CN102993437B - Polyamide as well as preparation method and application thereof - Google Patents
Polyamide as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN102993437B CN102993437B CN201210484972.3A CN201210484972A CN102993437B CN 102993437 B CN102993437 B CN 102993437B CN 201210484972 A CN201210484972 A CN 201210484972A CN 102993437 B CN102993437 B CN 102993437B
- Authority
- CN
- China
- Prior art keywords
- prepolymer
- polymeric amide
- acid
- preparation
- pressure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Polyamides (AREA)
Abstract
The invention discloses polyamide as well as a preparation method and an application thereof. The preparation method of the polyamide comprises the following steps of: adding binary acid, diamine and a reaction auxiliary into a reaction kettle, heating the reaction kettle, carrying out a prepolymerization reaction to obtain a prepolymer; making the prepolymer into granular prepolymer, wherein the percent by weight of the granular prepolymer with the grain size of 0.5-2mm in the granular prepolymer is not less than 71%; and tackifying the prepolymer subjected to granulation, so that polyamide is obtained. By adopting the preparation method of the polyamide disclosed by the invention, tackifying time is shortened, and tackifying rate is increased; meanwhile, a vacuum pipeline is hardly blocked as the percent by weight of the prepolymer with the grain size of being less than 0.5mm in the prepolymer is 9% at most. The invention also discloses the polyamide obtained by the preparation method disclosed by the invention. The polyamide disclosed by the invention is applied to the fields of electric electron materials, automobile components, office supplies and home supplies.
Description
Technical field
The present invention relates to field of polyamides, particularly relate to the application of a kind of polymeric amide, its preparation method and this polymeric amide.
Background technology
Polymeric amide is because having good over-all properties, comprise mechanical property, thermotolerance, wearability, chemical proofing and self lubricity, and frictional coefficient is low, there is certain flame retardant resistance, be easy to processing etc., it is extensively suitable for, by glass fibre and other filler filling enhancing modified, improving performance and broadened application scope.
In the process preparing polymeric amide, the particle form of Polvamide prepolymer determines the speed of thickening reaction and the molecular weight distribution of polymeric amide.And in prior art, usually the prepolymer of polymeric amide is pulverized as carrying out thickening reaction after powder.But, due to powder diameter wider distribution, cause polymeric amide thickening speed of reaction slower.And thickening speed of reaction affects the production process of polymeric amide.Therefore, improve the research of thickening speed of reaction and become the important research topic of polymeric amide one.
Summary of the invention
In sum, the present invention is necessary to provide a kind of preparation method improving the polymeric amide of thickening speed of reaction.
In addition, there is a need to the polymeric amide providing a kind of above-mentioned preparation method to obtain.
In addition, there is a need to the application of the polymeric amide providing a kind of above-mentioned preparation method to obtain.
A preparation method for polymeric amide, comprises the following steps:
Prepolymerization step: diprotic acid, diamine and reaction promoter are joined in reactor, reacting by heating still, carries out prepolymerization, obtained prepolymer;
Granulation step: described prepolymer is made particulate state prepolymer; In described particulate state prepolymer, particle diameter is that the weight fraction that the particulate state prepolymer of 0.5-2mm accounts for particulate state prepolymer is not less than 71%;
Thickening reactions steps: the prepolymer through granulation step is carried out thickening reaction, obtains polymeric amide.
In the present invention if no special instructions, particle diameter refers to volume footpath.
Wherein, in described granulation step, described particulate state prepolymer is cylindrical shape.
Wherein, in described granulation step, the height of described particulate state prepolymer is 1-5mm.
Wherein, in described granulation step, any equipment that can obtain particulate state prepolymer described in the application can be used to carry out granulation, as used tablets press to carry out granulation, preferably Pendulargranulator carries out granulation further.
Wherein, in described granulation step, the weight percentage that the prepolymer that particle diameter is less than 0.5mm accounts for prepolymer is no more than 9%.
Wherein, in described thickening reactions steps, the reacted polymeric amide of thickening maintains the shape of the particulate state prepolymer after granulation substantially.
Wherein, in polymeric amide obtained in described thickening reactions steps, particle diameter is that the weight fraction that the polymeric amide of 0.5-1.5mm accounts for obtained polymeric amide is not less than 70%.
Wherein, in polymeric amide obtained in described thickening reactions steps, the weight fraction that the polymeric amide that particle diameter is less than 0.5mm accounts for obtained polymeric amide is no more than 16%.
Further, when in granulation step, when described particulate state polymeric amide is cylindrical shape, the height of the cylindrical polymeric amide that described thickening reactions steps obtains is 0.5-3mm.
Wherein, described diprotic acid comprises aromatic acid and aliphatic dibasic acid.
Wherein, take diprotic acid as percent basis, described aromatic acid is 70-100mol%, and aliphatic dibasic acid is 0-30mol%.
Wherein, described aromatic acid is terephthalic acid.
Wherein, described aliphatic dibasic acid comprises oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, 2-methyl suberic acid, nonane diacid, sebacic acid, undecandioic acid, 12 diacid, 13 diacid, 14 diacid or the wherein mixture of at least two kinds.
Wherein, described diamine is C
2-13aliphatic diamine.
Wherein, described diamine comprises 1,10-decamethylene diamine, quadrol, propylene diamine, slough amine, cadaverine, 2 methyl pentamethylenediamine, hexanediamine, heptamethylene diamine, octamethylenediamine, 2-methyl octamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methyl-nonamethylene diamine, nonamethylene diamine, 11 carbon diamines, 12 carbon diamines, 13 carbon diamines or the wherein mixture of at least two kinds.
Wherein, with described diamine for percent basis, described diamine comprises 1 of 70-100mol%, the quadrol of 10-decamethylene diamine and 0-30mol%, propylene diamine, slough amine, cadaverine, 2 methyl pentamethylenediamine, hexanediamine, heptamethylene diamine, octamethylenediamine, 2-methyl octamethylenediamine, 2,2, at least one in 4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamines, 5-methyl-nonamethylene diamine, nonamethylene diamine, 11 carbon diamines, 12 carbon diamines or 13 carbon diamines.
Wherein, in described prepolymerization, can also add before reacting by heating still in nylon salt to described reactor.
Wherein, described nylon salt comprises at least one in hexanediamine adipate, hexanediamine sebacate, hexanediamine 12 diacid salt, hexanediamine 13 diacid salt, hexanediamine 14 diacid salt and hexanediamine 16 diacid salt.
Wherein, in described prepolymerization, the temperature of reaction of prepolymerization is 210-260 DEG C, prepolymerization 1-3 hour.
Wherein, in described prepolymerization, in described reactor, there is stirring.
Wherein, described reaction promoter comprises molecular weight regulator and catalyzer.
Wherein, described molecular weight regulator accounts for the 0.5-2.5mol% of the total amount of diprotic acid, aliphatic diamine and nylon salt; Or described molecular weight regulator accounts for the 0.5-2.5mol% of diprotic acid and aliphatic diamine total amount.
Wherein, described catalyzer accounts for the 0.02-0.2wt% of the total amount of diprotic acid, aliphatic diamine and molecular weight regulator; Or described catalyzer accounts for the 0.02-0.2wt% of the total amount of diprotic acid, aliphatic diamine and nylon salt; Or described catalyzer accounts for the 0.02-0.2wt% of the total amount of diprotic acid, aliphatic diamine, nylon salt and molecular weight regulator.
Wherein, described molecular weight regulator is monoprotic acid or monoamine.
Wherein, described monoprotic acid includes but are not limited to formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, sad, lauric acid, tridecanoic acid, tetradecanoic acid, palmitinic acid, stearic acid, trimethylacetic acid, isopropylformic acid, hexahydrobenzoic acid, phenylformic acid, toluic acid, α-naphthalene monocarboxylic acid, β-naphthalene monocarboxylic acid, methylnaphthalene carboxylic acid, phenylacetic acid or the wherein mixture of at least two kinds.
Wherein, described monoprotic acid is at least one in formic acid, acetic acid or phenylformic acid.
Wherein, described monoamine includes but are not limited to methylamine, ethamine, propylamine, butylamine, hexylamine, octylame, decyl amine, stearylamine, dimethylamine, diethylamine, dipropyl amine, dibutylamine, hexahydroaniline, dicyclohexyl amine, aniline, Tolylamine, diphenylamine, naphthylamines or the wherein mixture of at least two kinds.
Wherein, described monoamine is decyl amine and/or benzene methanamine.
Wherein, described catalyzer is at least one in phosphoric acid, phosphorous acid, Hypophosporous Acid, 50, phosphenylic acid, phenyl-phosphinic acid, phosphoric acid salt, phosphite, hypophosphite, phosphniline hydrochlorate, phenyl-phosphinic acid salt, triphenylphosphate, triphenyl phosphite or tris phosphite.
Wherein, described thickening reaction is carried out under vacuum or condition of nitrogen gas.
Wherein, the temperature of reaction of described thickening reaction is 230-250 DEG C.
The present invention also provides a kind of above-mentioned preparation method the polymeric amide obtained.
An application for the polymeric amide that above-mentioned preparation method obtains, described polymeric amide is applied to the field such as electric and electronic equipment, trolley part, office appliance, at home articles for use.
Compare in prior art and pulverize the prepolymer of polymeric amide for powder, usual particle diameter is less than 500 μm, and when carrying out thickening reaction under the effect of vacuum, prepolymer is easily drawn out of and is adsorbed on vacuum pipe inwall, causes vacuum pipe to block gradually.The vacuum tightness of thickening reaction system reduces gradually, and the water that thickening reaction produces can not be taken away in time, and water vapor concentration goes up not down, thus the forward of polycondensation equilibrium is moved become difficulty, and thickening speed of reaction slows down, and the reaction times extends.And be drawn out of and be adsorbed on the powder deposition on vacuum pipe inwall, causing the difficulty of cleaning.
The preparation method of polymeric amide of the present invention, particle diameter is made to be that the weight fraction that the particulate state prepolymer of 0.5-2mm accounts for particulate state prepolymer is not less than 71%, make thickening react the water molecules generated easily to spread to particulate state pre-polymer surface, thus polycondensation equilibrium forward is moved, prepolymer viscosity lift velocity is accelerated, improve thickening speed of reaction, the thickening reaction times shortens, and thickening reaction is able to evenly, carries out fast.Further, the weight percentage that the prepolymer being less than 0.5mm due to particle diameter accounts for prepolymer is no more than 9%, is not easy to block vacuum pipe.
Embodiment
Below in conjunction with some embodiments, polymeric amide of the present invention, preparation method and application thereof are described further.Specific embodiment is for further describing the present invention, non-limiting protection scope of the present invention.
The polymeric amide that the present invention prepares carries out following performance test according to standard system for batten:
Relative viscosity (η
r) test: with reference to man of People's Republic of China (PRC) standard GB12006.1-89, polymeric amide viscosity number measuring method is tested.Concrete testing method is in the vitriol oil of the 98wt% of 25 ± 0.01 DEG C, measure the relative viscosity η that concentration is the polymeric amide of 0.25g/dl
r, the NCY-2 automatic viscometer adopting Shanghai Si Erda scientific instrument company limited to produce is measured.
Fusing point (T
m) test: with reference to ASTM D3418-2003, Standard Test Method for Transition Temperatures of PolymersBy Differential Scanning Calorimetry tests.Concrete testing method is the fusing point adopting Perkin Elmer Dimond dsc analysis instrument test sample; Nitrogen atmosphere, flow velocity is 40mL/min; First be warming up to 340 DEG C with 10 DEG C/min during test, keep 2min at 340 DEG C, be then cooled to 50 DEG C with 10 DEG C/min, then be warming up to 340 DEG C with 10 DEG C/min, endotherm peak temperature is now set to fusing point T
m.
Size distribution ratio is tested: according to standard GB/T/T 20405.3-2006(incontinent person urine absorbent: the testing method of polymeric matrix imbibition material characteristic---the 3rd part: method of sieving is to the mensuration of size distribution) test.
The height of prepolymer and polyamide polymer directly adopts vernier caliper measurement.
In all embodiments provided by the invention, the starting material provided all can obtain from market buying.Wherein, terephthalic acid is top grade product, is selected from and raises sub-petrochemical industry.
1，10-diaminodecane is analytical pure, is selected from Guangzhou Chemical Reagent Factory.
Phenylformic acid is analytical pure, is selected from Guangzhou Chemical Reagent Factory.
Sodium hypophosphite is analytical pure, is selected from Guangzhou Chemical Reagent Factory.
Below in conjunction with specific embodiments the present invention is further detailed, it should be noted that, described in following embodiment, nylon salt selects nylon salt, described reaction promoter selects phenylformic acid and sodium hypophosphite, and the addition of described nylon salt and described reaction promoter is the preferred content of content of the present invention.Adopt any content within other nylon salt cited by the present invention, other reaction promoters and both content range aforementioned to be also applicable to the present invention, will not enumerate at this.
Embodiment 1
In the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 20mol terephthalic acid, the 1，10-diaminodecane of 20.8mol, 74.8g phenylformic acid, 6.98g sodium hypophosphite, after vacuumizing, fill N
2to normal pressure, after repeating to vacuumize, fill N
2process three times, finally by N
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure, having reacted rear discharging by removing formed water, prepolymer vacuum-drying 24 hours at 80 DEG C, obtains prepolymer.
Prepolymer granulation step: 600g water is added in 3000g prepolymer, mixes.After discharging, be placed in YK-160 type oscillating granulator.Adjustment screen cloth and drum rotational speed, thus control prepolymer particle diameter.Be transferred in GFG HighefficientFluidbeddrier by prepolyer granule rapidly afterwards, arranging drying temperature is 90 DEG C, and dry 10min, obtains particulate state prepolymer, and the size distribution of particulate state prepolymer is listed in table 1.Wherein, described YK-160 type oscillating granulator and GFG HighefficientFluidbeddrier are the manufacture of Changzhou Rong Zhen drying plant company limited.
Thickening reactions steps: after the prepolymer after granulation is warming up to 150 DEG C with the temperature rise rate of 50 DEG C/h; 200 DEG C are warming up to the temperature rise rate of 30 DEG C/h; 230 DEG C are warming up to again with the temperature rise rate of 10 DEG C/h; Last be warming up to 250 DEG C with the temperature rise rate of 5 DEG C/h after constant temperature, vacuum tightness is carry out thickening reaction under 50Pa condition, obtained polymeric amide relative viscosity and reach relative viscosity required time and list in table 1.
Embodiment 2
In the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 20mol terephthalic acid, the 1，10-diaminodecane of 20.8mol, 74.8g phenylformic acid, 6.98g sodium hypophosphite, after vacuumizing, fill N
2to normal pressure, after repeating to vacuumize, fill N
2process three times, finally by N
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure, having reacted rear discharging by removing formed water, prepolymer vacuum-drying 24 hours at 80 DEG C, obtains prepolymer.
The granulation step of prepolymer is with embodiment 1, but adjustment screen cloth and drum rotational speed, make prepolymer size distribution as shown in table 1.Thickening reactions steps with embodiment 1, obtained polymeric amide relative viscosity and reach relative viscosity required time and list in equally in table 1.
Embodiment 3
In the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 20mol terephthalic acid, the 1，10-diaminodecane of 20.8mol, 74.8g phenylformic acid, 6.98g sodium hypophosphite, after vacuumizing, fill N
2to normal pressure, after repeating to vacuumize, fill N
2process three times, finally by N
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure, having reacted rear discharging by removing formed water, prepolymer vacuum-drying 24 hours at 80 DEG C, obtains prepolymer.
The granulation step of prepolymer is with embodiment 1, but adjustment screen cloth and drum rotational speed, make prepolymer size distribution as shown in table 1.Thickening reactions steps with embodiment 1, obtained polymeric amide relative viscosity and reach relative viscosity required time and list in equally in table 1.
Embodiment 4
Add in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth 20mol terephthalic acid, 20.8mol 1, the nylon salt of 10-decamethylene diamine, 2.2mol, 78.6g phenylformic acid, 7.53g sodium hypophosphite, fill N after vacuumizing
2to normal pressure, after repeating to vacuumize, fill N
2process three times, finally by N
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure, having reacted rear discharging by removing formed water, prepolymer vacuum-drying 24 hours at 80 DEG C, obtains prepolymer.
The granulation step of prepolymer is with embodiment 1, but adjustment screen cloth and drum rotational speed, make prepolymer size distribution as shown in table 2.Thickening reactions steps with embodiment 1, obtained polymeric amide relative viscosity and reach relative viscosity required time and list in equally in table 2.
Embodiment 5
Add in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth 20mol terephthalic acid, 20.8mol 1, the nylon salt of 10-decamethylene diamine, 2.2mol, 78.6g phenylformic acid, 7.53g sodium hypophosphite, fill N after vacuumizing
2to normal pressure, after repeating to vacuumize, fill N
2process three times, finally by N
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure, having reacted rear discharging by removing formed water, prepolymer vacuum-drying 24 hours at 80 DEG C, obtains prepolymer.
The granulation step of prepolymer is with embodiment 1, but adjustment screen cloth and drum rotational speed, make prepolymer size distribution as shown in table 2.Thickening reactions steps with embodiment 1, obtained polymeric amide relative viscosity and reach relative viscosity required time and list in equally in table 2.
Embodiment 6
Add in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth 20mol terephthalic acid, 20.8mol 1, the nylon salt of 10-decamethylene diamine, 2.2mol, 78.6g phenylformic acid, 7.53g sodium hypophosphite, fill N after vacuumizing
2to normal pressure, after repeating to vacuumize, fill N
2process three times, finally by N
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure, having reacted rear discharging by removing formed water, prepolymer vacuum-drying 24 hours at 80 DEG C, obtains prepolymer.
The granulation step of prepolymer is with embodiment 1, but adjustment screen cloth and drum rotational speed, make prepolymer size distribution as shown in table 2.Thickening reactions steps with embodiment 1, obtained polymeric amide relative viscosity and reach relative viscosity required time and list in equally in table 2.
Embodiment 7
Add in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth 20mol terephthalic acid, 14.56mol 1,1 of 10-decamethylene diamine, 6.24mol, 8-octamethylenediamine, 74.8g phenylformic acid, 6.20g sodium hypophosphite, fill N after vacuumizing
2to normal pressure, after repeating to vacuumize, fill N
2process three times, finally by N
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure, having reacted rear discharging by removing formed water, prepolymer vacuum-drying 24 hours at 80 DEG C, obtains prepolymer.
The granulation step of prepolymer is with embodiment 1, but adjustment screen cloth and drum rotational speed, make prepolymer size distribution as shown in table 3.Thickening reactions steps with embodiment 1, its relative viscosity and reach relative viscosity required time and list in table 3.
Embodiment 8
In the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 1,12-ten two carbon diamines, 74.8g phenylformic acid, the 7.32g sodium hypophosphite of 20mol terephthalic acid, 20.8mol, after vacuumizing, fill N
2to normal pressure, after repeating to vacuumize, fill N
2process three times, finally by N
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure, having reacted rear discharging by removing formed water, prepolymer vacuum-drying 24 hours at 80 DEG C, obtains prepolymer.
The granulation step of prepolymer is with embodiment 1, but adjustment screen cloth and drum rotational speed, make prepolymer size distribution as shown in table 3.Thickening reactions steps with embodiment 1, its relative viscosity and reach relative viscosity required time and list in table 3.
Embodiment 9
Add in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth 14mol terephthalic acid, 6mol sebacic acid, 20.8mol 1,13-13 carbon diamines, 74.8g phenylformic acid, 7.32g sodium hypophosphite, fill N after vacuumizing
2to normal pressure, after repeating to vacuumize, fill N
2process three times, finally by N
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure, having reacted rear discharging by removing formed water, prepolymer vacuum-drying 24 hours at 80 DEG C, obtains prepolymer.
The granulation step of prepolymer is with embodiment 1, but adjustment screen cloth and drum rotational speed, make prepolymer size distribution as shown in table 3.Thickening reactions steps with embodiment 1, its relative viscosity and reach relative viscosity required time and list in table 3.
Embodiment 10
Add in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth 18mol terephthalic acid, 2mol 1,1 of 10-sebacic acid, 20.8mol, 10-decamethylene diamine, 72.4g phenylformic acid, 7.18g sodium hypophosphite, vacuumize, fill N
2to normal pressure, after repeating to vacuumize, fill N
2process three times three times, finally by N
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure, having reacted rear discharging by removing formed water, prepolymer vacuum-drying 24 hours at 80 DEG C, obtains prepolymer.
Use the granulation step that same embodiment 1 is same, but adjustment screen cloth and drum rotational speed, make prepolymer size distribution as shown in table 3.Wherein, particle diameter is the prepolymer of 0.5-2mm is the prepolymer of cylindrical shape, and testing its altitude distribution is 1-5mm.Obtained polymeric amide altitude distribution be 0.5-3mm.Thickening reactions steps with embodiment 1, its relative viscosity and reach relative viscosity required time and list in table 3.
Embodiment 11
Add in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth 20mol terephthalic acid, 16.64mol 1,1 of 10-decamethylene diamine, 4.16mol, 6-hexanediamine, 76.2g phenylformic acid, 6.39g sodium hypophosphite, vacuumize, fill N
2to normal pressure, after repeating to vacuumize, fill N
2process three times three times, finally by N
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure, having reacted rear discharging by removing formed water, prepolymer vacuum-drying 24 hours at 80 DEG C, obtains prepolymer.
Use the granulation step that same embodiment 1 is same, but adjustment screen cloth and drum rotational speed, make prepolymer size distribution as shown in table 3.Wherein, particle diameter is the prepolymer of 0.5-2mm is the prepolymer of cylindrical shape, and testing its altitude distribution is 1-5mm.Obtained polymeric amide altitude distribution be 0.5-3mm.Thickening reactions steps with embodiment 1, its relative viscosity and reach relative viscosity required time and list in table 3.
Comparative example 1-3
In the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 20mol terephthalic acid, the 1，10-diaminodecane of 20.8mol, 74.8g phenylformic acid, 6.98g sodium hypophosphite, after vacuumizing, fill N
2to normal pressure, after repeating to vacuumize, fill N
2process three times, finally by N
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure, having reacted rear discharging by removing formed water, prepolymer vacuum-drying 24 hours at 80 DEG C, obtains prepolymer.
Being pulverized by prepolymer makes prepolymer size distribution as shown in table 1.Its thickening reactions steps with embodiment 1, obtained polymeric amide relative viscosity and reach relative viscosity required time and list in equally in table 1.Carry out with solid-phase tack producing, vacuum tightness declines, and polymer viscosity increasess slowly.Shutdown inspection, finds that vacuum pipe blocking is serious.
Comparative example 4
In the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 20mol terephthalic acid, the 1，10-diaminodecane of 20.8mol, 74.8g phenylformic acid, 6.98g sodium hypophosphite, after vacuumizing, fill N
2to normal pressure, after repeating to vacuumize, fill N
2process three times, finally by N
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure, having reacted rear discharging by removing formed water, prepolymer vacuum-drying 24 hours at 80 DEG C, obtains prepolymer.
The granulation step of prepolymer is with embodiment 1, but adjustment screen cloth and drum rotational speed, make prepolymer size distribution as shown in table 1.Thickening reactions steps with embodiment 1, the relative viscosity of polymeric amide and reach relative viscosity required time and list in equally in table 1.
Comparative example 5
In the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 20mol terephthalic acid, the 1，10-diaminodecane of 20.8mol, 74.8g phenylformic acid, 6.98g sodium hypophosphite, after vacuumizing, fill N
2to normal pressure, after repeating to vacuumize, fill N
2process three times, finally by N
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure, having reacted rear discharging by removing formed water, prepolymer vacuum-drying 24 hours at 80 DEG C, obtains prepolymer.
The granulation step of prepolymer is with embodiment 1, but adjustment screen cloth and drum rotational speed, make prepolymer size distribution as shown in table 1.Thickening reactions steps with embodiment 1, the relative viscosity of polymeric amide and reach relative viscosity required time and list in equally in table 1.
Comparative example 6-8
Add in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth 20mol terephthalic acid, 20.8mol 1, the nylon salt of 10-decamethylene diamine, 2.2mol, 78.6g phenylformic acid, 7.53g sodium hypophosphite, fill N after vacuumizing
2to normal pressure, after repeating to vacuumize, fill N
2process three times, finally by N
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure, having reacted rear discharging by removing formed water, prepolymer vacuum-drying 24 hours at 80 DEG C, obtains prepolymer.
Being pulverized by prepolymer makes prepolymer size distribution as shown in table 2.Thickening reactions steps with embodiment 1, obtained polymeric amide relative viscosity and reach relative viscosity required time and list in equally in table 2.Carry out with solid-phase tack producing, vacuum tightness declines, and polymer viscosity increasess slowly.Shutdown inspection, finds that vacuum pipe blocking is serious.
Comparative example 9
Add in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth 20mol terephthalic acid, 20.8mol 1, the nylon salt of 10-decamethylene diamine, 2.2mol, 78.6g phenylformic acid, 7.53g sodium hypophosphite, fill N after vacuumizing
2to normal pressure, after repeating to vacuumize, fill N
2process three times, finally by N
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure, having reacted rear discharging by removing formed water, prepolymer vacuum-drying 24 hours at 80 DEG C, obtains prepolymer.
The granulation step of prepolymer is with embodiment 1, but adjustment screen cloth and drum rotational speed, make prepolymer size distribution as shown in table 2.Thickening reactions steps with embodiment 1, obtained polymeric amide relative viscosity and reach relative viscosity required time and list in equally in table 2.
Comparative example 10
Add in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth 20mol terephthalic acid, 20.8mol 1, the nylon salt of 10-decamethylene diamine, 2.2mol, 78.6g phenylformic acid, 7.53g sodium hypophosphite, fill N after vacuumizing
2to normal pressure, after repeating to vacuumize, fill N
2process three times, finally by N
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure, having reacted rear discharging by removing formed water, prepolymer vacuum-drying 24 hours at 80 DEG C, obtains prepolymer.
The granulation step of prepolymer is with embodiment 1, but adjustment screen cloth and drum rotational speed, make prepolymer size distribution as shown in table 2.Thickening reactions steps with embodiment 1, obtained polymeric amide relative viscosity and reach relative viscosity required time and list in equally in table 2.
Comparative example 11
Add in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth 20mol terephthalic acid, 14.56mol 1,1 of 10-decamethylene diamine, 6.24mol, 8-octamethylenediamine, 74.8g phenylformic acid, 6.20g sodium hypophosphite, fill N after vacuumizing
2to normal pressure, after repeating to vacuumize, fill N
2process three times, finally by N
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure, having reacted rear discharging by removing formed water, prepolymer vacuum-drying 24 hours at 80 DEG C, obtains prepolymer.
The granulation step of prepolymer is with embodiment 1, but adjustment screen cloth and drum rotational speed, make prepolymer size distribution as shown in table 3.Thickening reactions steps with embodiment 1, its relative viscosity and reach relative viscosity required time and list in table 3.
Comparative example 12
In the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add 1,12-ten two carbon diamines, 74.8g phenylformic acid, the 7.32g sodium hypophosphite of 20mol terephthalic acid, 20.8mol, after vacuumizing, fill N
2to normal pressure, after repeating to vacuumize, fill N
2process three times, finally by N
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure, having reacted rear discharging by removing formed water, prepolymer vacuum-drying 24 hours at 80 DEG C, obtains prepolymer.
The granulation step of prepolymer is with embodiment 1, but adjustment screen cloth and drum rotational speed, make prepolymer size distribution as shown in table 3.Thickening reactions steps with embodiment 1, its relative viscosity and reach relative viscosity required time and list in table 3.
Comparative example 13
Add in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth 14mol terephthalic acid, 6mol sebacic acid, 20.8mol 1,13-13 carbon diamines, 74.8g phenylformic acid, 7.32g sodium hypophosphite, fill N after vacuumizing
2to normal pressure, after repeating to vacuumize, fill N
2process three times, finally by N
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure, having reacted rear discharging by removing formed water, prepolymer vacuum-drying 24 hours at 80 DEG C, obtains prepolymer.
The granulation step of prepolymer is with embodiment 1, but adjustment screen cloth and drum rotational speed, make prepolymer size distribution as shown in table 3.Thickening reactions steps with embodiment 1, its relative viscosity and reach relative viscosity required time and list in table 3.
Comparative example 14
Add in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth 18mol terephthalic acid, 2mol 1,1 of 10-sebacic acid, 20.8mol, 10-decamethylene diamine, 72.4g phenylformic acid, 7.18g sodium hypophosphite, vacuumize, fill N
2to normal pressure, after repeating to vacuumize, fill N
2process three times three times, finally by N
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure, having reacted rear discharging by removing formed water, prepolymer vacuum-drying 24 hours at 80 DEG C, obtains prepolymer.
The granulation step of prepolymer is with embodiment 1, but adjustment screen cloth and drum rotational speed, make prepolymer size distribution as shown in table 3.Thickening reactions steps with embodiment 1, its relative viscosity and reach relative viscosity required time and list in table 3.
Comparative example 15
Add in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth 20mol terephthalic acid, 16.64mol 1,1 of 10-decamethylene diamine, 4.16mol, 6-hexanediamine, 76.2g phenylformic acid, 6.39g sodium hypophosphite, vacuumize, fill N
2to normal pressure, after repeating to vacuumize, fill N
2process three times three times, finally by N
2pressure rises to 0.3MPa.Be warmed up to 220 DEG C under agitation 2 hours, reaction mixture stirred 1 hour at 220 DEG C, then under agitation makes the temperature of reactant be elevated to 230 DEG C.React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure, having reacted rear discharging by removing formed water, prepolymer vacuum-drying 24 hours at 80 DEG C, obtains prepolymer.
The granulation step of prepolymer is with embodiment 1, but adjustment screen cloth and drum rotational speed, make prepolymer size distribution as shown in table 3.Thickening reactions steps with embodiment 1, its relative viscosity and reach relative viscosity required time and list in table 3.
Following table 1-3 is constituent part and the performance test table of embodiment and comparative example in the present invention.
Table 1
Table 2
Table 3
In upper table 1-3, reach the speed that polymeric amide relative viscosity required time is used for characterizing thickening reaction, reach polymeric amide relative viscosity required time shorter, the speed of thickening reaction is rapider.Wherein, reaching polymeric amide relative viscosity required time is timing from the oil bath temperature of thickening reaction reaches 150 DEG C.
Embodiment 1-3 and comparative example-3 contrast, embodiment 4-6 and comparative example 6-8 contrasts, can find out, when the prepolyer granule content that particle diameter is less than 0.5mm is more than or equal to 77%, the prepolymer that particle diameter is less than 0.5mm is adsorbed on vacuum pipe inwall by vacuum extraction, vacuum pipe is caused to block gradually, the vacuum tightness of polymer viscosified reaction system declines rapidly, the water that reaction system produces can not be taken away in time, water vapor concentration raises, the forward of polycondensation equilibrium moves and becomes difficulty, and vacuum reaction is forced to stop.
Embodiment 1-3 and comparative example 4-5 contrasts, embodiment 4-6 and comparative example 9-10 contrasts, embodiment 7-11 and comparative example 11-15 contrasts, can find out: in preparation method of the present invention, particle diameter is that the weight fraction that the particulate state prepolymer of 0.5-2mm accounts for particulate state prepolymer is not less than 71%, when the prepolyer granule content that particle diameter is less than 0.5mm is less than or equal to 9%, the ratio of particle diameter shared by the prepolyer granule of 0.5-2mm is larger, reaches the polymeric amide relative viscosity η that technique is predetermined
rthe time of the thickening reaction needed for 2.1-2.3 is shorter, and the speed of thickening reaction is higher.When the particle diameter of prepolyer granule is 0.5-2mm, the water molecules that thickening reaction generates is easier to particle surface diffusion, thus polycondensation equilibrium forward is moved, and accelerate thickening speed of reaction, the thickening reaction times shortens; When the prepolyer granule content that particle diameter is less than 0.5mm higher than 9% time, the thickening reaction times extends.This is because when carrying out thickening reaction under the effect of vacuum, the prepolymer that particle diameter is less than 0.5mm is easily drawn out of and is adsorbed on vacuum pipe inwall, causes vacuum pipe to block gradually.The vacuum tightness of thickening reaction system reduces gradually, and the water that thickening reaction produces can not be taken away in time, and water vapor concentration goes up not down, thus the forward of polycondensation equilibrium is moved become difficulty, and thickening speed of reaction slows down, and the reaction times extends.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every utilize description of the present invention to do equivalent structure or equivalent flow process conversion; or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (7)
1. a preparation method for polymeric amide, comprises the following steps:
Prepolymerization step: diprotic acid, diamine and reaction promoter are joined in reactor, reacting by heating still, carries out prepolymerization, obtained prepolymer;
Granulation step: described prepolymer is made particulate state prepolymer; In described particulate state prepolymer, particle diameter be 0.5 ?the particulate state prepolymer of the 2mm weight fraction that accounts for particulate state prepolymer be not less than 71%;
Thickening reactions steps: the prepolymer through granulation step is carried out thickening reaction, obtains polymeric amide, in described granulation step, the weight percentage that the prepolymer that particle diameter is less than 0.5mm accounts for prepolymer is no more than 9%.
2. the preparation method of polymeric amide as claimed in claim 1, it is characterized in that: in described granulation step, described particulate state prepolymer is cylindrical shape.
3. the preparation method of polymeric amide as claimed in claim 2, is characterized in that: the height of described particulate state prepolymer be 1 ?5mm.
4. the preparation method of polymeric amide as claimed in claim 1, is characterized in that: described diprotic acid comprises aromatic acid and aliphatic dibasic acid.
5. the preparation method of polymeric amide as claimed in claim 1, is characterized in that: described diamine be C2 ?13 aliphatic diamine.
6. the preparation method of polymeric amide as claimed in claim 1, is characterized in that: described reaction promoter comprises molecular weight regulator and catalyzer.
7. the preparation method of polymeric amide as claimed in claim 1, is characterized in that: in described prepolymerization, also adds in nylon salt to described reactor before reacting by heating still.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210484972.3A CN102993437B (en) | 2012-11-23 | 2012-11-23 | Polyamide as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210484972.3A CN102993437B (en) | 2012-11-23 | 2012-11-23 | Polyamide as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102993437A CN102993437A (en) | 2013-03-27 |
| CN102993437B true CN102993437B (en) | 2014-12-24 |
Family
ID=47922589
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210484972.3A Expired - Fee Related CN102993437B (en) | 2012-11-23 | 2012-11-23 | Polyamide as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102993437B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254423A (en) * | 2013-05-20 | 2013-08-21 | 金发科技股份有限公司 | Polyamide resin and polyamide composition composed thereof |
| CN108383996B (en) * | 2018-01-10 | 2020-10-30 | 金发科技股份有限公司 | High-crystallization-rate polyamide and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1011637C2 (en) * | 1999-03-22 | 2000-09-27 | Dsm Nv | Process for the preparation of polyamide pellets. |
| FR2794760B1 (en) * | 1999-06-11 | 2001-08-17 | Rhodianyl | PROCESS FOR THE MANUFACTURE OF POLYAMIDES |
| CN101020746A (en) * | 2007-03-19 | 2007-08-22 | 北京化工大学 | Prepn process of biodegradable polyamidoester |
| CN101456949B (en) * | 2007-12-14 | 2012-01-18 | 金发科技股份有限公司 | Semi-aromatic polyamide and preparation method thereof |
-
2012
- 2012-11-23 CN CN201210484972.3A patent/CN102993437B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102993437A (en) | 2013-03-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103539936B (en) | A kind of polymeric amide and synthetic method thereof and application and polyamide article | |
| JP5174921B2 (en) | Semi-aromatic polyamide and method for preparing semi-aromatic polyamide | |
| WO2019137303A1 (en) | Polyamide having high crystallization rate, preparation method therefor and application thereof | |
| CN110218311B (en) | Flame-retardant semi-aromatic polyamide and preparation method thereof | |
| CN103539935B (en) | A kind of method improving polymeric amide whiteness | |
| CN102993437B (en) | Polyamide as well as preparation method and application thereof | |
| US20220025120A1 (en) | Semi-aromatic polyamide resin and preparation method therefor | |
| CN110028665B (en) | Semi-aromatic polyamide with high heat resistance and low water absorption and preparation method thereof | |
| CN104774454B (en) | A kind of high temperature resistant nylon PA66T materials and preparation method thereof | |
| CN103570939B (en) | A kind of polymeric amide, preparation method and application thereof | |
| CN102775601A (en) | Preparation method of semi-aromatic polyamide-polyamide 11 copolymer | |
| CN114181390A (en) | Bio-based high-temperature-resistant polyamide and preparation method thereof | |
| CN1315912C (en) | Block copolyamide and preparation thereof | |
| CN102964590B (en) | Polyamide and preparation method and application thereof | |
| CN109180931B (en) | Preparation method of long-carbon-chain nylon PA1313 and product | |
| CN106893098A (en) | A kind of wear-resisting polyamide hot and preparation method thereof | |
| CN103122063B (en) | Preparation method of poly-p-aminobenzoylamonoundecylamine | |
| CN102703021A (en) | High-air permeability dimer acid type polyamide hot melt adhesive and preparation method thereof | |
| CN105111980A (en) | Special modified phenolic aldehyde high-temperature-resistant adhesive | |
| CN103468198A (en) | Preparation method of dimer acid type polyamide hot melt adhesive for heat-shrinkable sleeve | |
| CN109749695A (en) | A kind of novel polyamide hot melt adhesive and preparation method thereof | |
| WO2023185517A1 (en) | Bio-based high-temperature-resistant polyamide with high binding force, method for preparing same, and use thereof | |
| CN106380594A (en) | Preparation method of anti-yellowing polyamide | |
| CN106633040B (en) | A kind of polyamide and its synthetic method and application | |
| CN113004514A (en) | Low-hygroscopicity PA5T and synthesis method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141224 Termination date: 20201123 |