CN108503824A - A kind of polyamide 5X melts, resin and preparation method thereof - Google Patents
A kind of polyamide 5X melts, resin and preparation method thereof Download PDFInfo
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- CN108503824A CN108503824A CN201710102851.0A CN201710102851A CN108503824A CN 108503824 A CN108503824 A CN 108503824A CN 201710102851 A CN201710102851 A CN 201710102851A CN 108503824 A CN108503824 A CN 108503824A
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- polyamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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Abstract
Disclosure of the invention a kind of polyamide 5X melts and its polyamide 5X resins obtained.Polyamide 5X melts include the oligomer of 0.2 2.4wt%.The polyamide 5X resins of the present invention, by the adjusting to oligomer, greatly improves the fracture of wire occurred during pelletizing, influences the problem of pelletizing effect and resin quality so that pelletizing effect greatly improves, obtained polyamide 5X resin particles are full, good quality.
Description
Technical field
The present invention relates to a kind of polyamide 5X melts, resin and preparation method thereof.
Background technology
Polyamide refers to the polymer with amide groups repetitive unit on macromolecular chain, has excellent mechanical property, forming
The comprehensive performances such as processability, wearability, chemical-resistant, main application fields are fiber and engineering plastics, can be used for making on a small quantity
Standby film.The thirties in last century, E.I.Du Pont Company realizes the industrialized production of polyamide first, and is applied to fiber art.20 generation
It records the eighties, with the rapid development of auto industry and electronic apparatus industry, polyamide becomes dosage maximum, application field
Most wide engineering plastics.Now widely used polyamide has polyamide 6 (PA6) and polyamide 66 (PA66).
Polyamide 5X is a kind of novel polyamide, is polymerized by 1,5- pentanediamines and binary acid.The prior art
Polyamide 5X resins can be prepared by following technique：Concentration → high pressure precondensation → flash distillation → normal pressure or vacuum polycondensation → pelletizing
It is molded to obtain resin.But in the preparation process through above-mentioned polyamide 5X resins, broken end filament phenomenon is more serious when pelletizing, shadow
Ring pelletizing effect and resin quality.The phenomenon is urgently to be resolved hurrily.
Invention content
There is fracture of wire phenomenon to solve polyamide 5X resins during pelletizing in the present invention, influences pelletizing effect and resin
The defect of quality provides a kind of polyamide 5X resins and preparation method thereof.
Inventor has carried out numerous studies to the preparation process of polyamide 5X resins, the phenomenon that reduce pelletizing fracture of wire,
Obtain the polyamide 5X slices of good quality.In the course of the research, inventor carries out each step of polymerization technique
Deep discussion has carried out many experiments, it is found that the effect of pelletizing is affected by many factors to each parameter, wherein poly-
The content of oligomer in amide 5X, has a direct impact the quality of pelletizing effect, by oligomer control in particular range,
Pelletizing effect can greatly be improved, obtain particle uniformly, the resin of good quality, result in the technical side of the present invention
Case.
It is an object of the invention to：A kind of polyamide 5X melts are provided, the polyamide 5X melts include 0.2-
The oligomer of 2.4wt%, the percentage are the mass percent for accounting for polyamide 5X resins.
Another object of the present invention is：A kind of polyamide 5X resins, the polyamide 5X resins, by polyamide 5X are provided
Melt is obtained through pelletizing；Wherein, the polyamide 5X melts include the oligomer of 0.2-2.4wt%, and the percentage is to account for
The mass percent of polyamide 5X melts.
It is further described below for the preferred technical solution of the present invention：
A preferred technical solution of the invention, it is single that the polyamide 5X, which includes with 1,5- pentanediamines and dicarboxylic acids,
The polyamide that body polymerize.Wherein the dicarboxylic acids can be short chain diacid (carbon atom number is less than 10 in carbochain),
It can also be long carbochain biatomic acid；Wherein, the short chain diacid preferably includes succinic acid, glutaric acid, adipic acid, pimelic acid,
Suberic acid, one or more in azelaic acid and decanedioic acid, preferably adipic acid and/or decanedioic acid；The long carbochain biatomic acid is excellent
Choosing includes eleven carbon diacids, dodecanedicarboxylic acid, tridecanyldicarboxylic acid, tetradecane diacid, 15 carbon dicarboxylic acids, 16 carbon
Binary acid, seventeen carbon diacids, octadecane diacid, maleic acid and Δ 9-1, it is one or more in 18 octadecylene binary acid.
A preferred technical solution of the invention, the oligomer includes polyamide cyclic oligomer, such as：Polyamide
Unitary and/or polynary cyclic oligomer；Wherein, the polynary cyclic oligomer may include：Polyamide binary cyclic oligomer,
One kind or more in polyamide three membered cyclic oligomer, polyamide quaternary cyclic oligomer and polyamide five-membered cyclic oligomer
Kind.
Preferably, the structural formula of the polyamide cyclic oligomer can be：
It is wherein preferred, n=1-8, preferred n=1-5.
It is wherein preferred, m=2-16, preferred=4-10.
The content of a preferred technical solution of the invention, the oligomer is 0.4-2.0wt%, more preferable 0.5-
1.6wt%, the percentage are the mass percent for accounting for polyamide 5X melts.
The content of a preferred technical solution of the invention, the polyamide unitary cyclic oligomer is 20-45%, preferably
30-40%, the percentage are the mass percent for accounting for oligomer.
The content of a preferred technical solution of the invention, the polyamide binary cyclic oligomer is 15-35%, preferably
20-30%, the percentage are the mass percent for accounting for oligomer.
The content of a preferred technical solution of the invention, the polyamide three membered cyclic oligomer is 20-45%, preferably
30-40%, the percentage are the mass percent for accounting for oligomer.
A preferred technical solution of the invention, the content of the polyamide quaternary cyclic oligomer are 10% hereinafter, excellent
It selects 5% hereinafter, the percentage is the mass percent for accounting for oligomer.
A preferred technical solution of the invention, the content of the polyamide five-membered cyclic oligomer are 10% hereinafter, excellent
It selects 5% hereinafter, the percentage is the mass percent for accounting for oligomer.
Such as：When the polyamide 5X is polyamide 56, including the structural formula of oligomer can be：
It is wherein preferred, n=1-8, preferred n=1-5.
Again for example：When the polyamide 5X is polyamide 510, including the structural formula of oligomer can be：
It is wherein preferred, n=1-8, preferred n=1-5.
Oligomer is investigated to pelletizing influential effect, it has been recognised by the inventors that caused by may being due to the following reasons：It is oligomeric
The volatilization of object can increase the bubble in polyamide 5X melts, so that when melt wire drawing pelletizing, broken end occur, filament shows
As.By oligomer control in particular range, can greatly improve pelletizing effect, obtain particle uniformly, good quality
Resin, but the amount of oligomer, nor more lower better, when the amount of oligomer reduces to a certain extent, bubble rises instead.
And on the other hand, the content of the moisture in polyamide 5X melts also has very greatly the quality of polyamide 5X resin pellets
Influence.It is conventional often to think：Moisture is more, causes air bubble content in polyamide 5X melts to increase significantly, in pelletizing
The phenomenon that easily causing broken end, filament.And moisture is lower, broken end, filament phenomenon are fewer.However, inventor is by a large amount of real
It tests, obtained conclusion is really different from above-mentioned existing cognition, and experimental result is shown：It is controlled on the basis of certain content in oligomer
On, certain moisture is conducive to the reduction of bubble instead, that is to say, that：Oligomer coordinates specific polyamide 5X
Water content, the phenomenon that broken end when can be further reduced polyamide 5X resin pellets, filament.On this basis, this has been obtained
The preferred technical solution of invention.
The moisture of a preferred technical solution of the invention, the polyamide 5X melts is 600-18000ppm, excellent
It is to account for the mass percent of polyamide 5X melts to select 1200-9000ppm, the content.
Another object of the present invention is：A kind of polyamide 5X resins are provided, the polyamide 5X resins include 0.2-
The oligomer of 2.4wt%, the percentage are the mass percent for accounting for polyamide 5X resins.
The water content of a preferred technical solution of the invention, the polyamide 5X resins is 200-2000ppm, preferably
400-1500ppm。
The terminal amino group content of a preferred technical solution of the invention, the polyamide 5X resins is 20-70mol/ton,
It is preferred that 30-60mol/ton.
The content of carboxyl end group of a preferred technical solution of the invention, the polyamide 5X resins is 50mol/ton or more,
It is preferred that 60-100mol/ton.
It is a further object of the invention to provide a kind of preparation methods of polyamide 5X melts, include the following steps：
(1) under condition of nitrogen gas, 1,5- pentanediamines, aliphatic dibasic acid and water are uniformly mixed, the salt that polyamide is made is molten
Liquid；Wherein, the molar ratio of 1,5- pentanediamines and aliphatic dibasic acid is (1-1.05)：1；
(2) salting liquid of polyamide is heated, pressure rises to 0.3-2.0Mpa in reaction system, is vented, and pressurize makes pressurize
At the end of the temperature of reaction system be 232-265 DEG C, then being depressured makes in reaction system pressure be down to 0-0.2MPa (gauge pressure), and drops
The temperature of reaction system is 245-280 DEG C after pressure, vacuumizes, obtains polyamide melt；It is wrapped in the polyamide 5X melts
The oligomer of 0.2-2.4wt% is included, the percentage is the mass percent for accounting for polyamide 5X resins.
A preferred technical solution of the invention, the time vacuumized are 10-45min.
A preferred technical solution of the invention, it is described vacuumize after vacuum degree be -0.01~-0.08Mpa (gauge pressure).
A preferred technical solution of the invention, it is described vacuumize after temperature be 260-280 DEG C.
A preferred technical solution of the invention, a concentration of 30-90% of the salting liquid of the polyamide, preferably 50-
75%；The percentage is the mass percent for the salting liquid for accounting for polyamide.
A preferred technical solution of the invention, the salting liquid of the polyamide a concentration of 10% when pH value be 6 with
On, preferably 7.2-8.9, more preferable 7.5-8.2, the percentage are the mass percent for the salting liquid for accounting for polyamide.
Another object of the present invention is：A kind of preparation method of polyamide 5X resins is provided, the preparation method includes
Following steps：By polyamide 5X melts as described above, resin is obtained through pelletizing.
After the pelletizing, preferably it is dried under the normal condition of this field.
The polyamide 5X resins of the present invention are greatly improved pelletizing and are gone out in the process by the adjusting to oligomer
Existing fracture of wire influences the problem of pelletizing effect and resin quality so that pelletizing effect greatly improves, obtained polyamide 5X resins
Full grains, good quality.
Specific implementation mode
Below by embodiment, the present invention is described in detail, so that the features and advantages of the present invention become apparent from.But it answers
This points out that embodiment is used to understand that the design of the present invention, the scope of the present invention to be not limited only to reality listed herein
Apply example.
In the present invention, the detection method of each parameter is as follows：
1, the detection method of oligomer：
By 56 sample of polyamide in convection oven 130 DEG C of dryings 7 hours, be put into drying after being then placed in aluminium plastic bag sealing
Cooling in device, then 56 sample of precise polyamide about 2g, 56 sample of polyamide is placed in 250mL round-bottomed flasks, is added
100mL pure water is flowed back 24 hours with heating mantle heats, takes 56 sample of polyamide to be cleaned three times with pure water, 56 sample of polyamide
It is 7 hours dry in 130 DEG C of convection ovens, it is then transferred in the aluminium plastic bag weighed in advance, is put into after sealing cold in drier
But, claim aluminium plastic bag to subtract each other with aluminium plastic bag weight with 56 sample gross weight of polyamide, obtain 56 example weight of polyamide after boiling, pass through
The comparison forward and backward weight difference of polyamide sample boiling calculates oligomer.Each sample takes Duplicate Samples to detect.
2, Amino End Group and end carboxyl：After trifluoroethanol sample dissolution, normal hydrochloric acid liquid and sodium hydroxide mark are used respectively
Quasi- drop is fixed, and calculates.
3, the aqueous quantity measuring method of resin：1g resin samples are taken, are measured using karl Fischer moisture teller, detection temperature
200 DEG C of degree, detection time 20min.
Embodiment 1
(1) under condition of nitrogen gas, 1,5- pentanediamines, adipic acid and water are uniformly mixed, the salt that 80% polyamide is made is molten
Liquid, wherein salt weight 20kg；The molar ratio of 1,5- pentanediamines and adipic acid is (1-1.05)：1, the salting liquid of polyamide it is a concentration of
PH value when 10% is 8.2, and the percentage is the mass percent for the salting liquid for accounting for polyamide；
(2) salting liquid of polyamide is heated, pressure rises to 1.7Mpa in reaction system, is vented, pressurize, at the end of pressurize
The temperature of reaction system is 245 DEG C, then being depressured makes pressure in reaction system be down to 0.02MPa (gauge pressure), is reacted after decompression
The temperature of system is 260 DEG C, vacuumizes and maintains -0.01Mpa, pumpdown time 40min, and the temperature after vacuum is 268 DEG C,
Obtain polyamide melt；
56 melt of polyamide includes that (percentage is the quality percentage for accounting for 56 melt of polyamide for the oligomer of 0.9wt%
Than)；
Wherein, the composition of oligomer and its content are as follows：
(3) pelletizing, it is dry, obtain resin；
(percentage is the quality for accounting for 56 resin of polyamide to the middle oligomer 0.9wt% of 56 resin of polyamide obtained
Percentage).
Embodiment 2
(1) under condition of nitrogen gas, 1,5- pentanediamines, adipic acid and water are uniformly mixed, the salt that 60% polyamide is made is molten
Liquid, wherein salt weight 20kg；The molar ratio of 1,5- pentanediamines and adipic acid is (1-1.05)：1, the salting liquid of polyamide it is a concentration of
PH value when 10% is 7.3, and the percentage is the mass percent for the salting liquid for accounting for polyamide；
(2) salting liquid of polyamide is heated, pressure rises to 1.2Mpa in reaction system, is vented, pressurize, at the end of pressurize
The temperature of reaction system is 250 DEG C, then being depressured makes pressure in reaction system be down to 0.05MPa (gauge pressure), is reacted after decompression
The temperature of system is 265 DEG C, vacuumizes and maintains -0.02Mpa, pumpdown time 15min, and the temperature after vacuum is 275 DEG C,
Obtain polyamide melt；
56 melt of polyamide includes that (percentage is the quality percentage for accounting for 56 melt of polyamide for the oligomer of 1.3wt%
Than)；
Wherein, the composition of oligomer and its content are as follows：
(3) pelletizing, it is dry, obtain resin；
(percentage is the quality for accounting for 56 resin of polyamide to the middle oligomer 1.3wt% of 56 resin of polyamide obtained
Percentage).
Embodiment 3
(1) under condition of nitrogen gas, 1,5- pentanediamines, adipic acid and water are uniformly mixed, the salt that 75% polyamide is made is molten
Liquid, wherein salt weight 20kg；The molar ratio of 1,5- pentanediamines and adipic acid is (1-1.05)：1, the salting liquid of polyamide it is a concentration of
PH value when 10% is 7.5, and the percentage is the mass percent for the salting liquid for accounting for polyamide；
(2) salting liquid of polyamide is heated, pressure rises to 1.6Mpa in reaction system, is vented, pressurize, at the end of pressurize
The temperature of reaction system is 246 DEG C, then being depressured makes pressure in reaction system be down to 0.01MPa (gauge pressure), is reacted after decompression
The temperature of system is 262 DEG C, vacuumizes and maintains -0.07Mpa, pumpdown time 25min, and the temperature after vacuum is 270 DEG C,
Obtain polyamide melt；
56 melt of polyamide includes that (percentage is the quality percentage for accounting for polyamide 5X melts for the oligomer of 1.5wt%
Than), and water content is 3000ppm in polyamide 5X melts；
Wherein, the composition of oligomer and its content are as follows：
(3) pelletizing, it is dry, obtain resin；
The middle oligomer 1.5wt% of 56 resin of polyamide obtained, moisture are that (percentage is poly- to account for by 800ppm
The mass percent of 56 resin of amide).
Embodiment 4
(1) under condition of nitrogen gas, 1,5- pentanediamines, adipic acid and water are uniformly mixed, the salt that 60% polyamide is made is molten
Liquid, wherein salt weight 20kg；The molar ratio of 1,5- pentanediamines and adipic acid is (1-1.05)：1, the salting liquid of polyamide it is a concentration of
PH value when 10% is 8.1, and the percentage is the mass percent for the salting liquid for accounting for polyamide；
(2) salting liquid of polyamide is heated, pressure rises to 1.1Mpa in reaction system, is vented, pressurize, at the end of pressurize
The temperature of reaction system is 235 DEG C, then being depressured makes pressure in reaction system be down to 0.01MPa (gauge pressure), is reacted after decompression
The temperature of system is 262 DEG C, vacuumizes and maintains -0.04Mpa, pumpdown time 35min, and the temperature after vacuum is 271 DEG C,
Obtain polyamide melt；
56 melt of polyamide includes the oligomer of 1.2wt%, and water content is 5000ppm (hundred in polyamide 5X melts
Divide than being the mass percent for accounting for polyamide 5X melts)；
Wherein, the composition of oligomer and its content are as follows：
(3) pelletizing, it is dry, obtain resin；
The middle oligomer 1.2wt% of 56 resin of polyamide obtained, moisture are that (percentage is to account for 1200ppm
The mass percent of 56 resin of polyamide).
Embodiment 5
(1) under condition of nitrogen gas, 1,5- pentanediamines, decanedioic acid and water are uniformly mixed, the salt that 60% polyamide is made is molten
Liquid, wherein salt weight 20kg；The molar ratio of 1,5- pentanediamines and adipic acid is (1-1.05)：1, the salting liquid of polyamide it is a concentration of
PH value when 10% is 7.92, and the percentage is the mass percent for the salting liquid for accounting for polyamide；
(2) salting liquid of polyamide is heated, pressure rises to 1.3Mpa in reaction system, is vented, pressurize, at the end of pressurize
The temperature of reaction system is 235 DEG C, then being depressured makes pressure in reaction system be down to 0MPa (gauge pressure), reaction system after decompression
Temperature be 258 DEG C, vacuumize and maintain -0.02Mpa, pumpdown time 28min, the temperature after vacuum is 265 DEG C, is obtained
Polyamide melt；
The middle oligomer 0.4wt% of 510 melt of polyamide obtained, moisture are that (percentage is to account for 5000ppm
The mass percent of 56 melt of polyamide).
Wherein, the composition of oligomer and its content are as follows：
(3) pelletizing, it is dry, obtain resin；
The middle oligomer 0.4wt% of 510 resin of polyamide obtained, moisture are that (percentage is to account for 1200ppm
The mass percent of 56 resin of polyamide).
Comparative example 1
(1) under condition of nitrogen gas, 1,5- pentanediamines, adipic acid and water are uniformly mixed, the salt that 60% polyamide is made is molten
Liquid, wherein salt weight 20kg；The molar ratio of 1,5- pentanediamines and adipic acid is (1-1.05)：1, the salting liquid of polyamide it is a concentration of
PH value when 10% is 8.38, and the percentage is the mass percent for the salting liquid for accounting for polyamide；
(2) salting liquid of polyamide is heated, pressure rises to 1.8Mpa in reaction system, is vented, pressurize, at the end of pressurize
The temperature of reaction system is 250 DEG C, then being depressured makes pressure in reaction system be down to 0.01MPa (gauge pressure), is reacted after decompression
The temperature of system is 275 DEG C, vacuumizes and maintains -0.01Mpa, pumpdown time 50min, and the temperature after vacuum is 285 DEG C,
Obtain polyamide melt；
(3) pelletizing, it is dry, obtain resin.
The middle oligomer 2.5wt% of 56 resin of polyamide obtained.
Polyamide 5X resin slicers made from embodiment 1-5 must break end as shown in the table with filament number：
| Pelletizing effect | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 |
| Broken end | 5 | 9 | 3 | 4 | 1 | 25 |
| Filament | 3 | 7 | 2 | 3 | 2 | 31 |
| It amounts to | 8 | 16 | 5 | 7 | 3 | 56 |
Above example is the explanation to technical solution, does not constitute the limitation to the technology of the present invention.
Unless limited otherwise, term used herein is the normally understood meaning of those skilled in the art.
Embodiment described in the invention is merely for exemplary purpose, not to limit the scope of the invention,
Those skilled in the art can be made within the scope of the invention various other replacements, changes and improvements, thus, the present invention is not limited to
The above embodiment, and be only defined by the claims.
Claims (12)
1. a kind of polyamide 5X melts, the polyamide 5X melts include the oligomer of 0.2-2.4wt%, and the percentage is
Account for the mass percent of polyamide 5X melts.
2. a kind of polyamide 5X resins, the polyamide 5X resins are obtained by polyamide 5X melts through pelletizing；Wherein, described poly-
Amide 5X melts include the oligomer of 0.2-2.4wt%, and the percentage is the mass percent for accounting for polyamide 5X melts.
3. polyamide 5X resins as claimed in claim 2, it is characterised in that：The polyamide 5X refers to 1,5- pentanediamines
It is the polyamide that monomer polymerization obtains with binary acid；The wherein described binary acid preferably include succinic acid, glutaric acid, adipic acid,
Pimelic acid, suberic acid, azelaic acid, decanedioic acid, eleven carbon diacids, dodecanedicarboxylic acid, tridecanyldicarboxylic acid, 14 carbon binary
Acid, 15 carbon dicarboxylic acids, 16-dicarboxylic acid, seventeen carbon diacids, octadecane diacid, maleic acid and Δ 9-1,18 octadecylenes
It is one or more in binary acid.
4. polyamide 5X resins as claimed in claim 2 or claim 3, it is characterised in that：The oligomer includes：Polyamide ring-type is low
Polymers preferably includes：The unitary cyclic oligomer and/or polynary cyclic oligomer of polyamide；
The structural formula of the polyamide cyclic oligomer is：
It is wherein preferred, n=1-8, preferred n=1-5；
It is wherein preferred, m=2-16, preferred=4-10.
5. such as claim 2-4 any one of them polyamide 5X resins, it is characterised in that：The content of the oligomer is 0.4-
2.0wt%, preferably 0.5-1.6wt%, the percentage are the mass percent for accounting for polyamide 5X resins.
6. such as claim 2-5 any one of them polyamide 5X resins, the oligomer includes：Polyamide unitary cyclic oligomer
Five yuan of object, polyamide binary cyclic oligomer, polyamide three membered cyclic oligomer, polyamide quaternary cyclic oligomer and polyamide
It is one or more in cyclic oligomer；
And/or the content of the polyamide unitary cyclic oligomer is 20-45%, preferably 30-40%；
And/or the content of the polyamide binary cyclic oligomer is 15-35%, preferably 20-30%；
And/or the content of the polyamide three membered cyclic oligomer is 20-45%, preferably 30-40%；
And/or the content of the polyamide quaternary cyclic oligomer is 10% hereinafter, it is preferred that 5% or less；
And/or the content of the polyamide five-membered cyclic oligomer is 10% hereinafter, it is preferred that 5% or less；
The percentage is the mass percent for accounting for oligomer.
7. polyamide 5X resins as claimed in claim 2 or claim 3, it is characterised in that：The moisture of the polyamide 5X melts
For 600-18000ppm, preferably 1200-9000ppm, the content is to account for the mass percent of polyamide 5X melts.
8. a kind of polyamide 5X resins, the polyamide 5X resins include the oligomer of 0.2-2.4wt%, and the percentage is to account for
The mass percent of polyamide 5X resins.
9. polyamide 5X resins as claimed in claim 8, it is characterised in that：The water content of polyamide 5X resins of the present invention
For 200-2000ppm, preferably 400-1500ppm；
And/or the terminal amino group content of the polyamide 5X resins is 20-70mol/ton, preferably 30-60mol/ton；
And/or the content of carboxyl end group of the polyamide 5X resins is 50mol/ton or more, preferably 60-100mol/ton.
10. a kind of preparation method of polyamide 5X melts, includes the following steps：
(1) under condition of nitrogen gas, 1,5- pentanediamines, aliphatic dibasic acid and water are uniformly mixed, the salting liquid of polyamide is made；Its
In, the molar ratio of 1,5- pentanediamine and aliphatic dibasic acid is (1-1.05)：1；
(2) salting liquid of polyamide is heated, pressure rises to 0.3-2.0Mpa in reaction system, is vented, and pressurize makes pressurize terminate
When reaction system temperature be 232-265 DEG C, then being depressured makes in reaction system pressure be down to 0-0.2MPa, and the pressure is table
Pressure, and the temperature of reaction system is 245-280 DEG C after decompression, vacuumizes, obtains polyamide melt；
The polyamide 5X melts include the oligomer of 0.2-2.4wt%, and the percentage is the matter for accounting for polyamide 5X resins
Measure percentage.
11. preparation method as claimed in claim 10, it is characterised in that：The time vacuumized is 10-45min；
And/or it is described vacuumize after vacuum degree be -0.01~-0.08Mpa, the pressure be gauge pressure；
And/or it is described vacuumize after temperature be 260-280 DEG C；
And/or a concentration of 30-90% of the salting liquid of the polyamide, the percentage are the matter for the salting liquid for accounting for polyamide
Measure percentage；
And/or the salting liquid of the polyamide a concentration of 10% when pH value be 6 or more, preferably 7.2-8.9, more preferably
7.5-8.2, the percentage are the mass percent for the salting liquid for accounting for polyamide.
12. a kind of preparation method of polyamide 5X resins, the preparation method comprises the following steps：By claim 10 or 11 institutes
The polyamide 5X melts stated, resin is obtained through pelletizing；
After the pelletizing, preferably it is dried.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111040151A (en) * | 2018-10-15 | 2020-04-21 | 上海凯赛生物技术股份有限公司 | Polyamide 5X resin and preparation method and application thereof |
| WO2021031529A1 (en) | 2019-08-22 | 2021-02-25 | 上海凯赛生物技术股份有限公司 | Polyamide 56 fibre with low boiling water shrinkage rate, preparation method therefor, and application thereof |
| CN112759760A (en) * | 2019-11-02 | 2021-05-07 | 上海凯赛生物技术股份有限公司 | High-temperature and low-temperature aging resistant toughened polyamide 5X resin and preparation method thereof |
| WO2021088250A1 (en) | 2019-11-07 | 2021-05-14 | 上海凯赛生物技术股份有限公司 | Polyamide 5x industrial yarn, preparation method therefor and use thereof |
| CN115449070A (en) * | 2021-06-09 | 2022-12-09 | 上海凯赛生物技术股份有限公司 | Polyamide resin, preparation method thereof, composition and fiber product |
| WO2023087547A1 (en) * | 2021-11-19 | 2023-05-25 | 上海凯赛生物技术股份有限公司 | Polyamide resin, composition, and use thereof in engineering plastics |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006348276A (en) * | 2005-05-17 | 2006-12-28 | Mitsubishi Chemicals Corp | Self-hinging molding |
| JP2006348057A (en) * | 2004-05-21 | 2006-12-28 | Mitsubishi Chemicals Corp | Polyamide resin |
| JP2009191156A (en) * | 2008-02-14 | 2009-08-27 | Mitsubishi Chemicals Corp | Polyamide resin and polyamide resin composition |
| CN102046859A (en) * | 2008-03-26 | 2011-05-04 | 东丽株式会社 | Polyamide 56 filament, and fiber structure and air-bag base cloth each comprising the same |
| CN102449029A (en) * | 2009-03-30 | 2012-05-09 | 东丽株式会社 | Polyamide resin, polyamide resin composition, and molded article comprising same |
| CN103980486A (en) * | 2013-02-07 | 2014-08-13 | 上海凯赛生物技术研发中心有限公司 | Preparation method of nylon |
| CN104562271A (en) * | 2013-10-28 | 2015-04-29 | 上海凯赛生物技术研发中心有限公司 | Nylon fibers and preparation method thereof |
| CN106146831A (en) * | 2015-05-12 | 2016-11-23 | 上海凯赛生物技术研发中心有限公司 | Polyamide 56 material prepared by a kind of bio-based 1,5-pentanediamine |
| CN106147223A (en) * | 2015-05-12 | 2016-11-23 | 上海凯赛生物技术研发中心有限公司 | Polyamide 5X is as the application of fire proofing |
-
2017
- 2017-02-24 CN CN201710102851.0A patent/CN108503824B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006348057A (en) * | 2004-05-21 | 2006-12-28 | Mitsubishi Chemicals Corp | Polyamide resin |
| JP2006348276A (en) * | 2005-05-17 | 2006-12-28 | Mitsubishi Chemicals Corp | Self-hinging molding |
| JP2009191156A (en) * | 2008-02-14 | 2009-08-27 | Mitsubishi Chemicals Corp | Polyamide resin and polyamide resin composition |
| CN102046859A (en) * | 2008-03-26 | 2011-05-04 | 东丽株式会社 | Polyamide 56 filament, and fiber structure and air-bag base cloth each comprising the same |
| CN102449029A (en) * | 2009-03-30 | 2012-05-09 | 东丽株式会社 | Polyamide resin, polyamide resin composition, and molded article comprising same |
| CN103980486A (en) * | 2013-02-07 | 2014-08-13 | 上海凯赛生物技术研发中心有限公司 | Preparation method of nylon |
| CN104562271A (en) * | 2013-10-28 | 2015-04-29 | 上海凯赛生物技术研发中心有限公司 | Nylon fibers and preparation method thereof |
| CN106146831A (en) * | 2015-05-12 | 2016-11-23 | 上海凯赛生物技术研发中心有限公司 | Polyamide 56 material prepared by a kind of bio-based 1,5-pentanediamine |
| CN106147223A (en) * | 2015-05-12 | 2016-11-23 | 上海凯赛生物技术研发中心有限公司 | Polyamide 5X is as the application of fire proofing |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111040151A (en) * | 2018-10-15 | 2020-04-21 | 上海凯赛生物技术股份有限公司 | Polyamide 5X resin and preparation method and application thereof |
| CN111040151B (en) * | 2018-10-15 | 2023-10-13 | 上海凯赛生物技术股份有限公司 | Polyamide 5X resin and preparation method and application thereof |
| WO2021031529A1 (en) | 2019-08-22 | 2021-02-25 | 上海凯赛生物技术股份有限公司 | Polyamide 56 fibre with low boiling water shrinkage rate, preparation method therefor, and application thereof |
| CN112759760A (en) * | 2019-11-02 | 2021-05-07 | 上海凯赛生物技术股份有限公司 | High-temperature and low-temperature aging resistant toughened polyamide 5X resin and preparation method thereof |
| CN112759760B (en) * | 2019-11-02 | 2023-09-22 | 上海凯赛生物技术股份有限公司 | High-low temperature aging resistant toughened polyamide 5X resin and preparation method thereof |
| WO2021088250A1 (en) | 2019-11-07 | 2021-05-14 | 上海凯赛生物技术股份有限公司 | Polyamide 5x industrial yarn, preparation method therefor and use thereof |
| CN115449070A (en) * | 2021-06-09 | 2022-12-09 | 上海凯赛生物技术股份有限公司 | Polyamide resin, preparation method thereof, composition and fiber product |
| WO2022257462A1 (en) * | 2021-06-09 | 2022-12-15 | 上海凯赛生物技术股份有限公司 | Polyamide resin and preparation method therefor, composition, and fiber product |
| CN115449070B (en) * | 2021-06-09 | 2024-02-23 | 上海凯赛生物技术股份有限公司 | Polyamide resin and preparation method, composition and fiber product thereof |
| WO2023087547A1 (en) * | 2021-11-19 | 2023-05-25 | 上海凯赛生物技术股份有限公司 | Polyamide resin, composition, and use thereof in engineering plastics |
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