CN109970970A - A kind of high-strength and high ductility transparent nylon material and its preparation and application - Google Patents
A kind of high-strength and high ductility transparent nylon material and its preparation and application Download PDFInfo
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- CN109970970A CN109970970A CN201910312328.XA CN201910312328A CN109970970A CN 109970970 A CN109970970 A CN 109970970A CN 201910312328 A CN201910312328 A CN 201910312328A CN 109970970 A CN109970970 A CN 109970970A
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- nylon
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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
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
Abstract
The present invention relates to a kind of high-strength and high ductility transparent nylon material and its preparation and application, raw material includes: short carbon chain amorphous nylon salt, semi-aromatic nylon salt, Long carbon chain amorphous nylon salt, antioxidant, molecular weight regulator, deionized water etc..Preparation: raw material is thrown into polymeric kettle, can get the transparent terpolyamide material of high-strength and high ductility by polymerization procedures such as heating, pressure maintaining, pressure release, normal pressure, pressurization dischargings.It has the performances such as oil resistant more better than other transparent plastics, corrosion-resistant, wear-resistant, can be widely applied to the fields such as automobile, electronics, machinery, machinery, optics, sport.
Description
Technical field
The invention belongs to modified nylon materials and its preparation and application field, in particular to a kind of high-strength and high ductility transparent nylon
Material and its preparation and application.
Background technique
Transparent nylon is a kind of unformed or micro-crystallization thermoplastic nylon, and light transmittance can reach 90%, and transparency is excellent
In polycarbonate (PC), close to polymethyl methacrylate (PMMA).In addition, it also has good thermal stability, impact
Toughness, electrical insulating property, dimensional stability and resistance to ag(e)ing.Shrink of product rate is low, and linear expansion coefficient is low.Resistance to diluted acid, alkali, fat
Hydrocarbon, aromatic hydrocarbon, esters, ethers, oil & fat, but intolerant to alcohols, it can be dissolved in 80% chloroform and the mixed liquor of 20% methanol.
It is better than PC and PMMA in terms of resisting environmental stress and cracking.Transparent nylon have oil resistant more better than other transparent plastics, it is corrosion-resistant,
It is wear-resistant, resistance to the performances such as to scratch, it is widely used in the fields such as automobile, electronics, machinery, machinery, optics, sport.Currently, transparent poly-
The preparation of amide and relevant technology all rest in a few countries such as the U.S., Japan, France, the domestic research and development to transparent polyamide
It starts late, the novel transparent polyamide types of exploitation are less, and synthesis, processing technology and the related patents of grasp also compare
It is few.The transparent polyamide that China uses greatly will be from foreign procurement, while the selling price of transparent polyamide is all very high, Yi Xiegao
Even as high as ten tens of thousands of yuan per ton of performance.In order to solve the objective fact that transparent polyamide product relies on import for a long time, in order to
Meet the needs of domestic, just there is highly important practical significance to probing into for the polyamide product with high transparency.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of high-strength and high ductility transparent nylon material and its preparation and application,
Overcome prior art preparation complex process, the defects of raw material sources are limited, the present invention by heating, pressure maintaining, pressure release, normal pressure, add
Extruding the polymerization procedures such as material can get the transparent terpolyamide material of high-strength and high ductility.
A kind of terpolyamide material of the invention, in parts by weight, raw material components include:
The short carbon chain amorphous nylon salt be one of caprolactam, nylon salt, nylon 46 salt, 56 salt of nylon or
It is several；Semi-aromatic nylon salt is one of nylon 4T salt, nylon 6T salt, nylon 9 T salt, nylon 5I salt, nylon 6I salt or several
Kind；Long carbon chain nylon salt is one or more of nylon 610 salt, Nylon-1010 Salt, nylon 612 salt, Nylon 1012 salt；Molecule
Measuring regulator is one or more of glacial acetic acid, dodecanedicarboxylic acid, adipic acid；Antioxidant is repefral
One or more of DMP, antioxidant 1098, antioxidant 1010, antioxidant SEED, phosphorous acid.
The nylon 6I salt is synthesized by hexamethylene diamine with M-phthalic acid.
It is further preferred that the short carbon chain amorphous nylon salt is caprolactam, nylon salt；Semi-aromatic nylon salt
For nylon 6T salt (mole amount of substance ratio for be 1.00:1.01 by terephthalic acid (TPA) and hexamethylene diamine, control concentration of salt solution for 40~
60% mass ratio addition deionized water after vacuumizing logical nitrogen discharge air, opens heating device, at salt temperature in polymeric kettle
Degree is 110~150 DEG C, and unlatching stirring motor revolving speed is 30~80r/min；8~10h of reaction time；After the completion of salt-forming reaction
To the salting liquid of nylon 6T, nylon 6T salt is obtained through cooling, crystallization, filtering, vacuum drying)；Long carbon chain nylon salt is nylon
612；Antioxidant is antioxidant 1098.
A kind of preparation method of terpolyamide material of the invention, comprising:
(1) by weight, by 40~60 parts of short carbon chain amorphous nylon salt, 10~40 parts of semi-aromatic nylon salts, 10
~40 parts of long carbon chain nylon salt, 10~30 parts of deionized water, 0~1 part of molecular weight regulator, 0.05~0.2 part anti-
Oxidant is added in polymeric kettle；
(2) polymeric kettle is sealed, air, starting heating device heating is discharged by vacuumizing logical nitrogen, polymerization temperature is
190~280 DEG C, and stir, revolving speed is adjusted in due course within the scope of 30~120r/min, by pressure maintaining, pressure release, normal pressure, is vacuumized
Polymerization reaction leads to nitrogen pressurization discharging finally to get terpolyamide material.
The preferred embodiment of above-mentioned preparation method is as follows:
Short carbon chain amorphous nylon salt, semi-aromatic nylon salt, long carbon chain nylon salt pass through drying in the step (1)
It handles, dry 8~12h in specially 50~80 DEG C of vacuum oven.
Logical nitrogen discharge air is vacuumized in the step (2) specifically: be evacuated to 60~90kPa in polymeric kettle, fill
0.3~0.5Mpa in nitrogen to polymeric kettle makes to maintain normal pressure in kettle after being repeated 3 times.
Starting heating device heating in the step (2), and stir, it polymerize pressure maintaining period specifically: polymerization initial setting up
Heating device is 200~270 DEG C, reaches 190~260 DEG C to temperature in the kettle, and 1~3h is reacted in pressure maintaining, dwell pressure is 1.0~
1.5Mpa, speed of agitator are 100~120r/min.
Pressure release in the step (2) are as follows: certain voltage stabilized range, pressure maintaining knot are maintained by suitably exhaust in pressure maintaining period
It is 220~300 DEG C of pressure releases simultaneously, 0.5~1h of venting duration that heating device temperature, which is arranged, in beam.
Normal pressure in the step (2) specifically: after pressure release, keep polymerization under atmospheric pressure in kettle, 2~5h of time, temperature in kettle
Degree is stepped up to 240~280 DEG C, and motor speed of agitator is adjusted to 50~70r/min.
It is vacuumized in the step (2) are as follows: vacuumized by vacuum pump, vacuum degree is made in kettle to reach 75~95kPa, in kettle
Temperature reaches 250~290 DEG C, and whole process continues 0.5~1.5h, and motor speed of agitator is set as 15~30r/min.
Observation power of motor or torque reach requirement before discharging in the step (2), stop stirring, lead to nitrogen to atmospheric reverse
0.5h is answered, finally heated discharge port, pressurization discharging obtain copolymer nylon slice.
The present invention is by short carbon chain amorphous nylon salt, semi-aromatic nylon salt, long carbon chain nylon salt, deionized water, molecule
Amount regulator, antioxidant are uniformly mixed and are added in polymeric kettle, 190~260 DEG C are heated to, in 1.0~1.5Mpa (table
Pressure) pressure under polymerize 1~3h, be then decompressed to 2~5h of polymerization under atmospheric pressure；Then it is evacuated to 75~95kPa of negative pressure (table in kettle
Pressure), whole process continues 0.5~1.5h；After finally leading to nitrogen to 10~30min of synthesis under normal pressure again, pressurization discharging is produced
Product.
The present invention provides a kind of application of terpolyamide material, such as automobile, electronics, machinery, machinery, optics, body
Equal fields are educated, may be used as visual shield, isolation window, optical protection mirror and the various electronic apparatus, machinery of various devices
Equal fields.
Beneficial effect
The invention belongs to the modified preparation of nylon material, obtained by way of melting copolymerization it is strong with designability, at
Quality reliable and stable (keeping raw material proportioning obtained properties of product stabilization identical with polymerization technique), the advantages such as yield height and
A large amount of waste discharges will not be generated, which has the high-intensitive advantages such as high impact toughness and high transparency.
It has the performances such as oil resistant more better than other transparent plastics, corrosion-resistant, wear-resistant, can be widely applied to automobile,
The fields such as electronics, machinery, machinery, optics, sport.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Caprolactam: Hunan Ba Ling petrochemical industry Co., Ltd；Nylon salt: German BASF Co., Ltd；
Nylon 612 salt: Jianhu County prosperity nylon Co., Ltd；
Antioxidant 1098: Tianjin US business Jie Mei Science and Technology Ltd..
Nylon 6T salt: mole amount of substance ratio for being 1.00:1.01 by terephthalic acid (TPA) and hexamethylene diamine controls concentration of salt solution
Deionized water is added in polymeric kettle for 40~60% mass ratio, after vacuumizing logical nitrogen discharge air, opens heating device,
It is 110~150 DEG C at salt temperature, unlatching stirring motor revolving speed is 30~80r/min；8~10h of reaction time；Salt-forming reaction is complete
The salting liquid that nylon 6T is obtained after obtains nylon 6T salt through cooling, crystallization, filtering, vacuum drying.
Embodiment 1
To include: by the salt that was dried in vacuo 1000g nylon salt, 250g nylon 6T salt, 250g nylon 612 salt,
300ml deionized water, 1.5g antioxidant 1098 are added in 5L polymeric kettle.It is discharged first by vacuumizing logical nitrogen 10min
Air in kettle, unlatching are heated to pressure 1.5Mpa in kettle, and temperature is 200~230 DEG C at this time, motor rotations 120r/min；Start
During which packing stage, time 1h maintain pressure between 1.4~1.5Mpa；Pressure maintaining terminates to be vented to normal pressure time, time
0.5h, temperature rises to 250~270 DEG C at this time；Atmospheric phase reacts 2h, motor rotations 50r/min；Then decompression polymerization
0.5h is gradually evacuated to 80~90kpa of negative pressure, and temperature is 260~290 DEG C, and motor rotations are adjusted to 30r/min；Finally stop
It is stirred to react 10min pressurization discharging, obtains product slice.
Embodiment 2
To include: by the salt that was dried in vacuo 1000g caprolactam, 250g nylon 6T salt, 250g nylon 612 salt,
500ml deionized water, 1.5g antioxidant 1098 are added in 5L polymeric kettle.It is discharged first by vacuumizing logical nitrogen 10min
Air in kettle, unlatching are heated to pressure 1.5Mpa in kettle, and temperature is 200~230 DEG C at this time, motor rotations 120r/min；Start
During which packing stage, time 2h maintain pressure between 1.4~1.5Mpa；Pressure maintaining terminates to be vented to normal pressure time, time
0.5h, temperature rises to 240~260 DEG C at this time；Atmospheric phase reacts 4h, motor rotations 50r/min；Then decompression polymerization 1h,
It is gradually evacuated to 80~90kpa of negative pressure, temperature is 250~270 DEG C, and motor rotations are adjusted to 30r/min；It is anti-finally to stop stirring
10min pressurization discharging is answered, product slice is obtained.
Embodiment 3
To include: by the salt that was dried in vacuo 800g nylon salt, 500g nylon 6T salt, 200g nylon 612 salt,
300ml deionized water, 1.5g antioxidant 1098 are added in 5L polymeric kettle.Polymerization technique is the same as case study on implementation 1.
Embodiment 4
To include: by the salt that was dried in vacuo 800g nylon salt, 200g nylon 6T salt, 500g nylon 612 salt,
300ml deionized water, 1.5g antioxidant 1098 are added in 5L polymeric kettle.Polymerization technique is the same as case study on implementation 1.
Embodiment 5
To include: by the salt that was dried in vacuo 800g caprolactam, 200g nylon 6T salt, 500g nylon 612 salt,
300ml deionized water, 1.5g antioxidant 1098 are added in 5L polymeric kettle.Polymerization technique is the same as case study on implementation 2.
Embodiment 6
To include: by the salt that was dried in vacuo 800g caprolactam, 500g nylon 6T salt, 200g nylon 612 salt,
300ml deionized water, 1.5g antioxidant 1098 are added in 5L polymeric kettle.Polymerization technique is the same as case study on implementation 2.
Table 1: Examples 1 to 6 copolymer nylon performance table
Claims (10)
1. a kind of terpolyamide material, which is characterized in that in parts by weight, raw material components include:
2. nylon material according to claim 1, which is characterized in that the short carbon chain amorphous nylon salt be caprolactam,
One or more of nylon salt, nylon 46 salt, 56 salt of nylon；Semi-aromatic nylon salt is nylon 4T salt, nylon 6T salt, Buddhist nun
One or more of imperial 9T salt, nylon 6I salt；Long carbon chain nylon salt be nylon 610 salt, Nylon-1010 Salt, Nylon 1012 salt,
One or more of nylon 612 salt；Molecular weight regulator is one of glacial acetic acid, dodecanedicarboxylic acid, adipic acid or several
Kind；Antioxidant is repefral DMP, antioxidant 1098, antioxidant 1010, antioxidant SEED, phosphorous
One or more of acid.
3. a kind of preparation method of terpolyamide material, comprising:
(1) by weight, by 40~60 parts of short carbon chain amorphous nylon salt, 10~40 parts of semi-aromatic nylon salts, 10~40
Part long carbon chain nylon salt, 10~30 parts of deionized water, 0~1 part of molecular weight regulator, 0.05~0.2 part anti-oxidant
Agent is added in polymeric kettle；
(2) polymeric kettle is sealed, air, starting heating device heating is discharged by vacuumizing logical nitrogen, and stir, pressure maintaining is let out
Pressure, vacuumizes polymerization reaction at normal pressure, leads to nitrogen pressurization discharging finally to get terpolyamide material.
4. preparation method according to claim 3, which is characterized in that short carbon chain amorphous nylon salt, half in the step (1)
Aromatic nylon salt, long carbon chain nylon salt, which pass through, to be dried, dry 8 in specially 50~80 DEG C of vacuum oven~
12h。
5. preparation method according to claim 3, which is characterized in that vacuumize logical nitrogen discharge air in the step (2)
Specifically: it is evacuated to 60~90kPa in polymeric kettle, 0.3~0.5Mpa in inflated with nitrogen to polymeric kettle makes after being repeated 3 times
Normal pressure is maintained in kettle.
6. preparation method according to claim 3, which is characterized in that starting heating device heating in the step (2), and stir
It mixes, pressure maintaining specifically: setting heating device is 200~270 DEG C, reaches 190~260 DEG C to temperature in the kettle, pressure maintaining reaction 1~
3h, dwell pressure are 1.0~1.5Mpa, and speed of agitator is 100~120r/min.
7. preparation method according to claim 3, which is characterized in that pressure release in the step (2) are as follows: pressure maintaining terminates setting and adds
Thermal temperature is 220~300 DEG C of pressure releases simultaneously, 0.5~1h of venting duration.
8. preparation method according to claim 3, which is characterized in that normal pressure in the step (2) specifically: when polymerization under atmospheric pressure
Between 2~5h, temperature in the kettle is stepped up to 240~280 DEG C, and motor speed of agitator is adjusted to 50~70r/min.
9. preparation method according to claim 3, which is characterized in that vacuumized in the step (2) are as follows: final vacuum reaches
To 75~95kPa, temperature in the kettle reaches 250~290 DEG C, 0.5~1.5h of reaction time, and speed of agitator is 15~30r/min.
10. the application of terpolyamide material described in a kind of claim 1.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110615892A (en) * | 2019-09-09 | 2019-12-27 | 杭州聚合顺新材料股份有限公司 | Low-temperature-resistant multi-component copolymerized nylon resin and synthetic method thereof |
| CN111041592A (en) * | 2019-11-06 | 2020-04-21 | 浙江恒澜科技有限公司 | Preparation method of semi-aromatic polyether amide elastomer fiber |
| CN112675802A (en) * | 2020-12-30 | 2021-04-20 | 海阳科技股份有限公司 | Nylon 56 slice production device and preparation method |
| CN112920596A (en) * | 2021-01-27 | 2021-06-08 | 浙江工业大学 | Preparation method of high-transparency nylon material |
| CN115506047A (en) * | 2022-08-19 | 2022-12-23 | 邵阳深镁科技时尚有限公司 | High-strength wig and preparation method thereof |
| CN115894901A (en) * | 2021-08-20 | 2023-04-04 | 中国石油化工股份有限公司 | Block copolymer nylon and preparation method thereof |
| CN115975181B (en) * | 2023-01-09 | 2024-02-13 | 华润化学材料科技股份有限公司 | Ternary polymerization transparent nylon and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110615892A (en) * | 2019-09-09 | 2019-12-27 | 杭州聚合顺新材料股份有限公司 | Low-temperature-resistant multi-component copolymerized nylon resin and synthetic method thereof |
| CN111041592A (en) * | 2019-11-06 | 2020-04-21 | 浙江恒澜科技有限公司 | Preparation method of semi-aromatic polyether amide elastomer fiber |
| CN111041592B (en) * | 2019-11-06 | 2022-07-08 | 浙江恒逸石化研究院有限公司 | Preparation method of semi-aromatic polyether amide elastomer fiber |
| CN112675802A (en) * | 2020-12-30 | 2021-04-20 | 海阳科技股份有限公司 | Nylon 56 slice production device and preparation method |
| CN112920596A (en) * | 2021-01-27 | 2021-06-08 | 浙江工业大学 | Preparation method of high-transparency nylon material |
| CN115894901A (en) * | 2021-08-20 | 2023-04-04 | 中国石油化工股份有限公司 | Block copolymer nylon and preparation method thereof |
| CN115506047A (en) * | 2022-08-19 | 2022-12-23 | 邵阳深镁科技时尚有限公司 | High-strength wig and preparation method thereof |
| CN115506047B (en) * | 2022-08-19 | 2023-08-22 | 邵阳深镁科技时尚有限公司 | High-strength wig and preparation method thereof |
| CN115975181B (en) * | 2023-01-09 | 2024-02-13 | 华润化学材料科技股份有限公司 | Ternary polymerization transparent nylon and preparation method thereof |
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