CN103665375B - A kind of preparation method of nylon - Google Patents
A kind of preparation method of nylon Download PDFInfo
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- CN103665375B CN103665375B CN201310633632.7A CN201310633632A CN103665375B CN 103665375 B CN103665375 B CN 103665375B CN 201310633632 A CN201310633632 A CN 201310633632A CN 103665375 B CN103665375 B CN 103665375B
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Abstract
The invention discloses a kind of preparation method of nylon, the raw material that the method adopts is di-carboxylic acid and 4,4 '-diamino-dicyclohexyl methane, directly carries out melt polycondensation reaction by the temperature set, pressure change program, obtain water white transparency, the nylon product of excellent in mechanical performance.
Description
Technical field
The present invention relates generally to a kind of preparation method of high transparent nylon, is a kind of preparation method being synthesized a kind of high transparent nylon by 4,4 '-diamino-dicyclohexyl methane and di-carboxylic acid polycondensation specifically, 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 a kind of novel nylon material prepared by 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, the machinery of chemical resistant properties and equilibrium and thermal characteristics and easily machine-shaping, therefore has application widely in fields such as automotive industry, mechanical industry, athletic sports appliances.US Patent No. 3502624 and the synthesis of US3869400 to similar structures nylon are described, and its building-up process is divided into two steps: first salify, then polycondensation.Salification process needs continuous regulator solution pH, adds various additive, impels nylon salt to separate out etc. by heating and cooling, this just increases the input of equipment, improve operation easier, not only energy consumption is high, and the use of a large amount of solvent also result in pollution to environment.Same nylon synthesis also has description in US Patent No. 3661982 with US4213884, although improve to some extent to salification process, the problems referred to above still do not overcome.
Summary of the invention
The object of this invention is to provide a kind of preparation method of nylon, the method that have employed a step melt phase polycondensation eliminates salify operation, not only reduces cost of investment and has stopped the use pollution on the environment of organic solvent in salification process.As long as keep the temperature, pressure condition required for reaction in technology controlling and process, simple, and adding of suitable oxidation inhibitor also serves positive promoter action to the appearance investigation of product, the nylon product obtained by this preparation method has high transparent, erosion-resisting characteristics is strong, and chemical resistance is excellent.
In order to achieve the above object, the present invention adopts following technical scheme:
A preparation method for nylon, obtained by diamine and di-carboxylic acid polycondensation, concrete preparation process is as follows:
1) add the material comprising deionized water, di-carboxylic acid, diamine, oxidation inhibitor and catalyzer in the reactor, start to stir, be warming up to 100 ~ 150 DEG C, be preferably 135 ~ 145 DEG C; Maintain the temperature at 100 ~ 150 DEG C, be preferably 135 ~ 145 DEG C; Maintaining pressure by venting 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 DEG C, be preferably 220 ~ 225 DEG C, keep pressure 30 ~ 120min, step-down gradually after being preferably 80 ~ 90min, and it is persistently overheating in pressurize and pressure reduction, in 60min, be depressurized to normal pressure, and while step-down completes, rise to equilibrium temperature 250 ~ 310 DEG C, be preferably 265 ~ 275 DEG C;
3) keep equilibrium temperature, be adjusted to equilibrium pressure-0.1MPa ~ 0MPa, after being preferably-0.1 ~-0.08MPa, under the condition keeping equilibrium temperature and equilibrium pressure, continue maintenance 10 ~ 120min(and 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 the total restatement of 4,4 '-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 the transparency improving final nylon product.
In method of the present invention, described di-carboxylic acid is
in one, wherein, n is 4 ~ 10, and preferred 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, between preferred 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, preferred 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 selected can effectively stop nylon product etiolation, also can be used for regulating nylon molecular weight, and the oxidation inhibitor in preferable range can produce 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 has and strictly controls proportioning, could promote effective growth of molecular weight and then obtain high molecular weight products, form the equimolar ratio that salt operation just effectively can ensure functional group.But salify operation often needs more equipment investment, increase a lot of energy consumption, and need adopt organic solvent for the raw material salify of indissoluble in aqueous phase, this not only increases cost (such as solvent recovery process) further, also likely causes the pollution to environment.And monomer required in the NylonPACMn mentioned in this patent, solvability extreme difference in water, so the salification process that patent US3502624 and US3869400 adopts then employs organic solvent, this can increase investment with regard to inevasible, increasing energy consumption, affects environment and even reduces security in operating process.The present invention then adopts the method for a step direct melt polycondensation, without the need to extra salify operation, whole process need not be with an organic solvent, but adopt water cheap and easy to get as reaction medium, (molecular weight of product is embodied 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), what also show in the over-all propertieies such as the transparency and mechanical property is very excellent.Adopt and not only greatly reduce equipment investment and energy consumption in this way, and do not pollute environment, the operation workshop sections such as pH regulation and control when more decreasing salify, concentrated, crystallization, make whole production process become simply, are easy to control.By controlling the initial ratio of raw material, temperature, pressure and reaction times being optimized, the product of excellent performance can be obtained.
And in this patent, contriver overcomes existing prejudice and is balanced the time by experimental verification repeatedly and equilibrium temperature is larger for the performance impact of product itself, it is not numerous teaching material (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 increase along with the growth of starting time always, the present invention is by controlling starting time in 10 ~ 120min, preferably in 40 ~ 60min, the product of high limiting viscosity number can be obtained, stick several not high when starting time is less than 10min product performance, 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 DEG C of scopes is excellent, and synthesis failure or impaired performance after going beyond the scope, can be caused.This is because polycondensation is thermopositive reaction, be conducive to the carrying out of its reversed reaction i.e. molecular degradation reaction under the high temperature conditions, therefore higher, the overlong time of temperature will cause molecular degradation, reduces molecular weight, thus has influence on product performance.The nylon product adopting the processing condition optimized in this patent to obtain 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 DEG C, preferably 120 ~ 150 DEG C, erosion-resisting characteristics is strong, and shock strength can reach 6 ~ 16KJ/m
2, preferably 9 ~ 16KJ/m
2, chemical resistance is excellent, 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 Wanhua Chemical Group Co., Ltd., and DDA and ADA buys from the resistance to Jilin Chemical of peace, and oxidation inhibitor is provided by Taiwan Double Bond Chemical Ind.,Co.,Ltd..
In an embodiment, we change di-carboxylic acid, diamine proportioning successively, the interpolation kind of oxidation inhibitor and consumption, 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 the performance variation list that causes will be changed with this in table one, two.Its thermal characteristics of product of being synthesized in the process condition range that this patent provides as seen by table, mechanical property and optical property can have gratifying embodiment.
Comparative example 1
By PACM, DDA with methyl alcohol respectively according to mass ratio PACM: the ratio of methyl alcohol=1:2, DDA: methyl alcohol=1:8 mutually mixes under room temperature, normal pressure, be mixed with PACM methanol solution and DDA methanol solution, wherein PACM consumption is 300g, PACM and DDA mol ratio is 1:1.Under agitation two kinds of solution are mixed mutually, have crystal in mixing process and separate out, after mixing, filter suspension liquid, obtain NylonPACM12 salt, for subsequent use after drying.Get NylonPACM12 salt in glass flask, pour nitrogen excluding air, finally sealed is warming up to 250 DEG C gradually, keeps 2h, washes away generation moisture afterwards, be warming up to 300 degrees Celsius after sealing with nitrogen, keeps 1h, obtains product.Product colour yellowing, obtaining limiting viscosity number through test is 30.31ml/g.
Comparative example 2
Add deionized water, dodecanedioic acid (DDA) and PACM, catalyzer in the reactor successively, 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 and stir, reactor is warming up to 140 DEG C, maintains the temperature at 140 DEG C, and control pressure is 0.275MPa, keep pressure and temperature 60min.Then regulate that pressure is 2.068MPa, temperature is 220 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 90min, persistently overheating in pressurize and pressure reduction, rise to equilibrium temperature 310 DEG C while step-down completes.Keep equilibrium temperature, pressure is adjusted to equilibrium pressure 0Mpa, continue reaction 90min, react complete, stop stirring, release product.Product colour yellowing, limiting viscosity number is 31.66ml/g(phenol and formic acid mixed solvent, volume ratio 1:1,30 DEG C).
Comparative example 3
Add deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, DDA and PACM total mass 2.5 ‰, 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 DEG C, maintains the temperature at 140 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 60min.Then regulate pressure to be 2.068MPa, temperature is 225 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 90min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 320 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is 0Mpa, continues reaction 60min, reacts complete, stops stirring, releases product.The glutinous number of product performance is 28.95ml/g, and color is without yellowing phenomenon.
Comparative example 4
Add deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, DDA and PACM total mass 2.5 ‰, 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 DEG C, maintains the temperature at 140 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 60min.Then regulate pressure to be 2.068MPa, temperature is 225 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 90min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 300 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is 0Mpa, continues reaction 200min, reacts complete, stops stirring, releases product.The glutinous number of product performance is 25.14ml/g, and color is without yellowing phenomenon.
Embodiment 1
Add deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, DDA and PACM total mass 2.5 ‰, 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 DEG C.Maintain the temperature at 100 DEG C, and suitably venting control pressure is 0.206MPa, keeps pressure and temperature 30min.Then regulate that pressure is 1.723MPa, temperature is 200 DEG C.It is depressurized to normal pressure gradually after being about 90min by maintenance pressure again in 60min, persistently overheating in pressurize and pressure reduction, completes finally rising to equilibrium temperature 310 DEG C in step-down simultaneously.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is 0Mpa, continues reaction 90min, reacts complete, stops stirring, releases 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
Add deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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, its consumption be deionized water, DDA and PACM total mass 0.5 ‰, 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 DEG C.Maintain the temperature at 150 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 90min.Then regulate that pressure is 2.413MPa, temperature is 240 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 120min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 310 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is 0Mpa, continues reaction 90min, reacts complete, stops stirring, releases product.The glutinous number of product performance is 11.58ml/g, and color is without yellowing phenomenon.
Embodiment 3
Add deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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, its consumption be deionized water, DDA and PACM total mass 0.5 ‰, 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 DEG C.Maintain the temperature at 150 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 90min.Then regulate that pressure is 2.413MPa, temperature is 240 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 120min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 310 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is 0Mpa, continues reaction 90min, reacts complete, stops stirring, releases product.The glutinous number of product performance is 40.20ml/g, and color is without yellowing phenomenon.
Embodiment 4
Add deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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, its consumption be deionized water, DDA and PACM total mass 0.5 ‰, 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 DEG C.Maintain the temperature at 150 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 90min.Then regulate that pressure is 2.413MPa, temperature is 240 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 120min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 310 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is 0Mpa, continues reaction 90min, reacts complete, stops stirring, releases product.The glutinous number of product performance is 45.10ml/g, and color is without yellowing phenomenon.
Embodiment 5
Add deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, DDA and PACM total mass 3 ‰, 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 DEG C.Maintain the temperature at 140 DEG C, and suitably venting control pressure is 0.241MPa, keeps pressure and temperature 60min.Then regulate that pressure is 2.068MPa, temperature is 220 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 120min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 310 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is 0Mpa, continues reaction 90min, reacts complete, stops stirring, releases product.The glutinous number of product performance is 50.41ml/g, and color is without yellowing phenomenon.
Embodiment 6
Add deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, DDA and PACM total mass 3 ‰, 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 DEG C.Maintain the temperature at 140 DEG C, and suitably venting control pressure is 0.241MPa, keeps pressure and temperature 60min.Then regulate pressure to be 2.068MPa, temperature is 220 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 120min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 310 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is 0Mpa, continues reaction 90min, reacts complete, stops stirring, releases product.The glutinous number of product performance is 65.30ml/g, and color is without yellowing phenomenon.
Embodiment 7
Add deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, DDA and PACM total mass 4 ‰.After material drops into, open and stir, reactor is warming up to 150 DEG C.Maintain the temperature at 150 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 90min.Then regulate pressure to be 2.068MPa, temperature is 220 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 120min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 310 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is 0Mpa, continues reaction 90min, reacts complete, stops stirring, releases product.The glutinous number of product performance is 56.60ml/g, and color is without yellowing phenomenon.
Embodiment 8
Add deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, DDA and PACM total mass 2.5 ‰, 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 DEG C.Maintain the temperature at 140 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 60min.Then regulate pressure to be 2.068MPa, temperature is 220 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 90min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 310 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is 0Mpa, continues reaction 90min, reacts complete, stops stirring, releases product.The glutinous number of product performance is 61.76ml/g, and color is without yellowing phenomenon.
Embodiment 9
Add deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, DDA and PACM total mass 2.5 ‰, 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 DEG C.Maintain the temperature at 140 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 60min.Then regulate pressure to be 2.068MPa, temperature is 220 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 90min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 310 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is 0Mpa, continues reaction 90min, reacts complete, stops stirring, releases product.The glutinous number of product performance is 47.46ml/g, and color is without yellowing phenomenon.
Embodiment 10
Add deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, DDA and PACM total mass 2.5 ‰, 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 DEG C.Maintain the temperature at 140 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 60min.Then regulate pressure to be 2.068MPa, temperature is 220 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 90min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 310 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is 0Mpa, continues reaction 90min, reacts complete, stops stirring, releases product.The glutinous number of product performance is 72.13ml/g, and color is without yellowing phenomenon.
Embodiment 11
Add deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, DDA and PACM total mass 2.5 ‰, 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 DEG C, maintains the temperature at 140 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 60min.Then regulate pressure to be 2.068MPa, temperature is 225 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 90min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 310 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is 0Mpa, continues reaction 90min, reacts complete, stops stirring, releases product.The glutinous number of product performance is 73.99ml/g, and color is without yellowing phenomenon.
Embodiment 12
Add deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, DDA and PACM total mass 2.5 ‰, 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 DEG C, maintains the temperature at 140 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 60min.Then regulate pressure to be 2.068MPa, temperature is 225 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 90min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 310 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is 0Mpa, continues reaction 90min, reacts complete, stops stirring, releases product.The glutinous number of product performance is 60.80ml/g, and color is without yellowing phenomenon.
Embodiment 13
Add deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, DDA and PACM total mass 2.5 ‰, 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 DEG C, maintains the temperature at 140 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 60min.Then pressure is regulated to be 2.068MPa, temperature 225 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 90min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 250 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is 0Mpa, continues reaction 90min, reacts complete, stops stirring, releases product.The glutinous number of product performance is 95.11ml/g, and color is without yellowing phenomenon.
Embodiment 14
Add deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, DDA and PACM total mass 2.5 ‰, 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 DEG C, maintains the temperature at 140 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 60min.Then regulate pressure to be 2.068MPa, temperature is 225 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 90min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 270 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is 0Mpa, continues reaction 90min, reacts complete, stops stirring, releases product.The glutinous number of product performance is 108.72ml/g, and color is without yellowing phenomenon.
Embodiment 15
Add deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, DDA and PACM total mass 2.5 ‰, 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 DEG C, maintains the temperature at 140 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 60min.Then regulate pressure to be 2.068MPa, temperature is 225 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 90min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 290 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is 0Mpa, continues reaction 90min, reacts complete, stops stirring, releases product.The glutinous number of product performance is 105.88ml/g, and color is without yellowing phenomenon.
Embodiment 16
Add deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, DDA and PACM total mass 2.5 ‰, 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 DEG C, maintains the temperature at 140 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 60min.Then regulate pressure to be 2.068MPa, temperature is 225 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 90min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 270 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is 0Mpa, continues reaction 30min, reacts complete, stops stirring, releases product.The glutinous number of product performance is 102.25ml/g, and color is without yellowing phenomenon.
Embodiment 17
Add deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, DDA and PACM total mass 2.5 ‰, 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 DEG C, maintains the temperature at 140 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 60min.Then regulate pressure to be 2.068MPa, temperature is 225 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 90min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 270 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is 0Mpa, continues reaction 60min, reacts complete, stops stirring, releases product.The glutinous number of product performance is 108.50ml/g, and color is without yellowing phenomenon.
Embodiment 18
Add deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, DDA and PACM total mass 2.5 ‰, 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 DEG C, maintains the temperature at 140 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 60min.Then regulate pressure to be 2.068MPa, temperature is 225 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 90min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 270 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is 0Mpa, continues reaction 120min, reacts complete, stops stirring, releases product.The glutinous number of product performance is 105.95ml/g, and color is without yellowing phenomenon.
Embodiment 19
Add deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, DDA and PACM total mass 2.5 ‰, 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 DEG C, maintains the temperature at 140 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 60min.Then regulate pressure to be 2.068MPa, temperature is 225 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 90min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 270 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is-0.1Mpa, continues reaction 90min, reacts complete, stops stirring, releases product.The glutinous number of product performance is 209.02ml/g, and color is without yellowing phenomenon.
Embodiment 20
Add deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, DDA and PACM total mass 2.5 ‰, 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 DEG C, maintains the temperature at 140 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 60min.Then regulate pressure to be 2.068MPa, temperature is 225 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 90min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 270 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is-0.08Mpa, continues reaction 90min, reacts complete, stops stirring, releases product.The glutinous number of product performance is 209.13ml/g, and color is without yellowing phenomenon.
Embodiment 21
Add deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, DDA and PACM total mass 2.5 ‰, 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 DEG C, maintains the temperature at 140 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 60min.Then regulate pressure to be 2.068MPa, temperature is 225 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 90min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 270 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is-0.02Mpa, continues reaction 90min, reacts complete, stops stirring, releases product.The glutinous number of product performance is 145.75ml/g, and color is without yellowing phenomenon.
Embodiment 22
Add deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, DDA and PACM total mass 2.5 ‰, 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 DEG C, maintains the temperature at 140 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 60min.Then regulate pressure to be 2.068MPa, temperature is 225 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 90min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 270 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is-0.08Mpa, continues reaction 90min, reacts complete, stops stirring, releases product.The glutinous number of product performance is 213.28ml/g, and color is without yellowing phenomenon.
Embodiment 23
Add deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, DDA and PACM total mass 2.5 ‰, 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 DEG C, maintains the temperature at 140 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 60min.Then regulate pressure to be 2.068MPa, temperature is 225 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 90min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 270 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is-0.08Mpa, continues reaction 90min, reacts complete, stops stirring, releases product.The glutinous number of product performance is 188.97ml/g, and color is without yellowing phenomenon.
Embodiment 24
Add deionized water, dodecanedioic acid (DDA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, DDA and PACM total mass 2.5 ‰, 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 DEG C, maintains the temperature at 140 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 60min.Then regulate pressure to be 2.068MPa, temperature is 225 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 90min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 270 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is-0.08Mpa, continues reaction 90min, reacts complete, stops stirring, releases product.The glutinous number of product performance is 227.47ml/g, and color is without yellowing phenomenon.
Embodiment 25
Add deionized water, hexanodioic acid (ADA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, ADA and PACM total mass 2.5 ‰, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of ADA and PACM total mass.After material adds, open stirring and reactor is warming up to 140 DEG C.Maintain the temperature at 140 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 60min.Then regulate pressure to be 2.068MPa, temperature is 220 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 90min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 300 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is 0Mpa, continues reaction 10min, stops stirring, releases product.The glutinous number of product performance is 104.16ml/g, and color is without yellowing phenomenon.
Embodiment 26
Add deionized water, hexanodioic acid (ADA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, ADA and PACM total mass 2.5 ‰, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of ADA and PACM total mass.After material adds, open stirring and reactor is warming up to 140 DEG C.Maintain the temperature at 140 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 60min.Then regulate pressure to be 2.068MPa, temperature is 220 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 90min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 300 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is 0Mpa, continues reaction 20min, reacts complete, stops stirring, releases product.The glutinous number of product performance is 103.50ml/g, and color is without yellowing phenomenon.
Embodiment 27
Add deionized water, hexanodioic acid (ADA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, ADA and PACM total mass 2.5 ‰, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of ADA and PACM total mass.After material adds, open stirring and reactor is warming up to 140 DEG C, maintain the temperature at 140 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 60min.Then pressure is regulated to be 2.068MPa, 220 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 90min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 300 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is 0Mpa, continues reaction 40min.React complete, stop stirring, release product.The glutinous number of product performance is 101.35ml/g, and color is without yellowing phenomenon.
Embodiment 28
Add deionized water, hexanodioic acid (ADA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, ADA and PACM total mass 2.5 ‰, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of ADA and PACM total mass.Open to stir after material adds and reactor is warming up to 140 DEG C, maintain the temperature at 140 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 60min.Then regulate pressure to be 2.068MPa, temperature is 220 DEG C.In 60min, it is adjusted to normal pressure gradually again after keeping pressure 90min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 300 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is-0.1Mpa, and termination reaction after continuation reaction 10min, stops stirring, release product.The glutinous number of product performance is 93.94ml/g, and color is without yellowing phenomenon.
Embodiment 29
Add deionized water, hexanodioic acid (ADA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, ADA and PACM total mass 2.5 ‰, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of ADA and PACM total mass.Open to stir after material adds and reactor is warming up to 140 DEG C, maintain the temperature at 140 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 60min.Then pressure is regulated to be 2.068MPa, 220 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 90min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 300 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is-0.08Mpa, and termination reaction after continuation reaction 10min, stops stirring, release product.The glutinous number of product performance is 98.83ml/g, and color is without yellowing phenomenon.
Embodiment 30
Add deionized water, hexanodioic acid (ADA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, ADA and PACM total mass 2.5 ‰, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of ADA and PACM total mass.After material adds, open stirring and reactor is warming up to 140 DEG C, maintain the temperature at 140 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 60min.Then pressure is regulated to be 2.068MPa, temperature 220 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 90min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 300 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is-0.04Mpa, and termination reaction after continuation reaction 10min, stops stirring, release product.The glutinous number of product performance is 86.47ml/g, and color is without yellowing phenomenon.
Embodiment 31
Add deionized water, hexanodioic acid (ADA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, ADA and PACM total mass 2.5 ‰, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of ADA and PACM total mass.After material adds, open stirring and reactor is warming up to 140 DEG C, maintain the temperature at 140 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 60min.Then regulate pressure to be 2.068MPa, temperature is 220 DEG C.In 60min, it is adjusted to normal pressure gradually again after keeping pressure 90min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 290 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is 0Mpa, and termination reaction after continuation reaction 10min, stops stirring, release product.The glutinous number of product performance is 51.17ml/g, and color is without yellowing phenomenon.
Embodiment 32
Add deionized water, hexanodioic acid (ADA) and PACM, catalyzer and oxidation inhibitor in the reactor successively, 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 is composite, its consumption be respectively deionized water, ADA and PACM total mass 2.5 ‰, catalyzer is inferior sodium phosphate, and consumption is 1 ‰ of ADA and PACM total mass.Open to stir after material adds and reactor is warming up to 140 DEG C, maintain the temperature at 140 DEG C, and suitably venting control pressure is 0.275MPa, keeps pressure and temperature 60min.Then regulate pressure to be 2.068MPa, temperature is 220 DEG C.In 60min, it is depressurized to normal pressure gradually again after keeping pressure 90min, persistently overheating in pressurize and pressure reduction, while step-down completes, finally rise to equilibrium temperature 260 DEG C.Keep equilibrium temperature, pressure being adjusted to equilibrium pressure is 0Mpa, and termination reaction after continuation reaction 10min, stops stirring, release product.The glutinous number of product performance is 214.98ml/g, and color is without yellowing phenomenon.
The product obtained above embodiment has carried out 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 respectively, result as table one, table two, to being described its correlated performance.
Limiting viscosity number adopts Ubbelohde viscometer to measure, and solvent for use is phenol and formic acid mixed solvent mass ratio is 1:1, and probe temperature is 30 DEG C.
PEDSC7 differential scanning calorimeter is adopted to measure second-order transition temperature.Demarcate, at N with pure indium (In) and pure zinc (Zn)
2the lower operation of atmosphere protection.Get the crucible supporting with DSC7 differential scanning calorimeter, take polymkeric substance about 8mg and put into aluminum cup sample preparation.Temperature program(me) is: 1. heat up, 30.00 DEG C ~ 300.00 DEG C, 50.00 DEG C/min; 2. keep 5.0min at 300.00 DEG C; 3. cool, 300.00 DEG C ~ 30.00 DEG C, 10.00 DEG C/min; 4. keep 5.0min at 30.00 DEG C; 5. heat up, 30.00 DEG C ~ 300.00 DEG C, 10.00 DEG C/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: employing model is miniature high performance composite formation system and the TensilebarISO527-2-5A drawing die (L75mm of HAAKEMiniJetII, W12.5mm, H2mm) batten is prepared, injection temperature is 230 ~ 290 DEG C, die temperature is 50 ~ 80 DEG C, dwell pressure is 1150bar, and the dwell time is 15s.
Izod notched impact (shock strength) test adopts CE Λ ST pendulum percussion instrument, and impact energy is 1J, and probe temperature is normal temperature.Batten preparation method: employing model is miniature high performance composite formation system and the CharpyTestbarISO180/179 Impact Test mould (L80mm of HAAKEMiniJetII, W10mm, H4mm) batten is prepared, injection temperature is 230 ~ 290 DEG C, die temperature is 50 ~ 80 DEG C, dwell pressure is 1150bar, and the dwell time is 15s.
Measure the light transmission rate of polymkeric substance in the interscan of 300 ~ 900nm scope with UV-VIS spectrophotometer (VarianCary-100).Sample preparation methods: nylon product is mixed with the formic acid solution that mass concentration is 5% ~ 8%, filters after fully dissolving and pours glass mold into, dry under being then placed in vacuum drying oven 70 DEG C of conditions.
Table one NylonPACMn correlated performance
Contrast can find out by comparative example 1-4 and embodiments of the invention, adopt in the over-all propertieies such as the transparent index of salify condensation methods or the nylon product that do not use oxidation inhibitor or starting time and the equilibrium temperature technique not in invention scope to prepare, limiting viscosity number and mechanical property and 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
Can be found out by solvent resistance test, the nylon adopting method of the present invention to prepare is insoluble to conventional organic solvent substantially.
Claims (15)
1. a preparation method for nylon, is characterized in that: described method comprises following process:
1) add the material comprising deionized water, di-carboxylic acid, diamine, oxidation inhibitor and catalyzer in the reactor, start to stir, be warming up to 100 ~ 150 DEG C; Maintain the temperature at 100 ~ 150 DEG C; Maintaining pressure by venting is 0.206 ~ 0.275MPa; Continue 30 ~ 90min;
2) pressure is adjusted to 1.723 ~ 2.413MPa, temperature is adjusted to 200 ~ 240 DEG C, step-down gradually after keeping pressure 30 ~ 120min, and persistently overheating in pressurize and pressure reduction, in 60min, be depressurized to normal pressure, and while step-down completes, rise to equilibrium temperature 250 ~ 310 DEG C;
3) keep equilibrium temperature, after being adjusted to equilibrium pressure-0.1MPa ~ 0MPa, under the condition keeping equilibrium temperature and equilibrium pressure, continuing maintenance 10 ~ 120min, obtain product.
2. the method for claim 1, is characterized in that, described method comprises following process:
1) add the material comprising deionized water, di-carboxylic acid, diamine, oxidation inhibitor and catalyzer in the reactor, start to stir, be warming up to 135 ~ 145 DEG C; Temperature is kept to be 135 ~ 145 DEG C; Maintaining pressure by venting is 0.270 ~ 0.275MPa; Continue 50 ~ 60min;
2) pressure is adjusted to 2.000 ~ 2.100MPa, temperature is adjusted to 220 ~ 225 DEG C, keep pressure be 80 ~ 90min after step-down gradually, and it is persistently overheating in pressurize and pressure reduction, in 60min, be depressurized to normal pressure, and while step-down completes, rise to equilibrium temperature be 265 ~ 275 DEG C;
3) keep equilibrium temperature, being adjusted to equilibrium pressure is after-0.1 ~-0.08MPa, continues maintenance 40 ~ 60min, obtain product under the condition keeping equilibrium temperature and equilibrium pressure.
3. method as claimed in claim 1 or 2, it is characterized in that, described diamine is 4,4 '-diamino-dicyclohexyl methane
described di-carboxylic acid is
in one, wherein, n is 4 ~ 10.
4. method as claimed in claim 3, it is characterized in that, di-carboxylic acid is hexanodioic acid or dodecanedioic acid.
5. the method for claim 1, is characterized in that, step 1) described in di-carboxylic acid and the mol ratio of diamine be 1.03:1 ~ 1:1.03, the account for massfraction of ionized water of di-carboxylic acid consumption is 40% ~ 60%.
6. method as claimed in claim 5, is characterized in that, step 1) described in di-carboxylic acid and the mol ratio of diamine be 1:1 ~ 1:1.02, the account for massfraction of ionized water of di-carboxylic acid consumption is 45% ~ 50%.
7. the method for claim 1, is characterized in that, described catalyzer is the one or two or more in phosphoric acid salt, hypophosphite and hypophosphite, and the consumption of catalyzer is 0.5 ‰ ~ 1.5 ‰ of di-carboxylic acid and diamine total mass.
8. method as claimed in claim 7, it is characterized in that, described catalyzer is phosphoric acid alkali metal salt, and the one or two or more in Hypophosporous Acid, 50 an alkali metal salt and ortho phosphorous acid an alkali metal salt, the consumption of catalyzer is 0.6 ‰ ~ 0.8 ‰ of di-carboxylic acid and diamine total mass.
9. method as claimed in claim 8, it is characterized in that, described catalyzer is the one or two or more in sodium phosphate, sodium hypophosphite and inferior sodium phosphate.
10. method according to claim 3, is characterized in that, with the total restatement of 4,4 '-diamino-dicyclohexyl methane, and 4, the anti-trans isomer content of 4 '-diamino-dicyclohexyl methane is between 20wt% ~ 50wt%.
11. methods according to claim 10, is characterized in that, with the total restatement of 4,4 '-diamino-dicyclohexyl methane, and 4, the anti-trans isomer content of 4 '-diamino-dicyclohexyl methane is between 40wt% ~ 48wt%.
12. methods 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.
13. methods according to claim 12, is characterized in that, the consumption of oxidation inhibitor is 4 ‰ ~ 5 ‰ of deionized water, di-carboxylic acid and diamine total mass.
14. methods according to claim 1 or 12, it is characterized in that, described oxidation inhibitor is the one or two or more in chinox1098, chinox1589, H818D, chinox1325 and chinox1590.
15. methods according to claim 14, is characterized in that, described oxidation inhibitor is chinox1098 or chinox1589.
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