CN106680275A - Method for analyzing polyurethane in polyvinyl chloride system - Google Patents
Method for analyzing polyurethane in polyvinyl chloride system Download PDFInfo
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- CN106680275A CN106680275A CN201611214449.3A CN201611214449A CN106680275A CN 106680275 A CN106680275 A CN 106680275A CN 201611214449 A CN201611214449 A CN 201611214449A CN 106680275 A CN106680275 A CN 106680275A
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- polyurethane
- polyvinyl chloride
- degradation agent
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/84—Systems specially adapted for particular applications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
Abstract
The invention provides a method for analyzing polyurethane in a polyvinyl chloride system. The method comprises: dissolving a polyurethane-containing polyvinyl chloride resin sample in an organic solvent, adding a degradation agent and a degradation-assisting agent to make polyurethane into monomers, obtaining a decomposer layering containing polyols and oligomers, concentrating the solution at the lower layer till the solution is dried, adding ethanol, performing stirring, separating a soluble component from an insoluble component, adding toluene diisocynate and 1,4-butylenediol which is taken as a chain extender into the soluble component for polymerization to obtain polyurethane, performing infrared detection to the insoluble component and polyurethane, and performing GC-MS detection to the degradation liquid.
Description
Technical field
The invention belongs in a kind of polyvinyl chloride system polyurethane analysis method, more particularly it relates to polychlorostyrene
Polyvinyl chloride is separated and analysis with polyurethane in vinyl.
Background technology
Polyvinyl chloride (PVC) is that a kind of function admirable, cheap resins for universal use, but its fragility are big, heat endurance is poor,
Processing characteristics is good etc., needs to be modified.Changed by carrying out blending toughening to PVC with TPUE (TPU)
Property, high performance PVC composites are obtained.
TPU can significantly improve the thermal stability of PVC, improve the heat decomposition temperature of PVC, improve PVC and plasticating
Mixing time and stabilization time on machine, improves the processing fluidity of PVC.Shown by the microscopic appearance feature of composite
TPU is added, makes PVC matrix produce brittle-tough transition, improve the toughness of material.
For sample of the PVC/TPU simple physicals blending (without shearing force), can be determined by dissolving sex differernce and making a distinction
Property, and be to divide by deliquescent difference for PVC/TPU is through the sample of mechanical blending (such as extruder, mill)
From, because TPU is tangled during toughness reinforcing with PVC, cause the dissolving sex differernce of PVC and TPU little.
In addition, being decomposed TPU by the method for chemistry, then separate with PVC, but TPU decomposition needs (200 DEG C of height, high temperature
~320 DEG C) and high pressure under conditions of complete, and thermal stability of polyvinyl chloride is poor, starts to decompose when 170 DEG C.
For the problems referred to above, TPU in PVC systems is separated with PVC under conditions of now offer one kind is relatively mild, and carried out
Analysis.
The content of the invention
In order to solve the above problems, the analysis method of polyurethane in a kind of polyvinyl chloride system of offer of the present invention, including
Following steps：
(1) dissolve：Polyvinyl chloride resin samples containing polyurethane are dissolved in into organic solvent；
(2) decompose：Degradation agent is added in step (1) and degradation agent is helped, urethane monomer is made, is obtained containing polyalcohol
With the analyte of oligomer；
(3) separate：Solution in step (2) is layered, lower floor's solution concentration is dry, adds ethanol stirring, separating can in solution
Molten component and indissolvable component；
(4) it is polymerized：By step (3), at the middle and upper levels solution concentration is dry, and addition DMAC, toluene di-isocyanate(TDI) and chain extender Isosorbide-5-Nitrae-
Butanediol polymerisation obtains polyurethane；
(5) detect：Infrared detection will be carried out in indissolvable component in step (3) and step (4) after polyurethane drying；Step
(3) soluble constituent carries out GC-MS detections in.
In one embodiment, in the step (1) organic solvent be it is a kind of in 1-METHYLPYRROLIDONE, cyclohexanone or
It is various.
In one embodiment, the degradation agent be ethylene glycol, diglycol, propane diols, 1,3-PD, 1,
2- propane diols, dipropylene glycol, BDO, 1,5-PD, 1,6- hexylene glycols, polyoxyethylene glycol, polyoxypropylene glycol,
One or more in polyethylene glycol, phosphoric acid dialkyl.
In one embodiment, it is described to help degradation agent in diethanol amine, triethanolamine, alkaline earth metal stearate one
Plant or various.
In one embodiment, it is described to help degradation agent alkaline earth metal stearate for calcium stearate and/or magnesium stearate.
In one embodiment, reaction temperature is 100~170 DEG C when decomposing in the step (1).
In one embodiment, the sample of the Corvic containing polyurethane is with the weight ratio of degradation agent
1：(0.04~0.4).
In one embodiment, the degradation agent and the weight ratio for helping degradation agent are 1：(0.1~0.3).
In one embodiment, the degradation agent and the weight ratio for helping degradation agent are 1：(0.1~0.2).
In one embodiment, the testing conditions of the GC-MS are：Heating schedule：70 DEG C, keep 1min, with 20 DEG C/
Min rises to 280 DEG C, keeps 8.5min；CD-5MS chromatographic columns：30m×0.25mm×0.25μm；Carrier gas is that (purity is helium
99.999%), flow velocity 1.0mL/min；Splitless injecting samples, 250 DEG C of injector temperature, the μ L of sample size 1；Electron impact ion source
(EI sources), electron bombardment energy 70eV；280 DEG C of transmission line temperature；250 DEG C of ion source temperature；Solvent delay time 3.5min；Entirely
Scanner uni choice ion pattern (SCAN/SIM), 40~400amu of sweep limits.
The above-mentioned of the application and other features, aspect and advantage is more readily understood with reference to described further below.
Description of the drawings
Polyvinyl chloride infared spectrum in Fig. 1 embodiments 2
Polyurethane infared spectrum in Fig. 2 embodiments 2
Specific embodiment
The participation in the election detailed description for being preferable to carry out method of the invention below and including embodiment this can be more easily understood
Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with art of the present invention
The identical implication that technical staff is generally understood that.When there is contradiction, the definition in this specification is defined.
As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " including ",
" having ", " containing " or its any other deformation, it is intended that cover including for non-exclusionism.For example, the combination comprising listed elements
Thing, step, method, product or device are not necessarily solely those key elements, and can be including not expressly listed other key elements or
The intrinsic key element of this kind of composition, step, method, product or device.
Conjunction " Consists of " excludes any key element do not pointed out, step or component.If in being used for claim, this
Phrase will make claim for closed so as to not comprising the material in addition to the material that those are described, but it is relative often
Except rule impurity.When phrase " Consists of " is occurred in be rather than immediately following after theme in the clause of claim main body,
It is only limited to the key element described in the clause；Other key elements are not excluded outside as the overall claim.
Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit
During the Range Representation that choosing value is limited, this is appreciated that and specifically discloses by any range limit or preferred value and any scope
All scopes that arbitrary pairing of lower limit or preferred value is formed, regardless of whether whether the scope separately discloses.For example, when open
During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When number range is described herein, unless otherwise indicated, otherwise the scope is intended to include its end
Value and all integers within the range and fraction.
Singulative includes that plural number discusses object, unless the context clearly dictates otherwise." optional " or " arbitrarily
It is a kind of " refer to that the item for describing thereafter or event may or may not occur, and the description include situation that event occurs and
The situation that event does not occur.
Approximate term in specification and claims is used for modifying quantity, represents that the present invention is not limited to this concrete
Quantity, also includes the acceptable part without causing the amendment of the change of related basic function being close to the quantity.Phase
Answer, with " about ", a numerical value of the modification such as " about ", mean and the invention is not restricted to the exact numerical.In some examples, approximately
Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, scope is limited can be with
Combine and/or exchange, if not stated otherwise these scopes include all subranges contained therebetween.
Additionally, key element of the present invention or indefinite article " one kind " and " one " before component are to key element or the quantitative requirement of component
(i.e. occurrence number) unrestriction.Therefore " one " or " one kind " should be read as including one or at least one, and odd number
The key element or component of form also includes plural form, unless the obvious purport of the quantity refers to singulative.
" polymer " means the polymerizable compound prepared by the monomer by the identical or different type that is polymerized.Generic term
" polymer " includes term " homopolymers ", " copolymer ", " terpolymer " and " EVA ".
" EVA " means the polymer prepared by least two different monomers that are polymerized.Generic term " EVA " includes
(its is general with term " terpolymer " for term " copolymer " (it is typically to refer to the polymer prepared by two kinds of different monomers)
To refer to the polymer prepared by three kinds of different monomers).It is also comprising the polymer manufactured by the more kinds of monomers of polymerization.
" blend " means the polymer that two or more polymer is mixed and formed jointly by physics or chemistry method.
The analysis method of polyurethane, comprises the following steps in a kind of polyvinyl chloride system of offer of the present invention：
(1) dissolve：Polyvinyl chloride resin samples containing polyurethane are dissolved in into organic solvent；
(2) decompose：Degradation agent is added in step (1) and degradation agent is helped, urethane monomer is made, is obtained containing polyalcohol
With the analyte of oligomer；
(3) separate：Solution in step (2) is layered, lower floor's solution concentration is dry, adds ethanol stirring, separating can in solution
Molten component and indissolvable component；
(4) it is polymerized：By step (3), at the middle and upper levels solution concentration is dry, and addition DMAC, toluene di-isocyanate(TDI) and chain extender Isosorbide-5-Nitrae-
Butanediol polymerisation obtains polyurethane；
(5) detect：Infrared detection will be carried out in indissolvable component in step (3) and step (4) after polyurethane drying；Step
(1) decomposed solution carries out GC-MS detections in.
Polyvinyl chloride is a kind of macromolecular material for using a chlorine atom to replace a hydrogen atom in polyethylene, is to contain
There is the amorphous polymer of a small amount of crystalline texture.PVC is the line polymer that VCM monomers majority is connected with head-tail structure.Carbon is former
Son is zigzag arrangement, and all atoms are connected with σ keys.All carbon atoms are sp3Hydridization.Exist on PVC strands short
Syndiotactic ordered structure.With the reduction of polymeric reaction temperature, syndiotactic regularity is improved.Polyvinyl chloride macromolecular is tied
The unstability structures such as head-to-head structure, side chain, double bond, allyl chloride, tertiary chlorine are there is in structure, heat-resistant deforming and ageing-resistant is caused
The shortcomings of difference.
Polyvinyl chloride is industrial most thermal sensitivity, is also easy to produce one of high polymer of thermal degradation.In order to improve polyvinyl chloride
Hot-working stability and thermal stability, generally require to be added in its product heat stabilizer suppressing its thermal degradation.According to
The Thermal degradation mechanism of above-mentioned PVC, its corresponding thermostable mechanism mainly includes following several types.
(1) chlorine atom (allyl chloride or tertiary chlorine) unstable in polyvinyl chloride macromolecular is replaced or replaces, generation is compared
Stable structure, to suppress dehydrochlorination.
(2) HCl discharged in polyvinyl chloride process is absorbed and is consumed, its autocatalytic effect is reduced or eliminate, is delayed
The thermal degradation of PVC.The basic salt of inorganic acid and the slaine of weak organic acid can absorb the HCl of thermal degradation release, such as stearic
Sour calcium, lead stearate etc..
(3) there is addition reaction with the unsaturated bond (such as C=C, C=O) in polyvinyl chloride long-chain, reduce its conjugation effect
Should.
(4) being passivated or neutralize can be catalyzed the metal ion and other impurities ion for accelerating polyvinyl chloride thermal degradation.
Polyvinyl chloride do not had when auxiliary stabilizer is their independent roles or has a weaker thermostable effect, but energy
Enough class materials for effectively improving other heat stabilizing systems.Common auxiliary stabilizer mainly has beta-diketone compounds, many
First alcohols, organic phosphorous acid lipid and epoxies (such as linseed oil, epoxidized soybean oil, epoxyoleic acid) etc..
Polyalcohol does not have obvious thermostable effect when being used alone, but in calcium/zinc stabilizer system, but plays
Good auxiliary stablizing effect.When polyol hydroxyls number increases, its stablizing effect can be improved.Because the hydroxyl of polyalcohol
Ligand can be formed with metal ion, so as to reduce muriatic catalytic action, improve the stability of PVC.
TPUE is by polyisocyanates and polyester or polyether Glycols and low molecule with hydroxyl
Glycol chain extender, by wire made by progressively polyaddition reaction or slightly branched or crosslinking macromolecular material.TPU point
Not only containing flexible soft chain segment but also containing rigid hard segment in son, soft chain segment determines some final performances of TPU, such as elastic, low
Temperature is flexibility, to a certain extent the also expansion character of polymer and water-disintegrable.Equally, hard segment be then shown hardness,
Elastic modelling quantity, release property and high-temperature behavior (heat endurance).Hard segment obtains strong physical crosslinking structure by intermolecular hydrogen bonding,
Micro phase separation structure is formed, even if so also showing caoutchouc elasticity without chemical crosslinking structure.Its elastic modelling quantity is between plastics
And rubber between, remain to keep preferable elasticity, TPU also to have plastic processing performance concurrently in wider hardness range, and
With good resistance to low temperature and oil resistant, solvent resistant, ozone resistance.
Study on Microstructure finds that the addition of PVC destroys the hydrogen bond of TPU, and the α-H-shaped in TPU in carbonyl and PVC
Into new hydrogen bond, and, in polyvinyl chloride strand substantial amounts of polarity chlorine atom can also with amino in TPU molecular structures in
Hydrogen atom forms hydrogen bond, makes have very strong adhesion between TPU and PVC, and this demonstrating blend has preferable compatibility, can
To carry out blending and modifying.Soft section and polyvinyl chloride segment of the compatibility of blend essentially from polyurethane.Hard segment content increases
The compatibility of blend is had adverse effect on, the ratio of the hard section/soft section of thermoplastic polyurethane is lower, thermoplastic polyurethane
It is better with polychloroethylene blended compatibility.This is that the hard section ordered arrangement of TPU is improved therewith because TPU hard segment contents increase, and
Crystalline texture is formed, the increase of soft section relative molecular mass is conducive to the compatible of blend.Carbonyl leads to C-Cl in PVC in TPU
Dipole-dipole interaction is crossed, the compatibility of the two is improve, so as to improve the compatibility of blend.
In addition PVC and TPU is thermoplastic polar polymer, and the solubility parameters of PVC is 19.2~22.1 (J/cm3)1/2,
The solubility parameter of TPU is 19.0~21.8 (J/cm3)1/2, from the point of view of solubility parameter, polyvinyl chloride and thermoplastic polyurethane
Blend should have preferable compatibility, by both blendings, can obtain the material of performance complement.
In one embodiment, in the step (1) organic solvent be it is a kind of in 1-METHYLPYRROLIDONE, cyclohexanone or
It is various；Preferably, organic solvent is cyclohexanone in the step (1).
Alcoholysis method is a kind of most important method in current chemical method degraded waste polyurethane material, and polyurethane is in alcoholysis agent
With polyethers or polyester dihydric alcohol are degraded under the collective effect of catalyst, with the low molecular polymer segments of hydroxyl and binary
The mixture of amine etc.；After being fully completed Deng alcoholysis, this mixture is through cooling, and brand-new polyalcohol ratio mixing, directly
Just polymerisation can occur with isocyanates and recombines polyurethane.The method is with low molecular polylol class compound to decompose
Agent, in the case of normal heating, generally there is ester exchange reaction in the carbamate groups or urea groups in polyurethane with alcoholysis agent,
The catabolite of generation usually carries the mixed of low polymer fragment, polyethers or polyester dihydric alcohol, the diamine of hydroxyl etc.
Compound.
The distinguishing feature of alcoholysis method is：Reaction can be carried out in normal pressure, the reaction kit of middle temperature, be applicable to various poly- ammonia
The degraded of ester material, can adopt the methods such as vacuum distillation to separate excessive alcoholysis agent after the completion of reaction.It is many also dependent on regenerating
It is to carry out separation and recovery polyalcohol that the application target of first alcohol and the degraded mode of polyurethane are selected to catabolite, or directly again
It is secondary to use.
After alcoholysis reaction terminates, after catabolite is stood into a period of time, final product will be divided into two-layer；Lower floor
Product belongs to impurity, mainly includes containing urea groups, compound of unbroken carbamate groups etc.；And upper strata product is mainly wrapped
Include the higher regenerating polyol of excessive alcoholysis agent (such as small molecule dihydroxylic alcohols) and degraded target product i.e. relative molecular mass.
Polyurethane elastomer alcoholysis process：
Polyurethane elastomer pulverizes or is cut into little particle, loads in certain proportion equipped with mechanical agitation and ball with alcoholysis agent
In the 500mL there-necked flasks of shape condenser pipe, addition is a certain amount of to help alcoholysis agent, vacuum/inflated with nitrogen to replace three times, flask is placed in
In the oil bath of uniform temperature, a few hours are reacted, with the carrying out of reaction, polyurethane elastomer will be gradually dissolved in alcoholysis agent solution
In, the color of solution is gradually deepened with the prolongation of time, ultimately produces the transparency liquid of brown, after reaction terminates, filtration washing,
Obtain the supernatant liquid clarified.
In one embodiment, the PEPA for obtaining after the degradation of polyurethane or the average mark of PPG
Son amount is 500~3500.
Gel osmoticing chromatogram analysis
The supernatant liquid 0.5ml obtained after polyurethane elastomer alcoholysis, plus DMF to 5ml are taken, is mixed, filtered；Gel infiltration
A drop acetone, plus the DMF solution 2ml for mixing first are added dropwise in chromatograph test bottle, are mixed to be measured.Gel permeation chromatograph master
Test the mean molecule quantity of alcoholysis product.
In one embodiment, the degradation agent be ethylene glycol, diglycol, propane diols, 1,3-PD, 1,
2- propane diols, dipropylene glycol, BDO, 1,5-PD, 1,6- hexylene glycols, polyoxyethylene glycol, polyoxypropylene glycol,
One or more in polyethylene glycol, phosphoric acid dialkyl；Preferably, the degradation agent be ethylene glycol, diglycol, the third two
Alcohol, 1,3-PD, 1,2-PD, dipropylene glycol, BDO, 1,5-PD, 1,6- hexylene glycols, di(2-ethylhexyl)phosphate
One or more in hydrocarbon ester；Preferably, the degradation agent is one or more in ethylene glycol, diglycol.
In one embodiment, it is described to help degradation agent in diethanol amine, triethanolamine, alkaline earth metal stearate one
Plant or various.
In one embodiment, it is described help degradation agent alkaline earth metal stearate for calcium stearate, zinc stearate and/or
Magnesium stearate；Preferably, it is described to help degradation agent alkaline earth metal stearate to be calcium stearate.
Polyalcohol does not have obvious thermostable effect when being used alone, but in calcium/zinc stabilizer system, but plays
Good auxiliary stablizing effect.When polyol hydroxyls number increases, its stablizing effect can be improved.Because the hydroxyl of polyalcohol
Ligand can be formed with metal ion, improve the stability of PVC.
In one embodiment, reaction temperature is 100~170 DEG C when polyurethane elastomer decomposes in the step (1)；
Preferably, reaction temperature is 120~160 DEG C when decomposing in the step (1).
Alcoholysis reaction is one needs the process of a large amount of heat absorptions, forefathers' research to think that the general temperature of reaction is in 150-250
Between DEG C scope.In course of reaction, with the rising of temperature, alcoholysis agent molecular motion velocities are accelerated therewith, so as to increase PU with
The probability of alcoholysis agent molecule contacts, reaction is conducive to tending to positive reaction being reversed.It is generally acknowledged that starting when 150 DEG C to occur slow
Alcoholysis, but actual temp should again be modified according to alcoholysis agent feature, if reaction temperature is too high, not only can increase
The volatilization loss of alcoholysis agent, especially when temperature is higher than 200 DEG C, the pair such as the dihydroxylic alcohols in degraded system is easily etherified, aoxidizes
Reaction, reduces the chance of main reaction, and alcoholysis product regenerating polyol is also susceptible to decarboxylic reaction, and reaction will be made to lose it
Reaction center, in addition, the color of reaction system also can deepen therewith, so 200 DEG C of reactions for being generally polyurethane alcoholysis
Temperature upper limit.
With the rising of reaction temperature, the viscosity of alcoholysis product is gradually lowered, and hydroxyl value gradually rises, when reaction temperature reaches
160 DEG C and during the above, viscosity and hydroxyl value are varied less, it is seen that polyurethane elastomer mainly exists in the condition that alcoholysis agent is present
Polyalcohol is decomposed at 160 DEG C, therefore from 160 DEG C of glycolysis temperatures as polyurethane elastomer.
In one embodiment, it is 1~10h that polyurethane elastomer decomposes the reaction time in the step (1)；It is preferred that
Ground, it is 3~8h that polyurethane elastomer decomposes the reaction time in the step (1).
The determination of reaction end
The terminal of alcoholysis reaction is grasped, the time that just energy effective control fully reflects, this will be more to principal product regeneration of degrading
The performance of first alcohol produces large effect.If the alcoholysis reaction time is too short, what the alcoholysis reaction of polyurethane was carried out must not be complete
Entirely, unreacted PU is caused to remain or exist the of a relatively high oligomer of molecular weight in the product, what these were remained does not drop
The PU of solution increases the later stage and the difficulty of polyalcohol is purified from catabolite, and the oligomer for having larger relative molecular weight can also
The viscositys for affecting to regenerate first alcohol so as to which viscosity is significantly increased, cause regenerating polyol quality decline, range of application to reduce more；And
If alcoholysis reaction overlong time, the energy and time can be wasted first, at the same time, with the growth in reaction time, alcoholysis agent
Volatile quantity increase, prolonged heating can also increase alcoholysis agent and the possibility of the side reactions such as oxidation, etherificate occurs, and react
The color of system also can deepen, if preparing polyurethane foam, the face of manufactured goods again using the deeper recovery polyalcohol of color
Color also can be accordingly deeper.
The present invention determines alcoholysis reaction by measuring the degree that dissolves in organic solution of different time points alcoholysis product
Terminal, this method is not only practical, simple, time-consuming.The concrete operations of the method are：In the later stage of alcoholysis reaction
(after 120min) takes a certain amount of sample every half an hour or (15min changes time interval more accurate), first that sample is cold
But to after room temperature, then the sample of taking-up is put in methyl alcohol and is dissolved, the material (unreacted PU) for failing to dissolve is filtered
It is dried afterwards and weighs, even if calculates degradation rate；When certain time point sample methanol solution presentation clear shape, and wherein
Suspended material is not contained, at this moment, it is believed that own Jing reaches the terminal of alcoholysis reaction.
When alcoholysis reaction is to 5h, substantially completely, the viscosity and hydroxyl value of alcoholysis product are varied less for alcoholysis, and by gel
The molecular weight of the product that permeation chromatography draws basically reaches minimum when reaction proceeds to 5h.Examined in terms of production efficiency
Consider, it should choose the reaction time for 5h.
In one embodiment, the sample of the Corvic containing polyurethane is with the weight ratio of degradation agent
1：(0.04~0.4)；Preferably, the sample of the Corvic containing polyurethane and the weight ratio of degradation agent are 1:
(0.5~0.9).
In one embodiment, the degradation agent and the weight ratio for helping degradation agent are 1：(0.1~0.3).
In one embodiment, the degradation agent and the weight ratio for helping degradation agent are 1：(0.1~0.2).
In one embodiment, the hydroxyl value of the alcoholysis product is 15~40mgKOH/g.
In one embodiment, the viscosity of the alcoholysis product is 500~2500mPaS (25 DEG C)；Preferably, institute
The viscosity for stating alcoholysis product is 500~2300mPaS (25 DEG C).
Viscosity Analysis
The viscosity of the alcoholysis product that the clarified solution after a drop alcoholysis is tested at 25 DEG C on viscosimeter is taken, by carrying out viscosity
Contrast investigate the degree that carries out of alcoholysis, the bigger explanation molecular weight of viscosity is bigger, and alcoholysis is got over not thorough.Hydroxyl number analysis
The present invention determines the hydroxyl value of alcoholysis product using acetic anhydride-pyridine method, comprises the following steps that:
1) preparation of acetic anhydride-pyridine solution
Take 10.00ml acetic anhydride to mix with 30ml pyridines, in being stored in conical flask；
2) preparation of 1.000mol/L NaOH solutions and demarcation
Weigh 40g oxygen sodium oxide molybdenas to be dissolved in steaming feedback water, constant volume is in the volumetric flask of 1000ml.Accurately weighed with assay balance
Potassium Hydrogen Phthalate about 4g uses distilled water heating for dissolving in triangular flask, plus four and drips phenolphthalein, with the NaOH solution titration prepared
It is terminal to pink, parallel determination twice, is averaged；
3) measure of hydroxyl value
Alcoholysis product stirs, and accurately weighs sample 1-2g in 10ml conical flasks, plus 5.00ml acetic anhydride-pyridine is molten
Liquid, boiling water bath 30min is cooled to after room temperature addition 20ml distilled water, under acutely vibration, is given instruction agent with phenolphthalein, uses oxygen oxygen
Change sodium standard solution and be titrated to just appearance pink, and keep the colour-fast as terminals of Imin, write down NaOH solution consumption, put down
Row does twice, averages, while doing blank test；
Hydroxyl value (OHv)=(56.1X (V0-V2)C)/m
In formula, OHv is defined as acid-base neutralization reaction, and every gram of product is fully neutralized the milligram for needing to consume potassium hydroxide
Number, unit:mgKOH/g；
V0The volume (mL) of the blank NaOH solution used of one titration；
V2The volume (mL) of NaOH solution used by-titration sample；
The concentration (mol/L) of the NaOH solutions of C mono-；
M-sample mass (g).
In one embodiment, the testing conditions of the GC-MS are：Heating schedule：70 DEG C, keep 1min, with 20 DEG C/
Min rises to 280 DEG C, keeps 8.5min；CD-5MS chromatographic columns：30m×0.25mm×0.25μm；Carrier gas is that (purity is helium
99.999%), flow velocity 1.0mL/min；Splitless injecting samples, 250 DEG C of injector temperature, the μ L of sample size 1；Electron impact ion source
(EI sources), electron bombardment energy 70eV；280 DEG C of transmission line temperature；250 DEG C of ion source temperature；Solvent delay time 3.5min；Entirely
Scanner uni choice ion pattern (SCAN/SIM), 40~400amu of sweep limits.
Present invention Isosorbide-5-Nitrae -- butanediol is degradation agent, and triethanolamine is obtained to help degradation agent success degradable polyurethane elastomer
New polyurethane is generated to the polyalcohol that can be recycled with toluene di-isocyanate(TDI) polymerisation.
The synthesis of polyurethane
(1) synthesis of performed polymer
In the four-hole boiling flask equipped with thermometer, constant pressure funnel, agitator and nitrogen protection device, under nitrogen atmosphere
0.01mol toluene di-isocyanate(TDI)s are dissolved in DMAC input 100ml four-hole boiling flasks；System is warming up to 60 DEG C, and-secondary property is added
0.01mol degradation of polyurethane thing polyalcohols, stirring reaction 2h；
(2) chain extension, cross-linking reaction
During BDO (BDO is 3% with the mass ratio of performed polymer) is added to into above-mentioned performed polymer, heat up
To 75 DEG C of reaction 2.5h；
(3) end capping reaction
After chain extension is finished, add 20ml methyl alcohol to be blocked, obtain final product polyurethane crude product.
The present invention is by degradation agent and helps degradation agent that the polyurethane in polyvinyl chloride is carried out resolving into polyalcohol and contained
The compound of urea groups, unbroken carbamate groups, then by dissolving sex differernce, by polyvinyl chloride and degradation of polyurethane thing
Separated, add toluene di-isocyanate(TDI) and polyalcohol and carry out polymerisation and obtain new polyurethane, so as to by polychlorostyrene second
Polyurethane is separated in alkene.
Reaction temperature is less than polyvinyl chloride decomposition starting temperature when degradation of polyurethane is reacted in the present invention, in addition degradation agent two
First alcohol and help degradation agent calcium stearate that the degraded of polyurethane can not only be promoted to further promote the heat endurance of polyvinyl chloride.
The present invention is specifically described below by embodiment.Be necessary it is pointed out here that, following examples are only used
In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field
According to some nonessential modifications and adaptations that the content of the invention described above is made, protection scope of the present invention is still fallen within.
In addition, if without other explanation, it is raw materials used be all it is commercially available, be purchased from traditional Chinese medicines chemical reagent.
Embodiment 1
Sample is the Corvic containing 10% polyurethane.Weigh 10.0g samples and be dissolved in 200ml organic solvent hexamethylenes
Ketone, adds 0.1g degradation agents ethylene glycol and 0.015g to help degradation agent calcium stearate, vacuum/inflated with nitrogen to replace 3 times, flask is placed in
In the oil bath (160 DEG C) of uniform temperature, react 5 hours, with the carrying out of reaction, the color of solution gradually adds with the prolongation of time
It is deep, the transparency liquid of brown is ultimately produced, after reaction terminates, filtration washing obtains the supernatant liquid (polyalcohol) clarified, lower floor
Solution carries out concentration and does, and adds 200ml ethanol stirring 0.5h, filters, and separates soluble constituent and insoluble component (polychlorostyrene in solution
Ethene), it is then that upper solution concentration is dry, add 50mlDMAC, 0.01mol toluene di-isocyanate(TDI)s to be warming up to 60 DEG C, stirring
Reaction 2h, adds BDO (BDO is 3% with the mass ratio of performed polymer) and is eventually adding, and is warming up to 75 DEG C instead
2.5h is answered, 20ml methyl alcohol is eventually adding and is blocked, obtain polyurethane；Sampling after decomposed solution concentration is done carries out GC-MS detections,
The testing conditions of GC-MS are：Heating schedule：70 DEG C, 1min is kept, with 20 DEG C/min 280 DEG C are risen to, keep 8.5min；CD-
5MS chromatographic columns：30m×0.25mm×0.25μm；Carrier gas be helium (purity is 99.999%), flow velocity 1.0mL/min；Do not shunt
Sample introduction, 250 DEG C of injector temperature, the μ L of sample size 1；Electron impact ion source (EI sources), electron bombardment energy 70eV；Transmission line temperature
280 DEG C of degree；250 DEG C of ion source temperature；Solvent delay time 3.5min；Full scan and choice ion pattern (SCAN/SIM), sweep
Retouch 40~400amu of scope；Lower floor's indissolvable component and the polyurethane of synthesis carry out infrared detection, with reference to detection data, measure sample
The content of middle polytetramethylene ether glycol is 0.65%, and the weight of polyvinyl chloride is 7.19g.
Embodiment 2
Sample is the Corvic containing 10% polyurethane.Weigh 10.0g samples and be dissolved in 200ml organic solvent hexamethylenes
Ketone, adds 0.1g degradation agents diglycol and 0.015g to help degradation agent calcium stearate, vacuum/inflated with nitrogen to replace 3 times, will burn
Bottle is placed in the oil bath of uniform temperature (160 DEG C), is reacted 5 hours, with the carrying out of reaction, the color of solution with the time prolongation
Gradually deepen, ultimately produce the transparency liquid of brown, after reaction terminates, filtration washing, the supernatant liquid for obtaining clarifying is (polynary
Alcohol), it is dry that lower floor's solution carries out concentration, adds 200ml ethanol stirring 0.5h, filters, and separates in solution soluble constituent and insoluble
Component (polyvinyl chloride), it is then that upper solution concentration is dry, add 50mlDMAC, 0.01mol toluene di-isocyanate(TDI)s to be warming up to
60 DEG C, stirring reaction 2h adds BDO (BDO is 3% with the mass ratio of performed polymer) and is eventually adding, and rises
Temperature is eventually adding 20ml methyl alcohol and is blocked to 75 DEG C of reaction 2.5h, obtains polyurethane；By upper solution concentration it is dry after sample into
Row GC-MS detects that the testing conditions of GC-MS are：Heating schedule：70 DEG C, 1min is kept, with 20 DEG C/min 280 DEG C are risen to, kept
8.5min；CD-5MS chromatographic columns：30m×0.25mm×0.25μm；Carrier gas be helium (purity is 99.999%), flow velocity
1.0mL/min；Splitless injecting samples, 250 DEG C of injector temperature, the μ L of sample size 1；Electron impact ion source (EI sources), electron bombardment
Energy 70eV；280 DEG C of transmission line temperature；250 DEG C of ion source temperature；Solvent delay time 3.5min；Full scan and selection ion
Pattern (SCAN/SIM), 40~400amu of sweep limits；Lower floor's indissolvable component and the polyurethane of synthesis carry out infrared detection, with reference to
Detection data, the content for measuring polytetramethylene ether glycol in sample is 0.7%, and the weight of polyvinyl chloride is 7.25g.
Embodiment 3
Same as Example 2, difference is to help degradation agent to be magnesium stearate, measures polytetramethylene ether two in sample
The content of alcohol is 0.6%, and the weight of polyvinyl chloride is 7.08g.
Embodiment 4
Same as Example 2, it is 0.04g that difference is the consumption of degradation agent, and the consumption for helping degradation agent is 0.008g, is surveyed
The content for going out polytetramethylene ether glycol in sample is 0.2%, the weight of polyvinyl chloride be 8.6g (containing polyurethane, poly- ammonia
Ester is degradable).
Embodiment 5
Same as Example 2, it is 0.4g that difference is the consumption of degradation agent, and the consumption for helping degradation agent is 0.04g, is measured
The content of polytetramethylene ether glycol is 0.66% in sample, and the weight of polyvinyl chloride is 7.17g.
Embodiment 6
Same as Example 2, it is 0.4g that difference is the consumption of degradation agent, and the consumption for helping degradation agent is 0.4g, is measured
The content of polytetramethylene ether glycol is 0.69% in sample, and the weight of polyvinyl chloride is 7.26g.
Embodiment 7
Same as Example 2, difference is the degradation reaction time to be 1h, measures polytetramethylene ether glycol in sample
Content be 0.1%, the weight of polyvinyl chloride is 7.1g.
Embodiment 8
Same as Example 2, difference is the degradation reaction time to be 10h, measures polytetramethylene ether two in sample
The content of alcohol is 0.62%, and the weight of polyvinyl chloride is 7.3g.
Embodiment 9
Sample is the Corvic containing 15% polyurethane.Weigh 10.0g samples and be dissolved in 200ml organic solvent hexamethylenes
Ketone, adds 0.1g degradation agents diglycol and 0.015g to help degradation agent calcium stearate, vacuum/inflated with nitrogen to replace 3 times, will burn
Bottle is placed in the oil bath of uniform temperature (160 DEG C), is reacted 5 hours, with the carrying out of reaction, the color of solution with the time prolongation
Gradually deepen, ultimately produce the transparency liquid of brown, after reaction terminates, filtration washing, the supernatant liquid for obtaining clarifying is (polynary
Alcohol), it is dry that lower floor's solution carries out concentration, adds 200ml ethanol stirring 0.5h, filters, and separates in solution soluble constituent and insoluble
Component (polyvinyl chloride), it is then that upper solution concentration is dry, add 50mlDMAC, 0.01mol toluene di-isocyanate(TDI)s to be warming up to
60 DEG C, stirring reaction 2h adds BDO (BDO is 3% with the mass ratio of performed polymer) and is eventually adding, and rises
Temperature is eventually adding 20ml methyl alcohol and is blocked to 75 DEG C of reaction 2.5h, obtains polyurethane；Sampling after decomposed solution concentration is done is carried out
GC-MS detects that the testing conditions of GC-MS are：Heating schedule：70 DEG C, 1min is kept, with 20 DEG C/min 280 DEG C are risen to, kept
8.5min；CD-5MS chromatographic columns：30m×0.25mm×0.25μm；Carrier gas be helium (purity is 99.999%), flow velocity
1.0mL/min；Splitless injecting samples, 250 DEG C of injector temperature, the μ L of sample size 1；Electron impact ion source (EI sources), electron bombardment
Energy 70eV；280 DEG C of transmission line temperature；250 DEG C of ion source temperature；Solvent delay time 3.5min；Full scan and selection ion
Pattern (SCAN/SIM), 40~400amu of sweep limits；Lower floor's indissolvable component and the polyurethane of synthesis carry out infrared detection, with reference to
Detection data, the content for measuring polytetramethylene ether glycol in sample is 1.06%, and the weight of polyvinyl chloride is 7.0g.
Embodiment 10
With embodiment 9, difference is the degradation reaction time to be 10h, measures polytetramethylene ether glycol in sample
Content is 0.99%, and the weight of polyvinyl chloride is 6.8g.
Embodiment 11
With embodiment 2, it is 170 DEG C that difference is degradation reaction temperature, measures polytetramethylene ether glycol in sample
Content be 0.68%, the weight of polyvinyl chloride is 4.0g.
Embodiment 12
With embodiment 9, it is 170 DEG C that difference is degradation reaction temperature, measures polytetramethylene ether glycol in sample
Content be 1.08%, the weight of polyvinyl chloride is 3.1g.
Comparative example 1
With embodiment 2, it is 100 DEG C that difference is degradation reaction temperature, measures polytetramethylene ether glycol in sample
Content be 0.13%, the weight of polyvinyl chloride is 9.2g (degradation of polyurethane fewer).
Comparative example 2
With embodiment 2, it is 200 DEG C that difference is degradation reaction temperature, measures polytetramethylene ether glycol in sample
Content be 0.69%, the weight of polyvinyl chloride is 2.2g.
Comparative example 3
With embodiment 2, difference is degradation agent for triethanolamine, measures containing for polytetramethylene ether glycol in sample
Measure as 0.58%, the weight of polyvinyl chloride is 5.2g.
Comparative example 4
With embodiment 2, difference is not contain to help degradation agent calcium stearate, measures polytetramethylene ether glycol in sample
Content be 0.36%, the weight of polyvinyl chloride is 6.2g (polyvinyl chloride has decomposed, and polyurethane is degradable).
In sum, the present invention is degraded TPU by the method for chemistry, then is separated with PVC, ensure that polyvinyl chloride not
Degradation of polyurethane is polymerized again on the premise of decomposition, so that polyurethane and the polyvinyl chloride point analysis of variance.
Above-mentioned example is merely illustrative, for explaining some features of the feature of the present invention.Appended claim
The scope as wide as possible for requiring to be contemplated that is intended to, and embodiments as presented herein is only according to all possible embodiment
Combination selection embodiment explanation.Therefore, the purpose of applicant is appended claim not by the explanation present invention
Feature example selectional restriction, and the progress in science and technology will be formed due to language performance inaccurate reason and not
The possible equivalent or son being presently considered is replaced, and these changes also should be interpreted in the conceived case by appended
Claim is covered.
Claims (10)
1. in a kind of polyvinyl chloride system polyurethane analysis method, it is characterised in that comprise the following steps：
(1) dissolve：Polyvinyl chloride resin samples containing polyurethane are dissolved in into organic solvent；
(2) decompose：To degradation agent is added in step (1) and degradation agent is helped, urethane monomer is made, obtained containing polyalcohol and low
The analyte of polymers；
(3) separate：Solution in step (2) is layered, lower floor's solution concentration is dry, adds ethanol stirring, separated solvable group in solution
Divide and indissolvable component；
(4) it is polymerized：By step (3), at the middle and upper levels solution concentration is dry, adds DMAC, toluene di-isocyanate(TDI) and chain extender Isosorbide-5-Nitrae-fourth two
Alcohol polymerisation obtains polyurethane；
(5) detect：Infrared detection will be carried out in indissolvable component in step (3) and step (4) after polyurethane drying；In step (1)
Decomposed solution carries out GC-MS detections.
2. according to claim 1 in polyvinyl chloride system polyurethane analysis method, it is characterised in that the step (1)
Middle organic solvent is one or more in 1-METHYLPYRROLIDONE, cyclohexanone.
3. according to claim 1 in polyvinyl chloride system polyurethane analysis method, it is characterised in that the degradation agent is
Ethylene glycol, diglycol, propane diols, 1,3-PD, 1,2-PD, dipropylene glycol, BDO, 1,5-
One or more in pentanediol, 1,6- hexylene glycols, polyoxyethylene glycol, polyoxypropylene glycol, polyethylene glycol, phosphoric acid dialkyl.
4. according to claim 1 in polyvinyl chloride system polyurethane analysis method, it is characterised in that it is described to help degradation agent
For one or more in diethanol amine, triethanolamine, alkaline earth metal stearate.
5. according to claim 4 in polyvinyl chloride system polyurethane analysis method, it is characterised in that it is described to help degradation agent
Alkaline earth metal stearate is calcium stearate and/or magnesium stearate.
6. according to claim 1 in polyvinyl chloride system polyurethane analysis method, it is characterised in that the step (1)
Reaction temperature is 100~170 DEG C during middle decomposition.
7. according to claim 1 in polyvinyl chloride system polyurethane analysis method, it is characterised in that it is described containing poly- ammonia
The sample of the Corvic of ester is 1 with the weight ratio of degradation agent：(0.04~0.4).
8. according to claim 1 in polyvinyl chloride system polyurethane analysis method, it is characterised in that the degradation agent with
The weight ratio for helping degradation agent is 1：(0.1~0.3).
9. according to claim 1 in polyvinyl chloride system polyurethane analysis method, it is characterised in that the degradation agent with
The weight ratio for helping degradation agent is 1：(0.1~0.2).
10. according to claim 1 in polyvinyl chloride system polyurethane analysis method, it is characterised in that the GC-MS's
Testing conditions are：Heating schedule：70 DEG C, 1min is kept, with 20 DEG C/min 280 DEG C are risen to, keep 8.5min；CD-5MS chromatograms
Post：30m×0.25mm×0.25μm；Carrier gas be helium (purity is 99.999%), flow velocity 1.0mL/min；Splitless injecting samples, enter
250 DEG C of sample mouth temperature, the μ L of sample size 1；Electron impact ion source (EI sources), electron bombardment energy 70eV；Transmission line temperature 280
℃；250 DEG C of ion source temperature；Solvent delay time 3.5min；Full scan and choice ion pattern (SCAN/SIM), sweep limits
40~400amu.
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