CN115558102B - Long-chain nylon elastomer and transesterification preparation method - Google Patents
Long-chain nylon elastomer and transesterification preparation method Download PDFInfo
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Abstract
The invention discloses a long-chain nylon elastomer and an acyl ester exchange preparation method, and belongs to the technical field of material synthesis. The method comprises the following steps: putting the hard segment of double-end ester long-chain nylon and polyetheramine into a reaction kettle, adding water, a catalyst and an antioxidant, and using nitrogen to replace air in the system; mixing and stirring for 0-2 h at 80 ℃, and then mixing and stirring for 0-2 h at 150-200 ℃; slowly discharging small molecular products in the system, keeping the pressure below 1kPa, and reacting at 200-250 ℃ for 1-4 hours to complete polymerization; and (5) discharging, cooling in water, granulating and drying to obtain nylon elastomer slices. The nylon elastomer of the invention improves the accuracy of the molar ratio of materials through ester-amide exchange reaction, and can finish block copolymerization without pre-salifying, and the prepared elastomer has elongation at break of more than 500 percent, low processing temperature and hardness range of 40D-70D.
Description
Technical Field
The invention relates to the technical field of synthesis and preparation of high polymer materials, in particular to a long-chain nylon elastomer and an ester-amide exchange preparation method.
Background
Nylon has become a plastic variety with characteristics of multiple varieties, multifunction, specialization, serialization and the like as engineering plastic with the maximum dosage, and can realize the characteristics of super toughness, high strength, flame retardance, low temperature resistance, heat resistance, even an elastomer like rubber and the like. Nylon elastomers are thermoplastic elastomers that use nylon molecular chains as hard segments and polyether or polyester as soft segments.
By adjusting the molecular weight of the soft and hard segments, the type of monomers, the relative proportion and the block mode, a series of thermoplastic elastomers with different properties can be obtained. The nylon chain is folded and crystallized at normal temperature to form physical crosslinking points, and the crystallization is broken at high temperature, so that the crosslinking points are released, and the thermoplastic processing can be performed. The type of hard segment determines the final mechanical properties of the elastomer such as strength, modulus, and the like, as well as the physical properties such as melting point, hardness, density, and chemical stability. The type of soft segment determines the low temperature resistance, hydrophilicity, etc. of the elastomer.
The existing polyether ester type nylon elastomer occupies the mainstream market, is almost monopolized by foreign enterprises, such as Acomat, yingchuang, yu and the like, has higher market price, and has hard segments mainly comprising PA11 or PA12, more complex synthesis process and more working procedures. In the polymerization process of the polyether ester nylon elastomer, the polymerization constants of polyester and polyamide are different, and the process is controlled, so that the synthesis of a polyamide hard segment can be finished firstly when the copolymerization is carried out, and then the alternating copolymerization of a polyether ester soft segment and the polyamide hard segment is carried out, thereby obtaining the nylon elastomer with good performance. However, the process is complicated in process control, high in operation difficulty, and has a certain risk because raw materials need to be supplemented halfway.
At present, a few researches are carried out on nylon elastomers, but most of domestic products are only small in quantity on short-chain nylon elastomers, the hardness is high, and in practical application, elastomers with low hardness and good low temperature resistance are dominant. Secondly, most of elastomer polymerization processes need to be carried out in multiple steps, even feeding is carried out in the middle of high-temperature reaction, and the process is complex. It is urgent to break through the polymerization mode of nylon elastomer, thereby breaking monopoly and occupying the market.
Disclosure of Invention
In order to solve the problems in the prior art, the invention discloses a long-chain nylon elastomer and an ester amide exchange preparation method, which realize the alternate block copolymerization of the long-chain nylon elastomer, and obtain the nylon elastomer material with good performance, large elongation at break and low processing temperature, wherein the hardness is between 40D and 70D.
In order to solve the technical problems, the invention provides the following technical scheme:
on the one hand, the invention provides a preparation method of acyl ester exchange of a long-chain nylon elastomer, which comprises the steps of preparing a long-chain nylon hard segment with low molecular weight and double-end ester groups through prepolymerization end capping, and then carrying out block copolymerization on the nylon hard segment and a polyether amine soft segment through an ester amide exchange method to prepare the long-chain nylon elastomer with good performance. Specifically, the material is prepared from the following raw materials in parts by weight:
the molar ratio of the hard segment of the double-end ester group long-chain nylon to the polyether amine is 1:1, a step of;
the method specifically comprises the following steps:
putting the hard segment of double-end ester long-chain nylon and polyetheramine into a reaction kettle, adding water, a catalyst and an antioxidant, and using nitrogen to replace air in the system; mixing and stirring for 0-2 h at 80 ℃, and then mixing and stirring for 0-2 h at 150-200 ℃; slowly discharging small molecular products in the system, keeping the pressure below 1kPa, and reacting at 200-250 ℃ for 1-4 hours to complete polymerization; and (5) discharging, cooling in water, granulating and drying to obtain nylon elastomer slices.
Further, the hard segment structure of the double-end ester group long-chain nylon is as follows:
wherein, R' group is C0-C8 alkyl, R 1 Methyl or ethyl; x is 10 to 13, y is 8 to 11, and n is 2 to 8.
Further, the hard segment of the double-end ester long-chain nylon is prepared by the following method:
weighing 30-50 parts by weight of chain dibasic acid, 42-50 parts by weight of long-chain diamine, 5-25 parts by weight of end capping agent, 0.1-0.5 part by weight of second catalyst and 0-20 parts by weight of water; adding long-chain dibasic acid, long-chain diamine and a blocking agent into a reaction kettle, adding water and a second catalyst, and uniformly mixing; heating to 150-200 ℃, maintaining the pressure, reacting for 2 hours, and then releasing pressure to obtain the double-end ester long-chain nylon.
Preferably, the long chain diacid is selected from sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid; the long chain diamine is selected from decanediamine, undecanediamine, dodecanediamine and tridecanediamine;
the end capping agent has the following structural formula:
wherein the R' group is C0-C8 alkyl, R 1 Is methyl or ethyl.
Preferably, the second catalyst is one or more of sodium hypophosphite, pyrophosphoric acid and phosphoric acid.
Further, the polyetheramine has the structural formula:
wherein R is 1 The radical being methyl or ethyl, R 2 The group is hydrogen or methyl, the R group is methylene, ethyl, propyl or butyl, and the sum of x, y and z is 33-41.
Preferably, the catalyst is one or more of sodium hypophosphite, pyrophosphoric acid and phosphoric acid;
the antioxidant is a compound system of an antioxidant 1010 and an antioxidant 1098; the weight ratio of the antioxidant 1010 to the antioxidant 1098 is 1:0.5-2.
On the other hand, the invention also provides a long-chain nylon elastomer which is prepared by using the acyl ester exchange preparation method of the long-chain nylon elastomer and is used for plastics, antistatic agents and elastic fibers. The elastomer of 40D-55D can be used as skis, snow boots, flexible injection molding parts, silent gears, TPU processing aids and antistatic agents, and the elastomer of 55D-70D can be used as nylon 6, nylon 66 rubber coating materials, explosion-proof hoses, flexible films, high-grade door and window sealing materials and the like.
Compared with the prior art, the invention has the following beneficial effects:
1) The invention synthesizes the low molecular nylon hard segment in advance, and uses the ester group to protect the end group, so as to ensure that the functional group is not damaged by high temperature, and can carry out regular block copolymerization;
2) The end capping agent adopted by the invention has the same chain structure as nylon, and the final characteristics are not affected;
3) The nylon elastomer prepared by the method has almost no terminal carboxyl, does not generate ionized acid under long-time wetting condition, and has better hydrolysis resistance.
The invention utilizes the indigenous advantage of biological fermentation of long-chain diamine and long-chain diacid monomer, and takes the long-chain diamine and the long-chain diacid monomer as an elastomer hard segment to prepare the long-chain nylon elastomer, and has the characteristics of wide raw material source, good low-temperature impact property, excellent processability and the like.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention more apparent, the following detailed description will be made with reference to specific embodiments.
The materials and reagents used in the present invention are not specifically described and are commercially available.
The invention provides a long-chain nylon elastomer and a transesterification preparation method, and specific examples are as follows.
Example 1
A transesterification preparation method of a long-chain nylon elastomer comprises the following steps:
50 parts of dodecanediamine, 30 parts of sebacic acid, 20 parts of end-capping agent, 0.25 part of phosphoric acid and 20 parts of water are added into a reaction kettle, after the air in the system is replaced by nitrogen, the temperature is raised to 200 ℃, the mixture is kept at the temperature for 2 hours, the mixture is discharged after pressure relief, and the hard segment of double-end ester-based long-chain nylon with the number of repeating units being 2 is obtained.
The end capping agent has the structural formula:
37.5 parts of nylon hard segment and 62.5 parts of polyether amine soft segment are added into a reaction kettle, and 10 parts of water, 0.3 part of sodium hypophosphite, 0.25 part of antioxidant 1010 and 0.25 part of antioxidant 1098 are added. After replacing the air in the system with nitrogen, the temperature was raised to 80 ℃ to mix all materials uniformly. Heating to 180 ℃ within 2 hours, and gradually releasing small molecules such as water vapor, ethanol and the like. Keeping the vacuum degree of the system below 1kPa, reacting for 2 hours at 220 ℃, then charging nitrogen into the system, discharging and cooling through a lower discharge hole, and obtaining the long-chain nylon elastomer 1.
The polyether amine has the structure that:
wherein R is 1 The radical being methyl, R 2 The radicals are hydrogen, the sum of x and y is 33, and z is 0.
Example 2
A transesterification preparation method of a long-chain nylon elastomer comprises the following steps:
45 parts of decanediamine, 42 parts of decanedioic acid, 13 parts of end-capping agent, 0.5 part of phosphoric acid and 10 parts of water are added into a reaction kettle, after the air in the system is replaced by nitrogen, the temperature is raised to 200 ℃, the heat preservation and stirring are carried out for 2 hours, the double-end ester group long-chain nylon hard segment is obtained after pressure relief, and the number of repeated units is 4.
49 parts of nylon hard segment and 51 parts of polyether amine soft segment are added into a reaction kettle, and 20 parts of water, 0.5 part of sodium hypophosphite, 0.5 part of antioxidant 1010 and 0.25 part of antioxidant 1098 are added. After replacing the air in the system with nitrogen, the temperature was raised to 80 ℃ to mix all materials uniformly. Heating to 180 ℃ within 2 hours, and gradually releasing small molecules such as water vapor, ethanol and the like. Keeping the vacuum degree of the system below 1kPa, reacting for 2 hours at 220 ℃, then charging nitrogen into the system, discharging and cooling through a lower discharge hole, and obtaining the long-chain nylon elastomer 2.
The capping agent and polyetheramine structures are the same as in example 1.
Example 3
A transesterification preparation method of a long-chain nylon elastomer comprises the following steps:
42 parts of decanediamine, 48 parts of dodecanedioic acid, 10 end capping agent, 0.3 part of phosphoric acid and 15 parts of water are added into a reaction kettle, after the air in the system is replaced by nitrogen, the temperature is raised to 200 ℃, the heat preservation and stirring are carried out for 2 hours, the double-end ester group long-chain nylon hard segment is obtained after pressure relief, and the number of repeated units is 5.
55 parts of nylon hard segment and 45 parts of polyether amine soft segment are added into a reaction kettle, and 10 parts of water, 0.3 part of sodium hypophosphite, 0.5 part of antioxidant 1010 and 0.25 part of antioxidant 1098 are added. After replacing the air in the system with nitrogen, the temperature was raised to 80 ℃ to mix all materials uniformly. Heating to 180 ℃ within 2 hours, and gradually releasing small molecules such as water vapor, ethanol and the like. Keeping the vacuum degree of the system below 1kPa, reacting for 2 hours at 220 ℃, then charging nitrogen into the system, discharging and cooling through a lower discharge hole, and obtaining the long-chain nylon elastomer 3.
The capping agent and polyetheramine structures are the same as in example 1.
Example 4
A transesterification preparation method of a long-chain nylon elastomer comprises the following steps:
49 parts of dodecanediamine, 41 parts of sebacic acid, 10 parts of end-capping agent, 0.25 part of phosphoric acid and 20 parts of water are added into a reaction kettle, after the air in the system is replaced by nitrogen, the temperature is raised to 200 ℃, the heat preservation and stirring are carried out for 2 hours, the double-end ester group long-chain nylon hard segment is obtained after pressure relief, and the number of repeated units is 5.
The end capping agent has the structural formula:
62 parts of nylon hard segment and 38 parts of polyether amine soft segment are added into a reaction kettle, and 10 parts of water, 0.3 part of sodium hypophosphite, 0.2 part of antioxidant 1010 and 0.4 part of antioxidant 1098 are added. After replacing the air in the system with nitrogen, the temperature was raised to 80 ℃ to mix all materials uniformly. Heating to 180 ℃ within 2 hours, and gradually releasing small molecules such as water vapor, ethanol and the like. Keeping the vacuum degree of the system below 1kPa, reacting for 2 hours at 220 ℃, then charging nitrogen into the system, discharging and cooling through a lower discharge hole, and obtaining the long-chain nylon elastomer 4.
The polyether amine has the structure that:
wherein R is 1 The radical being methyl, R 2 The radicals are hydrogen, the radicals R are methylene, the sum of x and y is 6, and z is 35.
Example 5
A transesterification preparation method of a long-chain nylon elastomer comprises the following steps:
48 parts of dodecane diamine, 45.5 parts of undecanedioic acid, 6.5 parts of end-capping agent, 0.25 part of phosphoric acid and 20 parts of water are added into a reaction kettle, after the air in the system is replaced by nitrogen, the temperature is raised to 200 ℃, the temperature is kept for 2 hours, the mixture is stirred for 2 hours, and the mixture is discharged after pressure relief, so that the hard segment of the double-end ester-based long-chain nylon with the repeating unit number of 7 is obtained.
69 parts of nylon hard segment and 31 parts of polyether amine soft segment are added into a reaction kettle, and 10 parts of water, 0.3 part of sodium hypophosphite, 0.3 part of antioxidant 1010 and 0.2 part of antioxidant 1098 are added. After replacing the air in the system with nitrogen, the temperature was raised to 80 ℃ to mix all materials uniformly. Heating to 180 ℃ within 2 hours, and gradually releasing small molecules such as water vapor, ethanol and the like. Keeping the vacuum degree of the system below 1kPa, reacting for 2 hours at 220 ℃, then charging nitrogen into the system, discharging and cooling through a lower discharge hole, and obtaining the long-chain nylon elastomer 5.
The capping agent and polyetheramine structures are the same as in example 4.
Example 6
A transesterification preparation method of a long-chain nylon elastomer comprises the following steps:
45 parts of dodecanediamine, 50 parts of sebacic acid, 5 parts of end-capping agent, 0.25 part of phosphoric acid and 20 parts of water are added into a reaction kettle, after the air in the system is replaced by nitrogen, the temperature is raised to 200 ℃, the heat preservation and stirring are carried out for 2 hours, the discharge is carried out after pressure relief, and the double-end ester group long-chain nylon hard segment with the number of repeating units of 9 is obtained.
75 parts of nylon hard segment and 25 parts of polyether amine soft segment are added into a reaction kettle, and 10 parts of water, 0.3 part of sodium hypophosphite, 0.2 part of antioxidant 1010 and 0.3 part of antioxidant 1098 are added. After replacing the air in the system with nitrogen, the temperature was raised to 80 ℃ to mix all materials uniformly. Heating to 180 ℃ within 2 hours, and gradually releasing small molecules such as water vapor, ethanol and the like. Keeping the vacuum degree of the system below 1kPa, reacting for 2 hours at 220 ℃, then charging nitrogen into the system, discharging and cooling through a lower discharge hole, and obtaining the long-chain nylon elastomer 6.
The capping agent and polyetheramine structures are the same as in example 4.
Comparative example 1
36 parts of hexamethylenediamine, 53 parts of dodecanedioic acid, 10 parts of a blocking agent, 0.3 part of phosphoric acid and 15 parts of water are added into a reaction kettle to prepare a long-chain nylon hard segment.
56 parts of nylon hard segment and 44 parts of polyether amine soft segment are added into a reaction kettle, and 10 parts of water, 0.3 part of sodium hypophosphite, 0.5 part of antioxidant 1010 and 0.25 part of antioxidant 1098 are added. The other conditions were the same as in example 3 and were designated as elastomer D1.
Comparative example 2
56 parts of dodecanediamine, 34 parts of adipic acid, 10 parts of a blocking agent, 0.3 part of phosphoric acid and 15 parts of water are added into a reaction kettle to prepare a long-chain nylon hard segment.
59 parts of nylon hard segment and 41 parts of polyether amine soft segment are added into a reaction kettle, and 10 parts of water, 0.3 part of sodium hypophosphite, 0.5 part of antioxidant 1010 and 0.25 part of antioxidant 1098 are added. The other conditions were the same as in example 3 and were designated as elastomer D2.
The elastomers prepared in the examples and comparative examples of the present invention were subjected to performance tests, in particular:
tensile properties: with reference to the measurement of the tensile properties of GB/T1040.1-2018 plastics, tests were carried out on type 1BA bars at a speed of 50mm/min, at least 5 bars were tested, and the results averaged.
Hardness: the indentation hardness (Shore hardness) standard is measured by using a durometer with reference to GB/T2411-2008 plastic and hard rubber, the Shore hardness D/1s of a 6mm thick wafer sample is measured, at least five points are taken for testing, and the result is averaged.
The results of the performance test on the long chain nylon elastomers prepared in examples 1-6 are shown in Table 1. The results of the elastomer performance test prepared in comparative examples 1-2 are shown in Table 2.
TABLE 1
| Numbering device | Hardness D | Elongation at break% |
| Long chain nylon elastomer 1 | 40 | 600 |
| Long chain nylon elastomer 2 | 50 | 600 |
| Long chain nylon elastomer 3 | 55 | 600 |
| Long chain nylon elastomer 4 | 60 | 500 |
| Long chain nylon elastomer 5 | 65 | 500 |
| Long chain nylon elastomer 6 | 70 | 500 |
As can be seen from Table 1, the long-chain nylon elastomer prepared by the invention has a larger elongation at break, and the Shore hardness of the low hardness mark of the prepared long-chain nylon elastomer is in the range of 40D-70D.
The invention synthesizes the low molecular nylon hard segment in advance, and uses the ester group to protect the end group, so as to ensure that the functional group is not damaged by high temperature, and can carry out regular block copolymerization; and the adopted end capping agent has the same chain structure as nylon, and the final performance is not affected.
TABLE 2
| Numbering device | Hardness D | Fracture ofElongation% |
| Elastomer D1 | 55 | 250 |
| Elastomer D2 | 58 | 250 |
As can be seen from Table 2, the elongation at break of the present invention is significantly higher than that of the comparative examples, with little difference in hardness, compared with the elastomers prepared using different diamines (comparative example 1) and diacids (comparative example 2).
In conclusion, the nylon elastomer improves the accuracy of the molar ratio of materials through ester-amide exchange reaction, can complete block copolymerization without pre-salifying, and is prepared into a long-chain nylon elastomer material with good performance, wherein the elongation at break of the prepared elastomer is more than 500%, the processing temperature is low, and the hardness range is 40-70D.
While the foregoing is directed to the preferred embodiments of the present invention, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the principles of the invention.
Claims (7)
1. The acyl ester exchange preparation method of the long-chain nylon elastomer is characterized by comprising the following steps of:
the molar ratio of the hard segment of the double-end ester group long-chain nylon to the polyether amine is 1:1, a step of;
the acyl ester exchange preparation method of the long-chain nylon elastomer comprises the following steps:
putting the hard segment of double-end ester long-chain nylon and polyetheramine into a reaction kettle, adding water, a catalyst and an antioxidant, and using nitrogen to replace air in the system; mixing and stirring for 0-2 h at 80 ℃, and then mixing and stirring for 0-2 h at 150-200 ℃; slowly discharging small molecular products in the system, keeping the pressure below 1kPa, and reacting at 200-250 ℃ for 1-4 hours to complete polymerization; cooling the discharged materials in water, granulating and drying to obtain nylon elastomer slices;
the hard segment structure formula of the double-end ester group long-chain nylon is as follows:
wherein R is 1 Is methyl or ethyl, x is 10-13, y is 8-11, n is 2-8;
the double-end ester long-chain nylon hard segment is prepared by the following method:
weighing 30-50 parts by weight of long-chain dibasic acid, 42-50 parts by weight of long-chain diamine, 5-25 parts by weight of end capping agent, 0.1-0.5 part by weight of second catalyst and 0-20 parts by weight of water; adding long-chain dibasic acid, long-chain diamine and a blocking agent into a reaction kettle, adding water and a second catalyst, and uniformly mixing; heating to 150-200 ℃, maintaining the pressure, reacting for 2 hours, and then releasing pressure to obtain double-end ester long-chain nylon;
the end capping agent has the following structural formula:
wherein R is 1 Is methyl or ethyl.
2. The method for producing a long-chain nylon elastomer according to claim 1, wherein the long-chain dibasic acid is sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid; the long-chain diamine is decanediamine, undecanediamine, dodecanediamine and tridecanediamine.
3. The method for producing a long-chain nylon elastomer according to claim 2, wherein the second catalyst is one or more of sodium hypophosphite, pyrophosphoric acid and phosphoric acid.
4. The method for preparing the long-chain nylon elastomer by acyl ester exchange according to claim 1, wherein the polyether amine has the following structural formula:
wherein R is 1 The radical being methyl or ethyl, R 2 The group is hydrogen or methyl, the R group is methylene, ethylene, propylene or butylene, and the sum of x, y and z is 33-41.
5. The method for preparing acyl ester exchange of long-chain nylon elastomer according to claim 1, wherein the catalyst is one or more of sodium hypophosphite, pyrophosphoric acid and phosphoric acid;
the antioxidant is a compound system of an antioxidant 1010 and an antioxidant 1098; the weight ratio of the antioxidant 1010 to the antioxidant 1098 is 1:0.5-2.
6. The long-chain nylon elastomer is characterized by being prepared by the acyl ester exchange preparation method of the long-chain nylon elastomer according to any one of claims 1-5.
7. The long-chain nylon elastomer according to claim 6, wherein the shore hardness is 40D to 70D, and the elastomer is used for plastics, antistatic agents and elastic fibers.
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| CN104910377A (en) * | 2014-03-10 | 2015-09-16 | 湖南师范大学 | PA6 type polyamide thermoplastic elastomer preparation method |
| CN108299639A (en) * | 2018-02-01 | 2018-07-20 | 沧州旭阳科技有限公司 | A kind of transparent polyamide thermoplastic elastomer (TPE) and preparation method thereof |
| CN110655646A (en) * | 2019-09-16 | 2020-01-07 | 北京化工大学 | Preparation method of long carbon chain nylon elastomer |
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