CN116425983B - High-impact polyether ester amide thermoplastic elastomer and preparation method thereof - Google Patents
High-impact polyether ester amide thermoplastic elastomer and preparation method thereof Download PDFInfo
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- CN116425983B CN116425983B CN202310702456.1A CN202310702456A CN116425983B CN 116425983 B CN116425983 B CN 116425983B CN 202310702456 A CN202310702456 A CN 202310702456A CN 116425983 B CN116425983 B CN 116425983B
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- 229920006146 polyetheresteramide block copolymer Polymers 0.000 title claims abstract description 117
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 29
- 229920002614 Polyether block amide Polymers 0.000 claims abstract description 23
- 229920000570 polyether Polymers 0.000 claims abstract description 23
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- -1 aliphatic cyclic ester Chemical class 0.000 claims abstract description 12
- 150000004985 diamines Chemical class 0.000 claims abstract description 11
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 10
- 238000009833 condensation Methods 0.000 claims abstract description 10
- 239000004953 Aliphatic polyamide Substances 0.000 claims abstract description 8
- 229920003231 aliphatic polyamide Polymers 0.000 claims abstract description 8
- 229920003232 aliphatic polyester Polymers 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 230000009471 action Effects 0.000 claims abstract description 3
- XRHCAGNSDHCHFJ-UHFFFAOYSA-N Ethylene brassylate Chemical group O=C1CCCCCCCCCCCC(=O)OCCO1 XRHCAGNSDHCHFJ-UHFFFAOYSA-N 0.000 claims description 22
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 20
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 14
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical group NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000012643 polycondensation polymerization Methods 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 230000007423 decrease Effects 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 18
- 230000009467 reduction Effects 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 238000007789 sealing Methods 0.000 abstract description 2
- 229920001971 elastomer Polymers 0.000 description 59
- 239000000806 elastomer Substances 0.000 description 59
- 229920000642 polymer Polymers 0.000 description 24
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 20
- 150000002009 diols Chemical class 0.000 description 18
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 17
- 239000000047 product Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920000562 Poly(ethylene adipate) Polymers 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000009194 climbing Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FZWBABZIGXEXES-UHFFFAOYSA-N ethane-1,2-diol;hexanedioic acid Chemical compound OCCO.OC(=O)CCCCC(O)=O FZWBABZIGXEXES-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- 241000764238 Isis Species 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920006039 crystalline polyamide Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Abstract
The invention discloses a high-impact polyether ester amide thermoplastic elastomer and a preparation method thereof. The polyether ester amide thermoplastic elastomer comprises three block components of aliphatic polyester, aliphatic polyether and aliphatic polyamide; the polyether ester amide thermoplastic elastomer is prepared by ring opening-condensation cascade polymerization of diamine, polyether glycol and aliphatic cyclic ester under the action of a catalyst. The impact strength of the polyether ester amide thermoplastic elastomer at normal temperature and low temperature of minus 30 ℃ exceeds 10 kilojoules per square meter, and the impact strength of the polyether ester amide thermoplastic elastomer at minus 30 ℃ is increased along with the temperature reduction in a certain range, and the impact strength of the polyether ester amide thermoplastic elastomer at the low temperature of minus 30 ℃ can reach more than 100 kilojoules per square meter and is far higher than that of the common thermoplastic elastomer. The performance of the polyether ester amide thermoplastic elastomer can be regulated and controlled in a larger range by changing the copolymer structure, so that the polyether ester amide thermoplastic elastomer can be applied to the fields of silent gears, gas circuit oil way sealing, automobile and electric appliance parts, high-pressure hoses, high-end sports equipment and the like.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high-impact polyether ester amide thermoplastic elastomer and a preparation method thereof.
Background
Polyether ester amide (usually called polyether amide) is a block type thermoplastic elastomer composed of polyether soft block and crystalline polyamide (nylon) hard blockThe elastomer material has excellent low temperature impact resistance, good flexibility, high elastic recovery rate and good processability. Pebax, a major brand on the market today, is Acciaieria Almama ® The product can be used in various fields such as silent gears, gas circuit oil way seals, automobile and electric appliance parts, high-pressure hoses, high-end sports equipment such as mountain climbing boots, skis, sports shoes and the like.
Polyether ester amide elastomers are typically prepared by a condensation polymerization process, such as polymerization of a carboxyl-terminated polyamide prepolymer using a lactam and a diacid or a diamine and a diacid, followed by condensation polymerization with a polyether diol to synthesize a polyether ester amide copolymer. Since the ester bond content is small (generally about 10% of the amide bonds), it is generally called a polyether amide copolymer (hereinafter, collectively referred to as polyether amide copolymer). The method has the problems that carboxyl and hydroxyl are required to meet strict equivalent ratio to obtain a high molecular weight product, and the polymerization of the high molecular weight product needs to be carried out at different temperatures due to different activities of esterification reaction and amidation reaction, so that the side reaction is more, and the molecular weight of the obtained product is lower. Therefore, the polyether ester amide has high synthesis difficulty and high technical threshold, and the current price is 10-20 ten thousand yuan per ton, which is far higher than that of the common thermoplastic elastomer, and belongs to high-end thermoplastic elastomer materials.
Although polyether amide elastomers have better low temperature impact properties than other elastomers, their impact properties also decrease with decreasing temperature, with limited toughness at lower temperatures (e.g., -30 ℃). Such as polyether amide Pebax 7233 series products, the notch impact strength of which is reduced from 12 kilojoules per square meter to 3 kilojoules per square meter when the temperature is reduced from room temperature to-30 ℃, thus limiting part of the applications.
Patent US4230838 discloses a process for the preparation of polyether amide copolymers having good mechanical properties by reacting a lactam or amino acid or diamine with a dicarboxylic acid and a polyether diol to prepare a polyether amide. However, this method requires the preparation of a carboxylic acid-terminated polyamide oligomer, followed by the condensation polymerization of the polyamide oligomer with a polyether glycol at an equivalent ratio of carboxyl groups to hydroxyl groups to give a polyether amide copolymer. As mentioned above, this process is more difficult to prepare for high molecular weight polymers, and therefore requires the addition of polyfunctional compounds or chain extenders to increase the molecular weight of the copolymer. However, this makes the reaction complicated, increases the cost, and makes the copolymer structure difficult to control.
Patent ZL201911244454.2 discloses a polyester amide and a preparation method thereof, wherein the polyester amide is prepared by ring-opening-condensation cascade polymerization of macrocyclic diacid glycol ester and diamine or amino alcohol. The prepared polyesteramide copolymer has good biocompatibility and biodegradability and excellent mechanical property, solvent resistance and thermal stability. However, the copolymer is a polyesteramide copolymer, and there is a clear structural difference from the polyetheresteramide copolymer of the present invention. With the decrease of temperature, the shock resistance of the polyester amide copolymer synthesized by the method is reduced, and the low-temperature shock resistance of the polyester amide copolymer is poor. As in the comparative example, the PEBDA polyesteramide sample reduced its notched impact strength from 60 kilojoules per square meter to 3 kilojoules per square meter when the temperature was reduced from room temperature to-30 ℃.
In order to adapt to the development of society, development of a high polymer material with high impact resistance at normal temperature and low temperature is urgently needed, so that the high polymer material meets the requirements of more application fields.
Disclosure of Invention
In order to solve the technical problems, the invention provides a polyether ester amide thermoplastic elastomer with high impact resistance at normal temperature and low temperature and a preparation method thereof. The polyether ester amide elastomer is a multi-block copolymer composed of aliphatic polyester, aliphatic polyether and aliphatic polyamide. Compared with the polyester amide copolymer, the low-temperature impact resistance of the polyester amide copolymer is greatly improved by introducing the polyether soft segment. By introducing crystalline long-chain polyesters with low glass transition temperatures, the mechanical properties are not affected and the low-temperature impact resistance is increased compared with polyetheramides. Therefore, the polyether ester amide elastomer has good thermal performance, mechanical performance and excellent normal-temperature and low-temperature impact resistance, the strength of the polyether ester amide elastomer can reach more than 20 megapascals, the notch impact strength at normal temperature and low temperature of minus 30 ℃ exceeds 10 kilojoules per square meter, and in most systems, when the temperature is reduced from room temperature to minus 30 ℃, the notch impact strength is not reduced along with the reduction of the temperature, but is increased.
The invention also provides a preparation method of the high-impact polyether ester amide thermoplastic elastomer. Namely, an aliphatic cyclic ester such as musk T and cyclic oligomeric ethylene glycol adipate is blended with an aliphatic diamine such as 1, 6-hexamethylenediamine, 1, 10-decanediamine and 1, 12-dodecanediamine, a polyether glycol such as polytetrahydrofuran glycol and polyethylene glycol and a catalyst, and the polyether ester amide thermoplastic elastomer is synthesized by ring opening-condensation cascade polymerization (PROP). The properties of the polyether ester amide thermoplastic elastomer can be regulated and controlled by changing the proportion of soft segments to hard segments, the molecular weight and content of polyether glycol, the molecular weight of a polymer and other factors.
In order to achieve the purposes and effects, the invention is realized by the following technical scheme:
a first object of the present invention is to provide a high impact polyether ester amide thermoplastic elastomer comprising three block components of aliphatic polyester, aliphatic polyether and aliphatic polyamide; the chemical structural formula of the polyether ester amide elastomer is as follows:
，
wherein R is 1 Is (CH) 2 ) m M is any integer from 5 to 12; a is any integer of 2-11; b is any integer from 2 to 4; c is any integer from 4 to 44; d. e, f are determined by the content of aliphatic polyester, aliphatic polyether and aliphatic polyamide respectively, wherein the content of the aliphatic polyester is 10wt%~90wtThe content of the aliphatic polyether is 0.5 percentwt%~60wtThe content of the aliphatic polyamide is 10 percentwt%~80wtAnd the sum of the contents of the components is 100%.
In one embodiment of the invention, the polyether ester amide elastomer has a notched impact strength of 10 kilojoules per square meter or more at ambient to-30 ℃.
In one embodiment of the invention, when the aliphatic polyether content isIs 4 (4) wt%~25 wt% the notched impact strength of the polyether ester amide thermoplastic elastomer increases as the temperature decreases from ambient to a low temperature of-30 ℃.
The second object of the invention is to provide a method for preparing a polyether ester amide thermoplastic elastomer, which comprises the following steps: diamine, polyether glycol and aliphatic cyclic ester are subjected to ring opening-condensation cascade polymerization reaction under the action of a catalyst to prepare the polyether ester amide elastomer.
In one embodiment of the invention, the diamine is 1, 6-hexamethylenediamine, 1, 10-decanediamine or 1, 12-dodecanediamine; the polyether glycol is polytetrahydrofuran glycol or polyethylene glycol; the aliphatic cyclic ester is musk T or cyclic oligomeric ethylene glycol adipate; the catalyst is a titanate compound, preferably n-butyl titanate.
In one embodiment of the invention, the ring-opening-condensation cascade polymerization is carried out under inert atmosphere or vacuum conditions; directly obtaining the polyether ester amide elastomer without post-treatment after the reaction is finished; the inert atmosphere is a nitrogen atmosphere.
In one embodiment of the invention, the molecular weight of the polyether glycol is 200g/mol to 2900g/mol.
In one embodiment of the present invention, the molar ratio of the aliphatic cyclic ester to the diamine is 1.2 to 20:1.
in one embodiment of the invention, the polyether glycol is used in an amount of 1% -150% of the sum of the mass of musk T and the mass of diamine.
In one embodiment of the invention, the catalyst is used in an amount of 0.01% -1% of the total feed mass.
In one embodiment of the invention, the temperature of the ring-opening-condensation cascade polymerization reaction is 200 ℃ to 280 ℃.
In one embodiment of the invention, the time of the ring-opening-condensation cascade polymerization reaction is 30 minutes to 300 minutes.
A third object of the present invention is to provide the use of said polyether ester amide elastomer for the preparation of thermoplastic elastomer materials.
The polyether ester amide elastomer has good mechanical property, impact resistance and thermal stability.
The polymerization mechanism of the invention is a ring-opening-condensation cascade polymerization process, namely diamine and polyether glycol firstly carry out ring-opening polymerization on aliphatic cyclic ester to obtain polyester amide glycol and polyether ester glycol oligomer with hydroxyl end groups, condensation polymerization is carried out between the polyester amide glycol and polyether ester glycol to generate polyether ester amide products with higher molecular weight, and the reaction products do not need purification and separation.
Compared with the prior art, the technical scheme of the invention has the following advantages:
the invention provides a polyether ester amide thermoplastic elastomer with high impact resistance and a preparation method thereof. The preparation method of the polyether ester amide elastomer effectively solves the problem that the prior art is difficult to prepare a thermoplastic elastomer material with high impact resistance at low temperature (-30 ℃), and the polyether ester amide thermoplastic elastomer synthesized by the method has good mechanical property and thermal stability and has great application value.
The high impact resistance of the polyether ester amide thermoplastic elastomer prepared by the invention is that the notch impact strength at normal temperature and low temperature (-30 ℃) exceeds 10 kilojoules per square meter, and can be increased with temperature reduction in a certain range, and the notch impact strength at-30 ℃ can reach more than 100 kilojoules per square meter, which is far higher than that of the common thermoplastic elastomer. The performance of the polyether ester amide elastomer can be regulated and controlled in a large range by changing the copolymer structure, so that the polyether ester amide elastomer can be applied to various fields such as silent gears, gas circuit oil way sealing, automobiles and electric appliance parts, high-pressure hoses, high-end sports equipment such as mountain climbing boots, skis, sports shoes and the like.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings, in which
FIG. 1 is a synthetic route diagram of a polyetheresteramide of the present invention;
FIG. 2 is a stress-strain plot of PEEA-1 in example 1 of the present invention;
FIG. 3 is a stress-strain plot of PEEA-2 in example 2 of the present invention;
FIG. 4 is a graph of notched impact strength at low and low temperatures for an injection molded spline of PEEA-2 of example 2 of the present invention;
FIG. 5 is a stress-strain plot of PEEA-3 in example 3 of the present invention;
FIG. 6 is a stress-strain plot of PEEA-4 in example 4 of the present invention;
FIG. 7 is a stress-strain graph of PEEA-5 in example 5 of the present invention;
FIG. 8 is a stress-strain plot of PEEA-6 in example 6 of the present invention;
FIG. 9 is a stress-strain plot of PEEA-7 in example 7 of the present invention;
FIG. 10 is a graph of thermogravimetric plot of PEEA-8 (ramp rate: 10 ℃ C. Per minute, atmosphere: nitrogen) in example 8 of the present invention;
FIG. 11 is a stress-strain plot of PEEA-8 in example 8 of the present invention;
FIG. 12 is a differential scanning calorimetric curve of PEEA-9 in example 9 of the present invention (ramp rate: 10 ℃ C. Per minute, atmosphere: nitrogen);
FIG. 13 is a stress-strain plot of PEEA-9 in example 9 of the present invention;
FIG. 14 is a stress-strain plot of PEEA-10 in example 10 of the present invention;
FIG. 15 is a graph comparing impact resistance of polyether ester amide of the present invention with that of PEBDA polyester amide sample of comparative example 1 and Pebax 7233 sample of Achiller's Michaelis.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
The experimental methods used in the following examples are conventional methods unless otherwise specified, and materials, reagents, etc. used, unless otherwise specified, are commercially available.
The CAS numbers for the organic reagents used in the present invention are shown below:
TABLE 1
。
In the following examples of the present invention, the intrinsic viscosity of the product was measured using an Ubbelohde viscometer using m-cresol as a solvent at 25 ℃.
In the following examples of the invention, thermal properties of the product were measured using a thermogravimetric analyzer model SDT-2960TG/DTA TA at 10℃for min -1 The temperature is 25-700 ℃ and the nitrogen atmosphere.
In the following examples of the invention, DSC testing was performed on the product using an instrument of the TA Q2000 type at 10℃for a minute -1 Is increased and decreased at a rate of (2) and is in a nitrogen atmosphere. And selecting a first temperature lowering curve and a second temperature raising curve.
In the following examples of the invention, the tensile properties of the products were tested using an universal materials tester model Instron-5966. (stretching rate: 10 mm/min, temperature: 20.0 ℃, humidity: 75.0%).
In the following examples of the invention, the impact resistance of the product was tested according to ISO 179-1:2010 using a HIT25P impact tester.
Referring to FIG. 1, a series of polyether ester amide copolymers are obtained by a preparation method of the polyether ester amide thermoplastic elastomer, namely a ring-opening-condensation cascade polymerization method.
Example 1
The embodiment provides a preparation method of a polyether ester amide thermoplastic elastomer with high impact resistance, which comprises the following steps:
into a 250 ml flask were charged 1, 10-decanediamine (5.3 g), polytetrahydrofuran diol (0.6 g, molecular weight 1000 g per mole), musk T (24.7 g), 6.0. Mu.l of n-butyl titanate; introducing nitrogen, mechanically stirring, heating to 240 ℃, and vacuumizing and polymerizing for 90 minutes to obtain the corresponding polyether ester amide elastomer PEEA-1.
The intrinsic viscosity of the polyether ester amide elastomer PEEA-1 was measured to be 1.21 deciliters per gram (dL/g), indicating that the copolymer has a higher molecular weight. FIG. 2 is a stress-strain plot of the polyether ester amide elastomer PEEA-1, showing that the Young's modulus of the polymer is 132 megapascals (MPa), the breaking strength is 21.0MPa, and the elongation at break is 849%, indicating that the polymer has better mechanical properties.
The polyether ester amide elastomer PEEA-1 was tested for impact resistance. Its notch impact strength at normal temperature is 75 kilojoules per square meter (kJ/m) 2 ) The notch impact strength at low temperature (-30 ℃) is 25kJ/m 2 。
Example 2
The embodiment provides a preparation method of a polyether ester amide thermoplastic elastomer with high impact resistance, which comprises the following steps:
this example is similar to the preparation of example 1, except that: 1, 10-decanediamine (5.3 g), polytetrahydrofuran diol (1.5 g, molecular weight 1000 g per mole), musk T (24.7 g) and 6.0. Mu.l of n-butyl titanate were added for reaction to give the corresponding polyether ester amide elastomer PEEA-2.
The intrinsic viscosity of the polyether ester amide elastomer PEEA-2 was measured to be 1.38dL/g, indicating that the copolymer had a relatively high molecular weight. FIG. 3 is a stress-strain graph of the PEEA-2 polyether ester amide elastomer, showing that the Young's modulus of the polymer is 118MPa, the breaking strength is 18.0MPa, and the elongation at break is 881%, which indicates that the polymer has better mechanical properties.
The polyether ester amide elastomer PEEA-2 was tested for impact resistance, and its injection molded spline image and notched impact strength at low and low temperatures are shown in FIG. 4. Its notch impact strength at normal temperature is 63kJ/m 2 The notch impact strength at low temperature (-30 ℃) is 104kJ/m 2 。
Example 3
The embodiment provides a preparation method of a polyether ester amide thermoplastic elastomer with high impact resistance, which comprises the following steps:
this example is similar to the preparation of example 1, except that: 1, 10-decanediamine (5.3 g), polytetrahydrofuran diol (3.0 g, molecular weight 1000 g per mole), musk T (24.7 g) and 6.0. Mu.l of n-butyl titanate were added for reaction to give the corresponding polyether ester amide elastomer PEEA-3.
The intrinsic viscosity of the polyether ester amide elastomer was measured to be 1.16dL/g, indicating that the copolymer had a higher molecular weight. FIG. 5 is a stress-strain diagram of a polyether ester amide elastomer, showing that the Young's modulus of the polymer is 135MPa, the breaking strength is 16.8MPa, and the breaking elongation is 670%, indicating that the polymer has better mechanical properties.
The polyether ester amide elastomer was tested for impact resistance. The notch impact strength at normal temperature is 62kJ/m 2 The notch impact strength at low temperature (-30 ℃) is 94kJ/m 2 。
Example 4
The embodiment provides a preparation method of a polyether ester amide thermoplastic elastomer with high impact resistance, which comprises the following steps:
this example is similar to the preparation of example 1, except that: 1, 10-decanediamine (5.3 g), polytetrahydrofuran diol (6.0 g, molecular weight 1000 g per mole), musk T (24.7 g) and 6.0. Mu.l of n-butyl titanate were added for reaction to give the corresponding polyether ester amide elastomer PEEA-4.
The intrinsic viscosity of the polyether ester amide elastomer PEEA-4 was measured to be 1.63dL/g, indicating that the copolymer had a relatively high molecular weight. FIG. 6 is a stress-strain plot of the PEEA-4 polyether ester amide elastomer, showing that the Young's modulus of the polymer is 87MPa, the breaking strength is 20.9MPa, and the breaking elongation is 1263%, indicating that the polymer has better mechanical properties.
The polyether ester amide elastomer PEEA-4 was tested for impact resistance. Its notch impact strength at normal temperature is 66kJ/m 2 The notch impact strength at low temperature (-30 ℃) is 79kJ/m 2 。
Example 5
The embodiment provides a preparation method of a polyether ester amide thermoplastic elastomer with high impact resistance, which comprises the following steps:
this example is similar to the preparation of example 1, except that: 1, 10-decanediamine (5.3 g), polytetrahydrofuran diol (3.0 g, molecular weight 2000 g per mole), musk T (24.7 g) and 6.0. Mu.l of n-butyl titanate were added and reacted to give the corresponding polyether ester amide elastomer PEEA-5.
The intrinsic viscosity of the polyether ester amide elastomer PEEA-5 was measured to be 1.34dL/g, indicating that the copolymer had a higher molecular weight. FIG. 7 is a stress-strain plot of the polyether ester amide elastomer PEEA-5, showing that the Young's modulus of the polymer is 119MPa, the breaking strength is 20.5MPa, and the elongation at break is 976%, indicating that the polymer has better mechanical properties.
The polyether ester amide elastomer PEEA-5 was tested for impact resistance. Its notch impact strength at normal temperature is 64kJ/m 2 The notch impact strength at low temperature (-30 ℃) is 76kJ/m 2 。
Example 6
The embodiment provides a preparation method of a polyether ester amide thermoplastic elastomer with high impact resistance, which comprises the following steps:
this example is similar to the preparation of example 1, except that: 1, 10-decanediamine (4.2 g), polytetrahydrofuran diol (3.0 g, molecular weight 1000 g per mole), musk T (25.8 g) and 6.0. Mu.l of n-butyl titanate were added for reaction to give the corresponding polyether ester amide elastomer PEEA-6.
The intrinsic viscosity of the polyether ester amide elastomer PEEA-6 was measured to be 1.62dL/g, indicating that the copolymer had a relatively high molecular weight. FIG. 8 is a stress-strain plot of the polyether ester amide elastomer PEEA-6, showing that the Young's modulus of the polymer is 112MPa, the breaking strength is 13.0MPa, the breaking elongation is 553%, and the polymer has better mechanical properties.
Example 7
The embodiment provides a preparation method of a polyether ester amide thermoplastic elastomer with high impact resistance, which comprises the following steps:
into a 250 ml three-neck flask, 1, 10-decanediamine (4.2 g), polytetrahydrofuran diol (3.0 g, molecular weight 2000 g per mole), musk T (25.8 g) and 6.0. Mu.l of n-butyl titanate were charged, and the mixture was mechanically stirred and reacted at 240℃for 180 minutes to give the corresponding polyether ester amide elastomer PEEA-7.
The intrinsic viscosity of the polyether ester amide elastomer PEEA-7 was measured to be 1.11dL/g, indicating that the copolymer had a relatively high molecular weight. FIG. 9 is a stress-strain plot of PEEA-7, a polymer with a Young's modulus of 107MPa, a breaking strength of 12.5MPa, and an elongation at break of 647%, showing that the polymer has better mechanical properties.
Example 8
The embodiment provides a preparation method of a polyether ester amide thermoplastic elastomer with high impact resistance, which comprises the following steps:
into a 250 ml three-neck flask, 1, 10-decanediamine (3.5 g), polytetrahydrofuran diol (3.0 g, molecular weight 1000 g per mole), musk T (16.5 g) and 4.0. Mu.l of n-butyl titanate were charged, and the mixture was mechanically stirred and reacted at 250℃for 150 minutes to give the corresponding polyether ester amide elastomer PEEA-8.
The intrinsic viscosity of the polyether ester amide elastomer PEEA-8 was measured to be 1.15dL/g, indicating that the copolymer had a higher molecular weight. FIG. 10 is a graph of TGA test of polyether ester amide elastomer PEEA-8 with 5% decomposition temperature of 370℃demonstrating good thermal stability of polyether ester amide.
FIG. 11 is a stress-strain plot of PEEA-8, a polymer with a Young's modulus of 89MPa, a breaking strength of 11.9MPa, and an elongation at break of 539%, showing that the polymer has good mechanical properties.
Example 9
The embodiment provides a preparation method of a polyether ester amide thermoplastic elastomer with high impact resistance, which comprises the following steps:
this example is similar to the preparation of example 8, except that: 1, 10-decanediamine (3.5 g), polytetrahydrofuran diol (6.0 g, molecular weight 1000 g per mole), musk T (16.5 g) and 4.0. Mu.l of n-butyl titanate were added and reacted at 250℃for 180 minutes to give the corresponding polyether ester amide elastomer PEEA-9.
The intrinsic viscosity of the polyether ester amide elastomer PEEA-9 was measured to be 1.55dL/g, indicating that the copolymer had a relatively high molecular weight. FIG. 12 is a DSC plot of polyether ester amide elastomer PEEA-9 with a polymer melting point of 143 ℃.
FIG. 13 is a stress-strain plot of PEEA-9, a polymer with a Young's modulus of 56MPa, a breaking strength of 10.1MPa, and an elongation at break of 613% showing good mechanical properties.
Example 10
The embodiment provides a preparation method of a polyether ester amide thermoplastic elastomer with high impact resistance, which comprises the following steps:
this example is similar to the preparation of example 8, except that: 1, 10-decanediamine (3.5 g), polytetrahydrofuran diol (8.0 g, molecular weight 1000 g per mole), musk T (16.5 g) and 6.0. Mu.l of n-butyl titanate were added and reacted at 250℃for 180 minutes to give the corresponding polyether ester amide elastomer PEEA-10.
The intrinsic viscosity of the polyether ester amide elastomer PEEA-10 was measured to be 1.62dL/g, indicating that the copolymer had a relatively high molecular weight. FIG. 14 is a stress-strain plot of the PEEA-10 polyether ester amide elastomer, showing that the Young's modulus of the polymer is 44MPa, the breaking strength is 9.8MPa, and the elongation at break is 517%, indicating that the polymer has good mechanical properties.
Example 11
The embodiment provides a preparation method of a polyether ester amide thermoplastic elastomer with high impact resistance, which comprises the following steps:
this example is similar to the preparation of example 8, except that: 1, 10-decanediamine (3.5 g), polyethylene glycol (4.0 g, molecular weight 1000 g per mole), musk T (16.5 g) and 4.0 μl of n-butyl titanate were added and reacted at 250deg.C for 180 minutes to give the corresponding polyether ester amide elastomer PEEA-11. The intrinsic viscosity of the polyether ester amide elastomer PEEA-11 was measured to be 1.39dL/g, indicating that the copolymer has a relatively high molecular weight.
Example 12
The embodiment provides a preparation method of a polyether ester amide thermoplastic elastomer with high impact resistance, which comprises the following steps:
this example is similar to the preparation of example 8, except that: 1, 6-hexamethylenediamine (2.6 g), polytetrahydrofuran diol (4.0 g, molecular weight 1000 g per mole), musk T (17.4 g) and 4.0. Mu.l of n-butyl titanate were added and mixed and reacted at 250℃for 180 minutes to give the corresponding polyether ester amide elastomer PEEA-12. The intrinsic viscosity of the polyether ester amide elastomer PEEA-12 was measured to be 1.13dL/g, indicating that the copolymer had a relatively high molecular weight.
Example 13
The embodiment provides a preparation method of a polyether ester amide thermoplastic elastomer with high impact resistance, which comprises the following steps:
this example is similar to the preparation of example 8, except that: 1, 10-decanediamine (3.5 g), polytetrahydrofuran diol (20.0 g, molecular weight 1000 g per mole), musk T (16.5 g) and 6.0. Mu.l of n-butyl titanate were added and reacted at 250℃for 180 minutes to give the corresponding polyether ester amide elastomer PEEA-13.
Example 14
The embodiment provides a preparation method of a polyether ester amide thermoplastic elastomer with high impact resistance, which comprises the following steps:
this example is similar to the preparation of example 8, except that: 1, 10-decanediamine (0.6 g), polytetrahydrofuran diol (2.0 g, molecular weight 1000 g per mole), musk T (19.4 g) and 4.0. Mu.l of n-butyl titanate were added and reacted at 250℃for 150 minutes to give the corresponding polyether ester amide elastomer PEEA-14.
Example 15
The embodiment provides a preparation method of a polyether ester amide thermoplastic elastomer with high impact resistance, which comprises the following steps:
this example is similar to the preparation of example 8, except that: 1, 10-decanediamine (6.0 g), polytetrahydrofuran diol (2.0 g, molecular weight 1000 g per mole), musk T (14.0 g) and 4.0. Mu.l of n-butyl titanate were added and reacted at 250℃for 120 minutes to give the corresponding polyether ester amide elastomer PEEA-15.
Example 16
The embodiment provides a preparation method of a polyether ester amide thermoplastic elastomer with high impact resistance, which comprises the following steps:
this example is similar to the preparation of example 8, except that: 1, 10-decanediamine (5.3 g), polytetrahydrofuran diol (3.0 g, molecular weight 1000 g per mole), musk T (24.7 g) and 6.0. Mu.l of n-butyl titanate were added and reacted at 220℃for 300 minutes to give the corresponding polymer PEEA-16.
Example 17
The embodiment provides a preparation method of a polyether ester amide thermoplastic elastomer with high impact resistance, which comprises the following steps:
this example is similar to the preparation of example 8, except that: 1, 10-decanediamine (5.3 g), polytetrahydrofuran diol (3.0 g, molecular weight 1000 g per mole), musk T (24.7 g) and 6.0. Mu.l of n-butyl titanate were added and reacted at 270℃for 40 minutes to give the corresponding polymer PEEA-17.
Example 18
The embodiment provides a preparation method of a polyether ester amide thermoplastic elastomer with high impact resistance, which comprises the following steps:
into a 250 ml three-neck flask, 1, 12-dodecanediamine (5.3 g), polytetrahydrofuran glycol (3.0 g, molecular weight 1000 g per mole), cyclic oligo-ethylene adipate (24.7 g, from patent application No. 202111289134.6, polymerization degree 2-9) and 6.0. Mu.l of n-butyl titanate were added, and the mixture was stirred mechanically with nitrogen and reacted at 240℃for 180 minutes to give the corresponding polymer PEEA-18.
Comparative example 1
The comparative example provides a method for preparing a polyesteramide copolymer, which comprises the following steps:
1, 10-decanediamine (5.3 g), musk T (24.7 g), 6.0 microliter of n-butyl titanate were put into a 250 milliliter single neck flask; introducing nitrogen, mechanically stirring, heating to 240 ℃, and carrying out vacuum polymerization for 90 minutes to obtain the corresponding polyester amide copolymer PEBDA.
The intrinsic viscosity of the polyesteramide copolymer PEBDA was measured to be 1.28dL/g, indicating that the copolymer had a higher molecular weight. And (5) performing impact resistance test on the alloy. Its notch impact strength at normal temperature is 60kJ/m 2 The notch impact strength at low temperature (-30 ℃) is 3.0kJ/m 2 。
Comparative example 2
This comparative example provides a sample of Pebax 7233 available from alcima. Its notch impact strength at normal temperature is 12kJ/m 2 The notch impact strength at low temperature (-30 ℃) is 3.0kJ/m 2 。
FIG. 15 is a graph comparing notched impact strength at room temperature and low temperature for polyether ester amide elastomers prepared in the examples of the present invention with samples of polyester amide PEBDA and Pebax 7233 in the comparative examples. As can be seen from FIG. 15, the polyether ester amide elastomer obtained by the invention has the normal temperature notch impact resistance equivalent to that of PEBDA, and is superior to that of the PEBax 7233 sample, and the low temperature (-30 ℃) notch impact resistance is far superior to that of the polyester amide PEBDA and polyether amide PEBax 7233 samples. Unlike conventional thermoplastic elastomers, which have a notched impact strength that decreases with decreasing temperature, the low temperature (-30 ℃) notched impact strength is instead higher than the normal temperature notched impact strength for polyether ester amide copolymers with higher polyether content.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (9)
1. A high impact polyether ester amide thermoplastic elastomer, characterized in that the polyether ester amide thermoplastic elastomer comprises three block components of aliphatic polyester, aliphatic polyether and aliphatic polyamide; the chemical structural formula of the polyether ester amide thermoplastic elastomer is as follows:
，
wherein R is 1 Is (CH) 2 ) m M is any integer from 5 to 12; a is 11; b is any integer from 2 to 4; c is any integer from 4 to 44; d. e and f are respectively determined by the content of aliphatic polyester, aliphatic polyether and aliphatic polyamide, wherein the content of the aliphatic polyester is 24.7/36-24.7/31.5, and the content of the aliphatic polyether is 4wt%~25wtThe content of the aliphatic polyamide is 5.3/36-5.3/31.5%, and the sum of the contents of the components is 100%.
2. The polyether ester amide thermoplastic elastomer of claim 1, wherein the polyether ester amide thermoplastic elastomer has a notched impact strength of 10 kilojoules per square meter or greater at ambient to-30 ℃.
3. The polyether ester amide thermoplastic elastomer according to claim 1, wherein when the aliphatic polyether content is 4 wt%~25 wt% the notched impact strength of the polyether ester amide thermoplastic elastomer increases as the temperature decreases from ambient to a low temperature of-30 ℃.
4. The process for preparing a high impact polyether ester amide thermoplastic elastomer according to claim 1, comprising the steps of: diamine, polyether glycol and aliphatic cyclic ester are subjected to ring opening-condensation cascade polymerization reaction under the action of a catalyst to prepare the polyether ester amide thermoplastic elastomer.
5. The process according to claim 4, wherein the diamine is 1, 6-hexamethylenediamine, 1, 10-decamethylenediamine or 1, 12-dodecamethylenediamine; the polyether glycol is polytetrahydrofuran glycol or polyethylene glycol; the aliphatic cyclic ester is musk T; the catalyst is a titanate compound.
6. The process according to claim 4, wherein the ring-opening-condensation polymerization cascade is carried out under inert atmosphere or vacuum conditions; and directly obtaining the polyether ester amide thermoplastic elastomer without post-treatment after the reaction is finished.
7. The method according to claim 4, wherein the polyether glycol has a molecular weight of 200g/mol to 2900g/mol.
8. The method according to claim 4, wherein the ring-opening-condensation polymerization is carried out at a temperature of 200 ℃ to 280 ℃ for 30 minutes to 300 minutes.
9. Use of the polyether ester amide thermoplastic elastomer according to any of claims 1-3 for the preparation of thermoplastic elastomer materials.
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