Copolymerization modified PA 612 and preparation method thereof
Technical field
The present invention relates to a kind of modification by copolymerization nylon 612 (PA612) and preparation method thereof.
Background technology
Copolymerization modified PA 612 is mainly used in fiber industry, also can be widely used in the top layer that makes precision optical machinery parts, electric wire and transition pipeline etc.The preparation employed dodecanedioic acid of copolymerization modified PA 612 solubleness in water is very little, so traditional processing method uses ethanol, Virahol etc. to dissolve as solvent, neutralization reaction is carried out in homogeneous phase.PA612 monomer after the neutralization is through crystallisation by cooling, and dealcoholysis then, dehydration drop into monomer polymeric kettle at last and carry out polyreaction.Whole operational path is long, and has a large amount of ethanol to exist in whole technological process, and alcoholic acid consumption is also bigger, makes production process that bigger potentially dangerous be arranged, and pollutes also bigger to surrounding enviroment simultaneously.And, in dealcoholysis, dehydration, inevitably can cause the loss of monomer of minimal amounts of dissolved in ethanol, water, increased production cost.For overcoming above-mentioned defective, also there is relevant prior art to mention with the water instead of ethanol as dissolution with solvents and be neutralized into salt, can adopt ethanol or water as disclosing in the disclosed content of CN1663980A, but in this patent documentation, it is irrational only water being considered as carrying out simple substitution with the complete equivalent solvent of ethanol, especially the document thinks that also the mole proportion of composing of diprotic acid and hexanediamine should be between 1: 1~1: 1.2, with 1: 1.12 was the best, but think in this patent documentation that should there be technology prejudice greater than the mole number of hexanediamine in diprotic acid, if implement by the disclosed embodiment of this patent documentation, when adopting water to replace ethanol and above-mentioned proportion of composing, final product performance can not be guaranteed, therefore, this patent documentation still unresolved as how water replace the alcoholic acid technical problem.
Summary of the invention
The purpose of this invention is to provide a kind of water and replace ethanol, and can continuously, efficiently, stably make the preparation method of the copolymerization modified PA 612 of high-clarity and some property requirement (good abrasion resistance and mouthfeel etc.).
On the other hand, the invention provides a kind of copolymerization modified PA 612 of improvement in performance.
The technical scheme that realizes the foregoing invention purpose is:
A kind of preparation method of copolymerization modified PA 612 is provided, and this method comprises:
A) dodecanedioic acid and deionized water are made emulsion;
B) add the hexanediamine aqueous solution in the dodecanedioic acid emulsion and be neutralized into reactant salt, wherein the proportion of composing of dodecanedioic acid and hexanediamine is 1: 0.98~0.95 mol ratio;
C) amide monomer of adding copolymerization;
D) make the copolymerization modified PA 612 resin through thickening, polymerization.
Wherein, preferred, the mass percent that water accounts for total material is 35-50%.
Hexanediamine and water are made by 1: 0.3~0.5 mol ratio in the hexanediamine aqueous solution.
Preferred, a step also comprises makes the step that is warming up to 50 ℃~95 ℃ after the emulsion with dodecanedioic acid and deionized water, adds the hexanediamine aqueous solution again and is neutralized into reactant salt.
The b step also comprises the pH value of adding additive with regulator solution.
The amide monomer that the c step adds accounts for the per-cent of dodecanedioic acid and hexanediamine gross weight smaller or equal to 25%; Amide monomer is PA12, PA11, PA66, PA610 or PA1010.
The d step comprises that the solution that will prepare is pressed into and is heated to 130 ℃~145 ℃ in the concentration kettle and concentrates, solution after will concentrating again is pressed in the polymeric kettle, heat temperature raising to 200 ℃~270 ℃, under the condition of 1.0Mpa~2.0Mpa, carried out polymerization 1.5~3 hours, and be decompressed to normal pressure then and obtain product.
From above technological process as can be seen, the present invention has overcome the prejudice that exists in the prior art, proportion of composing by reasonable configuration dodecanedioic acid and hexanediamine, avoided the alcoholic acid use, make whole technological process safety, pollute and lack, production cost is low, higher more than 99% of theoretical yield that reaches of product yield.
The present invention has also overcome the prejudice that exists in the prior art, a kind of improved copolymerization modified PA 612 is provided, wherein dodecanedioic acid and hexanediamine are that 1: 0.98~0.95 mol ratio is made by proportion of composing, copolymerization modified PA 612 of the present invention, most of performance (transparency, tensile strength, Rockwell hardness, wear resisting property, mouthfeel etc.) is better than the PA612 resin of homopolymerization, workability is good, and cost is lower.Can be widely used in automobile, machinery, electronic product, wrapping material, nylon brush thread, abrasive filaments are with every field such as base materials.
Description of drawings
Fig. 1 process flow sheet of the present invention.
Embodiment
Below, 1 preparation method who provides a kind of concrete production copolymerization modified PA 612 resin of the present invention in conjunction with the accompanying drawings, at first dodecanedioic acid and deionized water are made emulsion, be warming up to 50 ℃~95 ℃, add the hexanediamine mixing again and carry out neutralization reaction, and add additive such as TIA at a certain temperature, pH value with regulator solution, add other amide monomer such as PA12, PA11, PA66, PA610, PA1010 afterwards again, monomer is by adjusting smaller or equal to 25% of dodecanedioic acid and hexanediamine gross weight.The solution press filtration for preparing is heated to 130 ℃~145 ℃ to the concentration kettle to be concentrated.Afterwards this concentrated solution is pressed in the polymeric kettle, heat temperature raising to 200 ℃~270 ℃ under the condition of 1.0Mpa~2.0Mpa, carried out polymerization 1.5~3 hours, was decompressed to normal pressure then and carried out the Cast Strip pelletizing and promptly obtain product.
Manufacturing process of the present invention, the hexanediamine aqueous solution that wherein preferably adds 1: 0.3~0.5 mol ratio in this solution is neutralized into reactant salt, add asymmetric diprotic acid, diamine comonomer afterwards as (PA12, PA11, PA66, PA610, PA1010) etc., utilize its asymmetry, the ordered arrangement of upsetting the PA612 molecule improves transparency of products.The salt of gained can also add other amide salt, carries out the product that polycondensation makes behind molecular weight regulator and other auxiliary agents.After making it fully dissolving mixing on request, the salts solution of gained is put into salt storage pipe, be pressed into concentration kettle then and carry out thickening, the monomer content after concentrating should reach 65~80% mass concentration, temperature reaches 130 ℃~145 ℃, and binder carries out polycondensation to polycondensation vessel.Polymerization is in earlier stage to dewater, to heat up, to boost, temperature should rise to 200 ℃~210 ℃ in 30min, pressure rises to 1.4Mpa~1.8Mpa, constantly carry out stirring reaction, the constant temperature that keep-ups pressure continues to rise to 240 ℃~265 ℃, and this process needs 60min~80min approximately, reduces pressure then, the Cast Strip pelletizing gets product.
In addition, related each component consists of in each step of preparation method of the present invention: dodecanedioic acid and hexanediamine are 1: 0.98~0.95 mol ratio, water accounts for the 35-50% of total quality of material ratio, monomer is amide monomer PA12, PA11, PA66, PA610, PA1010, TIA etc. for example, can adjust with interior smaller or equal to 25% by the weight ratio that always feeds intake as requested.
Simultaneously, adopt the made copolymerization modified PA 612 of preparation method of the present invention, wherein dodecanedioic acid and hexanediamine are that 1: 0.98~0.95 mol ratio is made by proportion of composing.
To those skilled in the art; be easy to know by inference the numerical range of the final protection of the present invention and should not be limited to preferred embodiment above-mentionedly, those skilled in the art are easy to rationally summarize on the basis of above-mentioned preferred implementation to obtain bigger numerical range.
In sum, whole process of production of the present invention is carried out continuously, process period is short, cost is low, product yield can reach 99% of theoretical yield, the copolymerization modified PA 612 resin that makes through the present invention is a kind of water medium of using, there is not inflammable danger, the product that the low relative low production method with energy consumption of raw materials consumption forms, PA612 resin with the present invention's production, most of performance (transparency, tensile strength, Rockwell hardness, wear resisting property, mouthfeel etc.) is better than the PA612 resin of homopolymerization, and workability is good, and cost is lower.Can be widely used in automobile, machinery, electronic product, wrapping material, nylon brush thread, abrasive filaments are with every field such as base materials.