CN103665375A - Preparation method of nylon - Google Patents
Preparation method of nylon Download PDFInfo
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- CN103665375A CN103665375A CN201310633632.7A CN201310633632A CN103665375A CN 103665375 A CN103665375 A CN 103665375A CN 201310633632 A CN201310633632 A CN 201310633632A CN 103665375 A CN103665375 A CN 103665375A
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Abstract
The invention discloses a preparation method of nylon. The method uses dicarboxylic acid and 4,4'-diaminodicyclohexylmethane as raw materials; the nylon product which is colorless and transparent and has excellent mechanical property is prepared by directly performing the melt phase polycondensation reaction according to a set temperature and pressure change program.
Description
Technical field
The present invention relates generally to a kind of preparation method of high transparent nylon, is a kind of by 4 specifically, and the preparation method of the synthetic a kind of high transparent nylon of 4 '-diamino-dicyclohexyl methane and di-carboxylic acid polycondensation, belongs to organic polymer material preparation field.
Background technology
Nylon has good over-all properties, comprise mechanical property, thermotolerance, wearability, chemical proofing and self lubricity etc., and have certain flame retardant resistance, be easy to processing, be suitable for, by glass fibre and other filler filling enhancing modified, improving performance and broadened application scope.
The main monomer that the prepared a kind of novel nylon material of the present invention is taked is PACM(4,4 '-diamino-dicyclohexyl methane) and di-carboxylic acid, its chemical general formula can be expressed as NylonPACMn, this series products has remarkable optical characteristics, chemical resistant properties and balanced machinery and thermal characteristics easily machine-shaping, therefore in fields such as automotive industry, mechanical industry, athletic sports appliances, has application very widely.US Patent No. 3502624 is described the synthetic of similar structures nylon with US3869400, and its building-up process is divided into two steps: first salify, then polycondensation.Salification process needs continuous regulator solution pH, adds various additives, by heating and cooling, impels nylon salt to separate out etc., this has just strengthened the input of equipment, improved operation easier, not only energy consumption is high, and the use of a large amount of solvents has also caused pollution to environment.Same nylon synthesizes in US Patent No. 3661982 and US4213884 also description, although salification process is improved to some extent, the problems referred to above still do not overcome.
Summary of the invention
The preparation method who the object of this invention is to provide a kind of nylon, has adopted the method for a step melt phase polycondensation to omit salify operation, has not only reduced cost of investment but also has stopped the use pollution on the environment of organic solvent in salification process.Aspect technology controlling and process, need only the needed temperature, pressure condition of reaction that keeps, simple, and adding of suitable oxidation inhibitor also played positive promoter action to the outward appearance improvement of product, the nylon product making by this preparation method has high transparent, erosion-resisting characteristics is strong, and chemical resistance is good.
In order to achieve the above object, the present invention adopts following technical scheme:
A preparation method for nylon, obtains by diamine and di-carboxylic acid polycondensation, and concrete preparation process is as follows:
1) in reactor, add the material that comprises deionized water, di-carboxylic acid, diamine, oxidation inhibitor and catalyzer, start to stir, be warming up to 100～150 ℃, be preferably 135～145 ℃; Maintain the temperature at 100～150 ℃, be preferably 135～145 ℃; By venting, maintaining pressure is 0.206～0.275MPa, is preferably 0.270～0.275MPa; Continue 30～90min, be preferably 50～60min;
2) pressure is adjusted to 1.723～2.413MPa, be preferably 2.000～2.100MPa, temperature is adjusted to 200～240 ℃, be preferably 220～225 ℃, keep pressure 30～120min, be preferably 80～90min step-down gradually afterwards, and persistently overheating in pressurize and step-down process, in 60min, be depressurized to normal pressure, and when step-down completes, rise to 250～310 ℃ of equilibrium temperatures, be preferably 265～275 ℃;
3) keep equilibrium temperature, be adjusted to equilibrium pressure-0.1MPa～0MPa, be preferably after-0.1～-0.08MPa, under the condition that keeps equilibrium temperature and equilibrium pressure, continuing to keep 10～120min(is starting time), be preferably 40～60min, obtain product.
In method of the present invention, described diamine is 4,4 '-diamino-dicyclohexyl methane
(PACM).Preferably, with 4, the total restatement of 4 '-diamino-dicyclohexyl methane, 4, the content of the anti-trans-isomer(ide) of 4 '-diamino-dicyclohexyl methane is 20wt%～50wt%, preferred 40wt%～48wt%, and the control of the content of anti-trans-isomer(ide) is conducive to improve the transparency of final nylon product.
In method of the present invention, described di-carboxylic acid is
in a kind of, wherein, n is 4～10, preferably di-carboxylic acid is hexanodioic acid (ADA) or dodecanedioic acid (DDA).
In method of the present invention, described di-carboxylic acid and the mol ratio of diamine are 1.03:1～1:1.03, preferably between 1:1～1:1.02.The account for massfraction of ionized water of di-carboxylic acid consumption is 40%～60%, preferably 45%～50%.
In method of the present invention, described catalyzer is the one or two or more in phosphoric acid salt, hypophosphite and hypophosphite, preferably phosphoric acid an alkali metal salt, one or two or more in Hypophosporous Acid, 50 an alkali metal salt and ortho phosphorous acid an alkali metal salt, more preferably the one or two or more in sodium phosphate, sodium hypophosphite and inferior sodium phosphate, its consumption is 0.5 ‰～1.5 ‰ of di-carboxylic acid and diamine total mass, preferably 0.6 ‰～0.8 ‰.
In method of the present invention, described oxidation inhibitor is selected from the one or two or more in chinox1098, chinox1589, H818D, chinox1325 and chinox1590, preferably chinox1098 or chinox1589.The consumption of oxidation inhibitor is 0.5 ‰～8 ‰ of deionized water, di-carboxylic acid and diamine total mass, preferably 4 ‰～5 ‰.The oxidation inhibitor of selecting can effectively stop nylon product etiolation, also can be used for regulating nylon molecular weight, and the oxidation inhibitor in preferable range can be produced color after using does not have yellow, and molecular weight is suitable, the product of excellent combination property.
Described in the present invention, pressure is gauge pressure.
Compared with prior art, beneficial effect of the present invention is: in traditional nylon production process, often take first salify aftercondensated two-step approach to synthesize, otherwise it is high to obtain molecular weight, the product of excellent performance.This is because polycondensation requires higher to functional group's equimolar ratio, only have strict control proportioning, could promote effective growth of molecular weight and then obtain high molecular weight products, forms salt operation and just can effectively guarantee the equimolar ratio of functional group.But salify operation often needs more equipment investment, increase a lot of energy consumptions, and need adopt organic solvent for the raw material salify of indissoluble in water, this not only further increases cost (such as solvent recuperation process), also likely causes the pollution to environment.And needed monomer in the NylonPACMn mentioning in this patent, solvability extreme difference in water, so the salification process that patent US3502624 and US3869400 adopt has been used organic solvent, this can increase investment with regard to inevasible, increasing energy consumption, affects environment and even reduces the security in operating process.The present invention adopts the method for a step direct melt polycondensation, without extra salify operation, whole process needn't be with an organic solvent, but adopt water cheap and easy to get as reaction medium, (molecular weight of product embodies by this index of limiting viscosity number can not only to obtain the product of high molecular, limiting viscosity number is higher, and molecular weight is larger), very excellent what also show aspect the over-all propertieies such as the transparency and mechanical property.Adopt and not only greatly reduce in this way equipment investment and energy consumption, and environment is not polluted, the operation workshop sections such as pH regulation and control while more having reduced salify, concentrated, crystallization, make whole production process become simply, be easy to control.By controlling the initial ratio of raw material, temperature, pressure and reaction times are optimized, can obtain the product of excellent performance.
And in this patent, contriver overcomes that existing prejudice is balanced the time by experimental verification repeatedly and equilibrium temperature is larger for the performance impact of product itself, be not numerous teaching materials (visible < < polymer chemistry > >-Chemical Industry Press, in January, 2003 third edition, chapter 7: 181～214 pages) and the nylon molecular weight thought of document can along with the growth of starting time, increase always, the present invention is by controlling starting time in 10～120min, preferably in 40～60min, can obtain the product of high limiting viscosity number, when starting time is less than 10min product performance, stick several not high, being greater than 120min can cause the glutinous number of product performance to decline, moreover, selection for equilibrium temperature is also most important, the product property that equilibrium temperature obtains within 250～310 ℃ of scopes is good, and after going beyond the scope, can cause synthetic failure or performance to weaken.This is because polycondensation is thermopositive reaction, be conducive to the carrying out of namely molecular degradation reaction of its reversed reaction, so temperature is higher, overlong time will cause molecular degradation under hot conditions, reduces molecular weight, thereby has influence on product performance.The nylon product that the processing condition of optimizing in employing this patent make has the transparency free from worldly cares, its 550nm transmitance is up to 80～90%, preferably 88%～90%, there is higher second-order transition temperature, second-order transition temperature can reach 101～161 ℃, preferably 120～150 ℃, erosion-resisting characteristics is strong, and shock strength can reach 6～16KJ/m
2, preferred 9～16KJ/m
2, chemical resistance is good, is easy to the feature of processing.Therefore can be widely used in the fields such as optical goods, precision instrument goods, water treating equipment, extraordinary ordnance, wrapping material, have a bright future.
Embodiment
The following examples will be further described technique provided by the present invention, but the invention is not restricted to listed embodiment, also should be included in other any known change in interest field of the presently claimed invention.
Main raw material PACM is provided by ten thousand magnificent chemical Group Plcs, and DDA and ADA buy from pacifying resistance to Jilin Chemical, and oxidation inhibitor is provided by Shuan Jian chemical inc, Taiwan.
In an embodiment, we change di-carboxylic acid, diamine proportioning successively, interpolation kind and the consumption of oxidation inhibitor, catalyst type and consumption, starting time, equilibrium temperature, the related process parameters such as equilibrium pressure and the anti-trans-isomer content of PACM, and will with this, change the performance variation list that causes in table one, two.Synthetic its thermal characteristics of product within the scope of the processing condition that provided at this patent as seen by table, mechanical property and optical property can have gratifying embodiment.
Comparative example 1
PACM, DDA are mixed under room temperature, normal pressure according to the ratio of mass ratio PACM: methyl alcohol=1:2, DDA: methyl alcohol=1:8 respectively mutually with methyl alcohol, be mixed with PACM methanol solution and DDA methanol solution, wherein PACM consumption is 300g, and PACM and DDA mol ratio are 1:1.Under agitation condition, two kinds of solution are mixed mutually, in mixing process, have crystal and separate out, after mixing, filter suspension liquid, obtain NylonPACM12 salt, through standby after drying.Get NylonPACM12 salt in glass flask, pour nitrogen excluding air, finally sealed is warming up to 250 ℃ gradually, keeps 2h, washes away generation moisture afterwards with nitrogen, after sealing, is warming up to 300 degrees Celsius, keeps 1h, obtains product.Product colour yellowing, through test, obtaining limiting viscosity number is 30.31ml/g.
Comparative example 2
In reactor, add successively deionized water, dodecanedioic acid (DDA) and PACM, catalyzer, the mol ratio of DDA/PACM is 1/1, wherein deionized water is about 600g, DDA is about 300g, in PACM, anti-trans-isomer content is 15wt%, catalyzer is inferior sodium phosphate, and catalyst levels is 1 ‰ of DDA and PACM total mass, does not add oxidation inhibitor.Open to stir, reactor is warming up to 140 ℃, maintain the temperature at 140 ℃, and control pressure is 0.275MPa, keep pressure and temperature 60min.Then regulating pressure is that 2.068MPa, temperature are 220 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 90min, persistently overheating in pressurize and step-down process, when completing, step-down rises to 310 ℃ of equilibrium temperatures.Keep equilibrium temperature, pressure is adjusted to equilibrium pressure 0Mpa, continue reaction 90min, react complete, stop stirring, emit product.Product colour yellowing, limiting viscosity number is 31.66ml/g(phenol and formic acid mixed solvent, volume ratio 1:1,30 ℃).
Comparative example 3
In reactor, add successively deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of DDA/PACM is 1/1.02, wherein deionized water is about 600g, DDA is about 300g, the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 2.5 ‰ of deionized water, DDA and PACM total mass, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of DDA and PACM total mass.After material drops into, open and stir, reactor is warming up to 140 ℃, maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.275MPa, keep pressure and temperature 60min.Then regulating pressure is 2.068MPa, and temperature is 225 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 90min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 320 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is 0Mpa that pressure is adjusted to equilibrium pressure, continues reaction 60min, reacts complete, stops stirring, and emits product.The glutinous number of product performance is 28.95ml/g, and color is without yellowing phenomenon.
Comparative example 4
In reactor, add successively deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of DDA/PACM is 1/1.02, wherein deionized water is about 600g, DDA is about 300g, the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 2.5 ‰ of deionized water, DDA and PACM total mass, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of DDA and PACM total mass.After material drops into, open and stir, reactor is warming up to 140 ℃, maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.275MPa, keep pressure and temperature 60min.Then regulating pressure is 2.068MPa, and temperature is 225 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 90min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 300 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is 0Mpa that pressure is adjusted to equilibrium pressure, continues reaction 200min, reacts complete, stops stirring, and emits product.The glutinous number of product performance is 25.14ml/g, and color is without yellowing phenomenon.
Embodiment 1
In reactor, add successively deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of DDA/PACM is 1/1, wherein deionized water is about 600g, DDA is about 240g, the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 2.5 ‰ of deionized water, DDA and PACM total mass, catalyzer is sodium phosphate, and consumption is 0.5 ‰ of DDA and PACM total mass.After all materials drop into, open and stir, reactor is warming up to 100 ℃.Maintain the temperature at 100 ℃, and the control pressure of suitably exitting is 0.206MPa, keeps pressure and temperature 30min.Then regulating pressure is that 1.723MPa, temperature are 200 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after the about 90min of pressure, persistently overheating in pressurize and step-down process, in step-down, complete and finally rise to 310 ℃ of equilibrium temperatures simultaneously.Keep equilibrium temperature, it is 0Mpa that pressure is adjusted to equilibrium pressure, continues reaction 90min, reacts complete, stops stirring, and emits product.The glutinous number of product performance is 71.74ml/g, and apparent shape is without xanthochromia, and oxidation inhibitor is respond well.
Embodiment 2
In reactor, add successively deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of DDA/PACM is 1/1, wherein deionized water is about 600g, DDA is about 300g, the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is H818D, and its consumption is 0.5 ‰ of deionized water, DDA and PACM total mass, catalyzer is sodium hypophosphite, and consumption is 1.5 ‰ of DDA and PACM total mass.After material drops into, open and stir, reactor is warming up to 150 ℃.Maintain the temperature at 150 ℃, and the control pressure of suitably exitting is 0.275MPa, keeps pressure and temperature 90min.Then regulating pressure is that 2.413MPa, temperature are 240 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 120min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 310 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is 0Mpa that pressure is adjusted to equilibrium pressure, continues reaction 90min, reacts complete, stops stirring, and emits product.The glutinous number of product performance is 11.58ml/g, and color is without yellowing phenomenon.
Embodiment 3
In reactor, add successively deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of DDA/PACM is 1/1, wherein deionized water is about 600g, DDA is about 360g, the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is chinox1325, and its consumption is 0.5 ‰ of deionized water, DDA and PACM total mass, catalyzer is sodium hypophosphite, and consumption is 1.5 ‰ of DDA and PACM total mass.After material drops into, open and stir, reactor is warming up to 150 ℃.Maintain the temperature at 150 ℃, and the control pressure of suitably exitting is 0.275MPa, keeps pressure and temperature 90min.Then regulating pressure is that 2.413MPa, temperature are 240 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 120min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 310 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is 0Mpa that pressure is adjusted to equilibrium pressure, continues reaction 90min, reacts complete, stops stirring, and emits product.The glutinous number of product performance is 40.20ml/g, and color is without yellowing phenomenon.
Embodiment 4
In reactor, add successively deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of DDA/PACM is 1/1, wherein deionized water is about 600g, DDA is about 300g, the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is chinox1590, and its consumption is 0.5 ‰ of deionized water, DDA and PACM total mass, catalyzer is inferior sodium phosphate, and consumption is 1.5 ‰ of DDA and PACM total mass.After material drops into, open and stir, reactor is warming up to 150 ℃.Maintain the temperature at 150 ℃, and the control pressure of suitably exitting is 0.275MPa, keeps pressure and temperature 90min.Then regulating pressure is that 2.413MPa, temperature are 240 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 120min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 310 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is 0Mpa that pressure is adjusted to equilibrium pressure, continues reaction 90min, reacts complete, stops stirring, and emits product.The glutinous number of product performance is 45.10ml/g, and color is without yellowing phenomenon.
Embodiment 5
In reactor, add successively deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of DDA/PACM is 1/1, wherein deionized water is about 600g, DDA is about 300g, and the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is that chinox1325 and chinox1590 are composite, its consumption is respectively 3 ‰ of deionized water, DDA and PACM total mass, catalyzer is sodium phosphate and inferior sodium phosphate, and mass ratio is 1:1, and consumption is 1 ‰ of DDA and PACM total mass.After material drops into, open and stir, reactor is warming up to 140 ℃.Maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.241MPa, keeps pressure and temperature 60min.Then regulating pressure is that 2.068MPa, temperature are 220 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 120min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 310 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is 0Mpa that pressure is adjusted to equilibrium pressure, continues reaction 90min, reacts complete, stops stirring, and emits product.The glutinous number of product performance is 50.41ml/g, and color is without yellowing phenomenon.
Embodiment 6
In reactor, add successively deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of DDA/PACM is 1/1, wherein deionized water is about 600g, DDA is about 300g, and the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, its consumption is respectively 3 ‰ of deionized water, DDA and PACM total mass, catalyzer is sodium phosphate and inferior sodium phosphate, and mass ratio is 1:1, and consumption is 1 ‰ of DDA and PACM total mass.After material drops into, open and stir, reactor is warming up to 140 ℃.Maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.241MPa, keeps pressure and temperature 60min.Then regulating pressure is 2.068MPa, and temperature is 220 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 120min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 310 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is 0Mpa that pressure is adjusted to equilibrium pressure, continues reaction 90min, reacts complete, stops stirring, and emits product.The glutinous number of product performance is 65.30ml/g, and color is without yellowing phenomenon.
Embodiment 7
In reactor, add successively deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of DDA/PACM is 1/1, wherein deionized water is about 600g, DDA is about 300g, the anti-trans-isomer content of PACM is 20wt%, and catalyzer is inferior sodium phosphate, and catalyst levels is 1 ‰ of DDA and PACM total mass, oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 4 ‰ of deionized water, DDA and PACM total mass.After material drops into, open and stir, reactor is warming up to 150 ℃.Maintain the temperature at 150 ℃, and the control pressure of suitably exitting is 0.275MPa, keeps pressure and temperature 90min.Then regulating pressure is 2.068MPa, and temperature is 220 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 120min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 310 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is 0Mpa that pressure is adjusted to equilibrium pressure, continues reaction 90min, reacts complete, stops stirring, and emits product.The glutinous number of product performance is 56.60ml/g, and color is without yellowing phenomenon.
Embodiment 8
In reactor, add successively deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of DDA/PACM is 1.01/1, wherein deionized water is about 600g, DDA is about 360g, the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 2.5 ‰ of deionized water, DDA and PACM total mass, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of DDA and PACM total mass.After material drops into, open and stir, reactor is warming up to 140 ℃.Maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.275MPa, keeps pressure and temperature 60min.Then regulating pressure is 2.068MPa, and temperature is 220 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 90min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 310 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is 0Mpa that pressure is adjusted to equilibrium pressure, continues reaction 90min, reacts complete, stops stirring, and emits product.The glutinous number of product performance is 61.76ml/g, and color is without yellowing phenomenon.
Embodiment 9
In reactor, add successively deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of DDA/PACM is 1.03/1, wherein deionized water is about 600g, DDA is about 300g, the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 2.5 ‰ of deionized water, DDA and PACM total mass, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of DDA and PACM total mass.After material drops into, open and stir, reactor is warming up to 140 ℃.Maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.275MPa, keeps pressure and temperature 60min.Then regulating pressure is 2.068MPa, and temperature is 220 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 90min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 310 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is 0Mpa that pressure is adjusted to equilibrium pressure, continues reaction 90min, reacts complete, stops stirring, and emits product.The glutinous number of product performance is 47.46ml/g, and color is without yellowing phenomenon.
Embodiment 10
In reactor, add successively deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of DDA/PACM is 1/1.01, wherein deionized water is about 600g, DDA is about 240g, the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 2.5 ‰ of deionized water, DDA and PACM total mass, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of DDA and PACM total mass.After material drops into, open and stir, reactor is warming up to 140 ℃.Maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.275MPa, keeps pressure and temperature 60min.Then regulating pressure is 2.068MPa, and temperature is 220 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 90min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 310 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is 0Mpa that pressure is adjusted to equilibrium pressure, continues reaction 90min, reacts complete, stops stirring, and emits product.The glutinous number of product performance is 72.13ml/g, and color is without yellowing phenomenon.
Embodiment 11
In reactor, add successively deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of DDA/PACM is 1/1.02, wherein deionized water is about 600g, DDA is about 300g, the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 2.5 ‰ of deionized water, DDA and PACM total mass, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of DDA and PACM total mass.After material drops into, open and stir, reactor is warming up to 140 ℃, maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.275MPa, keep pressure and temperature 60min.Then regulating pressure is 2.068MPa, and temperature is 225 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 90min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 310 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is 0Mpa that pressure is adjusted to equilibrium pressure, continues reaction 90min, reacts complete, stops stirring, and emits product.The glutinous number of product performance is 73.99ml/g, and color is without yellowing phenomenon.
Embodiment 12
In reactor, add successively deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of DDA/PACM is 1/1.03, wherein deionized water is about 600g, DDA is about 300g, the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 2.5 ‰ of deionized water, DDA and PACM total mass, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of DDA and PACM total mass.After material drops into, open and stir, reactor is warming up to 140 ℃, maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.275MPa, keep pressure and temperature 60min.Then regulating pressure is 2.068MPa, and temperature is 225 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 90min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 310 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is 0Mpa that pressure is adjusted to equilibrium pressure, continues reaction 90min, reacts complete, stops stirring, and emits product.The glutinous number of product performance is 60.80ml/g, and color is without yellowing phenomenon.
Embodiment 13
In reactor, add successively deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of DDA/PACM is 1/1.02, wherein deionized water is about 600g, DDA is about 300g, the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 2.5 ‰ of deionized water, DDA and PACM total mass, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of DDA and PACM total mass.After material drops into, open and stir, reactor is warming up to 140 ℃, maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.275MPa, keep pressure and temperature 60min.Then regulating pressure is 2.068MPa, 225 ℃ of temperature.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 90min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 250 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is 0Mpa that pressure is adjusted to equilibrium pressure, continues reaction 90min, reacts complete, stops stirring, and emits product.The glutinous number of product performance is 95.11ml/g, and color is without yellowing phenomenon.
Embodiment 14
In reactor, add successively deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of DDA/PACM is 1/1.02, wherein deionized water is about 600g, DDA is about 300g, the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 2.5 ‰ of deionized water, DDA and PACM total mass, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of DDA and PACM total mass.After material drops into, open and stir, reactor is warming up to 140 ℃, maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.275MPa, keep pressure and temperature 60min.Then regulating pressure is 2.068MPa, and temperature is 225 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 90min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 270 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is 0Mpa that pressure is adjusted to equilibrium pressure, continues reaction 90min, reacts complete, stops stirring, and emits product.The glutinous number of product performance is 108.72ml/g, and color is without yellowing phenomenon.
Embodiment 15
In reactor, add successively deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of DDA/PACM is 1/1.02, wherein deionized water is about 600g, DDA is about 300g, the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 2.5 ‰ of deionized water, DDA and PACM total mass, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of DDA and PACM total mass.After material drops into, open and stir, reactor is warming up to 140 ℃, maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.275MPa, keep pressure and temperature 60min.Then regulating pressure is 2.068MPa, and temperature is 225 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 90min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 290 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is 0Mpa that pressure is adjusted to equilibrium pressure, continues reaction 90min, reacts complete, stops stirring, and emits product.The glutinous number of product performance is 105.88ml/g, and color is without yellowing phenomenon.
Embodiment 16
In reactor, add successively deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of DDA/PACM is 1/1.02, wherein deionized water is about 600g, DDA is about 300g, the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 2.5 ‰ of deionized water, DDA and PACM total mass, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of DDA and PACM total mass.After material drops into, open and stir, reactor is warming up to 140 ℃, maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.275MPa, keep pressure and temperature 60min.Then regulating pressure is 2.068MPa, and temperature is 225 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 90min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 270 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is 0Mpa that pressure is adjusted to equilibrium pressure, continues reaction 30min, reacts complete, stops stirring, and emits product.The glutinous number of product performance is 102.25ml/g, and color is without yellowing phenomenon.
Embodiment 17
In reactor, add successively deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of DDA/PACM is 1/1.02, wherein deionized water is about 600g, DDA is about 300g, the anti-trans-isomer content of PACM is 2wt0%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 2.5 ‰ of deionized water, DDA and PACM total mass, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of DDA and PACM total mass.After material drops into, open and stir, reactor is warming up to 140 ℃, maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.275MPa, keep pressure and temperature 60min.Then regulating pressure is 2.068MPa, and temperature is 225 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 90min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 270 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is 0Mpa that pressure is adjusted to equilibrium pressure, continues reaction 60min, reacts complete, stops stirring, and emits product.The glutinous number of product performance is 108.50ml/g, and color is without yellowing phenomenon.
Embodiment 18
In reactor, add successively deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of DDA/PACM is 1/1.02, wherein deionized water is about 600g, DDA is about 300g, the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 2.5 ‰ of deionized water, DDA and PACM total mass, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of DDA and PACM total mass.After material drops into, open and stir, reactor is warming up to 140 ℃, maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.275MPa, keep pressure and temperature 60min.Then regulating pressure is 2.068MPa, and temperature is 225 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 90min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 270 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is 0Mpa that pressure is adjusted to equilibrium pressure, continues reaction 120min, reacts complete, stops stirring, and emits product.The glutinous number of product performance is 105.95ml/g, and color is without yellowing phenomenon.
Embodiment 19
In reactor, add successively deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of DDA/PACM is 1/1.02, wherein deionized water is about 600g, DDA is about 300g, the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 2.5 ‰ of deionized water, DDA and PACM total mass, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of DDA and PACM total mass.After material drops into, open and stir, reactor is warming up to 140 ℃, maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.275MPa, keep pressure and temperature 60min.Then regulating pressure is 2.068MPa, and temperature is 225 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 90min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 270 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is-0.1Mpa that continuation reaction 90min, reacts complete, stops stirring, and emits product that pressure is adjusted to equilibrium pressure.The glutinous number of product performance is 209.02ml/g, and color is without yellowing phenomenon.
Embodiment 20
In reactor, add successively deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of DDA/PACM is 1/1.02, wherein deionized water is about 600g, DDA is about 300g, the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 2.5 ‰ of deionized water, DDA and PACM total mass, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of DDA and PACM total mass.After material drops into, open and stir, reactor is warming up to 140 ℃, maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.275MPa, keep pressure and temperature 60min.Then regulating pressure is 2.068MPa, and temperature is 225 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 90min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 270 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is-0.08Mpa that continuation reaction 90min, reacts complete, stops stirring, and emits product that pressure is adjusted to equilibrium pressure.The glutinous number of product performance is 209.13ml/g, and color is without yellowing phenomenon.
Embodiment 21
In reactor, add successively deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of DDA/PACM is 1/1.02, wherein deionized water is about 600g, DDA is about 300g, the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 2.5 ‰ of deionized water, DDA and PACM total mass, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of DDA and PACM total mass.After material drops into, open and stir, reactor is warming up to 140 ℃, maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.275MPa, keep pressure and temperature 60min.Then regulating pressure is 2.068MPa, and temperature is 225 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 90min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 270 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is-0.02Mpa that continuation reaction 90min, reacts complete, stops stirring, and emits product that pressure is adjusted to equilibrium pressure.The glutinous number of product performance is 145.75ml/g, and color is without yellowing phenomenon.
Embodiment 22
In reactor, add successively deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of DDA/PACM is 1/1.02, wherein deionized water is about 600g, DDA is about 300g, the anti-trans-isomer content of PACM is 35wt%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 2.5 ‰ of deionized water, DDA and PACM total mass, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of DDA and PACM total mass.After material drops into, open and stir, reactor is warming up to 140 ℃, maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.275MPa, keep pressure and temperature 60min.Then regulating pressure is 2.068MPa, and temperature is 225 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 90min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 270 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is-0.08Mpa that continuation reaction 90min, reacts complete, stops stirring, and emits product that pressure is adjusted to equilibrium pressure.The glutinous number of product performance is 213.28ml/g, and color is without yellowing phenomenon.
Embodiment 23
In reactor, add successively deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of DDA/PACM is 1/1.02, wherein deionized water is about 600g, DDA is about 300g, the anti-trans-isomer content of PACM is 40wt%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 2.5 ‰ of deionized water, DDA and PACM total mass, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of DDA and PACM total mass.After material drops into, open and stir, reactor is warming up to 140 ℃, maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.275MPa, keep pressure and temperature 60min.Then regulating pressure is 2.068MPa, and temperature is 225 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 90min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 270 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is-0.08Mpa that continuation reaction 90min, reacts complete, stops stirring, and emits product that pressure is adjusted to equilibrium pressure.The glutinous number of product performance is 188.97ml/g, and color is without yellowing phenomenon.
Embodiment 24
In reactor, add successively deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of DDA/PACM is 1/1.02, wherein deionized water is about 600g, DDA is about 300g, the anti-trans-isomer content of PACM is 50wt%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 2.5 ‰ of deionized water, DDA and PACM total mass, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of DDA and PACM total mass.After material drops into, open and stir, reactor is warming up to 140 ℃, maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.275MPa, keep pressure and temperature 60min.Then regulating pressure is 2.068MPa, and temperature is 225 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 90min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 270 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is-0.08Mpa that continuation reaction 90min, reacts complete, stops stirring, and emits product that pressure is adjusted to equilibrium pressure.The glutinous number of product performance is 227.47ml/g, and color is without yellowing phenomenon.
Embodiment 25
In reactor, add successively deionized water, hexanodioic acid (ADA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of ADA/PACM is 1/1.02, wherein deionized water is about 600g, ADA is about 300g, the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 2.5 ‰ of deionized water, ADA and PACM total mass, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of ADA and PACM total mass.After material adds, open stirring reactor is warming up to 140 ℃.Maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.275MPa, keeps pressure and temperature 60min.Then regulating pressure is 2.068MPa, and temperature is 220 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 90min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 300 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is 0Mpa that pressure is adjusted to equilibrium pressure, continues reaction 10min, stops stirring, and emits product.The glutinous number of product performance is 104.16ml/g, and color is without yellowing phenomenon.
Embodiment 26
In reactor, add successively deionized water, hexanodioic acid (ADA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of ADA/PACM is 1/1.02, wherein deionized water is about 600g, ADA is about 300g, the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 2.5 ‰ of deionized water, ADA and PACM total mass, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of ADA and PACM total mass.After material adds, open stirring reactor is warming up to 140 ℃.Maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.275MPa, keeps pressure and temperature 60min.Then regulating pressure is 2.068MPa, and temperature is 220 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 90min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 300 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is 0Mpa that pressure is adjusted to equilibrium pressure, continues reaction 20min, reacts complete, stops stirring, and emits product.The glutinous number of product performance is 103.50ml/g, and color is without yellowing phenomenon.
Embodiment 27
In reactor, add successively deionized water, hexanodioic acid (ADA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of ADA/PACM is 1/1.02, wherein deionized water is about 600g, ADA is about 300g, the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 2.5 ‰ of deionized water, ADA and PACM total mass, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of ADA and PACM total mass.After material adds, open to stir reactor is warming up to 140 ℃, maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.275MPa, keep pressure and temperature 60min.Then regulating pressure is 2.068MPa, 220 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 90min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 300 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is 0Mpa that pressure is adjusted to equilibrium pressure, continues reaction 40min.React complete, stop stirring, emit product.The glutinous number of product performance is 101.35ml/g, and color is without yellowing phenomenon.
Embodiment 28
In reactor, add successively deionized water, hexanodioic acid (ADA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of ADA/PACM is 1/1.02, wherein deionized water is about 600g, ADA is about 300g, the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 2.5 ‰ of deionized water, ADA and PACM total mass, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of ADA and PACM total mass.After material adds, open to stir reactor is warming up to 140 ℃, maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.275MPa, keep pressure and temperature 60min.Then regulating pressure is 2.068MPa, and temperature is 220 ℃.Keep in 60min, it being adjusted to normal pressure gradually again after pressure 90min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 300 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is-0.1Mpa that termination reaction after continuation reaction 10min, stops stirring, and emits product that pressure is adjusted to equilibrium pressure.The glutinous number of product performance is 93.94ml/g, and color is without yellowing phenomenon.
Embodiment 29
In reactor, add successively deionized water, hexanodioic acid (ADA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of ADA/PACM is 1/1.02, wherein deionized water is about 600g, ADA is about 300g, the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 2.5 ‰ of deionized water, ADA and PACM total mass, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of ADA and PACM total mass.After material adds, open to stir reactor is warming up to 140 ℃, maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.275MPa, keep pressure and temperature 60min.Then regulating pressure is 2.068MPa, 220 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 90min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 300 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is-0.08Mpa that termination reaction after continuation reaction 10min, stops stirring, and emits product that pressure is adjusted to equilibrium pressure.The glutinous number of product performance is 98.83ml/g, and color is without yellowing phenomenon.
Embodiment 30
In reactor, add successively deionized water, hexanodioic acid (ADA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of ADA/PACM is 1/1.02, wherein deionized water is about 600g, ADA is about 300g, the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 2.5 ‰ of deionized water, ADA and PACM total mass, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of ADA and PACM total mass.After material adds, open to stir reactor is warming up to 140 ℃, maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.275MPa, keep pressure and temperature 60min.Then regulating pressure is 2.068MPa, 220 ℃ of temperature.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 90min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 300 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is-0.04Mpa that termination reaction after continuation reaction 10min, stops stirring, and emits product that pressure is adjusted to equilibrium pressure.The glutinous number of product performance is 86.47ml/g, and color is without yellowing phenomenon.
Embodiment 31
In reactor, add successively deionized water, hexanodioic acid (ADA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of ADA/PACM is 1/1.02, wherein deionized water is about 600g, ADA is about 360g, the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 2.5 ‰ of deionized water, ADA and PACM total mass, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of ADA and PACM total mass.After material adds, open to stir reactor is warming up to 140 ℃, maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.275MPa, keep pressure and temperature 60min.Then regulating pressure is 2.068MPa, and temperature is 220 ℃.Keep in 60min, it being adjusted to normal pressure gradually again after pressure 90min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 290 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is 0Mpa that pressure is adjusted to equilibrium pressure, and termination reaction after continuation reaction 10min, stops stirring, and emits product.The glutinous number of product performance is 51.17ml/g, and color is without yellowing phenomenon.
Embodiment 32
In reactor, add successively deionized water, hexanodioic acid (ADA) and PACM, catalyzer and oxidation inhibitor, the mol ratio of ADA/PACM is 1/1.02, wherein deionized water is about 600g, ADA is about 300g, the anti-trans-isomer content of PACM is 20wt%, and oxidation inhibitor used is that chinox1098 and chinox1589 are composite, and its consumption is respectively 2.5 ‰ of deionized water, ADA and PACM total mass, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of ADA and PACM total mass.After material adds, open to stir reactor is warming up to 140 ℃, maintain the temperature at 140 ℃, and the control pressure of suitably exitting is 0.275MPa, keep pressure and temperature 60min.Then regulating pressure is 2.068MPa, and temperature is 220 ℃.Keep in 60min, it being depressurized to normal pressure gradually again after pressure 90min, persistently overheating in pressurize and step-down process, when completing, step-down finally rises to 260 ℃ of equilibrium temperatures.Keep equilibrium temperature, it is 0Mpa that pressure is adjusted to equilibrium pressure, and termination reaction after continuation reaction 10min, stops stirring, and emits product.The glutinous number of product performance is 214.98ml/g, and color is without yellowing phenomenon.
The product that above embodiment is obtained has carried out respectively the sign of light transmission rate and solvent resistance under limiting viscosity number, second-order transition temperature, tensile strength, tensile modulus, shock strength and 550nm condition, result is as table one, table two, to its correlated performance is described.
Limiting viscosity number adopts Ubbelohde viscometer to measure, and solvent for use is that phenol and formic acid mixed solvent mass ratio are 1:1, and probe temperature is 30 ℃.
Adopt PE DSC7 differential scanning calorimeter to measure second-order transition temperature.With pure indium (In) and pure zinc (Zn), demarcate, at N
2the lower operation of atmosphere protection.Get the crucible supporting with DSC7 differential scanning calorimeter, take polymkeric substance 8mg left and right and put into the sample preparation of aluminum crucible.Temperature program(me) is: 1. heats up, and 30.00 ℃～300.00 ℃, 50.00 ℃/min; 2. at 300.00 ℃, keep 5.0min; 3. cooling, 300.00 ℃～30.00 ℃, 10.00 ℃/min; 4. at 30.00 ℃, keep 5.0min; 5. heat up, 30.00 ℃～300.00 ℃, 10.00 ℃/min.
Tensile property test adopts universal testing machine Zwick/Roell-Z020, and test rate is 50mm/min, and probe temperature is normal temperature, preloads 1N.Batten preparation method: adopting model is miniature high performance composite formation system and the Tensile bar ISO527-2-5A drawing die (L75mm of HAAKEMiniJet II, W12.5mm, H2mm) prepare batten, injection temperature is 230～290 ℃, die temperature is 50～80 ℃, dwell pressure is 1150bar, and the dwell time is 15s.
Socle girder notch shock (shock strength) test adopts CE Λ ST pendulum percussion instrument, and impact energy is 1J, and probe temperature is normal temperature.Batten preparation method: adopting model is miniature high performance composite formation system and the Charpy Test bar ISO180/179 Impact Test mould (L80mm of HAAKE MiniJet II, W10mm, H4mm) prepare batten, injection temperature is 230～290 ℃, die temperature is 50～80 ℃, dwell pressure is 1150bar, and the dwell time is 15s.
With UV-VIS spectrophotometer (Varian Cary-100), in the interscan of 300～900nm scope, measure the light transmission rate of polymkeric substance.Sample preparation methods: it is 5%～8% formic acid solution that nylon product is mixed with to mass concentration, filters and pours glass mold into after fully dissolving, and is then placed under 70 ℃ of conditions of vacuum drying oven and dries.
Table one NylonPACMn correlated performance
By the contrast of comparative example 1-4 and embodiments of the invention, can find out, adopt salify condensation methods or do not use aspect the over-all propertieies such as transparent index, limiting viscosity number and mechanical property of oxidation inhibitor or starting time and the equilibrium temperature nylon product that not prepared by the technique in invention scope to be obviously worse than the present invention.
Table two PACM nylon solvent resistance test
++: surface is not any change, insoluble
+: swelling, feel like jelly
-: surface blur, slightly soluble
--: dissolve completely
By solvent resistance test, can find out, adopt nylon prepared by method of the present invention to be substantially insoluble to conventional organic solvent.
Claims (7)
1. a preparation method for nylon, is characterized in that: described method comprises following process:
1) in reactor, add the material that comprises deionized water, di-carboxylic acid, diamine, oxidation inhibitor and catalyzer, start to stir, be warming up to 100～150 ℃, be preferably 135～145 ℃; Maintain the temperature at 100～150 ℃, be preferably 135～145 ℃; By venting, maintaining pressure is 0.206～0.275MPa, is preferably 0.270～0.275MPa; Continue 30～90min, be preferably 50～60min;
2) pressure is adjusted to 1.723～2.413MPa, be preferably 2.000～2.100MPa, temperature is adjusted to 200～240 ℃, be preferably 220～225 ℃, keep pressure 30～120min, be preferably 80～90min step-down gradually afterwards, and persistently overheating in pressurize and step-down process, in 60min, be depressurized to normal pressure, and when step-down completes, rise to 250～310 ℃ of equilibrium temperatures, be preferably 265～275 ℃;
3) keep equilibrium temperature, be adjusted to equilibrium pressure-0.1MPa～0MPa, be preferably after-0.1～-0.08MPa, under the condition that keeps equilibrium temperature and equilibrium pressure, continue to keep 10～120min, be preferably 40～60min, obtain product.
2. the method for claim 1, is characterized in that, described diamine is 4,4 '-diamino-dicyclohexyl methane
described di-carboxylic acid is
in a kind of, wherein, n is 4～10, preferably di-carboxylic acid is hexanodioic acid or dodecanedioic acid.
3. the method for claim 1, it is characterized in that, the mol ratio of the di-carboxylic acid described in step 1) and diamine is 1.03:1～1:1.03, preferably 1:1～1:1.02, the account for massfraction of ionized water of di-carboxylic acid consumption is 40%～60%, preferably 45%～50%.
4. the method for claim 1, it is characterized in that, described catalyzer is the one or two or more in phosphoric acid salt, hypophosphite and hypophosphite, preferably phosphoric acid an alkali metal salt, one or two or more in Hypophosporous Acid, 50 an alkali metal salt and ortho phosphorous acid an alkali metal salt, more preferably the one or two or more in sodium phosphate, sodium hypophosphite and inferior sodium phosphate, the consumption of catalyzer is 0.5 ‰～1.5 ‰ of di-carboxylic acid and diamine total mass, is preferably 0.6 ‰～0.8 ‰.
5. according to the method described in any one in claim 2-4, it is characterized in that, with 4, the total restatement of 4 '-diamino-dicyclohexyl methane, 4, the anti-trans isomer content of 4 '-diamino-dicyclohexyl methane between 20wt%～50wt%, preferred 40wt%～48wt%.
6. method according to claim 1, is characterized in that, the consumption of oxidation inhibitor is 0.5 ‰～8 ‰ of deionized water, di-carboxylic acid and diamine total mass, preferably 4 ‰～5 ‰.
7. according to the method described in claim 1 or 6, it is characterized in that, described oxidation inhibitor is the one or two or more in chinox1098, chinox1589, H818D, chinox1325 and chinox1590, preferably chinox1098 or chinox1589.
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| CN102459414A (en) * | 2009-06-19 | 2012-05-16 | 巴斯夫欧洲公司 | Copolyamides |
| CN102757556A (en) * | 2011-04-27 | 2012-10-31 | 合肥杰事杰新材料股份有限公司 | Nanodiamond powder-filled nylon composite material and preparation method thereof |
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| US5360891A (en) * | 1993-04-03 | 1994-11-01 | Huels Aktiengesellschaft | Colorless and transparent, amorphously processable polyamide molding composition having good resistance to stress cracking and good impact strength |
| CN1696177A (en) * | 2004-05-14 | 2005-11-16 | 阿克马公司 | Transparent amorphous polyamides based on diamines and on tetradecanedioic acid |
| CN102459414A (en) * | 2009-06-19 | 2012-05-16 | 巴斯夫欧洲公司 | Copolyamides |
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