CN116535639A - Novel PA6 polyamide thermoplastic elastomer and preparation method and application thereof - Google Patents
Novel PA6 polyamide thermoplastic elastomer and preparation method and application thereof Download PDFInfo
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- CN116535639A CN116535639A CN202310407715.8A CN202310407715A CN116535639A CN 116535639 A CN116535639 A CN 116535639A CN 202310407715 A CN202310407715 A CN 202310407715A CN 116535639 A CN116535639 A CN 116535639A
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- thermoplastic elastomer
- polyamide thermoplastic
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- caprolactam
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- 229920006345 thermoplastic polyamide Polymers 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 90
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 23
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 23
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 37
- 229920000570 polyether Polymers 0.000 claims description 37
- 150000001412 amines Chemical class 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 9
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 6
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 claims description 6
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims 1
- 239000004677 Nylon Substances 0.000 abstract description 15
- 229920001778 nylon Polymers 0.000 abstract description 15
- 238000007142 ring opening reaction Methods 0.000 abstract description 15
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 4
- 238000009833 condensation Methods 0.000 abstract description 3
- 230000005494 condensation Effects 0.000 abstract description 3
- 238000002834 transmittance Methods 0.000 abstract description 2
- 229920001971 elastomer Polymers 0.000 description 31
- 239000000806 elastomer Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 22
- 238000012360 testing method Methods 0.000 description 9
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical group NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- -1 small molecule diamine Chemical class 0.000 description 2
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08G69/40—Polyamides containing oxygen in the form of ether groups
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
- A43B1/0009—Footwear characterised by the material made at least partially of alveolar or honeycomb material
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
- A43B1/14—Footwear characterised by the material made of plastics
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polyamides (AREA)
Abstract
The invention discloses a novel PA6 polyamide thermoplastic elastomer, a preparation method and application thereof, wherein the preparation method is to carry out ring opening reaction on caprolactam and long-chain dibasic acid to form carboxylic acid end capped nylon prepolymer, and then to carry out condensation with polyetheramine to form the novel PA6 polyamide thermoplastic elastomer. Wherein the ring opening of the caprolactam is thorough, and the formed prepolymer can be subjected to polycondensation reaction with polyetheramine to form the PA6 polyamide thermoplastic elastomer with larger molecular weight and transparency, and good mechanical properties are maintained. The prepared PA6 polyamide thermoplastic elastomer has good elasticity, transmittance of more than 90%, lower water absorption and higher hydrophobicity, and can be widely applied to products such as films, sheets, shoes and the like.
Description
Technical Field
The invention belongs to the technical field of polyamide, and particularly relates to a preparation method and application of a novel PA6 polyamide thermoplastic elastomer.
Background
PA6 is a high molecular compound polymerized by caprolactam, and has excellent properties of toughness, wear resistance, impact resistance, fatigue resistance, corrosion resistance, oil resistance and the like. In order to enhance the performance of PA6, the prior art has incorporated polyamide with polyether to form polyamide thermoplastic elastomer molecular chains formed by the incorporation of hard blocks comprised of polyamide and soft blocks comprised of polyether. The original performance of the PA6 is maintained, and meanwhile, the service performance of the PA6 is improved.
The prior method for preparing the polyamide thermoplastic elastomer is to directly mix caprolactam with dibasic acid and polyether and carry out one-step hydrolysis reaction under the action of a ring-opening agent, which leads to the defect that polyether is easily coated by PA6 formed by the caprolactam and is difficult to be combined together in a block form, thereby causing the performance of the polyamide thermoplastic elastomer. The caprolactam is subjected to ring opening under a ring opening agent, and the residual ring opening agent can cause the performance reduction of the polyamide thermoplastic elastomer; meanwhile, the product transparency caused by incomplete ring opening is too low, which also affects the application of the polyamide thermoplastic elastomer. It is thus a current problem how to achieve a more efficient and high quality preparation of polyamide thermoplastic elastomers.
Disclosure of Invention
In order to overcome the defects of the prior art, the first aim of the invention is to provide a novel preparation method of PA6 polyamide thermoplastic elastomer, wherein caprolactam is firstly subjected to thorough ring opening and binary acid to form carboxylic acid end-capped nylon prepolymer, and then is condensed with polyetheramine, so that the formed PA6 has larger molecular weight and transparency, and good mechanical properties are maintained.
The second object of the invention is to provide a novel PA6 polyamide thermoplastic elastomer, which is prepared by the preparation method of the novel PA6 polyamide thermoplastic elastomer.
A third object of the present invention is to provide the use of a novel PA6 polyamide thermoplastic elastomer.
One of the purposes of the invention can be achieved by adopting the following technical scheme:
a method for preparing a novel PA6 polyamide thermoplastic elastomer, comprising the following steps:
and (3) carrying out a prepolymerization reaction on caprolactam and long-chain dibasic acid to obtain a prepolymerization product, and carrying out a polycondensation reaction on the prepolymerization product and polyetheramine to obtain the novel PA6 polyamide thermoplastic elastomer.
Further, the long-chain dibasic acid is one or a combination of more than two of sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid or tetradecanedioic acid.
Further, the polyether amine is one or a combination of more than two of polyethylene glycol polyether amine, polypropylene glycol polyether amine or polytetramethylene ether glycol polyether amine; the molecular weight of the polyether amine is 230-2000g/mol.
Further, the reaction condition of the prepolymerization reaction is that the reaction is carried out for 1 to 3 hours under the pressure of 0.5 to 2MPa and the temperature of 245 to 270 ℃.
Further, water accounting for 0.0 to 3 percent of the mass of the caprolactam is added into the prepolymerization reaction raw material.
Further, before the pre-polymerization product and polyetheramine are subjected to polycondensation reaction, the pre-polymerization product is subjected to drainage treatment; the polycondensation reaction is carried out for 2-6h under the condition that the absolute pressure is 0-5KPa and the temperature is 220-235 ℃.
Further, the addition amount of the caprolactam is 30% -55% of the mass of the PA6 polyamide thermoplastic elastomer; the molar weight ratio of the long-chain dibasic acid to the polyetheramine is 1: (0.95-1.05).
The second aim of the invention can be achieved by adopting the following technical scheme:
a novel PA6 polyamide thermoplastic elastomer is prepared by the preparation method of any one of the novel PA6 polyamide thermoplastic elastomers.
Further, the polyether amine soft segment accounts for 35 to 60 percent of the total mass of the PA6 polyamide thermoplastic elastomer, and the PA6 hard segment accounts for 30 to 55 percent of the total mass of the PA6 polyamide thermoplastic elastomer.
The third object of the invention can be achieved by adopting the following technical scheme:
the novel PA6 polyamide thermoplastic elastomer is used for films, sheets and foaming shoe materials.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the preparation method of the novel PA6 polyamide thermoplastic elastomer, long-chain dibasic acid is used for ring opening of caprolactam, after the ring opening is thorough and carboxylic acid end-capped nylon prepolymer is formed, unreacted caprolactam is reduced, condensation is carried out with polyetheramine, and the PA6 polyamide thermoplastic elastomer with larger molecular weight can be formed, and the hardness of the elastomer is stable; and the content of impurities in the elastomer is reduced, so that the transparency of the elastomer is improved.
2. The novel PA6 polyamide thermoplastic elastomer has stable hardness and excellent transparency, and maintains good mechanical properties.
3. The novel PA6 polyamide thermoplastic elastomer has stable hardness and excellent transparency, and can be widely applied to the fields of films and sheets.
Drawings
FIG. 1 is a diagram of a novel PA6 polyamide thermoplastic elastomer product prepared in example 1;
FIG. 2 is a diagram of an elastomeric product prepared in comparative example 1.
Detailed Description
The technical scheme of the present invention will be clearly and completely described in the following in connection with specific embodiments. It will be apparent that the described embodiments are merely some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Nylon 66 based plastics can also have improved properties over those of nylon 66, and thus nylon 66 based performance improvements have long been a work in the art. The polyurethane thermoplastic elastomer combined by polyamide and polyether blocks in the prior art has excellent performance and wide application, but has the problems of unstable product hardness, poor transparency and other low quality in the preparation process. Therefore, in order to solve the problems, the invention provides a preparation method of a high-quality PA6 polyamide thermoplastic elastomer.
A method for preparing a novel PA6 polyamide thermoplastic elastomer, comprising the following steps:
and (3) carrying out a prepolymerization reaction on caprolactam and long-chain dibasic acid to obtain a prepolymerization product, and carrying out a polycondensation reaction on the prepolymerization product and polyetheramine to obtain the novel PA6 polyamide thermoplastic elastomer.
In the prior art, if caprolactam, polyetheramine and long-chain dibasic acid are reacted simultaneously, the formed nylon prepolymer can coat polyetheramine instead of polymerization combination, so that an unstable point exists in the formed elastomer, and the mechanical property of the elastomer is defective. The present application uses long chain dibasic acids to ring-open caprolactam, after which the ring opening is complete and a carboxylic acid terminated nylon prepolymer is formed, in which polyetheramine is subjected to polycondensation. Firstly, the coating of the nylon prepolymer on polyetheramine in the production process is avoided. Secondly, ring-opening prepolymerization is carried out on the caprolactam, so that nylon prepolymer with uniform molecular weight can be obtained, unreacted caprolactam is reduced, and the PA6 hard segment in the PA6 polyamide thermoplastic elastomer is uniform in molecular weight and stable in hardness in the subsequent reaction process with polyetheramine. And thirdly, reducing the content of caprolactam in the polycondensation reaction process, wherein the excessive caprolactam in the polycondensation reaction stage leads to difficult increase of the viscosity of a polycondensation product, so that the PA6 polyamide thermoplastic elastomer has larger molecular weight change range and unstable hardness. And too much caprolactam crystallizes during the reaction, so that the PA6 polyamide thermoplastic elastomer contains crystals, which appear white, and its transparency is greatly reduced.
As one embodiment, the long-chain dibasic acid is one or a combination of more than two of sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid or tetradecanedioic acid.
In the embodiment, the long-chain dibasic acid is a long-chain dibasic acid with 10-14C atoms, two carboxyl groups react at two ends of an alkyl chain, more methylene is provided with the C atoms of 10-14, and the polyamide has higher hydrophobic property, so that the novel PA6 polyamide thermoplastic elastomer has lower water absorption rate and can be applied to a film material.
As one embodiment, a fourth monomer is further added in the prepolymerization reaction, wherein the fourth monomer is one or more of phthalic acid, isophthalic acid or adipic acid, or a composition of more than two or a small molecular diamine substance. Preferably, the small molecule diamine is hexamethylenediamine.
As one embodiment, the addition amount of the fourth monomer is 0-5% of the mass of the long-chain dibasic acid.
The addition of the fourth monomer can further reduce crystallization in the elastomer and improve the transparency of the elastomer.
As one embodiment, the polyether amine is one or a combination of more than two of polyethylene glycol polyether amine, polypropylene glycol polyether amine or polytetramethylene ether glycol polyether amine; the molecular weight of the polyether amine is 230-2000g/mol.
The polyether amine used in the invention is polyethylene glycol polyether amine, polypropylene glycol polyether amine or polytetramethylene ether glycol polyether amine, and is obtained after polyethylene glycol, polypropylene glycol or polytetramethylene ether glycol is aminated. The molecular weight of the polyetheramine is selected to be 230-2000g/mol, preferably 500-1500g/mol; further preferred polyetheramines have a molecular weight of 500 to 1000, which provides excellent elastic properties and which does not show a white presence in the elastomer after sufficient condensation with the nylon prepolymer, resulting in high transparency of the elastomer.
As one embodiment, the reaction condition of the prepolymerization reaction is that the reaction is carried out for 1 to 3 hours at the temperature of 245 to 270 ℃ under the gauge pressure of 0.5 to 2 MPa.
The ring opening of the caprolactam is carried out under long-chain dibasic acid to form nylon prepolymer, which can be completed in a shorter time, and the time of the whole preparation process is shortened.
As one embodiment, 0.0 to 3% by mass of water based on the mass of caprolactam is added to the prepolymerization feed.
Long chain dibasic acid is favorable for ring-opening reaction, so that the ring-opening reaction of caprolactam can be carried out with little or no water.
As one embodiment, the prepolymer is subjected to drainage treatment before polycondensation reaction of the prepolymer and polyetheramine; the polycondensation reaction is carried out for 2-6h under the condition that the absolute pressure is 0-5KPa and the temperature is 220-235 ℃.
Polyetheramines are unstable, so in this embodiment, water from the prepolymerization process is first removed, allowing the polycondensation reaction to proceed in a relatively stable environment. In addition, polyether amine can degrade at high temperature for a long time, so that the viscosity of the elastomer is difficult to be increased to the target viscosity, and the mechanical properties of the prepared elastomer are insufficient. Therefore, the polycondensation reaction is carried out at 220-235 ℃, the temperature of the polycondensation reaction is reduced, and the stability of polyether amine is facilitated, so that the elastomer with good quality is obtained. The total time of the prepolymerization and polycondensation reaction can be controlled within 10 hours, so that the reaction time is greatly shortened, the cost is saved, and the economic benefit is improved.
As one embodiment, the caprolactam is added in an amount of 30% -55% of the mass of the PA6 polyamide thermoplastic elastomer; the method comprises the steps of carrying out a first treatment on the surface of the The molar weight ratio of the long-chain dibasic acid to the polyetheramine is 1: (0.95-1.05).
The main raw materials of the invention are caprolactam and polyetheramine, wherein the caprolactam is maintained at a relatively low addition level. In the reaction process of caprolactam in the field, the addition amount of caprolactam is large, the reaction is easy to carry out, the addition amount is small, and the reaction is difficult to carry out. However, when the amount of the additive is large, the strength of the obtained elastomer is high, but the elasticity is lowered; and caprolactam does not completely crystallize easily, so that the elastomer appears white and the transparency is greatly reduced. The caprolactam content in the invention is less than 60%, the reaction can be smoothly carried out, and the formed elastomer has better transparency.
As one embodiment, the invention adds a catalyst and an antioxidant into the nylon prepolymer and the polyetheramine before the polycondensation reaction, wherein the catalyst is one or a combination of more than two of sodium hypophosphite, sodium phosphite or sodium hydroxide; the antioxidant is one or more of N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine and pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and DEOX S80 or IRGANOX 1330.
The invention also provides a preparation method of the novel PA6 polyamide thermoplastic elastomer, which is used for preparing the novel PA6 polyamide thermoplastic elastomer.
As one embodiment, the polyether amine soft segment accounts for 35 to 60 percent of the total mass of the PA6 polyamide thermoplastic elastomer, and the PA6 hard segment accounts for 30 to 55 percent of the total mass of the PA6 polyamide thermoplastic elastomer.
The elastomer has stable hardness, good compression set performance and excellent mechanical property.
The novel PA6 polyamide thermoplastic elastomer can be used for films, sheets and shoe materials.
The following is a further description of specific examples.
Example 1
Adding 1kg of caprolactam and 2% of distilled water with the mass of caprolactam into a reactor, heating 202g of sebacic acid to 260 ℃, maintaining the pressure for 2 hours at 1MPa for reaction, discharging water after the reaction is finished to obtain a diacid end-capped nylon prepolymer, cooling the prepolymer to 230 ℃, adding 1kg of polyethylene glycol polyether amine with the average molecular weight of 1000g/mol, a catalyst and an antioxidant, and carrying out polycondensation reaction for 4 hours at the absolute pressure of 2.5KPa and the temperature of 230 ℃ to obtain the novel PA6 polyamide thermoplastic elastomer after the reaction is finished.
Example 2
Adding 1kg of caprolactam and 186.8kg of distilled water with the mass of 0.5% of caprolactam into a reactor, heating to 245 ℃ and maintaining the pressure for 3 hours under the condition of 0.5MPa for reaction, discharging water after the reaction is finished to obtain a diacid end-capped nylon prepolymer, cooling the prepolymer to 220 ℃, adding 1.71kg of polypropylene glycol polyether amine with the molecular weight of 2000g/mol, a catalyst and an antioxidant, and carrying out polycondensation reaction for 6 hours at the absolute pressure of 5KPa and the temperature of 230 ℃ to obtain the novel PA6 polyamide thermoplastic elastomer.
Example 3
Adding 1kg of caprolactam, 270.9g of distilled water with the mass of 0.3% of caprolactam, 3.52g of terephthalic acid, heating to 270 ℃, maintaining the pressure for 1h under 2MPa, reacting, discharging water after the reaction is finished to obtain diacid end-capped nylon prepolymer, cooling the prepolymer to 235 ℃, adding 376g of polytetramethylene ether glycol polyether amine with the molecular weight of 230g/mol, reacting and polycondensing the prepolymer at the absolute pressure of 0.1KPa and 235 ℃ for 2h, and obtaining the novel PA6 polyamide thermoplastic elastomer after the reaction is finished.
Example 4
Adding 1kgmol of caprolactam and 134.7g of hexamethylenediamine into a reactor, heating to 250 ℃, maintaining the pressure at 1.5MPa for 1.5 hours for reaction, draining water after the reaction is finished to obtain a diacid end-capped nylon prepolymer, cooling the prepolymer to 225 ℃, adding 1kg of polyethylene glycol polyether amine with the molecular weight of 1500g/mol, a catalyst and an antioxidant, and carrying out polycondensation reaction for 5 hours at the absolute pressure of 0.01KPa and 225 ℃ to obtain the novel PA6 polyamide thermoplastic elastomer.
Comparative example 1
Adding 1kg mol of caprolactam, 202g of distilled water with 2% of caprolactam mass, 1kg of polyethylene glycol polyether amine with 1000g/mol of molecular weight, a catalyst and an antioxidant into a reactor, and carrying out polycondensation reaction for 4 hours at the absolute pressure of 2.5KPa and the temperature of 230 ℃ to obtain the elastomer after the reaction.
Comparative example 2
Comparative example 2 was different from example 1 in that the long-chain dibasic acid was adipic acid, and the mass of adipic acid added was 146.1g, except that the conditions were the same as in example 1.
Comparative example 3
Comparative example 3 differs from example 1 in that the caprolactam is added in an amount of 1kg of distilled water of 2% by mass of caprolactam, 87g of sebacic acid, 430g of polyethylene glycol-based polyetheramine having a molecular weight of 1000g/mol, with the other conditions being identical to example 1.
Comparative example 4
Comparative example 4 differs from example 1 in that the polyethylene glycol-based polyether amine has a molecular weight of 3000, and 67.4g of sebacic acid was added, with the other conditions being the same as in example 1.
Performance testing
The products of examples 1-4 and comparative examples 1-4 were subjected to transparency and haze tests, and the elastomers of examples 1-4 and comparative examples 1-4 were sampled and tested according to the GB/T2410-2008 standard, the test results are shown in Table 1, wherein the appearance of the elastomer of example 1 is shown in FIG. 1.
The products of examples 1-4 and comparative examples 1-4 were subjected to a water absorption test and a hydrophobicity test, wherein the water absorption test was carried out in accordance with the standard of GB/T1034-2008 and was tested; the water contact angle of the material was measured by the hydrophobicity test, and the results are shown in table 1.
The products of examples 1-4 and comparative examples 1-4 were tested for hardness, tensile strength, elongation at break properties, wherein hardness was measured to Shore hardness according to ISO7619, and the test results are shown in Table 1; tensile strength and elongation at break were measured and sampled according to GB/T528-2009 standard, and the test results are shown in Table 1.
TABLE 1 results of Performance test of examples 1-4 and comparative examples 1-4
As can be seen from the data in Table 1, the elastomers prepared in examples 1 to 4 of the present invention were moderately hard, and the hardness was greatly reduced relative to that of comparative example 1, but the elongation at break was nearly 2 times that of comparative example 1, indicating that the elastomers in examples 1 to 4 of the present invention are excellent in elasticity, and therefore the elastomers in examples 1 to 4 of the present invention had soft properties, enabling good processability. The elastomer of comparative example 1 has a large hardness, is a hard material, and is not suitable for products having high elasticity. Therefore, the film material can be prepared by casting, and products with high requirements on elasticity, such as sheets, shoe materials and the like, can be produced by blow molding.
As can be seen from the haze and clarity data in Table 1, the clarity of examples 1-4 of the present invention all reached greater than 90%, and as can be seen in conjunction with FIG. 1, the product was visibly transparent and was not white or otherwise affected. In comparative example 1, the crystallinity caused by decomposition of polyethylene glycol polyetheramine and the coating of the polyethylene glycol polyetheramine by nylon prepolymer lead to a great decrease in transparency of the elastomer of comparative example 1, as shown in fig. 2, the elastomer prepared in comparative example 1 is white and has poor transparency, and in comparative example 3, too much caprolactam leads to crystallization and decreases in transparency of the elastomer; the polyethylene glycol-based polyether amine with larger molecular weight in comparative example 4 causes the volume of the polyethylene glycol-based polyether amine in the formed elastomer block chain to be too large, so that the elastomer is white, and the transmittance is affected.
From the water contact angle and water absorbency data of Table 1, it is known that examples 1 to 4 employ long chain dibasic acids having increasing numbers of carbon atoms, the hydrophobicity is gradually enhanced, and the water absorbency is gradually reduced, because the methylene group in the long chain dibasic acid is increased, so that the hydrophobic group in the elastomer is increased in hydrophobicity, thereby also reducing the water absorbency. Comparative example 2 using adipic acid increased the water absorption by a factor of 5 relative to example 1, indicating a large change in hydrophobicity and water absorption from 6 carbon atoms to 10 carbon atoms or more. Therefore, when the elastomer is used as a mulching film, the elastomer has better water retention property and avoids evaporation and loss of water.
In summary, the invention provides a novel PA6 polyamide thermoplastic elastomer, a preparation method and application thereof, wherein the novel PA6 polyamide thermoplastic elastomer has better elastic property, transparency and mechanical property, and can be used in products with high requirements on elasticity and transparency.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention are intended to be within the scope of the present invention as claimed.
Claims (10)
1. The preparation method of the novel PA6 polyamide thermoplastic elastomer is characterized by comprising the following steps:
and (3) carrying out a prepolymerization reaction on caprolactam and long-chain dibasic acid to obtain a prepolymerization product, and carrying out a polycondensation reaction on the prepolymerization product and polyetheramine to obtain the novel PA6 polyamide thermoplastic elastomer.
2. A process for the preparation of a novel PA6 polyamide thermoplastic elastomer as claimed in claim 1, characterized in that,
the long-chain dibasic acid is one or more than two of sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid or tetradecanedioic acid.
3. A process for the preparation of a novel PA6 polyamide thermoplastic elastomer as claimed in claim 1, characterized in that,
the polyether amine is one or a combination of more than two of polyethylene glycol polyether amine, polypropylene glycol polyether amine or polytetramethylene ether glycol polyether amine; the molecular weight of the polyether amine is 230-2000/mol.
4. A process for the preparation of a novel PA6 polyamide thermoplastic elastomer as claimed in claim 1, characterized in that,
the reaction condition of the prepolymerization reaction is that the gauge pressure is 0.5-2MPa and the temperature is 245-270 ℃ for 1-3h.
5. A process for the preparation of a novel PA6 polyamide thermoplastic elastomer as claimed in claim 1, characterized in that,
adding water accounting for 0.0-3% of the mass of the caprolactam into the prepolymerization reaction raw material.
6. A process for the preparation of a novel PA6 polyamide thermoplastic elastomer as claimed in claim 1, characterized in that,
before the pre-polymerization product and polyetheramine are subjected to polycondensation reaction, the pre-polymerization product is subjected to drainage treatment; the polycondensation reaction is carried out under the condition of absolute pressure of 0-5KPa and temperature of 220-235 ℃ for 2-6h.
7. A process for the preparation of a novel PA6 polyamide thermoplastic elastomer as claimed in claim 1, characterized in that,
the addition amount of the caprolactam is 30% -55% of the mass of the PA6 polyamide thermoplastic elastomer; the molar weight ratio of the long-chain dibasic acid to the polyetheramine is 1: (0.95-1.05).
8. A novel PA6 polyamide thermoplastic elastomer prepared by the process of any one of claims 1-7.
9. The novel PA6 polyamide thermoplastic elastomer of claim 8, wherein the polyether amine soft segment accounts for 35-60% of the total mass of the PA6 polyamide thermoplastic elastomer, and the PA6 hard segment accounts for 30-55% of the total mass of the PA6 polyamide thermoplastic elastomer.
10. Use of a novel PA6 polyamide thermoplastic elastomer as claimed in claim 8 or 9, for films, sheets, foam shoes.
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