
the polyamide 6 modified high-strength and high-toughness copolyamide has the tensile strength of 40-70 MPa and the elongation at break of 200-1000 percent; the toughening modification method for polyamide 6 in the prior art generally comprises three methods: the inorganic material physical and mechanical toughening, the polyolefin/rubber elastomer blending toughening and the polyether or polyester glycol block copolymerization toughening are performed, but the polyether or polyester glycol block copolymerization toughening method is difficult to simultaneously achieve the purposes of toughening and reinforcing the material, so that the strength is often greatly reduced, for example, the elongation at break of the polyamide elastomer prepared in the patent with the publication number of CN 111607080B (published as 2021.03.12) is improved to 789%, but the tensile strength is only 30.8MPa, the high-strength and high-toughness copolyamide prepared in the invention has the tensile strength of 40-70 MPa and the elongation at break of 200-1000%, the toughness and the strength are both achieved, and the problems in the prior art are solved.
As a preferred technical scheme:
the polyamide 6 modified high-strength high-toughness copolyamide has the relative viscosity of 2.2-3.0.
The invention also provides a preparation method of the polyamide 6 modified high-strength high-toughness copolyamide, during the reaction process of preparing the polyamide 6 from caprolactam, odd-numbered carboxamide salt is added into the caprolactam before the reaction starts or in the initial stage of the reaction, and the polyamide 6 modified high-strength high-toughness copolyamide is obtained after the reaction is finished; the amount of odd-numbered carboxamide salt added is 5-30% of the total molar amount of caprolactam and odd-numbered carboxamide salt.
As a preferable technical scheme:
according to the preparation method of the polyamide 6 modified high-strength high-toughness copolyamide, odd-numbered amide salts are added in the form of dry salts; the polyamide modified by amide salt copolymerization is a known technology, but the prior art mostly adopts a salt aqueous solution for addition copolymerization, for example, CN 111171312B (2022.08.02 on the publication date) adopts a polyamide 56/66 salt aqueous solution to prepare the copolyamide, and the invention adopts a dry salt form rather than a salt solution, so that on one hand, the energy consumption is greatly saved, and the cost is saved; on the other hand, the dry salt form of the copolyamide can be used to produce a higher degree of polymerization than the salt solution, which is advantageous for producing a high molecular weight copolyamide.
According to the preparation method of the polyamide 6-modified high-strength high-toughness copolyamide, odd-numbered carboxamide salts are PAXY salts and are prepared from equimolar amounts of X and Y, wherein X is alpha, omega-diamine, Y is aliphatic dibasic acid, and when alpha, omega-diamine is odd-numbered, the aliphatic dibasic acid is even-numbered; when the alpha, omega-diamine is an even number of carbons, then the aliphatic diacid is an odd number of carbons.
The preparation method of the polyamide 6 modified high-strength high-toughness copolyamide is based on 1, 3-propane diamine, 1, 4-butane diamine, 1, 5-pentane diamine, 1, 6-hexane diamine, 1, 7-heptane diamine, 1, 8-octane diamine, 1, 9-diamino nonane, 1, 10-decane diamine, 1, 11-undecane diamine or 1, 12-diamino dodecane; the aliphatic dibasic acid is succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid or dodecanedioic acid.
The preparation method of the polyamide 6 modified high-strength high-toughness copolyamide comprises the following specific steps:
(1) Adding caprolactam, odd-numbered carboxamide salt, molecular weight regulator, antioxidant and other auxiliary agents into a high-temperature high-pressure reaction kettle, removing air in the high-temperature high-pressure reaction kettle by nitrogen replacement, slowly heating to 150-220 ℃, reacting for 1-2 h, continuously heating to 220-260 ℃, and continuously reacting for 1-2 h under the condition that the pressure is 1.0-1.5 MPa;
(2) Slowly releasing the pressure to the normal pressure within 0.5 to 1 hour, removing water vapor in the high-temperature high-pressure reaction kettle, raising the temperature to 240 to 280 ℃ again, controlling the vacuumizing rate to enable the high-temperature high-pressure reaction kettle to reach a vacuum state within 0.5 to 1 hour, and continuously reacting for 1 to 3 hours under the condition that the vacuum degree is 50 to 500Pa to obtain the polyamide 6 modified high-strength high-toughness copolyamide.
According to the preparation method of the polyamide 6 modified high-strength high-toughness copolyamide, the molecular weight regulator is the monoacid or the diacid; the antioxidant is a hindered phenol antioxidant or a mixture of the hindered phenol antioxidant and other antioxidants, and the other antioxidants are phosphite antioxidants or thioester antioxidants; other auxiliary agents are water and aminocaproic acid.
According to the preparation method of the polyamide 6-modified high-strength high-toughness copolyamide, the addition amount of the molecular weight regulator is 1-3% of the total mass of materials in the high-temperature high-pressure reaction kettle; the addition amount of the antioxidant is 0.2-0.5% of the total mass of the materials in the high-temperature high-pressure reaction kettle; the addition amount of the aminocaproic acid is 0.1-1% of the mass addition amount of the caprolactam, and the addition amount of the water is 1-10% of the total mass of the materials in the high-temperature high-pressure reaction kettle.
According to the preparation method of the polyamide 6 modified high-strength high-toughness copolyamide, in the step (1), the whole reaction process is accompanied by stirring, and the stirring speed is 100-200 r/min.
The principle of the invention is as follows:
in the polyamide, hydrogen bonds can be formed among amide groups, and have larger cohesive energy, and the hydrogen bonds are main acting forces for maintaining the secondary structure of the polyamide and have larger influence on the tensile property of the polyamide. Polyamide 6 molecular chains are non-centrosymmetric, the anti-parallel adjacent molecular chains form most hydrogen bonds, and only half of the parallel adjacent molecular chains form bonds. The conventional even-numbered polyamide molecular chain carbonyl and amino can theoretically form a hydrogen bond structure, namely the maximum proportion of hydrogen bonds formed among molecules is 100%; at least 50% of carbonyl and amino of odd-carbon polyamide molecular chains do not form hydrogen bonds, so that the hydrogen bond density of the molecular chains is relatively low, the acting force among the molecules is small, the molecular chains are limited by the hydrogen bonds and are easy to rearrange in an external force stretching field, and the breaking elongation is higher. Meanwhile, the stable crystal form of the even-number carbon polyamide at normal temperature is an alpha crystal form, the stable crystal form of the odd-number carbon polyamide at normal temperature is a gamma crystal form, and compared with the alpha crystal form, the gamma crystal form has better toughness, and the existence of a large number of gamma crystal forms under large strain is beneficial to the improvement of elongation at break. The odd-carbon polyamide and the polyamide 6 belong to amides, and the compatibility can be better improved by introducing the modified monomer in a copolymerization mode, so that the problem of great strength reduction caused by heterogeneous strong interface action is avoided. When odd-carbon polyamide reacts with polyamide 6, the arrangement regularity of molecular chains is reduced, the formation of hydrogen bonds among the molecular chains is influenced, the density of the hydrogen bonds is greatly reduced, and the toughness of the polyamide 6 is improved.
Advantageous effects
(1) According to the polyamide 6 modified high-strength high-toughness copolyamide, the copolyamide prepared by taking odd-numbered carboxamide salt as a modifier has excellent toughness, the problem that the existing polyamide is difficult to modify, toughen and strengthen is solved, and the polyamide 6 has excellent strength while the toughness is greatly improved;
(2) According to the preparation method of the polyamide 6-modified high-strength high-toughness copolyamide, the modification component is added in the form of amide salt, so that the decomposition reaction of the reaction monomer due to overhigh temperature in the initial polymerization stage can be prevented, and the improvement of the polymerization degree can be ensured;
(3) The copolymerization technology can adjust the toughness and strength of the final copolyamide by regulating and controlling the parameters such as the addition amount of the odd-numbered monomer carboxamide salt, the polymerization time and the like, can be used for preparing the high-strength high-toughness copolyamide, can be applied to the requirements of different fields, and has strong operability and designability.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a polyamide prepared in example 3 and comparative example 1;
FIG. 2 is a thermogram of a polyamide 6-modified high-strength and high-toughness copolyamide prepared in example 3;
FIG. 3 shows the mechanical tensile curve of a polyamide 6-modified copolyamide of high strength and toughness obtained in example 3.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The test methods referred to in the examples and comparative examples are as follows:
method for measuring relative viscosity: the products of examples and comparative examples were dissolved in 96% sulfuric acid to prepare solutions having a concentration of 1.0g/dl, and tested with reference to GB/T12006.1-2009 plastics, part 1: viscosity determination Standard.
Test methods for tensile strength and elongation at break: the products of the examples and comparative examples were made into type 5A test specimens (75X 4X 2 mm), part 2 of the determination of tensile properties of plastics referred to GBT 1040.2-2006: test conditions for molded and extruded plastics were tested.
For the preparation of odd-numbered and even-numbered carboxamides in the following examples and comparative examples reference is made to the following documents:
[1] sequence distribution, crystallization behavior and reaction kinetics study of Tongjie nylon 6/66 in situ copolymer [ D ] university of east China Phytology, 2018.
[2] Preparation of transparent polyamide with odd number of carbon and performance study [ D ] university of college, 2016.
The molecular structural formula of the polyamide 6 modified high-strength high-toughness copolyamide prepared by the following examples is as follows:
wherein m ranges from 3 to 12, n ranges from 1 to 10, one of m and n is an odd number, the other is an even number, i =5, p represents the number of odd-numbered carbon polyamide structural units, q represents the number of polyamide 6 structural units, p: q =0.05 to 0.3.
Example 1
A preparation method of polyamide 6 modified high-strength high-toughness copolyamide comprises the following specific steps:
(1) Preparing raw materials;
caprolactam;
odd-numbered carboxamide salts: is PAXY salt prepared from 1, 5-pentanediamine and adipic acid in equal molar amount;
molecular weight regulator: adipic acid;
antioxidant: hindered phenol antioxidants 1098 (manufactured by Shandong Youso chemical science and technology Co., ltd.);
other auxiliary agents: water, aminocaproic acid;
(2) Adding caprolactam, odd-numbered carboxamide salt, molecular weight regulator, antioxidant and other auxiliary agents into a high-temperature high-pressure reaction kettle, removing air in the high-temperature high-pressure reaction kettle, heating to 220 ℃, reacting for 2 hours, continuously heating to 260 ℃, and continuously reacting for 2 hours under the condition that the pressure is 1.2 MPa; wherein the odd-numbered carboxamide salt is added into a high-temperature high-pressure reaction kettle in a form of dry salt, and the addition amount of the odd-numbered carboxamide salt accounts for 5 percent of the total molar amount of caprolactam and the odd-numbered carboxamide salt; the addition amount of the molecular weight regulator is 1 percent of the total mass of the materials in the high-temperature high-pressure reaction kettle; the addition amount of the antioxidant is 0.3 percent of the total mass of the materials in the high-temperature high-pressure reaction kettle; the addition amount of aminocaproic acid is 1% of the mass addition amount of caprolactam, and the addition amount of water is 1% of the total mass of materials in the high-temperature high-pressure reaction kettle; stirring is carried out along with the whole reaction process, and the stirring speed is 100r/min;
(3) The pressure is relieved to the normal pressure (namely 1 multiplied by 10) within 0.5h 5 Pa), removing water vapor in the high-temperature high-pressure reaction kettle, raising the temperature to 270 ℃ again, controlling the vacuumizing rate to ensure that the high-temperature high-pressure reaction kettle reaches a vacuum state within 0.5h, and continuously reacting for 2.5h under the condition that the vacuum degree is 100Pa to obtain the polyamide 6 modified high-strength high-toughness copolyamide.
The prepared polyamide 6 modified high-strength high-toughness copolyamide has the tensile strength of 70MPa, the elongation at break of 280 percent and the relative viscosity of 2.8.
Example 2
A preparation method of polyamide 6 modified high-strength high-toughness copolyamide comprises the following specific steps:
(1) Preparing raw materials;
caprolactam;
odd-numbered carboxamide salts: is PAXY salt prepared from 1, 5-pentanediamine and adipic acid in equal molar amount;
molecular weight regulator: adipic acid;
antioxidant: hindered phenol antioxidants 1098 (manufactured by Shandong Youso chemical science and technology Co., ltd.);
other auxiliary agents: water, aminocaproic acid;
(2) Adding caprolactam, odd-numbered carboxamide salt, molecular weight regulator, antioxidant and other auxiliary agents into a high-temperature high-pressure reaction kettle, removing air in the high-temperature high-pressure reaction kettle, heating to 200 ℃, reacting for 2 hours, continuously heating to 260 ℃, and continuously reacting for 2 hours under the condition that the pressure is 1.3 MPa; wherein the odd-numbered carboxamide salt is added into a high-temperature high-pressure reaction kettle in a form of dry salt, and the addition amount of the odd-numbered carboxamide salt accounts for 10 percent of the total molar weight of caprolactam and the odd-numbered carboxamide salt; the addition amount of the molecular weight regulator is 2 percent of the total mass of the materials in the high-temperature high-pressure reaction kettle; the addition amount of the antioxidant is 0.2 percent of the total mass of the materials in the high-temperature high-pressure reaction kettle; the addition amount of aminocaproic acid is 1% of the mass addition amount of caprolactam, and the addition amount of water is 5% of the total mass of materials in the high-temperature high-pressure reaction kettle; stirring is carried out along with the whole reaction process, and the stirring speed is 100r/min;
(3) The pressure is relieved to the normal pressure (namely 1 multiplied by 10) within 0.5h 5 Pa), removing water vapor in the high-temperature high-pressure reaction kettle, raising the temperature to 270 ℃ again, controlling the vacuumizing rate to enable the high-temperature high-pressure reaction kettle to reach a vacuum state within 0.5h, and continuously reacting for 3h under the condition that the vacuum degree is 50Pa to obtain the polyamide 6 modified high-strength high-toughness copolyamide.
The prepared polyamide 6 modified high-strength high-toughness copolyamide has the tensile strength of 64MPa, the elongation at break of 450 percent and the relative viscosity of 3.0.
Example 3
A preparation method of polyamide 6 modified high-strength high-toughness copolyamide comprises the following specific steps:
(1) Preparing raw materials;
caprolactam;
odd-numbered carboxamide salts: is a PAXY salt prepared from equimolar amounts of 1, 5-pentanediamine and adipic acid;
molecular weight regulator: adipic acid;
antioxidant: a mixture of a hindered phenol antioxidant 1010 (manufactured by Shandong Youso chemical science and technology Co., ltd.) and a phosphite antioxidant 168 (manufactured by Shandong Youso chemical science and technology Co., ltd.) in a mass ratio of 1;
other auxiliary agents: water, aminocaproic acid;
(2) Adding caprolactam, odd-numbered carboxamide salt, molecular weight regulator, antioxidant and other auxiliary agents into a high-temperature high-pressure reaction kettle, removing air in the high-temperature high-pressure reaction kettle, heating to 190 ℃, reacting for 2 hours, continuously heating to 260 ℃, and continuously reacting for 2 hours under the condition that the pressure is 1.4 MPa; wherein the odd-numbered carboxamide salt is added into a high-temperature high-pressure reaction kettle in a form of dry salt, and the addition amount of the odd-numbered carboxamide salt accounts for 20 percent of the total molar amount of caprolactam and the odd-numbered carboxamide salt; the addition amount of the molecular weight regulator is 2 percent of the total mass of the materials in the high-temperature high-pressure reaction kettle; the addition amount of the antioxidant is 0.3 percent of the total mass of the materials in the high-temperature high-pressure reaction kettle; the addition amount of aminocaproic acid is 1% of the addition amount of caprolactam by mass, and the addition amount of water is 8% of the total mass of materials in the high-temperature high-pressure reaction kettle; stirring is carried out along with the whole reaction process, and the stirring speed is 100r/min;
(3) The pressure is relieved to the normal pressure within 1h (namely 1X 10) 5 Pa), removing water vapor in the high-temperature high-pressure reaction kettle, raising the temperature to 270 ℃ again, controlling the vacuumizing rate to enable the high-temperature high-pressure reaction kettle to reach a vacuum state within 1h, and continuously reacting for 1.5h under the condition that the vacuum degree is 100Pa to obtain the polyamide 6 modified high-strength high-toughness copolyamide.
As shown in the figure3, the prepared polyamide 6 modified high-strength and high-toughness copolyamide has the tensile strength of 58MPa, the elongation at break of 580 percent and the relative viscosity of 2.5; as shown in figure 2, the initial decomposition temperature T of the polyamide 6 modified high-strength high-toughness copolyamide is obtained d5％ About 390.8 ℃, therefore, the copolyamide prepared by adding the odd-numbered carboxamide salt has good thermal stability and can meet the subsequent processing requirements.
Comparative example 1
A process for producing polyamide 6, which is substantially the same as in example 3, except that no odd-numbered carboxamide salt is prepared in step (1) and no odd-numbered carboxamide salt is added in step (2).
The resulting polyamide 6 had a tensile strength of 75MPa, an elongation at break of 130% and a relative viscosity of 2.6.
Compared with example 3, comparative example 1 has a low elongation at break because of the strong crystallization ability of the PA6 due to the existence of the repeat amide group, the high proportion of hydrogen bonds between molecular chains, and the close arrangement of molecular chains in the crystal region, thus showing strong mechanical strength and low toughness.
As shown in fig. 1, comparative example 1 is pure polyamide 6, which exhibits proton signals at 3.83, 3.01, 2.07, 2.01, and 1.75 ppm; with the introduction of odd numbered carboxamide salt fragments into polyamide 6, the new characteristic peaks in example 3 appeared at 3.05, 2.13 and 1.71ppm, which correspond to the carboxyl groups in odd numbered polyamide fragments (NHCOCH), respectively 2 ) Alpha-methylene proton of (2), beta-position of amine group (CH) 2 CH 2 NHCO) and gamma (CH) 2 CH 2 CH 2 NHCO) chemical shift of the methylene proton, from which it was known that odd numbered carboxamide salt fragments were successfully introduced into the PA6 backbone.
Comparative example 2
A process for the preparation of a copolyamide substantially as in example 3, except that in step (1) the odd-numbered carboxamide salt is replaced by the even-numbered carboxamide salt PA66 salt, and in step (2) the even-numbered carboxamide salt PA66 salt is added instead of the odd-numbered carboxamide salt.
The resulting copolyamide had a tensile strength of 40MPa, an elongation at break of 525% and a relative viscosity of 2.4.
Compared with example 3, comparative example 2 has lower levels of elongation at break and tensile strength than example 3 because theoretically the maximum ratio of hydrogen bonds formed between even-numbered carbon polyamide molecules is 100%, and at least 50% of carbonyl groups and amino groups between odd-numbered carbon polyamide molecules do not form hydrogen bonds, so that the molecular chain hydrogen bond density is relatively low, and when the added molar amounts are equal, the copolyamide prepared from the odd-numbered carbon polyamide has poor structural regularity, weaker intermolecular forces, and molecular chains in an external force tensile field are more easily rearranged, thereby obtaining higher toughness.
Example 4
A preparation method of polyamide 6 modified high-strength high-toughness copolyamide comprises the following specific steps:
(1) Preparing raw materials;
caprolactam;
odd-numbered carboxamide salts: is PAXY salt prepared from 1, 5-pentanediamine and adipic acid in equal molar amount;
molecular weight regulator: adipic acid;
antioxidant: a mixture of a hindered phenol antioxidant 1010 (manufactured by Shandong Youso chemical science and technology Co., ltd.) and a phosphite antioxidant 168 (manufactured by Shandong Youso chemical science and technology Co., ltd.) in a mass ratio of 1;
other auxiliary agents: water, aminocaproic acid;
(2) Adding caprolactam, odd-numbered carboxamide salt, molecular weight regulator, antioxidant and other auxiliary agents into a high-temperature high-pressure reaction kettle, removing air in the high-temperature high-pressure reaction kettle, heating to 180 ℃, reacting for 2 hours, then continuously heating to 260 ℃, and continuously reacting for 2 hours under the condition that the pressure is 1.5 MPa; wherein the odd-numbered carboxamide salt is added into a high-temperature high-pressure reaction kettle in a form of dry salt, and the addition amount of the odd-numbered carboxamide salt accounts for 30 percent of the total molar weight of caprolactam and the odd-numbered carboxamide salt; the addition amount of the molecular weight regulator is 1 percent of the total mass of the materials in the high-temperature high-pressure reaction kettle; the addition amount of the antioxidant is 0.4 percent of the total mass of the materials in the high-temperature high-pressure reaction kettle; the addition amount of aminocaproic acid is 1% of the mass addition amount of caprolactam, and the addition amount of water is 8% of the total mass of materials in the high-temperature high-pressure reaction kettle; stirring is carried out along with the whole reaction process, and the stirring speed is 100r/min;
(3) The pressure is relieved to the normal pressure within 1h (namely 1 multiplied by 10) 5 Pa), removing water vapor in the high-temperature high-pressure reaction kettle, raising the temperature to 260 ℃ again, controlling the vacuumizing rate to enable the high-temperature high-pressure reaction kettle to reach a vacuum state within 1h, and continuously reacting for 1.5h under the condition that the vacuum degree is 200Pa to obtain the polyamide 6 modified high-strength high-toughness copolyamide.
The prepared polyamide 6 modified high-strength high-toughness copolyamide has the tensile strength of 44MPa, the elongation at break of 820% and the relative viscosity of 2.5.
Example 5
A preparation method of polyamide 6 modified high-strength high-toughness copolyamide comprises the following specific steps:
(1) Preparing raw materials;
caprolactam;
odd-numbered carboxamide salts: is PAXY salt prepared from 1, 3-propane diamine and adipic acid in equal molar amount;
molecular weight regulator: adipic acid;
antioxidant: a mixture of hindered phenol antioxidant 1010 (manufactured by Shandong Yousio chemical science and technology Co., ltd.) and thioester antioxidant DLTP (manufactured by Shandong Yousio chemical science and technology Co., ltd.) in a mass ratio of 2;
other auxiliary agents: water, aminocaproic acid;
(2) Adding caprolactam, odd-numbered carboxamide salt, molecular weight regulator, antioxidant and other auxiliary agents into a high-temperature high-pressure reaction kettle, removing air in the high-temperature high-pressure reaction kettle, heating to 190 ℃, reacting for 1 hour, continuously heating to 260 ℃, and continuously reacting for 1.5 hours under the condition that the pressure is 1.4 MPa; wherein the odd-numbered carboxamide salt is added into a high-temperature high-pressure reaction kettle in a form of dry salt, and the addition amount of the odd-numbered carboxamide salt accounts for 20 percent of the total molar amount of caprolactam and the odd-numbered carboxamide salt; the addition amount of the molecular weight regulator is 2 percent of the total mass of the materials in the high-temperature high-pressure reaction kettle; the addition amount of the antioxidant is 0.5 percent of the total mass of the materials in the high-temperature high-pressure reaction kettle; the addition amount of the aminocaproic acid is 0.5 percent of the mass addition amount of the caprolactam, and the addition amount of the water is 5 percent of the total mass of the materials in the high-temperature high-pressure reaction kettle; stirring is carried out along with the whole reaction process, and the stirring speed is 200r/min;
(3) The pressure is relieved to the normal pressure within 1h (namely 1X 10) 5 Pa), removing water vapor in the high-temperature high-pressure reaction kettle, raising the temperature to 280 ℃ again, controlling the vacuumizing rate to ensure that the high-temperature high-pressure reaction kettle reaches a vacuum state within 1h, and continuously reacting for 1h under the condition that the vacuum degree is 100Pa to obtain the polyamide 6 modified high-strength high-toughness copolyamide.
The prepared polyamide 6 modified high-strength high-toughness copolyamide has the tensile strength of 56MPa, the elongation at break of 300 percent and the relative viscosity of 2.4.
Example 6
A preparation method of polyamide 6 modified high-strength high-toughness copolyamide comprises the following specific steps:
(1) Preparing raw materials;
caprolactam;
odd-numbered carboxamide salts: is PAXY salt prepared from 1, 3-propane diamine and sebacic acid in equal molar amount;
molecular weight regulator: adipic acid;
antioxidant: a mixture of hindered phenol antioxidant 1010 (manufactured by Shandong Yousio chemical science and technology Co., ltd.) and thioester antioxidant DLTP (manufactured by Shandong Yousio chemical science and technology Co., ltd.) in a mass ratio of 2;
other auxiliary agents: water, aminocaproic acid;
(2) Adding caprolactam, odd-numbered carboxamide salt, molecular weight regulator, antioxidant and other auxiliary agents into a high-temperature high-pressure reaction kettle, removing air in the high-temperature high-pressure reaction kettle, heating to 180 ℃, reacting for 1 hour, continuously heating to 260 ℃, and continuously reacting for 1.5 hours under the condition that the pressure is 1.4 MPa; wherein the odd-numbered carboxamide salt is added into a high-temperature high-pressure reaction kettle in a form of dry salt, and the addition amount of the odd-numbered carboxamide salt accounts for 20 percent of the total molar amount of caprolactam and the odd-numbered carboxamide salt; the addition amount of the molecular weight regulator is 2 percent of the total mass of the materials in the high-temperature high-pressure reaction kettle; the addition amount of the antioxidant is 0.5 percent of the total mass of the materials in the high-temperature high-pressure reaction kettle; the addition amount of aminocaproic acid is 0.5 percent of the mass addition amount of caprolactam, and the addition amount of water is 5 percent of the total mass of materials in the high-temperature high-pressure reaction kettle; stirring is carried out along with the whole reaction process, and the stirring speed is 200r/min;
(3) The pressure is relieved to the normal pressure within 1h (namely 1 multiplied by 10) 5 Pa), removing water vapor in the high-temperature high-pressure reaction kettle, heating to 260 ℃ again, controlling the vacuumizing rate to ensure that the high-temperature high-pressure reaction kettle reaches a vacuum state within 1h, and continuously reacting for 1h under the condition that the vacuum degree is 300Pa to obtain the polyamide 6 modified high-strength high-toughness copolyamide.
The prepared polyamide 6 modified high-strength high-toughness copolyamide has the tensile strength of 46MPa, the elongation at break of 550% and the relative viscosity of 2.5.
Example 7
A preparation method of polyamide 6 modified high-strength high-toughness copolyamide comprises the following specific steps:
(1) Preparing raw materials;
caprolactam;
odd-numbered carboxamide salts: is PAXY salt prepared from equimolar amounts of 1, 5-pentanediamine and sebacic acid;
molecular weight regulator: adipic acid;
antioxidant: a mixture of hindered phenol antioxidant 1098 (made by Shandong Yousio chemical Co., ltd.) and phosphite antioxidant 168 (made by Shandong Yousio chemical Co., ltd.) in a mass ratio of 1;
other auxiliary agents: water, aminocaproic acid;
(2) Adding caprolactam, odd-numbered carboxamide salt, molecular weight regulator, antioxidant and other auxiliary agents into a high-temperature high-pressure reaction kettle, removing air in the high-temperature high-pressure reaction kettle, heating to 180 ℃, reacting for 1h, continuously heating to 240 ℃, and continuously reacting for 1h under the condition that the pressure is 1.3 MPa; wherein the odd-numbered carboxamide salt is added into a high-temperature high-pressure reaction kettle in a form of dry salt, and the addition amount of the odd-numbered carboxamide salt accounts for 20 percent of the total molar amount of caprolactam and the odd-numbered carboxamide salt; the addition amount of the molecular weight regulator is 1 percent of the total mass of the materials in the high-temperature high-pressure reaction kettle; the addition amount of the antioxidant is 0.3 percent of the total mass of the materials in the high-temperature high-pressure reaction kettle; the addition amount of the aminocaproic acid is 0.4 percent of the mass addition amount of the caprolactam, and the addition amount of the water is 5 percent of the total mass of the materials in the high-temperature high-pressure reaction kettle; stirring is carried out along with the whole reaction process, and the stirring speed is 200r/min;
(3) The pressure is relieved to the normal pressure (namely 1 multiplied by 10) within 0.5h 5 Pa), removing water vapor in the high-temperature high-pressure reaction kettle, raising the temperature to 260 ℃ again, controlling the vacuumizing rate to enable the high-temperature high-pressure reaction kettle to reach a vacuum state within 0.5h, and continuously reacting for 2h under the condition that the vacuum degree is 500Pa to obtain the polyamide 6 modified high-strength high-toughness copolyamide.
The prepared polyamide 6 modified high-strength high-toughness copolyamide has the tensile strength of 42MPa, the elongation at break of 630 percent and the relative viscosity of 2.6.
Example 8
A preparation method of polyamide 6 modified high-strength high-toughness copolyamide comprises the following specific steps:
(1) Preparing raw materials;
caprolactam;
odd-numbered carboxamide salts: as a PAXY salt, from equimolar amounts of 1, 5-pentanediamine and dodecanedioic acid;
molecular weight regulator: acetic acid;
antioxidant: a mixture of a hindered phenol antioxidant 1098 (manufactured by Shandong Youso chemical science and technology Co., ltd.) and a phosphite antioxidant 168 (manufactured by Shandong Youso chemical science and technology Co., ltd.) in a mass ratio of 1;
other auxiliary agents: water, aminocaproic acid;
(2) Adding caprolactam, odd-numbered carboxamide salt, molecular weight regulator, antioxidant and other auxiliary agents into a high-temperature high-pressure reaction kettle, removing air in the high-temperature high-pressure reaction kettle, heating to 170 ℃, reacting for 1 hour, continuously heating to 240 ℃, and continuously reacting for 1 hour under the condition that the pressure is 1.5 MPa; wherein the odd-numbered carboxamide salt is added into a high-temperature high-pressure reaction kettle in a form of dry salt, and the addition amount of the odd-numbered carboxamide salt accounts for 20 percent of the total molar amount of caprolactam and the odd-numbered carboxamide salt; the addition amount of the molecular weight regulator is 1 percent of the total mass of the materials in the high-temperature high-pressure reaction kettle; the addition amount of the antioxidant is 0.3 percent of the total mass of the materials in the high-temperature high-pressure reaction kettle; the addition amount of aminocaproic acid is 0.3 percent of the mass addition amount of caprolactam, and the addition amount of water is 5 percent of the total mass of materials in the high-temperature high-pressure reaction kettle; stirring is carried out along with the whole reaction process, and the stirring speed is 200r/min;
(3) The pressure is relieved to the normal pressure (namely 1 multiplied by 10) within 0.5h 5 Pa), removing water vapor in the high-temperature high-pressure reaction kettle, raising the temperature to 260 ℃ again, controlling the vacuumizing rate to ensure that the high-temperature high-pressure reaction kettle reaches a vacuum state within 0.5h, and continuously reacting for 2h under the condition that the vacuum degree is 300Pa to obtain the polyamide 6 modified high-strength high-toughness copolyamide.
The prepared polyamide 6 modified high-strength high-toughness copolyamide has the tensile strength of 41MPa, the elongation at break of 800 percent and the relative viscosity of 2.6.
Example 9
A preparation method of polyamide 6 modified high-strength high-toughness copolyamide comprises the following specific steps:
(1) Preparing raw materials;
caprolactam;
odd-numbered carboxamide salts: as a PAXY salt, from equimolar amounts of 1, 12-diaminododecane and undecanedioic acid;
molecular weight regulator: acetic acid;
antioxidant: a mixture of hindered phenol antioxidant 1010 (made by Shandong Youso chemical science and technology Co., ltd.) and phosphite antioxidant 168 (made by Shandong Youso chemical science and technology Co., ltd.) in a mass ratio of 2;
other auxiliary agents: water, aminocaproic acid;
(2) Adding caprolactam, odd-numbered carboxamide salt, molecular weight regulator, antioxidant and other auxiliary agents into a high-temperature high-pressure reaction kettle, removing air in the high-temperature high-pressure reaction kettle, heating to 150 ℃, reacting for 1h, continuously heating to 220 ℃, and continuously reacting for 1h under the condition that the pressure is 1.5 MPa; wherein the odd-numbered carboxamide salt is added into a high-temperature high-pressure reaction kettle in a form of dry salt, and the addition amount of the odd-numbered carboxamide salt accounts for 20 percent of the total molar amount of caprolactam and the odd-numbered carboxamide salt; the addition amount of the molecular weight regulator is 3 percent of the total mass of the materials in the high-temperature high-pressure reaction kettle; the addition amount of the antioxidant is 0.5 percent of the total mass of the materials in the high-temperature high-pressure reaction kettle; the addition amount of the aminocaproic acid is 0.1 percent of the mass addition amount of the caprolactam, and the addition amount of the water is 10 percent of the total mass of the materials in the high-temperature high-pressure reaction kettle; stirring is carried out along with the whole reaction process, and the stirring speed is 200r/min;
(3) The pressure is relieved to the normal pressure (namely 1 multiplied by 10) within 0.5h 5 Pa), removing water vapor in the high-temperature high-pressure reaction kettle, raising the temperature to 240 ℃ again, controlling the vacuumizing rate to ensure that the high-temperature high-pressure reaction kettle reaches a vacuum state within 0.5h, and continuously reacting for 2.5h under the condition that the vacuum degree is 200Pa to obtain the polyamide 6 modified high-strength high-toughness copolyamide.
The prepared polyamide 6 modified high-strength high-toughness copolyamide has the tensile strength of 45MPa, the elongation at break of 980% and the relative viscosity of 2.8.
Example 10
A preparation method of polyamide 6 modified high-strength high-toughness copolyamide, which is basically the same as that in example 1, except that in step (2), odd-numbered carboxamide salt is added into a warm-high pressure reaction kettle in the form of solution, specifically, aqueous solution of odd-numbered carboxamide salt with the concentration of 55wt% (at this time, the addition amount of water in step (2) refers to the total amount of water in the aqueous solution of odd-numbered carboxamide salt and water in other auxiliary agents);
the relative viscosity of the prepared polyamide 6 modified high-strength high-toughness copolyamide is 2.2.
Compared with example 1, the relative viscosity of the high-strength and high-toughness copolyamide of example 10 is relatively low, because example 1 can obtain higher polymerization degree by taking part in the copolymerization reaction in the form of dry salt, which is beneficial to obtaining high-molecular-weight copolyamide, while example 10 needs to discharge excessive water in the system when salt solution is used for carrying out the post-polycondensation, and the forward progress of the polymerization reaction is influenced by the excessive water content, and the growth of the molecular chain of the copolyamide is limited.
Example 11
A process for the preparation of a polyamide 6-based modified copolyamide of high strength and toughness which is essentially the same as that of example 1, except that the odd-numbered carboxamide salt is a PAXY salt, prepared from equimolar amounts of 1, 6-hexanediamine and azelaic acid.
The prepared polyamide 6 modified high-strength high-toughness copolyamide has the tensile strength of 66MPa, the elongation at break of 310 percent and the relative viscosity of 2.7.
Example 12
A process for the preparation of a polyamide 6-based modified copolyamide of high strength and toughness which is essentially the same as in example 1, except that the odd-numbered carboxamide salt is a PAXY salt, prepared from equimolar amounts of 1, 7-heptanediamine and succinic acid.
The prepared polyamide 6 modified high-strength high-toughness copolyamide has the tensile strength of 68MPa, the elongation at break of 250% and the relative viscosity of 2.6.
Example 13
A process for the preparation of a polyamide 6-based modified copolyamide of high strength and toughness which is essentially the same as that of example 1, except that the odd-numbered carboxamide salt is a PAXY salt, prepared from equimolar amounts of 1, 8-octanediamine and undecanedioic acid.
The prepared polyamide 6 modified high-strength high-toughness copolyamide has the tensile strength of 62MPa, the elongation at break of 330 percent and the relative viscosity of 2.5.
Example 14
A process for the preparation of a polyamide 6-based modified copolyamide of high strength and toughness, which is essentially the same as in example 1, except that the odd-numbered carboxamide salt is a PAXY salt, prepared from equimolar amounts of 1, 9-diaminononane and dodecanedioic acid.
The prepared polyamide 6 modified high-strength high-toughness copolyamide has the tensile strength of 60MPa, the elongation at break of 370 percent and the relative viscosity of 2.4.
Claims (10)
1. The polyamide 6 modified high-strength high-toughness copolyamide is characterized by having the following molecular structural formula:
wherein m ranges from 3 to 12, n ranges from 1 to 10, one of m and n is odd number, the other is even number, i =5, p represents the number of odd number carboxamide salt structural units, q represents the number of polyamide 6 structural units, p is q = 0.05-0.3;
the polyamide 6 modified high-strength and high-toughness copolyamide has the tensile strength of 40-70 MPa and the elongation at break of 200-1000%.
2. The polyamide 6-based modified high-strength high-toughness copolyamide according to claim 1, wherein the polyamide 6-based modified high-strength high-toughness copolyamide has a relative viscosity of 2.2-3.0.
3. A preparation method of polyamide 6 modified high-strength high-toughness copolyamide is characterized in that during the reaction process of preparing polyamide 6 from caprolactam, odd-numbered amide salt is added into the caprolactam before the reaction starts or in the initial stage of the reaction, and the polyamide 6 modified high-strength high-toughness copolyamide is obtained after the reaction is finished; the amount of odd-numbered carboxamide salt added is 5-30% of the total molar amount of caprolactam and odd-numbered carboxamide salt.
4. The method for preparing polyamide 6 modified high-strength high-toughness copolyamide according to claim 3, wherein the odd-numbered carboxamide salt is added in the form of a dry salt.
5. The method for preparing polyamide 6-modified high-strength high-toughness copolyamide according to claim 3, wherein the odd-numbered carboxamide salt is a PAXY salt prepared from equimolar amounts of X and Y, wherein X is α, ω -diamine and Y is an aliphatic dibasic acid, and when α, ω -diamine is an odd-numbered diamine, the aliphatic dibasic acid is an even-numbered carbon; when the alpha, omega-diamine is an even number of carbons, then the aliphatic diacid is an odd number of carbons.
6. The process for preparing polyamide 6-modified high-strength high-toughness copolyamides according to claim 5, wherein the α, ω -diamine is 1, 3-propanediamine, 1, 4-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine, 1, 7-heptanediamine, 1, 8-octanediamine, 1, 9-diaminononane, 1, 10-decanediamine, 1, 11-undecanediamine or 1, 12-diaminododecane; the aliphatic dibasic acid is succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid or dodecanedioic acid.
7. The preparation method of polyamide 6-modified high-strength high-toughness copolyamide according to claim 3 is characterized by comprising the following steps:
(1) Adding caprolactam, odd-numbered carboxamide salt, molecular weight regulator, antioxidant and other auxiliary agents into a high-temperature high-pressure reaction kettle, removing air in the high-temperature high-pressure reaction kettle, slowly heating to 150-220 ℃, reacting for 1-2 h, continuously heating to 220-260 ℃, and continuously reacting for 1-2 h under the pressure of 1.0-1.5 MPa;
(2) And (3) relieving the pressure to normal pressure within 0.5-1 h, removing water vapor in the high-temperature high-pressure reaction kettle, raising the temperature to 240-280 ℃ again, controlling the vacuumizing rate to ensure that the high-temperature high-pressure reaction kettle reaches a vacuum state within 0.5-1 h, and continuously reacting for 1-3 h under the condition that the vacuum degree is 50-500 Pa to obtain the polyamide 6 modified high-strength high-toughness copolyamide.
8. The preparation method of polyamide 6 modified high-strength high-toughness copolyamide according to claim 7, wherein the molecular weight regulator is a monobasic acid or a dibasic acid; the antioxidant is a hindered phenol antioxidant or a mixture of the hindered phenol antioxidant and other antioxidants, and the other antioxidants are phosphite antioxidants or thioester antioxidants; other adjuvants are water and aminocaproic acid.
9. The method for preparing polyamide 6 modified high-strength high-toughness copolyamide according to claim 8, wherein the addition amount of the molecular weight regulator is 1-3% of the total mass of the materials in the high-temperature high-pressure reaction kettle; the addition amount of the antioxidant is 0.2-0.5% of the total mass of the materials in the high-temperature high-pressure reaction kettle; the addition amount of the aminocaproic acid is 0.1-1% of the mass addition amount of the caprolactam, and the addition amount of the water is 1-10% of the total mass of the materials in the high-temperature high-pressure reaction kettle.
10. The method for preparing polyamide 6-modified high-strength high-toughness copolyamide according to claim 7, wherein in the step (1), stirring is carried out during the whole reaction process, and the stirring speed is 100-200 r/min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024166916A1 (en) * | 2023-02-08 | 2024-08-15 | 株式会社クラレ | Artificial leather base material, and artificial leather base material manufacturing method |
| WO2024166917A1 (en) * | 2023-02-08 | 2024-08-15 | 株式会社クラレ | Artificial leather base material, and method for producing artificial leather base material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE20211531U1 (en) * | 2002-07-13 | 2002-09-12 | Orbita-Film GmbH, 06369 Weißandt-Gölzau | Vapor barrier film with increased elongation at break in the longitudinal and transverse directions and variable water vapor permeability |
| CN106519219A (en) * | 2016-11-15 | 2017-03-22 | 中国纺织科学研究院 | Continuous polymerization process for PA6-5X copolymer, and PA6-5X copolymer |
| CN107915846A (en) * | 2017-11-22 | 2018-04-17 | 中国科学院化学研究所 | A kind of polyamide copolymer and preparation method and application |
| CN108250433A (en) * | 2017-12-19 | 2018-07-06 | 浙江恒逸锦纶有限公司 | A kind of PA6-56 copolymeric materials and preparation method thereof |
-
2022
- 2022-09-06 CN CN202211082421.4A patent/CN115322366A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE20211531U1 (en) * | 2002-07-13 | 2002-09-12 | Orbita-Film GmbH, 06369 Weißandt-Gölzau | Vapor barrier film with increased elongation at break in the longitudinal and transverse directions and variable water vapor permeability |
| CN106519219A (en) * | 2016-11-15 | 2017-03-22 | 中国纺织科学研究院 | Continuous polymerization process for PA6-5X copolymer, and PA6-5X copolymer |
| CN107915846A (en) * | 2017-11-22 | 2018-04-17 | 中国科学院化学研究所 | A kind of polyamide copolymer and preparation method and application |
| CN108250433A (en) * | 2017-12-19 | 2018-07-06 | 浙江恒逸锦纶有限公司 | A kind of PA6-56 copolymeric materials and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| P. SCARFATO ET AL.,: "Influence of co-monomer structure on properties of co-polyamide packaging films", PACKAGING TECHNOLOGY AND SCIENCE, vol. 15, no. 1, pages 9 - 16, XP002660836, DOI: 10.1002/pts.561 * |
| 海市纺织工业局七.二一工人大学: "锦纶生产工艺", 30 June 1977, 上海人民出版社出版, pages: 34 * |
| 韦军: "高分子合成工艺学", 28 February 2011, 上海：华东理工大学出版社, pages: 376 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024166916A1 (en) * | 2023-02-08 | 2024-08-15 | 株式会社クラレ | Artificial leather base material, and artificial leather base material manufacturing method |
| WO2024166917A1 (en) * | 2023-02-08 | 2024-08-15 | 株式会社クラレ | Artificial leather base material, and method for producing artificial leather base material |
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