CN105461919A - Atomization and polymerization method and device of polyoxamide - Google Patents
Atomization and polymerization method and device of polyoxamide Download PDFInfo
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- B01J19/14—Production of inert gas mixtures; Use of inert gases in general
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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Abstract
The invention provides an atomization and polymerization method of polyoxamide. The method is characterized by including the steps that, diester oxalate and diamine are pumped into the same nozzle or different nozzles through a feeding pump, atomized, mixed and polymerized in inert gas flow, and polyoxamide is obtained. The atomization and polymerization method of polyoxamide is suitable for large-scale industrial production, has the advantages that operation is easy, conditions are moderate, solvents are not used, processing is easy and cost is low, and meanwhile guarantees viscosity and high molecular weight of polyoxamide.
Description
Technical field
The invention belongs to macromolecular material polymerization field, be specifically related to a kind of method and apparatus being prepared polyoxamide by atomization polymerization.
Background technology
Nylon, since nineteen thirty-nine, du pont company realized PA66 industrialization, has been all achieve remarkable development from kind, output or production technology.Since 20th century, along with updating of processing technology, also more and more stricter to the requirement of material.Electronic apparatus aspect, the Pb-free solder that novel surface mounting technique SurfaceMournTechnology adopts makes the heat resisting temperature of material bring up to 215 DEG C from original 186 DEG C, and this proposes requirements at the higher level to the resistance to elevated temperatures of material and dimensional stability; Automotive field uses to mould Dai Gang therefore also increasing at the high temperature material of engine environment use.But existing general-purpose plastics PA6 and PA66 (occupying about 90% of nylon market) goes back Shortcomings in thermotolerance, water-absorbent and dimensional stability, therefore, development of new high temperature resistant low water absorption nylon is extremely urgent, probes into the preparation method being applicable to industrial mass production and is therefore significant.
Polyoxamide is called by diamines and the barkite nylon that is polymerized, current research shows, polyoxamide, meeting dystectic while, also has that water-intake rate is low, solvent resistant corrodes, acid and alkali-resistance and hydrolysis ability is strong, modulus advantages of higher, has obvious Practical significance.
The polyoxamide of higher molecular weight can not adopt easily to be produced, because raw material oxalic acid and low-grade polymer easily thermolysis occur from the oxalate of diamines through traditional Carothers route of melt phase polycondensation.Equally, also there will be thermolysis slowly when the oxamide of ring-type does raw material monomer ring-opening polymerization.The synthetic method of polyoxamide depends on interface polycondensation in early days, as reference ChangHJ, PA6 in VoglO.Regularcopolyamides.JPolymSciPolymChemEd (1977), 2/9, the preparation of 2, interfacial polycondensation has mild condition, operates at normal temperatures, time short advantage, but it is not high to generate polymkeric substance viscosity, can not meet industrial requirement; Propose ammonia depolymerization afterwards legal, as reference PattonDL, PA10 in FarleyJM.Copolyamideoxygenbarrier.US5223603, the preparation of 2, but reaction needed high-temperature operation, time are long, also require by product propyl carbinol to remove.In addition, as described in reference DicksteinW, VoglO.JMacromolSci-Chem (1984), some aromatic polyoxamides can be undertaken by the method for solution polymerization, but one to carry out products therefrom molecular weight little, two use solvent to be difficult to suitability for industrialized production.
Summary of the invention
The problem being polyoxamide and not being applicable to industrial mass production method at present to be solved by this invention.
In order to solve the problems of the technologies described above, the invention provides a kind of atomization polymerization process of polyoxamide, it is characterized in that, comprise and oxalate diester and diamine are pumped in same nozzle or different spray nozzles respectively by the pump that feeds intake, carry out being atomized, mixing and being polymerized in inert gas, obtain polyoxamide.
Preferably, the atomization polymerization process of described polyoxamide also comprises: the polyoxamide of gained is carried out melt polymerization or solid state polymerization.
More preferably, before the polyoxamide of gained is carried out melt polymerization or solid state polymerization, first by polyoxamide under nitrogen protection at room temperature-200 DEG C of constant temperature process 1-4h, be decompressed to pressure subsequently and be less than 100-200Pa.
More preferably, the time of described melt polymerization is between 0.5-6h.
More preferably, the temperature of described solid state polymerization is between Tm-50 DEG C to Tm-10 DEG C, and Tm is the fusing point of polyoxamide, and the time of solid state polymerization is 0.5h ~ 20h.
Preferably, described oxalate diester is one or more in dimethyl oxalate, oxalic acid diethyl ester, DPO, oxalic acid diisopropyl ester, dibutyl oxalate, di-isobutyl oxalate, oxalic acid di tert butyl carbonate and phenyloxalate.
Preferably, described diamine is at least one in the alkyl dicarboxylic amine of C4-C12.
Preferably, described inert gas be nitrogen gas stream and its linear velocity between 5-200m/s.
Preferably, described oxalate diester and the mol ratio of diamine are between 0.95-1.05.
Preferably, described oxalate diester and diamine being pumped into respectively by the pump that feeds intake to carry out envrionment temperature when being atomized, mixing and being polymerized independently between room temperature is to 200 DEG C in same nozzle or different spray nozzles and in inert gas.
Preferably, the nozzle of described oxalate diester and the nozzle of diamine are concentric nozzle.
Present invention also offers a kind of atomization poly-unit, it is characterized in that, comprise container, nozzle is provided with in described container 4, described nozzle is provided with gas feed and Liquid sample introduction pipe, and described Liquid sample introduction pipe comprises outer tube and is located at the interior pipe in outer tube, and described outer tube connects barkite and to feed intake pump, described interior pipe connects diamines and to feed intake pump, and described container 4 has pneumatic outlet.
Preferably, the atomization polymerization process of described polyoxamide adopts above-mentioned atomization poly-unit.
Preferably, described outer tube and interior pipe are arranged with one heart.
Polymerization process of the present invention, can only have this step of atomization polymerization, also after atomization polymerization, can carry out solid phase polycondensation or melt phase polycondensation further, to improve molecular weight further.
The kind of the present invention to oxalate diester there is no particular restriction, can be one or more in dimethyl oxalate, oxalic acid diethyl ester, DPO, oxalic acid diisopropyl ester, dibutyl oxalate, di-isobutyl oxalate, oxalic acid di tert butyl carbonate and phenyloxalate.Preferably, described oxalate diester can be one or both in dimethyl oxalate, oxalic acid diethyl ester and dibutyl oxalate.Most preferably, described oxalate diester is dibutyl oxalate.
In the present invention, diamine unit is selected from the alkyl dicarboxylic amine of C4-C12.When diamine unit carbonatoms lower than 4 time, likely occur that the viscosity of polyamide resin is difficult to improve or the too high unmanageable tendency of fusing point of polyamide resin; When diamine unit carbonatoms higher than 12 time, likely there is the fusing point of the polyamide resin tendency causing thermotolerance to reduce on the low side.From the viewpoint of the crystallinity of polyamide resin, the diamine unit of preferred straight chain.Preferably, described diamine can be Putriscine, 1,5-pentamethylene diamine, 1,6-hexanediamine, 1,12-diamino dodecane and 2-methyl isophthalic acid, one or more in 5-pentamethylene diamine.From the viewpoint of the high-melting-point of polyamide resin, one or more more preferably in Putriscine, 1,5-pentamethylene diamine, 1,6-hexanediamine.Most preferably, described diamine is 1,5-pentamethylene diamine.
The rare gas element adopted in atomization polymerization process of the present invention can be helium, neon, argon gas, Krypton, xenon, carbonic acid gas or nitrogen, but is preferably nitrogen.Under the prerequisite ensureing atomization, the present invention is not particularly limited the flow velocity of rare gas element at nozzle place, is generally advisable with 5-400m/s, and preferred 5-300m/s, more preferably 5-200m/s, most preferably be 10-50m/s.Rare gas element is not only carrier gas stream in the method and has been assisted to be atomized polymerization and to protect polyamide resin by the interference of the impurity such as the water vapour in air and carbonic acid gas.
Owing at high temperature carrying out polyreaction, thus the straight-chain aliphatic diamines based on short carbon chain volatilizees or makes the reasons such as lower boiling product volatilization by deamination reaction in polymerization system, along with the carrying out of polymerization, in polymerization system, the content of total amino and total oxalic acid ester group may change, therefore, in the stage adding raw material, add the short carbon chain straight-chain aliphatic diamine of different mol ratio and barkite in advance to measure the amount of amino in system and oxalic acid ester group, be rational for the polyamide resin synthesizing high molecular.When the mole number of the short carbon chain used as raw material straight-chain aliphatic diamines is set to a, the mole number of oxalate diester is set to b.Preferably, be 0.95-1.05 by raw material ratio of components furnishing a/b.If a/b is less than 0.95, then in polymerization system, total amino amount is relative very few with the amount of total oxalic acid ester group, is difficult to obtain high-molecular weight polymer; If a/b is greater than 1.05, then in polymerization system, total amino is relative with the amount of total oxalic acid ester group too much, is also difficult to obtain high-molecular weight polymer.Adopt atomization polymerization process of the present invention, the envrionment temperature that oxalate diester and diamine pump into when being atomized, mixing and being polymerized in respective nozzle and inert gas respectively by the pump that feeds intake is not particularly limited by described, pump into the fusing point that temperature generally should be greater than reactant monomer, but from the stability of polyamide reaction with to realize good mass-and heat-transfer angle temperature unsuitable too high or too low.Preferably, described oxalate diester and diamine being pumped in respective nozzle and inert gas respectively by the pump that feeds intake carries out envrionment temperature when being atomized, mixing and being polymerized independently between room temperature is to 200 DEG C.Temperature is lower than room temperature, and polymeric amide may can not get good mass-and heat-transfer and cause molecular weight to reduce; Temperature is higher than 200 DEG C, and polymeric amide decomposition may occur in the reaction and causes molecular weight to reduce.Adopt atomization polymerization process of the present invention, particular restriction is not had to the time of melt polymerization used.But consider that the melt polymerization time is too short, molecular weight is difficult to improve, long then side reaction aggravation, affect polymerization efficiency, the impact that generally can cause the viscosity of polyamide resin and molecular weight, the time of general melt polymerization is preferably 0.5-6h.
Adopt atomization polymerization process of the present invention, do not have particular requirement, but consider that solid state polymerization time is too short to the temperature of solid state polymerization used and time, molecular weight is difficult to improve, and long then side reaction aggravation, affects polymerization efficiency; Solid phase polymerization temperature is too low, and polymeric amide viscosity does not reach requirement, and solid-state temperature crosses high polymers meeting decomposes, and therefore solid-state temperature and time can make a big impact to the viscosity of polyamide resin and molecular weight.Preferably, the temperature of described solid state polymerization is between Tm-50 DEG C to Tm-10 DEG C, and Tm is the fusing point of polyoxamide, and solid state polymerization time is between 0.5h ~ 20h.
Compared with prior art, the invention has the beneficial effects as follows:
The atomization polymerization process kind of polyoxamide of the present invention is applicable to industrial mass production, have simple to operate, mild condition, solvent-free, be easy to processing, the advantage such as with low cost, meanwhile, also assures that viscosity and the high molecular of polyamide resin.
Accompanying drawing explanation
Fig. 1 is atomization poly-unit schematic diagram.
Fig. 2 is the polyoxamide N52 second time intensification DSC figure that embodiment 4 is synthesized.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
The raw material that embodiment 1-12 and comparative example 1 adopt is: 1, 4-butanediamine (> 98%, TCI, CAS110-60-1), 1, 5-pentamethylene diamine (> 98%, TCI, CAS462-94-2), 1, 6-hexanediamine (> 99%, TCI, CAS124-09-4), 1, 12-diamino dodecane (> 98%, TCI, CAS2783-17-7), dimethyl oxalate (> 98%, TCI, CAS553-90-2), oxalic acid diethyl ester (> 99%, TCI, CAS95-92-1), dibutyl oxalate (> 99%, TCI, CAS2050-60-4), phenyloxalate (> 98%, TCI, CAS3155-16-6).Equipment and instrument adopt TADSC-Q100 instrument, constant temperature viscosity measurement instrument.
DSC measuring method, adopt TADSC-Q100 instrument, accurately take about 5mg sample, test condition is as follows: in a nitrogen atmosphere, and gained polyamide resin is warmed up to temperature (T than occurred endotherm(ic)peak with the temperature rise rate of 20 DEG C/min
0) exceed 30 DEG C, keep 2 minutes at this temperature, then drop to 30 DEG C with the cooling rate of 20 DEG C/min, keep 2 minutes at 30 DEG C.Next, be warmed up to the temperature rise rate of 20 DEG C/min and compare T
0the temperature Tm of the endotherm(ic)peak observed when exceeding 30 DEG C.
Viscosity measurement: at the vitriol oil with 96% under solvent and 25 DEG C of conditions, the polyamide solution of configuration 0.01g/ml measures.
As shown in Figure 1, various embodiments of the present invention atomization poly-unit used comprises container 4, nozzle 5 is provided with in described container 4, described nozzle 5 is provided with gas feed 3 and Liquid sample introduction pipe, described Liquid sample introduction pipe comprises outer tube 1 and is located at the interior pipe 1 in outer tube 2, described outer tube 2 connects barkite and to feed intake pump, and described interior pipe 1 connects diamines and to feed intake pump, and described container 4 has pneumatic outlet 6.
During use, oxalate diester and diamine feed intake in outer tube 2 and interior pipe 1 that pump is pumped into the Liquid sample introduction pipe of nozzle 5 respectively by feed intake pump and diamines of barkite, nitrogen gas stream enters nozzle 5 from gas feed 3, oxalate diester and diamine spray into container 4 through nozzle 5 under the effect of nitrogen gas stream, realize mixing and polymerization while being atomized in nitrogen gas stream, obtain polyoxamide prepolymer.
Embodiment 1
A kind of atomization polymerization process of polyoxamide, concrete steps are: adopt above-mentioned atomization poly-unit, at room temperature, by 202.25g dibutyl oxalate (1mol), 102.18g1, 5-pentamethylene diamine (1mol) feeds intake in outer tube 2 and interior pipe 1 that pump is pumped into the Liquid sample introduction pipe of nozzle 5 respectively by feed intake pump and diamines of barkite, nitrogen gas stream enters nozzle 5 from gas feed 3, at room temperature, dibutyl oxalate and 1, 5-pentamethylene diamine sprays into container 4 (nozzle exit nitrogen gas stream linear velocity is 14.74m/s) through nozzle 5 under the effect of this nitrogen gas stream, be atomized in this nitrogen gas stream, mixing and polymerization 25min, obtain polyoxamide prepolymer, by aforementioned prepolymer under nitrogen protection at 150 DEG C of constant temperature process 3h, be decompressed to pressure subsequently and be less than 200Pa, with the heat-up rate of 10 DEG C/min, temperature is risen to 250 DEG C, and solid state polymerization 4h at this temperature, obtain the polyoxamide product of white.After measured, its solution solvent viscosity ratio is 2.77, Tm is 301.5 DEG C.
Embodiment 2
A kind of atomization polymerization process of polyoxamide, concrete steps are: adopt above-mentioned atomization poly-unit, at room temperature, by 202.25g dibutyl oxalate (1mol), 100.14g1, 5-pentamethylene diamine (0.98mol) feeds intake in outer tube 2 and interior pipe 1 that pump is pumped into the Liquid sample introduction pipe of nozzle 5 respectively by feed intake pump and diamines of barkite, nitrogen gas stream enters nozzle 5 from gas feed 3, at room temperature, dibutyl oxalate and 1, 5-pentamethylene diamine sprays into container 4 (nozzle exit nitrogen gas stream linear velocity is 14.74m/s) through nozzle 5 under the effect of this nitrogen gas stream, be atomized in this nitrogen gas stream, mixing and polymerization 25min, obtain Polvamide prepolymer, by aforementioned prepolymer under nitrogen protection at 150 DEG C of constant temperature process 3h, be decompressed to pressure subsequently and be less than 200Pa, with the heat-up rate of 10 DEG C/min, temperature is risen to 250 DEG C, and solid state polymerization 4h at this temperature, obtain the polyoxamide product of white.After measured, its solution solvent viscosity ratio is 2.69, Tm is 301.7 DEG C.
Embodiment 3
A kind of atomization polymerization process of polyoxamide, concrete steps are: adopt above-mentioned atomization poly-unit, at room temperature, by 202.25g dibutyl oxalate (1mol), 104.22g1, 5-pentamethylene diamine (1.02mol) feeds intake in outer tube 2 and interior pipe 1 that pump is pumped into the Liquid sample introduction pipe of nozzle 5 respectively by feed intake pump and diamines of barkite, nitrogen gas stream enters nozzle 5 from gas feed 3, at room temperature, dibutyl oxalate and 1, 5-pentamethylene diamine sprays into container 4 (nozzle exit nitrogen gas stream linear velocity is 14.74m/s) through nozzle 5 under the effect of this nitrogen gas stream, be atomized in this nitrogen gas stream, mixing and polymerization 25min, obtain Polvamide prepolymer, by aforementioned prepolymer at 150 DEG C of constant temperature process 3h under nitrogen protection, be decompressed to pressure subsequently and be less than 200Pa, with the heat-up rate of 10 DEG C/min, temperature is risen to 250 DEG C, and solid state polymerization 4h at this temperature, obtain the polyoxamide product of white.After measured, its solution solvent viscosity ratio is 2.85, Tm is 301.9 DEG C.
Embodiment 4
A kind of atomization polymerization process of polyoxamide, concrete steps are: adopt above-mentioned atomization poly-unit, at room temperature, by 202.25g dibutyl oxalate (1mol), 102.18g1, 5-pentamethylene diamine (1mol) feeds intake in outer tube 2 and interior pipe 1 that pump is pumped into the Liquid sample introduction pipe of nozzle 5 respectively by feed intake pump and diamines of barkite, nitrogen gas stream enters nozzle 5 from gas feed 3, at room temperature, dibutyl oxalate and 1, 5-pentamethylene diamine sprays into container 4 (nozzle exit nitrogen gas stream linear velocity is 33.97m/s) through nozzle 5 under the effect of this nitrogen gas stream, be atomized in this nitrogen gas stream, mixing and polymerization 25min, obtain Polvamide prepolymer, by aforementioned prepolymer under nitrogen protection at 150 DEG C of constant temperature process 3h, be decompressed to pressure subsequently and be less than 200Pa, with the heat-up rate of 10 DEG C/min, temperature is risen to 250 DEG C, and solid state polymerization 4h at this temperature, obtain the polyoxamide product (N52) of white.After measured, its solution solvent viscosity ratio is 2.95, Tm is 302.2 DEG C.
Embodiment 5
A kind of atomization polymerization process of polyoxamide, concrete steps are: adopt above-mentioned atomization poly-unit, at room temperature, by the mixture of 101.13g dibutyl oxalate (0.5mol) and 59.05g dimethyl oxalate (0.5mol), 102.18g1, 5-pentamethylene diamine (1mol) feeds intake in outer tube 2 and interior pipe 1 that pump is pumped into the Liquid sample introduction pipe of nozzle 5 respectively by feed intake pump and diamines of barkite, nitrogen gas stream enters nozzle 5 from gas feed 3, at room temperature, dibutyl oxalate, the mixture of dimethyl oxalate and 1, 5-pentamethylene diamine sprays into container 4 (nozzle exit nitrogen gas stream linear velocity is 14.74m/s) through nozzle 5 under the effect of this nitrogen gas stream, be atomized in this nitrogen gas stream, mixing and polymerization 25min, obtain Polvamide prepolymer, by aforementioned prepolymer under nitrogen protection at 150 DEG C of constant temperature process 3h, be decompressed to pressure subsequently and be less than 200Pa, with the heat-up rate of 10 DEG C/min, temperature is risen to 250 DEG C, and solid state polymerization 4h at this temperature, obtain the polyoxamide product of white.After measured, its solution solvent viscosity ratio is 2.76, Tm is 301.8 DEG C.
Embodiment 6
A kind of atomization polymerization process of polyoxamide, concrete steps are: adopt above-mentioned atomization poly-unit, at room temperature, by the mixture of 101.13g dibutyl oxalate (0.5mol) and 121.12g phenyloxalate (0.5mol), 102.18g1, 5-pentamethylene diamine (1mol) feeds intake in outer tube 2 and interior pipe 1 that pump is pumped into the Liquid sample introduction pipe of nozzle 5 respectively by feed intake pump and diamines of barkite, nitrogen gas stream enters nozzle 5 from gas feed 3, at room temperature, dibutyl oxalate, the mixture of phenyloxalate and 1, 5-pentamethylene diamine sprays into container 4 (nozzle exit nitrogen gas stream linear velocity is 14.74m/s) through nozzle 5 under the effect of this nitrogen gas stream, be atomized in this nitrogen gas stream, mixing and polymerization 25min, obtain Polvamide prepolymer, by aforementioned prepolymer under nitrogen protection at 150 DEG C of constant temperature process 3h, be decompressed to pressure subsequently and be less than 200Pa, with the heat-up rate of 10 DEG C/min, temperature is risen to 250 DEG C, and solid state polymerization 4h at this temperature, obtain the polyoxamide product of white.After measured, its solution solvent viscosity ratio is 2.82, Tm is 302.5 DEG C.
Embodiment 7
A kind of atomization polymerization process of polyoxamide, concrete steps are: adopt above-mentioned atomization poly-unit, at room temperature, by 202.25g dibutyl oxalate (1mol), 86.85g1, 5-pentamethylene diamine (0.85mol) and 30.05g1, the mixture of 12-diamino dodecane (0.15mol) feeds intake in outer tube 2 and interior pipe 1 that pump is pumped into the Liquid sample introduction pipe of nozzle 5 respectively by feed intake pump and diamines of barkite, nitrogen gas stream enters nozzle 5 from gas feed 3, at room temperature, dibutyl oxalate and 1, 5-pentamethylene diamine, 1, the mixture of 12-diamino dodecane sprays into container 4 (nozzle exit nitrogen gas stream linear velocity is 14.74m/s) through nozzle 5 under the effect of this nitrogen gas stream, be atomized in this nitrogen gas stream, mixing and polymerization 25min, obtain Polvamide prepolymer, by aforementioned prepolymer under nitrogen protection at 150 DEG C of constant temperature process 3h, be decompressed to pressure subsequently and be less than 200Pa, with the heat-up rate of 10 DEG C/min, temperature is risen to 250 DEG C, and solid state polymerization 4h at this temperature, obtain the polyoxamide product of white.After measured, its solution solvent viscosity ratio is 2.68, Tm is 267.3 DEG C.
Embodiment 8
A kind of atomization polymerization process of polyoxamide, concrete steps are: adopt above-mentioned atomization poly-unit, at room temperature, by 202.25g dibutyl oxalate (1mol), 86.85g1, 5-pentamethylene diamine (0.85mol) and 17.43g1, the mixture of 6-hexanediamine (0.15mol) feeds intake in outer tube 2 and interior pipe 1 that pump is pumped into the Liquid sample introduction pipe of nozzle 5 respectively by feed intake pump and diamines of barkite, nitrogen gas stream enters nozzle 5 from gas feed 3, at room temperature, dibutyl oxalate and 1, 5-pentamethylene diamine and 1, the mixture of 6-hexanediamine sprays into container 4 (nozzle exit nitrogen gas stream linear velocity is 14.74m/s) through nozzle 5 under the effect of this nitrogen gas stream, be atomized in this nitrogen gas stream, mixing and polymerization 25min, obtain Polvamide prepolymer, by aforementioned prepolymer under nitrogen protection at 150 DEG C of constant temperature process 3h, be decompressed to pressure subsequently and be less than 200Pa, with the heat-up rate of 10 DEG C/min, temperature is risen to 250 DEG C, and solid state polymerization 4h at this temperature, obtain the polyoxamide product of white.After measured, its solution solvent viscosity ratio is 2.72, Tm is 269.1 DEG C.
Embodiment 9
A kind of atomization polymerization process of polyoxamide, concrete steps are: adopt above-mentioned atomization poly-unit, at room temperature, by 202.25g dibutyl oxalate (1mol), 86.85g1, 5-pentamethylene diamine (0.85mol) and 13.22g1, the mixture of 4-butanediamine (0.15mol) feeds intake in outer tube 2 and interior pipe 1 that pump is pumped into the Liquid sample introduction pipe of nozzle 5 respectively by feed intake pump and diamines of barkite, nitrogen gas stream enters nozzle 5 from gas feed 3, at room temperature, dibutyl oxalate and 1, 5-pentamethylene diamine, 1, the mixture of 4-butanediamine sprays into container 4 (nozzle exit nitrogen gas stream linear velocity is 14.74m/s) through nozzle 5 under the effect of this nitrogen gas stream, be atomized in this nitrogen gas stream, mixing and polymerization 25min, obtain Polvamide prepolymer, by aforementioned prepolymer under nitrogen protection at 150 DEG C of constant temperature process 3h, be decompressed to pressure subsequently and be less than 200Pa, with the heat-up rate of 10 DEG C/min, temperature is risen to 290 DEG C, and melt polymerization 0.5h at this temperature, obtain the polyoxamide product of white.After measured, its solution solvent viscosity ratio is 2.74, Tm is 273.4 DEG C.
Embodiment 10
A kind of atomization polymerization process of polyoxamide, concrete steps are: adopt above-mentioned atomization poly-unit, at 60 DEG C, by 202.25g dibutyl oxalate (1mol), 116.20g1, 6-hexanediamine (1mol) feeds intake in outer tube 2 and interior pipe 1 that pump is pumped into the Liquid sample introduction pipe of nozzle 5 respectively by feed intake pump and diamines of barkite, nitrogen gas stream enters nozzle 5 from gas feed 3, at 60 DEG C, dibutyl oxalate and 1, 6-hexanediamine sprays into container 4 (nozzle exit nitrogen gas stream linear velocity is 14.74m/s) through nozzle 5 under the effect of this nitrogen gas stream, be atomized in nitrogen gas stream, mixing and polymerization 25min, obtain Polvamide prepolymer, by aforementioned prepolymer under nitrogen protection at 150 DEG C of constant temperature process 3h, be decompressed to pressure subsequently and be less than 200Pa, with the heat-up rate of 10 DEG C/min, temperature is risen to 250 DEG C, and solid state polymerization 4h at this temperature, obtain the polyoxamide product of white.After measured, its solution solvent viscosity ratio is 2.88, Tm is 301.7 DEG C.
Embodiment 11
A kind of atomization polymerization process of polyoxamide, concrete steps are: adopt above-mentioned atomization poly-unit, at room temperature, by 202.25g dibutyl oxalate (1mol), 116.20g1, 6-hexanediamine (1mol) feeds intake in outer tube 2 and interior pipe 1 that pump is pumped into the Liquid sample introduction pipe of nozzle 5 respectively by feed intake pump and diamines of barkite, nitrogen gas stream enters nozzle 5 from gas feed 3, at room temperature, dibutyl oxalate and 1, 6-hexanediamine sprays into container 4 (nozzle exit nitrogen gas stream linear velocity is 47.53m/s) through nozzle 5 under the effect of this nitrogen gas stream, be atomized in nitrogen gas stream, mixing and polymerization 25min, obtain Polvamide prepolymer, by aforementioned prepolymer under nitrogen protection at 150 DEG C of constant temperature process 3h, be decompressed to pressure subsequently and be less than 200Pa, with the heat-up rate of 10 DEG C/min, temperature is risen to 250 DEG C, and solid state polymerization 4h at this temperature, obtain the polyoxamide product of white.After measured, its solution solvent viscosity ratio is 2.83, Tm is 301.4 DEG C.
Embodiment 12
A kind of atomization polymerization process of polyoxamide, concrete steps are: adopt above-mentioned atomization poly-unit, at room temperature, by 146.14g oxalic acid diethyl ester (1mol), 116.20g1, 6-hexanediamine (1mol) feeds intake in outer tube 2 and interior pipe 1 that pump is pumped into the Liquid sample introduction pipe of nozzle 5 respectively by feed intake pump and diamines of barkite, nitrogen gas stream enters nozzle 5 from gas feed 3, at room temperature, oxalic acid diethyl ester and 1, 6-hexanediamine sprays into container 4 (nozzle exit nitrogen gas stream linear velocity is 14.74m/s) through nozzle 5 under the effect of this nitrogen gas stream, be atomized in nitrogen gas stream, mixing and polymerization 25min, obtain the polyoxamide prepolymer product of white.After measured, its solution solvent viscosity ratio is 1.25, Tm is 301.6 DEG C.
Comparative example 1
By 102.18g1,5-pentamethylene diamine (1mol) to be dissolved in 1000ml toluene and to add the there-necked flask of 2L, slowly 202.25g dibutyl oxalate (1mol) is dripped again in flask, at room temperature after solution polymerization 3h, decompress filter, vacuum-drying 3h, obtains polyoxamide prepolymer white powder.Get 100g prepolymer and put into solid state polymerization pipe, be decompressed to pressure after nitrogen replacement 3 times and be less than 200Pa, with the heat-up rate of 10 DEG C/min, temperature is risen to 250 DEG C, and solid state polymerization 4h at this temperature, obtain the polyoxamide product of white.After measured, its solution solvent viscosity ratio is 2.76, Tm is 302.7 DEG C.
The DSC of the product that specific embodiment 4 is obtained as shown in Figure 2.
Each performance perameter of the product that embodiment 1-12 and comparative example 1 obtain is as shown in table 1.
Each performance perameter of the product that table 1 embodiment 1-12 and comparative example 1 obtain:
From Fig. 2 and table 1, the relative viscosity adopting the embodiment 1-11 gained polyoxamide of the method for atomization polymerization is substantially suitable with the relative viscosity of comparative example 1 products therefrom adopting conventional solution polymerization method, all can be met the polyoxamide of actual operation requirements.But advantage of the present invention is do not use solvent in whole polymerization process, more environmental protection and economy.
Claims (10)
1. an atomization polymerization process for polyoxamide, is characterized in that, comprises and is pumped in same nozzle or different spray nozzles by oxalate diester and diamine respectively by the pump that feeds intake, carry out being atomized, mixing and being polymerized, obtain polyoxamide in inert gas.
2. the atomization polymerization process of polyoxamide as claimed in claim 1, it is characterized in that, the atomization polymerization process of described polyoxamide also comprises: the polyoxamide of gained is carried out melt polymerization or solid state polymerization.
3. the atomization polymerization process of polyoxamide as claimed in claim 2, it is characterized in that, the time of described melt polymerization is between 0.5-6h.
4. the atomization polymerization process of polyoxamide as claimed in claim 2, it is characterized in that, the temperature of described solid state polymerization is between Tm-50 DEG C to Tm-10 DEG C, and Tm is the fusing point of polyoxamide, and the time of solid state polymerization is 0.5h ~ 20h.
5. the atomization polymerization process of polyoxamide as claimed in claim 1, it is characterized in that, described oxalate diester is one or more in dimethyl oxalate, oxalic acid diethyl ester, DPO, oxalic acid diisopropyl ester, dibutyl oxalate, di-isobutyl oxalate, oxalic acid di tert butyl carbonate and phenyloxalate.
6. the atomization polymerization process of polyoxamide as claimed in claim 1, it is characterized in that, described diamine is at least one in the alkyl dicarboxylic amine of C4-C12.
7. the atomization polymerization process of polyoxamide as claimed in claim 1, is characterized in that, described inert gas be nitrogen gas stream and its linear velocity between 5-200m/s.
8. the atomization polymerization process of polyoxamide as claimed in claim 1, it is characterized in that, described oxalate diester and the mol ratio of diamine are between 0.95-1.05.
9. the atomization polymerization process of polyoxamide as claimed in claim 1, it is characterized in that, described oxalate diester and diamine being pumped in respective nozzle and inert gas respectively by the pump that feeds intake carries out envrionment temperature when being atomized, mixing and being polymerized independently between room temperature is to 200 DEG C.
10. an atomization poly-unit, it is characterized in that, comprise container (4), nozzle (5) is provided with in described container (4), described nozzle (5) is provided with gas feed (3) and Liquid sample introduction pipe, described Liquid sample introduction pipe comprises outer tube (2) and is located at the interior pipe (1) in outer tube (2), described outer tube (2) connects barkite and to feed intake pump, described interior pipe (1) connects diamines and to feed intake pump, and described container (4) has pneumatic outlet (6).
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| CN106008963A (en) * | 2016-06-29 | 2016-10-12 | 东华大学 | Polyoxamide powder and preparation method thereof |
| CN106220845A (en) * | 2016-07-26 | 2016-12-14 | 广东新会美达锦纶股份有限公司 | A kind of polyoxamide powder and preparation method thereof |
| CN108148199A (en) * | 2016-12-02 | 2018-06-12 | 北京伊克希德化工技术有限公司 | A kind of polymerization of Fanglun l414 |
| CN108395695A (en) * | 2018-03-28 | 2018-08-14 | 东华大学 | A kind of continuous preparation process of thermoplastic resin-based carbon fiber composite |
| CN111440313A (en) * | 2020-06-01 | 2020-07-24 | 南京工业大学 | Novel nylon polymerization process and reaction device thereof |
| CN111495312A (en) * | 2020-05-22 | 2020-08-07 | 河南心连心化学工业集团股份有限公司 | Synthetic device and synthetic method for oxamide |
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| CN106008963A (en) * | 2016-06-29 | 2016-10-12 | 东华大学 | Polyoxamide powder and preparation method thereof |
| CN106220845A (en) * | 2016-07-26 | 2016-12-14 | 广东新会美达锦纶股份有限公司 | A kind of polyoxamide powder and preparation method thereof |
| CN108148199A (en) * | 2016-12-02 | 2018-06-12 | 北京伊克希德化工技术有限公司 | A kind of polymerization of Fanglun l414 |
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| CN108395695A (en) * | 2018-03-28 | 2018-08-14 | 东华大学 | A kind of continuous preparation process of thermoplastic resin-based carbon fiber composite |
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| CN111440313A (en) * | 2020-06-01 | 2020-07-24 | 南京工业大学 | Novel nylon polymerization process and reaction device thereof |
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