CN108440956A - A kind of heat-resisting polyamide fibre 6 of high resiliency and preparation method - Google Patents
A kind of heat-resisting polyamide fibre 6 of high resiliency and preparation method Download PDFInfo
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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Abstract
The invention discloses a kind of heat-resisting polyamide fibre 6 of high resiliency and preparation methods, are related to fibre the relevant technologies technical field；The heat-resisting polyamide fibre 6 of high resiliency of the present invention prepares the preparation by organic layer phosphonic acids aluminium and is added in caprolactam, plant fiber lignin, the heat-resisting polyamide fibre 6 of the high resiliency of preparation is because of special laminar structured of stratiform organic aluminum phosphate, it uniformly disperses in macromolecule matrix, caprolactam polymerization can be made to be uniformly distributed, molecular skeleton is stablized, subsequently prepare stability when material conducive to polyamide fibre 6, such as conducive to level dyeing, high temperature resistant, it is low temperature resistant, be unlikely to deform, reduce water content, non-moisture-sensitive, high resiliency, thermostabilization.
Description
Technical field
The present invention relates to textile technology fields, and in particular to polyamide fibre preparing technical field is more particularly to a kind of high resiliency
Heat-resisting polyamide fibre 6 and preparation method.
Background technology
Polyamide fibre is the trade name of Fypro, also known as nylon, nylon (Nylon), abbreviation PA, basic component
It is the fatty polyamide connected by amido bond-[NHCO]-, is to contain recurring amide radical group-on molecular backbone
The thermoplastic resin general name of [NHCO]-, including aliphatic PA, fat-aromatic series PA and aromatic series PA.Wherein aliphatic PA product
Kind is more, and yield is big, is widely used, depending on name is by the specific carbon atom number of synthon.6 molecular formula of polyamide fibre is-[NH
(CH2) 5CO]-n, it dissolves in phenol and the concentrated sulfuric acid of heat, electrical insulation capability is superior, alkaline-resisting, good corrosion resistance, is that synthesis is fine
The best fiber of wear-resisting property in dimension.
The quality problems of existing polyamide fibre 6 mainly have slice molecular weight it is unstable, moisture content is higher, content of monomer is higher, cuts
Piece jaundice has impurity etc..In the production of the polyamide fibre 6 of early stage, once there are the feelings that slice extraction rear surface has white point to generate
Condition, then in subsequent drying process, white point disappears slice after drying when most, but also has slice white point still
In the presence of.During subsequent high speed spinning, the slice spinnability with white point is substantially reduced, and easily causes spinning break, waste silk rate
It obviously increases.
China market slices of caprone main application at present：
(1) fibers grade pet chip can be used for spinning civilian silk, make underwear, socks, shirt etc.；For spinning industrial yarn, tire is made
Cord, twine, parachute, insulating materials, netting twine, safety belt etc..
(2) engineering plastics grade pet chip can be used for producing gear, shell, hose, resistance to oil vessel, the cable protection of precision machinery
It covers, the equipment part etc. of textile industry.
(3) membranes grade pet chip can be used for packaging industry, such as food packaging, medical package.
(4) nylon composite materials, including shock resistance nylon, enhancing high temperature resistant nylon etc., have specific demand for making
Apparatus, such as enhancing high temperature resistant nylon can be used for manufacturing impact drill, grass mower.
Polyamide fibre can obtain the material with more excellent properties by modification, and more, performance is more preferable for modified quality.
In the art, as CN201510048786.9 discloses a kind of smooth heat stabilized nylon 6 and preparation method thereof,
Again by adding hindered amine stabilizer and hypophosphites stabilizer in 6 preparation process of nylon in the present invention, in the collaboration of the two
Under effect, improve the dyeability and spinning properties of product.
Invention content
The purpose of the present invention is to provide a kind of heat-resisting polyamide fibre 6 of high resiliency and preparation methods, to solve above-mentioned background technology
The problem of middle proposition.
To achieve the above object, the present invention provides the following technical solutions：
The heat-resisting polyamide fibre 6 of high resiliency, is made of following raw material according to parts by weight：0.1-1.2 parts of microcrystalline cellulose, adjacent benzene
0.5-1.7 parts of dicarboxylate, 100-130 parts of caprolactam, 2-7 parts of expanded PTFE, a waterside sodium phosphate 3-4
Part, 2-3 parts of paraformaldehyde, 30-40% 4-6 parts of 0.2-0.3 parts of hydrochloric acid, bisphenol A polycarbonate, Aluminium chloride hexahydrate 5-7
Part, 0.1-0.2 parts of triethylamine, 0.6-1 parts of ammonium oxalate, 0.7-1 parts of 2- mercapto benzimidazoles, 2-3 parts of lauryl mercaptan, ten
1-2 parts of dialkyl group trimethyl ammonium chloride, 16-36 parts of plant fiber lignin, 1-2 parts of calcium mahogany sulfonate, polyoxyethylene sorbitan monoleate 0.1-
0.2 part, 1.4-2 parts of potassium dihydrogen phosphate.
The above-mentioned heat-resisting polyamide fibre 6 of high resiliency, preferably following raw material are formed according to parts by weight：0.6 part of blanc fixe, adjacent benzene two
1.5 parts of formic acid diethylester, 130 parts of caprolactam, 4 parts of expanded PTFE, 3 parts of a waterside sodium phosphate, 2 parts of paraformaldehyde,
0.15 part of 5 parts of 4 parts of 0.2 part of hydrochloric acid, bisphenol A polycarbonate, Aluminium chloride hexahydrate, triethylamine, the ammonium oxalate 0.6 of 35-37%
Part, 0.8 part of 2- mercaptos benzimidazole, 2.5 parts of lauryl mercaptan, 1.5 parts of dodecyl trimethyl ammonium chloride, plant fiber
26 parts of lignin, 2 parts of calcium mahogany sulfonate, 0.2 part of polyoxyethylene sorbitan monoleate, 1.4 parts of potassium dihydrogen phosphate.
The preparation method of the heat-resisting polyamide fibre of the high resiliency 6, is as follows：
(1) claim each raw material by above-mentioned weight proportion；
(2) above-mentioned waterside sodium phosphate is taken, is added in the deionized water of 5-7 times of its weight, stirs evenly, is sent into constant temperature
In water-bath, it is slowly added to above-mentioned paraformaldehyde, the hydrochloric acid of above-mentioned 30-40% is added under stirring condition, keeps the temperature under nitrogen protection
Stirring 8-9 hours, discharging cooling, filters, will be deposited at 80-85 DEG C and be dried in vacuo 10-12 hours, obtains hydroxyalkylation time phosphine
Acid；
(3) above-mentioned hydroxyalkylation phosphinic acids are added in the tetrahydrofuran of 2-5 times of its weight, are stirred evenly, obtained organic
The tetrahydrofuran solution of phosphoric acid；
(4) above-mentioned bisphenol A polycarbonate, triethylamine are mixed, is added to the tetrahydrofuran of 7-8 times of mixture weight
In, temperature, and insulated and stirred 20-30 minute are increased, is mixed with the tetrahydrofuran solution of above-mentioned organic phosphoric acid, raising temperature, in nitrogen
Protection lower insulated and stirred 2-6 hours, filtering with microporous membrane removes precipitation, and filtrate decompression is concentrated and removes tetrahydrofuran to get poly-
Close organic phospho acid；
(5) above-mentioned potassium dihydrogen phosphate is added in the deionized water of 1-6 times of its weight, is stirred evenly, ammonium oxalate is added
And triethylamine obtained phosphoric acid dispersion liquid in insulated and stirred 3-4 minutes；
(6) above-mentioned Aluminium chloride hexahydrate, dodecyl trimethyl ammonium chloride are mixed, is added to mixture weight 20-30
In deionized water again, stirs evenly, obtain aluminium chloride dispersion liquid；
(7) above-mentioned calcium mahogany sulfonate, lauryl mercaptan are mixed, increases temperature, insulated and stirred 4-5 minutes, in addition
It in the toluene for stating 6-10 times of mixture weight, stirring evenly, polyoxyethylene sorbitan monoleate is added, 100-200 revs/min is stirred 10-13 minutes,
Obtain toluene lotion；
(8) it takes above-mentioned steps 4 to polymerize organic phospho acid, is added in the ethanol water of 7-10 times of its weight, stirs evenly,
Acetic acid or sodium hydroxide is added dropwise, adjusts pH, it is 80-85 DEG C to increase temperature, sequentially adds above-mentioned aluminium chloride dispersion liquid, phosphoric acid dispersion
Liquid, insulated and stirred 6-7 hours filter, and filter cake is washed 3-4 times, is dried in vacuo 30-40 minutes at 50-60 DEG C, obtains organic layer
Shape phosphonic acids aluminium；
(9) above-mentioned organic layer phosphonic acids aluminium is taken, is added in the acetone soln of 70-80 times of its weight, ultrasonic 20-30 points
Above-mentioned expanded PTFE is added in clock, continues ultrasound 10-14 minutes, and heating is added above-mentioned 2- mercaptos benzimidazole, protects
Temperature stirring 1.5-2 hours, is dried under reduced pressure to get the resistance to thermal material of high resiliency；
(10) by the resistance to thermal material of above-mentioned high resiliency and plant fiber lignin, caprolactam, microcrystalline cellulose, O-phthalic
Each raw material mixing of diethyl phthalate, stirs evenly, is sent into extruder, through melting extrusion and is post-processed, and the rear twin-screw that puts into squeezes
Go out in machine to carry out melt extruded to be granulated to get the heat-resisting polyamide fibre of high resiliency 6.
Further, the temperature of water bath with thermostatic control described in step 1 is 75-85 DEG C.
Further, it is 60-65 DEG C that temperature is increased described in step 4, and miillpore filter selects 3.0-10.0 μm of pore diameter range.
Further, insulated and stirred described in step 5, temperature are 50-65 DEG C, mixing speed 800-1000rpm/min.
Further, it heats up described in step 7, insulated and stirred, temperature is 60-75 DEG C, mixing speed 600-1000rpm/
min。
Further, ethanol water described in step 8, concentration of alcohol 50-75%.
Further, pH is adjusted ranging from described in step 8：6.5-8.0.
Further, it is filtered described in step 8, filters and select quantitative filter paper, 30-50 μm of quantitative filter paper pore diameter range.
Further, a concentration of 55-75% of acetone soln described in step 9, it is 75-90 DEG C to increase temperature, is dried under reduced pressure
Pressure is 1.0-1.5MPa.
Further, each mixed material described in step 10 through melting extrusion and is post-processed, and the post-processing is freezing
Processing.
Further cold treatment is divided into first time freezing processing, second of freezing processing and third time freezing processing, and first
After secondary freezing processing, after material is restored room temperature 1 hour, then second of freezing processing is carried out, after second of freezing processing, equally
After material is restored room temperature 1 hour, then carry out third time freezing processing.
Further, first time freezing processing is continuously to be freezed in the environment of subzero 5-10 DEG C 2-3 hours, second
Freezing processing is continuously to be freezed in the environment of subzero 10-20 DEG C 3-5 hours, and second of freezing processing is at subzero 20-25 DEG C
In the environment of continuously freeze 2-3 hours.
Further, melt extruded granulation conditions described in step 10 is：It is divided into three phases, 40-80 DEG C of first stage,
Pressure 1.0-3.0MPa, 80-150 DEG C of second stage, pressure 3.0-4.5MPa, 150-220 DEG C of phase III, pressure 4.5-
5.5MPa。
Further, the resistance to thermal material of the high resiliency of preparation carries out curing process, and processing step is by the resistance to thermal material of high resiliency
0.05-0.1% glutaraldehydes-glycerine water solution is sprayed, and the resistance to thermal material of high resiliency is placed in 35-45 DEG C of placement 3-4h in baking oven,
By treated, the resistance to thermal material of high resiliency is placed in removing glutaraldehyde in ventilated box afterwards.
It is an advantage of the invention that：
(1) the organic layer phosphonic acids aluminium of the present invention is added in caprolactam, plant fiber lignin and prepares high resiliency
Heat-resisting polyamide fibre 6 is uniformly disperseed due to special laminar structured of stratiform organic aluminum phosphate in macromolecule matrix, can be with
Caprolactam polymerization is set to be uniformly distributed, molecular skeleton is stablized, and stability when material is subsequently prepared conducive to polyamide fibre 6, is such as conducive to equal
Level dyeing color, high temperature resistant, it is low temperature resistant, be unlikely to deform；
(2) the organic layer phosphonic acids aluminium in preparation process effectively plays lamella iris action, prevents extraneous flammable gas
The entrance of body, hydrone etc. inhibits the chain degradation process of macromolecule matrix, some components generated when its heated pyrolysis are such as
The gases such as C02, CO, phosphorus-containing compound, they can play the role of reduction regional temperature can prevent when wet environment
In the immersion polyamide fibre 6 of hydrone, therefore water content is reduced, not moisture-sensitive；
(3) free radical that phosphorus oxygen free radical etc. can generate around capturing ambient improves the heat resisting temperature of polyamide fibre 6 to improve
The thermal stability of material.
(4) the fine and close layer of charcoal that organic layer phosphonic acids aluminium is stablized, improves the toughness of material, the heat-resisting polyamide fibre of high resiliency of the invention
6 have good resilience, and anti-towing property is strong, not easily damaged.
(5) pass through curing process and post-processing in preparation process, the rebound of heat-resisting 6 material of polyamide fibre of high resiliency can be strengthened
Property, the heat-resisting polyamide fibre 6 of high resiliency is homogeneous, flexible.
Specific implementation mode
The technical solution of this patent is described in more detail With reference to embodiment.
Embodiment 1
A kind of heat-resisting polyamide fibre 6 of high resiliency and preparation method.
To achieve the above object, the present invention provides the following technical solutions：
The heat-resisting polyamide fibre 6 of high resiliency, is made of following raw material according to parts by weight：0.6 part of blanc fixe, O-phthalic
1.5 parts of diethyl phthalate, 130 parts of caprolactam, 4 parts of expanded PTFE, 3 parts of a waterside sodium phosphate, 2 parts of paraformaldehyde, 35-
37% 0.2 part of hydrochloric acid, 4 parts of bisphenol A polycarbonate, 5 parts of Aluminium chloride hexahydrate, 0.15 part of triethylamine, 0.6 part of ammonium oxalate,
0.8 part of 2- mercaptos benzimidazole, 2.5 parts of lauryl mercaptan, 1.5 parts of dodecyl trimethyl ammonium chloride, plant fiber wood
26 parts of quality, 2 parts of calcium mahogany sulfonate, 0.2 part of polyoxyethylene sorbitan monoleate, 1.4 parts of potassium dihydrogen phosphate.
The preparation method of the heat-resisting polyamide fibre of the high resiliency 6, is as follows：
(1) claim each raw material by above-mentioned weight proportion；
(2) above-mentioned waterside sodium phosphate is taken, is added in the deionized water of 5 times of its weight, stirs evenly, is sent into 75 DEG C of perseverances
In tepidarium, it is slowly added to above-mentioned paraformaldehyde, the hydrochloric acid of above-mentioned 30-40% is added under stirring condition, protects under nitrogen protection
Temperature stirring 8 hours, discharging cooling, filters, will be deposited at 80 DEG C and be dried in vacuo 10 hours, obtain hydroxyalkylation phosphinic acids；
(3) above-mentioned hydroxyalkylation phosphinic acids are added in the tetrahydrofuran of 2.5 times of its weight, are stirred evenly, obtained organic
The tetrahydrofuran solution of phosphoric acid；
(4) above-mentioned bisphenol A polycarbonate, triethylamine are mixed, are added in the tetrahydrofuran of 7 times of mixture weight,
Temperature is increased to 60 DEG C, and insulated and stirred 20 minutes, mix with the tetrahydrofuran solution of above-mentioned organic phosphoric acid, raising temperature, in nitrogen
The lower insulated and stirred of protection 3 hours, 10.0 μm of filtering with microporous membrane remove precipitation, and filtrate decompression is concentrated and removes tetrahydrofuran, i.e.,
Organic phospho acid must be polymerize；
(5) above-mentioned potassium dihydrogen phosphate is added in the deionized water of 4 times of its weight, is stirred evenly, be added ammonium oxalate and
Triethylamine, in 55 DEG C of heat preservation, 1000rpm/min is stirred 3 minutes, obtains phosphoric acid dispersion liquid；
(6) above-mentioned Aluminium chloride hexahydrate, dodecyl trimethyl ammonium chloride are mixed, is added to mixture weight 20-30
In deionized water again, stirs evenly, obtain aluminium chloride dispersion liquid；
(7) above-mentioned calcium mahogany sulfonate, lauryl mercaptan are mixed, increases temperature 60 C, 600rpm/min insulated and stirreds 4
Minute, it is added in the toluene of 6 times of above-mentioned mixture weight, stirs evenly, polyoxyethylene sorbitan monoleate is added, 100 revs/min are stirred 10 points
Clock obtains toluene lotion；
(8) it takes above-mentioned steps 4 to polymerize organic phospho acid, is added in 55% ethanol water of 7 times of its weight, stirring is equal
It is even, acetic acid or sodium hydroxide is added dropwise, adjusts pH6.5, it is 80 DEG C to increase temperature, sequentially adds above-mentioned aluminium chloride dispersion liquid, phosphoric acid
Dispersion liquid, insulated and stirred 6 hours, 50 μm of quantitative filter papers filter, filter cake are washed 3 times, is dried in vacuo 30 minutes, obtains at 50 DEG C
Organic layer phosphonic acids aluminium；
(9) above-mentioned organic layer phosphonic acids aluminium is taken, is added in 55% acetone soln of 70 times of its weight, ultrasound 20 minutes,
Above-mentioned expanded PTFE is added, continues ultrasound 10 minutes, heats up 75 DEG C, above-mentioned 2- mercaptos benzimidazole is added, keeps the temperature
Stirring 1.5 hours, 1.0MPa is dried under reduced pressure to get the resistance to thermal material of high resiliency；
(10) by the resistance to thermal material of above-mentioned high resiliency and plant fiber lignin, caprolactam, microcrystalline cellulose, O-phthalic
Each raw material mixing of diethyl phthalate, stirs evenly, is sent into extruder, through melting extrusion and is post-processed, and the rear twin-screw that puts into squeezes
Go out in machine to carry out melt extruded to be granulated to get the heat-resisting polyamide fibre of high resiliency 6.
Further, each mixed material described in step 10 through melting extrusion and is post-processed, and the post-processing is freezing
Processing.
Further cold treatment is divided into first time freezing processing, second of freezing processing and third time freezing processing, and first
After secondary freezing processing, after material is restored room temperature 1 hour, then second of freezing processing is carried out, after second of freezing processing, equally
After material is restored room temperature 1 hour, then carry out third time freezing processing.
Further, first time freezing processing is continuously to be freezed in the environment of subzero 10 DEG C 2 hours, second of freezing
Processing is continuously to be freezed in the environment of subzero 120 DEG C 3 hours, and second of freezing processing is continuous in the environment of subzero 20 DEG C
Freezing 2 hours.
Further, melt extruded granulation conditions described in step 10 is：It is divided into three phases, 50 DEG C of first stage, pressure
Power 2.0MPa, 120 DEG C, pressure 3.0MPa of second stage, 200 DEG C of phase III, pressure 4.5MPa.
Further, the resistance to thermal material of the high resiliency of preparation carries out curing process, and processing step is by the resistance to thermal material of high resiliency
Spray 0.05-0.1% glutaraldehydes-glycerine water solution, and the resistance to thermal material of high resiliency be placed in 35 DEG C of placement 3h in baking oven, after will place
The resistance to thermal material of high resiliency after reason, which is placed in ventilated box, removes glutaraldehyde.
Embodiment 2
The heat-resisting polyamide fibre 6 of high resiliency, is made of following raw material according to parts by weight：1.2 parts of microcrystalline cellulose, O-phthalic
0.5 part of diethyl phthalate, 120 parts of caprolactam, 2.5 parts of expanded PTFE, 3 parts of a waterside sodium phosphate, 2 parts of paraformaldehyde,
0.1 part of 5 parts of 4 parts of 0.2 part of hydrochloric acid, bisphenol A polycarbonate, Aluminium chloride hexahydrate, triethylamine, the ammonium oxalate 0.6 of 30-40%
Part, 0.7 part of 2- mercaptos benzimidazole, 2.5 parts of lauryl mercaptan, 2 parts of dodecyl trimethyl ammonium chloride, plant fiber wood
16 parts of quality, 1 part of calcium mahogany sulfonate, 0.2 part of polyoxyethylene sorbitan monoleate, 1.4 parts of potassium dihydrogen phosphate.
The preparation method of the heat-resisting polyamide fibre of the high resiliency 6, the step cold treatment are as follows：It is further cold in preparation process
It handles and is divided into first time freezing processing, second of freezing processing and third time freezing processing, after first time freezing processing, by material
Restore room temperature after 1 hour, then carry out second of freezing processing, after second of freezing processing, material is equally restored into room temperature 1 hour
Afterwards, then third time freezing processing is carried out.
Further, first time freezing processing is continuously to be freezed in the environment of subzero 5 DEG C 2 hours, second of freezing
Processing is continuously to be freezed in the environment of subzero 10 DEG C 3 hours, and second of freezing processing is continuous in the environment of subzero 20 DEG C
Freezing 3 hours.
It is other same in embodiment 1, and without curing process.
Embodiment 3
The heat-resisting polyamide fibre 6 of high resiliency, is made of following raw material according to parts by weight：1.0 parts of microcrystalline cellulose, O-phthalic
1.2 parts of diethyl phthalate, 130 parts of caprolactam, 2 parts of expanded PTFE, 3 parts of a waterside sodium phosphate, 2 parts of paraformaldehyde, 30-
40% 0.2 part of hydrochloric acid, 4 parts of bisphenol A polycarbonate, 5 parts of Aluminium chloride hexahydrate, 0.1 part of triethylamine, 0.6 part of ammonium oxalate, 2-
0.7 part of mercapto benzimidazole, 2 parts of lauryl mercaptan, 1 part of dodecyl trimethyl ammonium chloride, plant fiber lignin 16
Part, 1.5 parts of calcium mahogany sulfonate, 0.1 part of polyoxyethylene sorbitan monoleate, 1.4 parts of potassium dihydrogen phosphate.
The preparation method of the heat-resisting polyamide fibre of the high resiliency 6, the step granulation conditions are as follows：Further, in step 10
The melt extruded granulation conditions are：It is divided into three phases, 60 DEG C, pressure 1.5MPa of first stage, 150 DEG C of second stage, pressure
Power 3.0MPa, 220 DEG C of phase III, pressure 5.0MPa.
Reference examples 1
1 polyamide fibre 6 of the control, is made of following raw material according to parts by weight：1.2 parts of microcrystalline cellulose, phthalic acid two
1.7 parts of ethyl ester, 100 parts of caprolactam, 2 parts of expanded PTFE, 16 parts of plant fiber lignin, 2- mercapto benzimidazoles
0.7。
The preparation method of 1 polyamide fibre 6 of the control, is as follows：
(1) above-mentioned expanded PTFE is taken to be added in above-mentioned 2- mercaptos benzimidazole and 55-75% acetone solns, after
Continuous ultrasound 14 minutes, heats up 75 DEG C, insulated and stirred 1.5 hours, 1.0MPa is dried under reduced pressure to get the resistance to thermal material of high resiliency, high-elastic
The resistance to thermal material of property simultaneously carries out curing process.
(2) by the resistance to thermal material of above-mentioned high resiliency and plant fiber lignin, caprolactam, microcrystalline cellulose, O-phthalic
Each raw material mixing of diethyl phthalate, stirs evenly, is sent into extruder, through melting extrusion and is post-processed, and the rear twin-screw that puts into squeezes
Go out in machine to carry out melt extruded to be granulated to get the heat-resisting polyamide fibre of high resiliency 6.
Reference examples 2
2 polyamide fibres 6 of the control, are made of following raw material according to parts by weight：1.0 parts of microcrystalline cellulose, phthalic acid two
0.8 part of ethyl ester, 100 parts of caprolactam, 2 parts of expanded PTFE, 20 parts of plant fiber lignin, 2- mercapto benzimidazoles
0.7。
The preparation method of 2 polyamide fibres 6 of the control, is as follows：
(1) above-mentioned expanded PTFE is taken to be added in above-mentioned 2- mercaptos benzimidazole and 55-75% acetone solns, after
Continuous ultrasound 14 minutes, heats up 80 DEG C, insulated and stirred 1.5 hours, 1.5MPa is dried under reduced pressure to get the resistance to thermal material of high resiliency；
(2) by the resistance to thermal material of above-mentioned high resiliency and plant fiber lignin, caprolactam, microcrystalline cellulose, O-phthalic
Each raw material mixing of diethyl phthalate, stirs evenly, is sent into extruder, through melting extrusion and is post-processed, and the rear twin-screw that puts into squeezes
Go out in machine to carry out melt extruded to be granulated to get the heat-resisting polyamide fibre of high resiliency 6.
The resistance to thermal material of high resiliency is without curing process wherein in reference examples 2.
Reference examples 3
3 polyamide fibres 6 of the control, are made of following raw material according to parts by weight：0.8 part of microcrystalline cellulose, phthalic acid two
1.7 parts of ethyl ester, 130 parts of caprolactam, 5 parts of expanded PTFE, 22 parts of plant fiber lignin, 2- mercapto benzimidazoles
1。
The preparation method of 3 polyamide fibres 6 of the control, is as follows：
(1) above-mentioned expanded PTFE is taken to be added in above-mentioned 2- mercaptos benzimidazole and 55-75% acetone solns, after
Continuous ultrasound 1 minute, heats up 90 DEG C, insulated and stirred 2 hours, 1.5MPa is dried under reduced pressure to get the resistance to thermal material of high resiliency；
(2) by the resistance to thermal material of above-mentioned high resiliency and plant fiber lignin, caprolactam, microcrystalline cellulose, O-phthalic
Each raw material mixing of diethyl phthalate, stirs evenly, is sent into extruder, put into double screw extruder and melted after melting extrusion
Extruder grain is to get the heat-resisting polyamide fibre of high resiliency 6.
The resistance to thermal material of high resiliency carries out curing process wherein in reference examples 3, and is post-processed without squeezing out.
Table 1 is the embodiment of the present invention and 6 performance test of polyamide fibre made from reference examples, as a result such as following table：
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Profit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent requirements of the claims
Variation is included within the present invention.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiment being appreciated that.
Claims (12)
1. the heat-resisting polyamide fibre of a kind of high resiliency 6, it is characterised in that：It is made of according to parts by weight following raw material：Microcrystalline cellulose 0.1-
1.2 parts, 0.5-1.7 parts of diethyl phthalate, 100-130 parts of caprolactam, 2-7 parts of expanded PTFE, a waterside
3-4 parts of sodium phosphate, 2-3 parts of paraformaldehyde, 4-6 parts of 0.2-0.3 parts of hydrochloric acid, the bisphenol A polycarbonate of 30-40%, six hydrations
5-7 parts of aluminium chloride, 0.1-0.2 parts of triethylamine, 0.6-1 parts of ammonium oxalate, 0.7-1 parts of 2- mercapto benzimidazoles, dodecyl sulphur
2-3 parts of alcohol, 1-2 parts of dodecyl trimethyl ammonium chloride, 16-36 parts of plant fiber lignin, 1-2 parts of calcium mahogany sulfonate, poly- mountain
80 0.1-0.2 parts of pear ester, 1.4-2 parts of potassium dihydrogen phosphate.
2. the heat-resisting polyamide fibre of high resiliency according to claim 16, which is characterized in that preferred following raw material is according to parts by weight group
At：0.6 part of blanc fixe, 1.5 parts of diethyl phthalate, 130 parts of caprolactam, 4 parts of expanded PTFE, a water
4 parts of 0.2 part of hydrochloric acid, bisphenol A polycarbonate, the Aluminium chloride hexahydrate 5 of 3 parts of sodium hypophosphite, 2 parts of paraformaldehyde, 35-37%
Part, 0.15 part of triethylamine, 0.6 part of ammonium oxalate, 0.8 part of 2- mercaptos benzimidazole, 2.5 parts of lauryl mercaptan, dodecyl
1.5 parts of trimethyl ammonium chloride, 26 parts of plant fiber lignin, 2 parts of calcium mahogany sulfonate, 0.2 part of polyoxyethylene sorbitan monoleate, potassium dihydrogen phosphate
1.4 part.
3. a kind of preparation method of the heat-resisting polyamide fibre of high resiliency 6, which is characterized in that steps are as follows：
(1) claim each raw material by above-mentioned weight proportion；
(2) above-mentioned waterside sodium phosphate is taken, is added in the deionized water of 5-7 times of its weight, stirs evenly, is sent into water bath with thermostatic control
In, it is slowly added to above-mentioned paraformaldehyde, the hydrochloric acid of above-mentioned 30-40% is added under stirring condition, under nitrogen protection insulated and stirred
8-9 hours, discharging cooling filtered, will be deposited at 80-85 DEG C and be dried in vacuo 10-12 hours, obtain hydroxyalkylation phosphinic acids；
(3) above-mentioned hydroxyalkylation phosphinic acids are added in the tetrahydrofuran of 2-5 times of its weight, stir evenly, obtains organic phosphoric acid
Tetrahydrofuran solution；
(4) above-mentioned bisphenol A polycarbonate, triethylamine are mixed, is added in the tetrahydrofuran of 7-8 times of mixture weight, risen
High-temperature, and insulated and stirred 20-30 minutes, mix with the tetrahydrofuran solution of above-mentioned organic phosphoric acid, increase temperature, under nitrogen protection
Insulated and stirred 2-6 hours, filtering with microporous membrane remove precipitation, and it is organic to get polymerizeing that filtrate decompression is concentrated removing tetrahydrofuran
Phosphonic acids；
(5) above-mentioned potassium dihydrogen phosphate is added in the deionized water of 1-6 times of its weight, is stirred evenly, ammonium oxalate and three is added
Ethamine obtained phosphoric acid dispersion liquid in insulated and stirred 3-4 minutes；
(6) above-mentioned Aluminium chloride hexahydrate, dodecyl trimethyl ammonium chloride are mixed, is added to 20-30 times of mixture weight
It in deionized water, stirs evenly, obtains aluminium chloride dispersion liquid；
(7) above-mentioned calcium mahogany sulfonate, lauryl mercaptan are mixed, increases temperature, insulated and stirred 4-5 minutes is added above-mentioned mixed
It in the toluene for closing 6-10 times of weight of material, stirs evenly, polyoxyethylene sorbitan monoleate is added, 100-200 revs/min is stirred 10-13 minutes, and first is obtained
Benzene lotion；
(8) it takes above-mentioned steps 4 to polymerize organic phospho acid, is added in the ethanol water of 7-10 times of its weight, stirs evenly, be added dropwise
Acetic acid or sodium hydroxide adjust pH, and it is 80-85 DEG C to increase temperature, sequentially adds above-mentioned aluminium chloride dispersion liquid, phosphoric acid dispersion liquid,
Insulated and stirred 6-7 hours filters, and filter cake is washed 3-4 times, is dried in vacuo 30-40 minutes at 50-60 DEG C, obtains organic layer
Phosphonic acids aluminium；
(9) above-mentioned organic layer phosphonic acids aluminium is taken, is added in the acetone soln of 70-80 times of its weight, it is 20-30 minutes ultrasonic, add
Enter above-mentioned expanded PTFE, continue ultrasound 10-14 minutes, above-mentioned 2- mercaptos benzimidazole, insulated and stirred is added in heating
It 1.5-2 hours, is dried under reduced pressure to get the resistance to thermal material of high resiliency；
(10) by the resistance to thermal material of above-mentioned high resiliency and plant fiber lignin, caprolactam, microcrystalline cellulose, phthalic acid two
Each raw material mixing of ethyl ester, stirs evenly, is sent into extruder, through melting extrusion and is post-processed, put into double screw extruder afterwards
Middle progress melt extruded is granulated to get the heat-resisting polyamide fibre of high resiliency 6.
4. the heat-resisting polyamide fibre of high resiliency according to claim 1-3 6, which is characterized in that the temperature of water bath with thermostatic control described in step 1
It is 75-85 DEG C.
5. according to the heat-resisting polyamide fibre of any one of claim 1-3 high resiliency 6, which is characterized in that increasing temperature described in step 4 is
60-65 DEG C, miillpore filter selects 3.0-10.0 μm of pore diameter range.
6. according to the heat-resisting polyamide fibre of any one of claim 1-3 high resiliency 6, which is characterized in that insulated and stirred described in step 5, temperature
It is 50-65 DEG C, mixing speed 800-1000rpm/min.
7. according to the heat-resisting polyamide fibre of any one of claim 1-3 high resiliency 6, which is characterized in that it heats up described in step 7, insulated and stirred,
Temperature is 60-75 DEG C, mixing speed 600-1000rpm/min.
8. according to the heat-resisting polyamide fibre of any one of claim 1-3 high resiliency 6, which is characterized in that ethanol water described in step 8,
Concentration of alcohol is 50-75%.
9. according to the heat-resisting polyamide fibre of any one of claim 1-3 high resiliency 6, which is characterized in that adjust pH ranges described in step 8
For：6.5-8.0.
10. according to the heat-resisting polyamide fibre of any one of claim 1-3 high resiliency 6, which is characterized in that filtered described in step 8, filter choosing
With quantitative filter paper, 30-50 μm of quantitative filter paper pore diameter range.
11. according to the heat-resisting polyamide fibre of any one of claim 1-3 high resiliency 6, which is characterized in that acetone soln described in step 9 is dense
Degree is 55-75%, and it is 75-90 DEG C to increase temperature, and it is 1.0-1.5MPa to be dried under reduced pressure pressure.
12. according to the heat-resisting polyamide fibre of any one of claim 1-3 high resiliency 6, which is characterized in that each mixed material described in step 10
It through melting extrusion and is post-processed, the post-processing is freezing processing；
Further cold treatment is divided into first time freezing processing, second of freezing processing and third time freezing processing, cold for the first time
After jelly processing, after material is restored room temperature 1 hour, then second of freezing processing is carried out, after second of freezing processing, equally by object
Material restored room temperature after 1 hour, then carried out third time freezing processing.
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| WO2019210587A1 (en) * | 2018-05-04 | 2019-11-07 | 江苏弘盛新材料股份有限公司 | High-elasticity heat-resistant nylon 6 and preparation method |
| CN110713712A (en) * | 2019-11-22 | 2020-01-21 | 安徽微威减震降噪技术研究院 | Copolymerization modified polyamide material and preparation method thereof |
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| CN108440956A (en) * | 2018-05-04 | 2018-08-24 | 江苏弘盛新材料股份有限公司 | A kind of heat-resisting polyamide fibre 6 of high resiliency and preparation method |
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| CN104562276A (en) * | 2014-12-05 | 2015-04-29 | 淮安锦纶化纤有限公司 | Method for modifying chinlon 6 fibers and modified product |
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| WO2019210587A1 (en) * | 2018-05-04 | 2019-11-07 | 江苏弘盛新材料股份有限公司 | High-elasticity heat-resistant nylon 6 and preparation method |
| CN110713712A (en) * | 2019-11-22 | 2020-01-21 | 安徽微威减震降噪技术研究院 | Copolymerization modified polyamide material and preparation method thereof |
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