CN102321231A - Method for preparing hexamethylene diisocyanate biuret curing agent - Google Patents
Method for preparing hexamethylene diisocyanate biuret curing agent Download PDFInfo
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Abstract
The invention relates to a method for preparing a hexamethylene diisocyanate biuret curing agent. The method comprises the following step of: adding different crystallized hydrates or a mixture of acetone and water to make water react with hexamethylene diisocyanate, removing white polyurea particles generated in the reaction process by performing vacuum filtration, filtering a mixed liquor with filtering cloth of 200 meshes, and collecting clear filtrate serving as a crude product; and separating free HDI (Hexamethylene Diisocyanate) monomers left in the product by adopting a molecular distiller or a cyclohexane continuous extraction method, and performing infrared spectrum detection and gel permeation chromatography detection to judge whether biuret is generated and the size of the biuret relative to the content of other components and obtaining the hexamethylene diisocyanate biuret curing agent. The hexamethylene diisocyanate biuret curing agent is often prepared into paint together with hydroxy acrylic resin, polyester resin and the like, and a paint film does not turn yellow. The curing agent has the advantages of superior light fastness, superior weather resistance, superior chemical resistance and gorgeous luster.
Description
Technical field
The present invention relates to a kind of polyurethane coating of not flavescence, the reaction method of adhesive solidification agent, the preparation method of solidifying agent in particularly a kind of aliphatics polyurethane paint is specifically related to a kind of preparation method of hexamethylene diisocyanate biuret solidifying agent.
Background technology
Have [CO-NH-R-NH-CO-O-R`-O-]
nThe macromolecular compound of structure is called polyurethane(s), abbreviates urethane (polyurethane is called for short PU) as.It is by POLYMETHYLENE POLYPHENYLISOCYANATE and the compound that contains reactive hydrogen through " progressively condensation " reaction forms carbamate (NH-CO-O-) repeating segment and must.See that from net result in this reaction, the active hydrogen atom in molecule is transferred in another molecule and gone:
Since in the structure of urethane except containing ammonia ester bond; Still can contain phenol key, ehter bond, urea key, allophanic acid ester bond, isocyanurate-bond or greasy unsaturated double-bond etc.; Therefore the performance of urethane resin had both had characteristic such as HS, wear resistance, oil-proofness and the water tolerance of similar phthalein amido; To uncompatibility of softening agent etc., have thermotolerance and the solvent resistance of polyester, the hydrolytic resistance and the snappiness of polyethers again.Because isocyanic ester is very active, can combine to form firm chemical bond and hydrogen bond with the hydroxyl in the ground, therefore very strong with the adhesive power of ground.The appearance of repeating unit has given resin fabulous performance again in the structure.Thus, polyurethane coating is the advantage that integrates various coating, has both had excellent defencive function, has attractive in appearance ornamentally again, has outstanding over-all properties.No matter be abroad or domestic, urethane series coating all is one of the fastest coating variety of present rate of growth, becomes extremely rising new coating.Before 1962, the used isocyanic ester of polyurethane coating is a raw material with aromatic TDI nearly all.Good combination property, the output of this polyurethane coating is big, wide in variety, application is wide; But an important disadvantages is arranged; Yellowing property is serious after receiving solar light irradiation exactly; And under the effect of weather, tarnish soon, should not can only be used for dark indoor paint as the high-decoration coating of weathering resistance.Someone thinks that yellowing mainly is that the benzene nucleus of aromatic amine is rearranged into quinone structure after oxidation owing to the amino-formate bond uviolize decomposes the generation aromatic amine, or oxidation formation azo cpd makes the coating yellowing.
Abroad, the application of aromatic urethane lacquer is ripe in fact already, and research and development in recent years mainly concentrate on the aliphatics polyurethane paint.The thermostability of aliphatic carbamate key, antioxidant effect and anti-hydrolytic action are superior to aromatic series, even and resolve into aliphatic amide and also can not be oxidized to quinone structure, do not have the phenyl ring conjugation to help look, thereby not yellowing yet.The two-pack aliphatic polyurethane coating has outstanding ornamental and weather resisteant (the lasting retention of color and luster and color), for a long time in the very strong chemical environment of slight, moderate even corrodibility, also has excellent anti-physics and anti-chemical transformation property.Particularly when adding suitable ultraviolet absorbers with stablizer, its ornamental and outward appearance can keep 15 years.Aliphatic polyurethane coating has rarely possessed flexibility and hardness, and the toughness that it provides can be used to make the most attrition resistant coating system (like high performance terrace lacquer).Aliphatic polyurethane coating based on hexamethylene diisocyanate (HDI) is the ornamental extremely excellent coating of the most widely used weather resisteant.Its paint film flexibility is good, and ultimate tensile elongation can reach 100～120%, and anti-mechanical carwash snag has been used for metallic color automobile varnish Lacquer finish, can overcome the deficiency of trimeric cyanamide/acrylic varnish commonly used.The hexamethylene diisocyanate biuret is called for short the HDI biuret; The HDI biuret is meant the polyisocyanate prepolymers that has biuret structure with HDI and another component synthetic; Be fabulous a kind of of ageing-resistant performance in all polyurethane curing agents; Be applicable to the linking agent in the various materials, like coating, tackiness agent, leather, urethanes, polyurethane elastomer etc.HDI biuret and verivate thereof have lower relative molecular mass, lower vp and satisfactory stability property; Many and Hydroxylated acrylic resin, vibrin etc. are joined lacquer; Paint film can yellowing; Have excellent photostabilization, weathering resistance, chemical-resistant and magnificent gloss, and matter is soft, non-volatile component is high.Compare with amino/vinyl resin and other type coatings; Solidification value is low, viscosity is low, solids constituent is high; Construction road number is few; Decorative coating film property, weathering resistance, erosion resistance are all fine, and fast doing, and get widespread use at aspects such as aircraft industry, automotive industry, rail truck, electrical instrumentation, building and high-class woodenware furniture in recent years.China's hexamethylene diisocyanate (HDI) raw material is dependence on import all always; Bayer A.G had built up the HDI production line in the Shanghai Chemical district in 2006; Yantai Wanhua Polyurethane Co., Ltd in 2011 in the base, Ningbo 20,000 tons of HDI projects normally move, Chinese weapons Gansu silver light gathers (Gansu Yinda Chemicals Co., Ltd.) HDI of patina worker ltd production line and goes into operation at present.The HDI production domesticization will promote developing rapidly of weathering resistance polyurethane coating and high temperature resistant (135 ℃) cooking food wrapping material.The HDI monomer is because of its volatility is big, toxicity is big, and transportation and use are extremely inconvenient, and toxicity is also big during construction, generally all is to sell with HDI solidifying agent form.External at present hexamethylene diisocyanate (HDI) and the H of adopting
2The O reaction generates the biuret triisocyanate and becomes tripolymer with the HDI autohemagglutination, ability nontoxic pollution-free when two kinds of HDI prepolymers processing are like this used.Though German Bayer company just reacted through HDI and water and successfully makes the HDI biuret polyisocyanate as far back as 1958, its compound method and production technique are still being updated.Domestic employing spray method has been synthesized the HDI biuret; Adopt short-path distillation to remove the free HDI monomer that remains in the HDI biuret; Successfully made HDI biuret polyisocyanate sample of light color, that viscosity is low, the viscosity 56s of specimen ,-NCO content 21.4%, HDI residual quantity 0.4%.
The principal reaction of HDI and the synthetic biuret of water reaction is divided into following 3 steps:
1)OCN-(CH
2)
6-NCO+H
2O→OCN-(CH
2)
6-NH
2+CO
2↑
(urea groups vulcabond) (biuret triisocyanate)
As a H
2The NCO base of O molecule and HDI reacts and generates NH
2Behind the base, because NH
2The reactive behavior of base is very big, immediately just with another NCO radical reaction generation urea groups; The activity of aliphatics urea groups is also greater than H
2O has generated biuret groups with another NCO radical reaction very soon after the generation, and the molecule that obtains at this moment is that above-mentioned relative molecular mass is 478 ideal tripolymer.In actual procedure, the reaction that is taken place is complicated more than said process.At first be because the NCO base at HDI two ends is active identical, when the two ends group is participated in reaction simultaneously, will generate the molecule bigger than desirable tripolymer; Secondly, the biuret of generation or bigger molecule can continue to react with the NCO base, generate more high-molecular weight product.This has caused the complicacy and the difficult operability of reaction system.In this process, the formation speed of urea groups is bigger than the formation speed of biuret groups, H
2The reacting phase of O and NCO base is to becoming long response time.In HDI and the synthetic biuret reaction system of water reaction; The material of every containing-NCO end group all can contain the material generation side reaction of reactive hydrogen with any one; Therefore being difficult to control raw material transforms to the purpose product; Product is formed very complicated, judges that therefore content that whether reaction has obtained purpose product and purpose product is that what method is extremely important.Because two isocyano reactivities of HDI are identical, for avoiding the generation of side reaction, often need adopt the excessive feed ratio of HDI.Therefore, reaction finishes also to contain a large amount of unreacted HDI monomers in the system of back, in order to reach requirement on environmental protection, must remove free HDI.Therefore HDI steam forces down, volatility is big, toxicity is big, need take effective post-treating method that excessive HDI monomer is removed from product, with reduce in the use harm to operator ' s health, to the pollution of environment and to the detrimentally affect of product performance.The selection of aftertreatment technology is directly connected to color and luster, outward appearance, viscosity and the free monomer content of product.If remove the free monomer in the raw product only according to simple distillation, then must be with the long-time heat of raw product, but isocyanic ester is being prone to generate allophanate more than 150 ℃, make product rotten, and free HDI is but still residual a lot.
The solvent that the polyisocyanate component of polyurethane coating is contained is also few, and its toxicity mainly is the free isocyanate monomer that wherein contained volatility is higher.The extensive chemical activity of isocyanic ester is reflected in the coenocorrelation significantly.It can react with human body protein, and enzyme is lost activity, and therefore piquant acceptor and destruction cell have strong impulse effect and toxicity.The isocyanic ester of vaporous or fine mist can stimulate eyes and mucous membrane, has the intensive lacrimation, if suck respiratory system, then can cause dry cough, laryngalgia and expiratory dyspnea, and long-term suction can cause headache, bronchitis, asthma and pulmonary lesion etc.Therefore, if contain overproof volatile free monomer, in storage or construction process, will cause very big harm in the polyurethane coating to human body and environment.
The Chinese invention patent application number is that 200710051761.X relates to a kind of solidifying agent 1; Hexamethylene-diisocyanate prepolymer and preparation method thereof comprises: in reaction kettle, add HDI and organic solvent, stir; Adding is through vacuumizing the polyvalent alcohol of dehydration; At room temperature cold stirring 0.5 hour was reacted 2～5 hours down at 60～100 ℃, made the HDI modifier; Be cooled to 50～80 ℃, under agitation, drip the mixed solution 1～4 hour of TriMethylolPropane(TMP) and organic solvent in the reaction kettle; 60～100 ℃ of dropping temperatures; Insulation reaction 1～3 hour rises to 80～100 ℃ of insulation reaction 2～5 hours again, is cooled to 60 ℃; Make the transparent viscous fluid of HDI prepolymer, add organic solvent diluting to required solid content.
The Chinese invention patent application number is 200910003621.4 to relate to the method for a kind of spray method synthesizing hexamethylene diisocyanate (HDI) biuret; Adopt high pressure that water is sprayed into the form of droplet the reaction of HDI reaction kettle is housed; 60～130 ℃ of temperature, the mol ratio of HDI and water are 2～15, and water spraying time is 0.5～8 hour; Reacted the back 80～150 ℃ of insulations 0～5 hour, separated with tripping device then.Separation temperature is between 70～200 ℃, and pressure is between 0.5～50000Pa.The steaming excess of separating has with the pump suction in the latting drown container of stirring and dissolves; Add the solvent that measures in the latting drown container in advance; Along with the suction of steaming excess, the uninterrupted solvent that measures that adds in the latting drown container, it is 25～100% HDI biuret product that dilution obtains solid content.
The HDI biuret synthesizes and separates necessary three technical barriers that solve: the one, improve reaction efficiency, and reduce the generation of polyureas; The 2nd, reduce HDI content in the HDI biuret, reduce the use toxicity of HDI biuret; The 3rd, this process should economy environmental protection again.Finding out from the structure of biuret triisocyanate, should be by 3 moles of HDI and 1 mole of H
2The O reaction forms, and can produce a large amount of oyster white dopes but feed intake like this, can not get product; Need with mol ratio greater than 3: 1, HDI is just excessive like this, when reacting end, must carry out aftertreatment to unreacted HDI; Promptly reclaim excessive HDI, in order to reusing with thin film evaporation technology.The thin film evaporation equipment price is expensive, complex process, and existing enterprise is difficult to grasp this cover technology.HDI and water reaction generate the technology of biuret, and temperature of reaction will reach 140 ℃, need with the oil bath heating, and energy consumption is bigger.
The objective of the invention is in order to overcome the deficiency of prior art; A kind of method of synthesizing hexamethylene diisocyanate biuret solidifying agent is provided; And a kind of content of judging whether reaction has obtained purpose product and purpose product is provided what method be, to remedy the synthetic HDI biuret solidifying agent of prior art and to remove the deficiency of free HDI method.
Summary of the invention
Test portion of the present invention comprises that test is with main raw material table, key instrument, EL, TP, detection method, synthesis technique.
Table 1HDI biuret solidifying agent quality index
The main raw material table is used in table 2 test
| Raw material | Purity |
| HDI | Purity 99.9% |
| Na 2SO 4·10H 2O | Analytical pure |
| CuSO 4·5H 2O | Analytical pure |
| KAl(SO 4) 2·12H 2O | Analytical pure |
| FeSO 4·7H 2O | Analytical pure |
| Na 2CO 3·10H 2O | Analytical pure |
| ZnSO 4·7H 2O | Analytical pure |
| Na 2B 4O 7·10H 2O | Analytical pure |
| MgSO 4·7H 2O | Analytical pure |
| Zero(ppm) water | Self-control |
| Acetone | Analytical pure |
| Hexanaphthene | Analytical pure |
| N-tetradecane | Analytical pure |
| Toluene | Analytical pure |
| Virahol | Analytical pure |
| Di-n-Butyl Amine | Analytical pure |
Table 3 test is with key instrument, EL
| Instrument, equipment | Specification |
| Four-hole boiling flask | |
| Kerosene thermometer | |
| 0～200 ℃, 2 ℃ of precision | |
| Digital display thermostatical oil bath | Room temperature～300 ℃ |
| Reflux condensing tube | Supporting with four-hole boiling flask |
| The powerful motor stirrer | The JB90-D type |
Install reaction kit, water and HDI are put in the four-hole bottle that has stirring and reflux condensing tube by a certain percentage, start power supply; Begin to stir, be warming up to certain temperature after, insulation for some time; After reaction finishes; Lower the temperature, and remove the white polyureas particle that generates in the reaction process, collect clear filtrate as thick product with vacuum filtration.Thick product also need carry out aftertreatment, to remove the free HDI monomer that remains in the product.
Method among the employing HG/T 2409-1992 " NCO Determination on content in the base polyurethane prepolymer for use as " is measured solidifying agent-NCO content.Solidifying agent-NCO content adopts the Di-n-Butyl Amine volumetry to measure.
Adopt GB/T 18446-2009 " paint and varnish is with the mensuration of diisocyanate monomer in the lacquer based isocyanate resin " to measure free HDI content in the solidifying agent.Internal standard substance is a n-tetradecane.
The infrared measurement of HDI biuret: adopting Fourier infrared spectrograph device model is FT-IRSpectrometer, and SPEC-TRUM 2000.
The content of biuret adopts gel osmoticing chromatogram analysis in the solidifying agent, pillar: Styragel HT-5, Styragel HT-4 and Styragel HT-3 three posts series connection (made in USA); Moving phase: THF; Chromatographic instrument: Waters 515 type gel chromatographs; Detector: Waters 2410 differential refraction detectors (U.S. Waters company); Sample size: 50 μ L; Column temperature: 40 ℃; Standard specimen is MP (molecular-weight average) and is respectively 200000 (Da), 110000 (Da), 35000 (Da), 3600 (Da), the PS PS of 2350 (Da) (U.S. Sigma company).
Solidifying agent is joined the mensuration of lacquer back paint film property, comprises time of drying (GB/T 1728-1979 (1989) paint film, putty membrane assay method time of drying), sticking power (cross cut test of GB/T 9286-1998 paint and varnish paint film), pencil hardness (GB/T 6739-2006 paint and varnish pencil method is measured hardness), shock-resistance (the shock-resistant assay method of GB/T 1732-1993 paint film), snappiness (GB/T 6742-2007 paint and varnish pliability test (cylinder axis)) etc.
The present invention has investigated direct Jia Shui, water and acetone mixture, three kinds of influences that add the water mode to synthetic HDI biuret of crystal water respectively.
Table 4 difference adds the influence of water mode to solidifying agent
| Add the water mode | NCO％ | Free HDI% | Biuret Content/% |
| Directly add water | 38.78 | 61.14 | 39.35 |
| Acetone and water mixture | 37.08 | 60.99 | 40.32 |
| Crystal water | 35.45 | 52.62 | 41.32 |
Visible by table 4, three kinds add in the water mode, and the Biuret Content that the water mode that adds of crystal water obtains is the highest, explain that crystallization water law transfer rate is slightly high than other two kinds of methods.
Investigated the consistency experiment, pressed HDI: H
2O (mol ratio) ratio 6: 1 is directly mixed HDI earlier with water, after HDI is mixed with the mixture of water and acetone, contrast and experiment is seen table 5.
Table 5 consistency experimental result
| Hybrid mode | Consistency |
| HDI+ water | Consistency is poor, presents two phases |
| HDI+ (water+acetone) | Consistency is better, and is insoluble on a small quantity |
Can find out that by table 5 the different water modes that adds has certain influence to formation, product structure and the MWD of biuret.Acetone is better than the reaction that directly adds water with water mixture, and the consistency experiment of this and last table coincide, and explains that the consistency of system is good more, and reaction effect is good more.
Select the suitable compound that contains crystal water for use, the character according to its crystal water release rate changes with temperature can make it discharge quantitative water and di-isocyanate reaction through strict control reaction temperature.Crystalline compounds discharges water molecules in reaction system, can disperse more equably.This is a kind of method that changes the adding mode of water.The present invention has investigated the influence of different crystal water compounds to synthetic solidifying agent, and the result sees table 6.
The different crystal water compounds of table 6 are to the influence of synthetic solidifying agent
| The crystal water compound | NCO％ | Free HDI% |
| Na 2SO 4·10H 2O | 35.45 | 52.62 |
| CuSO 4·5H 2O | 36.28 | 55.75 |
| KAl(SO 4) 2·12H 2O | 34.87 | 48.17 |
| FeSO 4·7H 2O | 37.82 | 57.08 |
| Na 2CO 3·10H 2O | 35.98 | 53.62 |
| ZnSO 4·7H 2O | 35.05 | 50.52 |
| Na 2B 4O 7·10H 2O | 36.21 | 54.93 |
| MgSO 4·7H 2O | 38.53 | 67.81 |
Can find out that by table 6 the free HDI content and the nco value of different crystal water compound reaction back systems differ bigger, explain that crystalline compounds is bigger to the influence of synthetic solidifying agent; Be not that crystal water content is high more; The solidifying agent that obtains is good more, and relevant with the crystal water decomposition temperature, like ZnSO
47H
2O can emit 6 crystal water, MgSO under temperature of reaction
47H
2O can only emit 5 crystal water under temperature of reaction, so by ZnSO
47H
2The solidifying agent reaction that O obtains is than Mg SO
47H
2O is abundant.Na
2SO
410H
2O, Na
2CO
310H
2O and Na
2B
4O
710H
2O releasable water yield under temperature of reaction is respectively 10,9 and 8, can find out that from nco value and free value the degree that reaction carries out is proportional with the crystallization water yield that the three discharges, and the water yield of release is many more, react carry out thorough more.So decomposable crystal water is many more even more under temperature of reaction, helps the synthetic of solidifying agent more.
The compatibility that directly adds water and HDI is very poor, when water droplet is in the HDI system, in fact presents two phases; The reaction that takes place sees from the part that carrying out at the interface water possibly be excessive; Make the HDI two ends-the NCO base all reacts, and can not obtain the ideal biuret.Simultaneously, fail the timely water that reacts at high temperature because of evaporation can break away from reaction system, though after condensation, return system, but still caused loss inevitably.Sodium sulfate crystal (Na in the hydrated inorganic salt
2SO
410H
2O) disperse water in system uniformly, water cut is high, and dehydration temperaturre is low, and it is more complete to dewater, the Na of generation
2SO
4Powder can remove by filter with the white polyureas material that generates in the product.Ir spectra detects and to utilize with GPC that molecular size is different to separate component, and generally molecular weight is big more, and elution volume is more little, goes out the peak more early; Molecular weight is more little, and elution volume is big more, and it is more late to go out the peak.Simultaneously, under the same operation condition, the size of certain elution volume place response value is corresponding with components contents.According to the area at the corresponding peak of different components in the product, relative percentage composition that can the various components of quantitative analysis.Like this, from the relative size that spectrogram is observed corresponding elution volume peak area, just can judge whether very intuitively that biuret generates and the size of relative other component concentrations of biuret.According to the area at the corresponding peak of different elution volumes, relative content that can the various components of quantitative analysis so that confirm synthetic reaction condition, makes reaction carry out to ideal purpose product direction.
For a large amount of free HDI that exist in the HDI biuret, can remove through molecular distillation method, solvent extration etc.Adopt molecular still can make heated time shorten to several minutes, evaporation area is big, and free monomer steams soon, can reduce greatly through the product free monomer of short-path distillation.The molecular still model: German VTA-70, treatment capacity 1-1.5L/h, evaporator temperature 130-180 ℃, rotating speed 100-400 commentaries on classics/min, different when pressure 50Pa is following according to material, handle one to twice, can the HDI biuret be dissociated and reduce to below 0.5%.Solvent extration is divided into Direx process and continuous extraction method.Because along with partial monosomy is separated from raw product, the raw product viscosity is increasing, extraction agent can not get into its inside effectively and extract free monomer, therefore adopts Direx process can not effectively reduce the free monomeric content of HDI in the raw product.The advantage of continuous extraction method is not need raw product is heated, and can not produce by product, and equipment price is cheap relatively, and operating procedure is easy to grasp; Shortcoming is to use high amounts of solvents to cause environmental pollution and need unreacted monomer be separated from extraction agent through operations such as further distillations.
Summing up above technical scheme, to form the technical scope that the present invention need protect following:
1, a kind of method for preparing hexamethylene diisocyanate biuret solidifying agent is characterized in that: comprise the following steps:
The first step: in the reaction kettle (4) that has stirring and reflux exchanger (5), add hexamethylene diisocyanate, be warmed up between 30～180 ℃ and stirring;
Second step: adopt two kinds to add the water mode and guarantee that water reacts with hexamethylene diisocyanate, temperature of reaction is controlled between 30～180 ℃, and the mol ratio of HDI and water is 2～15: 1, and the reaction times is 0.5～12 hour;
The 3rd step: lower the temperature, and remove the white polyureas particle that generates in the reaction process, mixed solution is collected clear filtrate as thick product through filter cloth (7) with strainer (6);
The 4th step: adopt two kinds of separate modes through the free HDI monomer of separator (9) separating residual in product, separation temperature is between 10～180 ℃, and pressure is isolated hexamethylene diisocyanate biuret and free HDI monomer between 0.5～50000Pa;
The 5th step: the hexamethylene diisocyanate biuret of separating has the middle dissolving of latting drown container (10) of whipping appts with the pump suction; Add the solvent that measures in the latting drown container in advance; Suction along with the hexamethylene diisocyanate biuret; Constantly add the solvent that measures in the latting drown container; Dilution obtains solids content at 25～100% HDI biuret product, and solvent for use is a kind of or more than one mixtures in vinyl acetic monomer, N-BUTYL ACETATE, toluene, the YLENE;
The 6th step: the HDI monomer of separating adds in the reaction kettle (4), follows the adding of new HDI raw material, gets into the first step, reacts, separates by aforesaid method then, goes round and begins again.
2, a kind of method for preparing hexamethylene diisocyanate biuret solidifying agent according to claim 1 is characterized in that: described two kinds of second step adds the water mode and comprises and add different crystal water compounds and add acetone and water mixture in the step.
3, a kind of method for preparing hexamethylene diisocyanate biuret solidifying agent according to claim 1 and 2 is characterized in that: said two kinds of separate modes comprised with molecular still or hexanaphthene continuous extraction method and carry out the free HDI monomer of separating residual in product the 4th step in the step.
4, according to claim 1 or 2 or 3 described a kind of methods that prepare hexamethylene diisocyanate biuret solidifying agent; It is characterized in that: the purpose product utilization ir spectra that the 4th step separated in the step detects and gel permeation chromatography detects the size that judges whether biuret generation and relative other component concentrations of biuret; Area according to the corresponding peak of different elution volumes; Relative content that can the various components of quantitative analysis; So that confirm synthetic reaction condition, reaction carried out to ideal purpose product direction.
5, according to claim 1 or 2 or 3 described a kind of methods that prepare hexamethylene diisocyanate biuret solidifying agent, it is characterized in that: the different crystal water compounds of the second described adding of step comprise Na in the step
2SO
410H
2O, CuSO
45H
2O, KAl (SO
4)
212H
2O, FeSO
47H
2O, Na
2CO
310H
2O, ZnSO
47H
2O, Na
2B
4O
710H
2O, Mg SO
47H
2O.
6, according to claim 1 or 2 or 3 described a kind of methods that prepare hexamethylene diisocyanate biuret solidifying agent, it is characterized in that: the acetone of the second described adding of step and the mol ratio of water mixture are 2～15: 1 in the step.
7, according to claim 1 or 2 or 3 described a kind of methods that prepare hexamethylene diisocyanate biuret solidifying agent; It is characterized in that: in the step the 4th step said during with the hexanaphthene continuous extraction when free HDI monomer≤70%; The amount of extraction liquid was 60mL when the thick product of 10mL extracted at every turn, and extraction times is 3 times.
8, according to claim 1 or 2 or 3 described a kind of methods that prepare hexamethylene diisocyanate biuret solidifying agent; It is characterized in that: join when experiment lacquer with said biuret solidifying agent of the 5th step in the step, different hydroxy components is joined lacquer back performance to the HDI biuret has certain influence, when hydroxy component is selected Hydroxylated acrylic resin, Viscotrol C, soft section polyethers, hard section polyethers; The paint film property that obtains is better; Sticking power is 1 grade, and pencil hardness is H, and snappiness is 2mm; Time of drying≤6h is passed through in shock-resistance 50cm recoil.
9, according to claim 1 or 2 or 3 described a kind of methods that prepare hexamethylene diisocyanate biuret solidifying agent, it is characterized in that: strainer (6) keeps the vacuum filtration state, and filter cloth (7) is 80～220 purposes.
Description of drawings
Fig. 1 HDI biuret reaction device technique general flow chart.
Code name explanation among the figure: 1-HDI storage tank, 2-HDI transferpump, 3-aqueous mixture storage tank, 4-reactor drum, 5-reflux exchanger, 6-strainer, 7-filter cloth, 8-bullion transferpump, 9-separator, 10-latting drown container, 11-join paint bath.
The synthetic HDI biuret solidifying agent infrared spectrum characterization figure of the different crystal water compounds of Fig. 2
The synthetic solidifying agent has been carried out infrared spectrum characterization, judged whether formed the HDI biuret according to the charateristic avsorption band that occurs in the infrared spectrogram.Adopt the determination of infrared spectroscopy difference to add the ir spectra of sample under the water mode, the test collection of illustrative plates is seen Fig. 2.Seven spectrograms are roughly the same, 2285cm
-1Near be-the NCO absorption peak 2964cm
-1Neighbouring is the absorption peak of methyl and methylene radical, 3321cm
-1Near be-the NH-absorption peak 1723cm
-1Near be-absorption peak of CO-so to think in the sample HDI biuret is arranged.
Fig. 3 difference adds gel permeation chromatography (GPC) figure of HDI biuret solidifying agent under the water mode
Can be found out that by Fig. 3 three kinds of each component elution volumes that adds the water mode are more or less the same, three kinds add that each component concentration of synthetic solidifying agent is more or less the same under the water mode.
Fig. 4 different treatment method is to removing the influence curve figure of free HDI
Visible by Fig. 4, common underpressure distillation does not have any effect basically to aftertreatment, and after the extraction process processing, the free HDI content of solidifying agent drops to about 5%, and effect is better, but the demand of the extraction liquid that needs is bigger.Extraction liquid to after using carries out underpressure distillation, and purpose is to reclaim HDI and extraction liquid through underpressure distillation.
The usage quantity of Fig. 5 extraction liquid is to the influence curve figure of extraction results
Visible by Fig. 5; Increase along with the extraction liquid usage quantity; The nco value and the free HDI content of the agent of extraction after fixing are on a declining curve, but after the amount of extraction liquid reached 60mL, nco value and free HDI content fall diminished; From extraction liquid usage quantity and consideration economically, the amount of extraction liquid is 60mL when extracting at every turn.
Fig. 6 extraction times is to removing free influence curve figure
Visible by Fig. 6, along with the increase of extraction times, nco value and the free HDI content of handling the after fixing agent are on a declining curve; But after extraction three times; The free HDI content of solidifying agent is below 8%, but viscosity is very big, and the loss amount of solidifying agent is very big in the treating processes; Nco value and free HDI content are also not obvious, so confirm that extraction times is 3 times.
Embodiment
Come further explain the present invention below in conjunction with specific embodiment.
Add hexamethylene diisocyanate (HDI) 100mol in the reaction kettle, stir and be warmed up to 110 ℃; With 1.5mol sodium sulfate crystal (Na
2SO
410H
2O) water is added in the reaction kettle, is warmed up to 130 ℃, and the reaction times is 5 hours, lowers the temperature, and removes the white polyureas particle that generates in the reaction process with vacuum filtration, mixed solution is filtered through 200 purpose filter cloths collect clear filtrate as thick product.Thick product separates through molecular still, and separation temperature is at 130 ℃, and separating pressure obtains HDI biuret product at 30Pa after the separation, its free HDI mass content 0.48%, and NCO content is 21.6%, solids content 99.5%.
Crystal water is when adding the water mode, and feed ratio is seen table 7 to the influence of synthetic solidifying agent.
Table 7 feed ratio is to the influence of synthetic solidifying agent
| Mol ratio | NCO％ | Free HDI% | Biuret Content/% |
| 3∶1 | 27.14 | 29.95 | 21.23 |
| 4∶1 | 33.18 | 45.55 | 34.49 |
| 5∶1 | 34.29 | 50.06 | 38.92 |
| 6∶1 | 35.45 | 52.62 | 41.32 |
Visible by table 7, under 130 ℃ reaction conditions, the proportioning of HDI and water is high more, and then the biuret relative content of product is high more.This is because reactant ratio is high, and excessive HDI can limit biuret derivatives and increase relative molecular mass, is beneficial to the formation of biuret, but equally also exists proportioning high more, and the content of free HDI is high more, and aftertreatment is the problem of trouble more.
Crystal water is when adding the water mode, and temperature of reaction is seen table 8 to the influence of solidifying agent.
The physico-chemical property of solidifying agent under the table 8 differential responses temperature
| Temperature of reaction/℃ | NCO％ | Free HDI% | Biuret Content/% |
| 100 | 38.72 | 57.12 | 36.67 |
| 110 | 39.76 | 45.10 | 37.31 |
| 120 | 38.34 | 53.05 | 38.76 |
| 130 | 35.45 | 52.62 | 41.32 |
| 140 | 33.89 | 49.25 | 34.10 |
| 150 | 33.98 | 48.32 | 33.01 |
Visible by table 8, in the time, with the rising of temperature of reaction, Biuret Content is the back downward trend that rises earlier in same reaction, and the Biuret Content of products obtained therefrom was the highest when temperature of reaction was 130 ℃.This explanation temperature of reaction also is very important to the reaction of synthetic HDI biuret.Because the activity of HDI is lower, the reaction that generates biuret belongs to the cross-linking type reaction again, in order in reaction process, to obtain sufficiently high speed of reaction, needs the rising temperature of reaction, the carrying out of the rising meeting accelerated reaction of temperature of reaction.During low temperature mainly be-NCO and-react formations-NH-CO-NH-NH-CO-NH structure and precipitating easily between OH; And during high temperature;-NCO and-when reacting between OH; In the HDI biuret-NH-participates in reaction easily; Can impel-NCO and affixture molecule in-crosslinked or chain extending reaction takes place in NHCOO-, cause reaction system-NCO content and free HDI reduce, so be necessary to select suitable reaction temperature.
Under the proportioning of identical HDI and water; Relatively products obtained therefrom is found under the differing temps; The product of reaction gained is more stable under comparatively high temps, and product also almost is a clear after placing the long period, and the product of lower slightly temperature (as 100 ℃-120 ℃) gained turbid phenomenon all can occur after placing; 100 ℃ product occurs muddy after about one day, 120 ℃ product also turbid phenomenon can occur at a distance from about ten days.The product colour of reaction gained is darker under comparatively high temps, appears light yellowly, and the product that obtains at a lower temperature is almost colourless.
Crystal water is when adding the water mode, and the reaction times is seen table 9 to the influence of solidifying agent.
The physico-chemical property of solidifying agent under the table 9 differential responses time
| Reaction times/h | NCO％ | Free HDI% | Biuret Content/% |
| 4 | 36.02 | 59.73 | 33.10 |
| 5 | 35.76 | 55.71 | 35.42 |
| 6 | 35.45 | 52.62 | 41.32 |
| 7 | 35.06 | 47.81 | 35.53 |
| 8 | 35.65 | 48.78 | 34.22 |
Visible by table 9, along with the prolongation in reaction times, the nco value of reactant, free HDI content and synthetic solidifying agent biuret amount increase gradually, and after surpassing 6h, three's value reduces gradually.This is because at a certain temperature, and with the prolongation in reaction times, it is abundant more that reaction is carried out; But the time is oversize, when under being reflected at higher temperature, carrying out, not only can not make the HDI monomer continue to change into product; The situation that product decomposes can appear on the contrary; Cause the nco value of reactant, free HDI content to increase, and Biuret Content reduces, this is relevant with the thermostability of various keys in the product.
Add hexamethylene diisocyanate (HDI) 200mol in the reaction kettle, stir and be warmed up to 30 ℃; The mixture of 60mol acetone and water is added in the reaction kettle; Be warmed up to 60 ℃; Reaction times is 4 hours, and removes the white polyureas particle that generates in the reaction process with vacuum filtration, mixed solution is filtered through 200 purpose filter cloths collect clear filtrate as thick product.Thick product separates through molecular still, and separation temperature is at 140 ℃, and separating pressure obtains HDI biuret product at 50Pa after the separation, its free HDI mass content 0.38%, and NCO content is 22.6%, solids content 99.5%.
When the mixture of acetone and water added the water mode, feed ratio was seen table 10 to the influence of synthetic solidifying agent.
Table 10 feed ratio is to the influence of synthetic solidifying agent
| Mol ratio | NCO％ | Free HDI% | Biuret Content/% |
| 3∶1 | 28.18 | 30.99 | 18.43 |
| 4∶1 | 33.21 | 44.63 | 27.60 |
| 5∶1 | 35.93 | 52.64 | 37.65 |
| 6∶1 | 37.08 | 60.99 | 40.32 |
| 7∶1 | 40.74 | 68.16 | 51.35 |
| 8∶1 | 42.70 | 78.09 | 52.79 |
Visible by table 10, different mol ratio has considerable influence to Biuret Content in the synthetic solidifying agent, along with the increase of mol ratio; Nco value, the free corresponding increase of HDI content with Biuret Content; But the increase amplitude is different, and it is maximum that free HDI content increases amplitude, explains along with mol ratio increases; Unreacted HDI increases in the system, and the amount that generates by product reduces.When the mol ratio of HDI and water during in stoichiometric(al) 3, the monomeric content of HDI residual in the product is minimum, and when the mol ratio of HDI and water during in stoichiometric(al) 8, the monomeric content of HDI residual in the product is the highest, and the amount of biuret is maximum relatively simultaneously.The physico-chemical property of test HDI biuret sample comprises free HDI content, nco value, Biuret Content etc.The synthetic solidifying agent is joined lacquer test, detect paint film property.
Paint film property under table 11 different solvents
Visible by table 11, different solvents mainly has considerable influence to the paint film dryness, and other paint film properties are not produced big influence.The paint film dryness is basic consistent with the velocity of evaporation of using solvent, and the time of drying of vinyl acetic monomer is the fastest, and the velocity of evaporation of YLENE is the slowest, and the velocity of evaporation of mixed solvent is moderate.
The synthetic solidifying agent has been carried out joining the lacquer experiment, and the paint film property that obtains is better, and sticking power is 1 grade, and pencil hardness is H, and snappiness is 2mm, and shock-resistance 50cm recoil is passed through.Not only paint film property is superior to the TDI type, and anti-yellowing property is also good than TDI type paint film.
Add hexamethylene diisocyanate (HDI) 100mol in the reaction kettle, stir and be warmed up to 140 ℃; With 2mol crystalline sulfuric acid zinc (ZnSO
47H
2O) water is added in the reaction kettle, is warmed up to 150 ℃, and the reaction times is 3 hours, and removes the white polyureas particle that generates in the reaction process with vacuum filtration, mixed solution is filtered through 200 purpose filter cloths collect clear filtrate as thick product.Thick product separates through hexanaphthene continuous extraction method, and extraction temperature is at 30 ℃, and the amount of the thick product extraction liquid of 10mL is 60mL when extracting at every turn, and extraction times is 3 times, its free HDI mass content 0.28%, and NCO content is 22.4%, solids content 99.5%.
The synthetic solidifying agent is joined lacquer test, detect paint film property.
Several kinds of hydroxy components and HDI biuret are joined lacquer back paint film property and are seen table 12.
The different hydroxy components of table 12 are joined the lacquer performance
Visible by table 12, different hydroxy components is joined lacquer back performance to the HDI biuret has certain influence.The time of drying of hard section polyethers is the shortest.The paint film flexibility that hydroxy component more than soft section obtains is good than hard section polyethers, but hardness is not so good as the good of hard section polyethers.
Add hexamethylene diisocyanate (HDI) 120mol in the reaction kettle, stir and be warmed up to 130 ℃; With 2mol sal soda (Na
2CO
310H
2O) water is added in the reaction kettle, is warmed up to 150 ℃, and the reaction times is 6 hours, and removes the white polyureas particle that generates in the reaction process with vacuum filtration, mixed solution is filtered through 200 purpose filter cloths collect clear filtrate as thick product.Thick product separates through hexanaphthene continuous extraction method, and the extraction liquid after using is carried out underpressure distillation, and purpose is to reclaim HDI and extraction liquid through underpressure distillation.Extraction temperature is at 30 ℃, and the amount of the thick product extraction liquid of 10mL is 60mL when extracting at every turn, and extraction times is 3 times.Obtain HDI biuret product after the separation, its free HDI mass content 0.18%, NCO content is 21.9%, solids content 99.5%.
Each influence factor to the size order that influences of synthetic solidifying agent is: the mol ratio＞temperature of reaction of HDI and water＞reaction times; Be that this reaction is had the greatest impact by the mol ratio of HDI and water; It must be excessive that explanation will obtain high-load HDI biuret product HDI; But unsuitable excessive too many, in order to avoid increase the workload that free HDI is removed in aftertreatment; Next is a temperature of reaction, is the reaction times at last, and temperature of reaction and reaction times cooperatively interact; Has identical effect because prolong the reaction times under certain condition with the rising temperature of reaction; So control both size well, make it to be complementary, so that obtain the ideal title product.
Package stability under the table 13 crystal water condition
| Numbering | Fate | NCO％ | |
| 1 | 0 | 35.45 | 52.62 |
| 2 | 7 | 35.30 | 50.12 |
| 3 | 14 | 35.09 | 49.95 |
| 4 | 30 | 34.85 | 49.82 |
| 5 | 60 | 34.70 | 49.69 |
Visible by table 13; The package stability of HDI biuret is all fine, and along with the prolongation of period of storage, nco value all is downward trend with the trip monomer content substantially; But fall is little, stores after 60 days that nco value has descended 2.0%, free HDI content has descended 5.6%.Crystallization water law nco value has descended 2.0%, free HDI content has descended 5.6%; Acetone water feeding method nco value has descended 3.8%, free HDI content has descended 8.4%, and visible crystallization water law package stability is good than the acetone water feeding method.
The above only is preferred embodiment of the present invention, is not structure of the present invention is done any pro forma restriction.Every foundation technical spirit of the present invention all still belongs in the scope of technical scheme of the present invention any simple modification, equivalent variations and modification that above embodiment did.
Claims (9)
1. a method for preparing hexamethylene diisocyanate biuret solidifying agent is characterized in that: comprise the following steps:
The first step: in the reaction kettle (4) that has stirring and reflux exchanger (5), add hexamethylene diisocyanate, be warmed up between 30～180 ℃ and stirring;
Second step: adopt two kinds to add the water mode and guarantee that water reacts with hexamethylene diisocyanate, temperature of reaction is controlled between 30～180 ℃, and the mol ratio of HDI and water is 2～15: 1, and the reaction times is 0.5～12 hour;
The 3rd step: lower the temperature, and remove the white polyureas particle that generates in the reaction process, mixed solution is collected clear filtrate as thick product through filter cloth (7) with strainer (6);
The 4th step: adopt two kinds of separate modes through the free HDI monomer of separator (9) separating residual in product, separation temperature is between 10～180 ℃, and pressure is isolated hexamethylene diisocyanate biuret and free HDI monomer between 0.5～50000Pa;
The 5th step: the hexamethylene diisocyanate biuret of separating has the middle dissolving of latting drown container (10) of whipping appts with the pump suction; Add the solvent that measures in the latting drown container in advance; Suction along with the hexamethylene diisocyanate biuret; Constantly add the solvent that measures in the latting drown container; Dilution obtains solids content at 25～100% HDI biuret product, and solvent for use is a kind of or more than one mixtures in vinyl acetic monomer, N-BUTYL ACETATE, toluene, the YLENE;
The 6th step: the HDI monomer of separating adds in the reaction kettle (4), follows the adding of new HDI raw material, gets into the first step, reacts, separates by aforesaid method then, goes round and begins again.
2. a kind of method for preparing hexamethylene diisocyanate biuret solidifying agent according to claim 1 is characterized in that: described two kinds of second step adds the water mode and comprises and add different crystal water compounds and add acetone and water mixture in the step.
3. a kind of method for preparing hexamethylene diisocyanate biuret solidifying agent according to claim 1 and 2 is characterized in that: said two kinds of separate modes comprised with molecular still or hexanaphthene continuous extraction method and carry out the free HDI monomer of separating residual in product the 4th step in the step.
4. according to claim 1 or 2 or 3 described a kind of methods that prepare hexamethylene diisocyanate biuret solidifying agent; It is characterized in that: the purpose product utilization ir spectra that the 4th step separated in the step detects and gel permeation chromatography detects the size that judges whether biuret generation and relative other component concentrations of biuret; Area according to the corresponding peak of different elution volumes; Relative content that can the various components of quantitative analysis; So that confirm synthetic reaction condition, reaction carried out to ideal purpose product direction.
5. according to claim 1 or 2 or 3 described a kind of methods that prepare hexamethylene diisocyanate biuret solidifying agent, it is characterized in that: the different crystal water compounds of the second described adding of step comprise Na in the step
2SO
410H
2O, CuSO
45H
2O, KAl (SO
4)
212H
2O, FeSO
47H
2O, Na
2CO
310H
2O, ZnSO
47H
2O, Na
2B
4O
710H
2O, Mg SO
47H
2O.
6. according to claim 1 or 2 or 3 described a kind of methods that prepare hexamethylene diisocyanate biuret solidifying agent, it is characterized in that: the HDI of the second described adding of step and the mol ratio of water are 2～15: 1 in the step.
7. according to claim 1 or 2 or 3 described a kind of methods that prepare hexamethylene diisocyanate biuret solidifying agent; It is characterized in that: in the step the 4th step said during with the hexanaphthene continuous extraction when free HDI monomer≤70%; The amount of extraction liquid was 60mL when the thick product of 10mL extracted at every turn, and extraction times is 3 times.
8. according to claim 1 or 2 or 3 described a kind of methods that prepare hexamethylene diisocyanate biuret solidifying agent; It is characterized in that: join when experiment lacquer with said biuret solidifying agent of the 5th step in the step, different hydroxy components is joined lacquer back performance to the HDI biuret has certain influence, when hydroxy component is selected Hydroxylated acrylic resin, Viscotrol C, soft section polyethers, hard section polyethers; The paint film property that obtains is better; Sticking power is 1 grade, and pencil hardness is H, and snappiness is 2mm; Time of drying≤6h is passed through in shock-resistance 50cm recoil.
9. according to claim 1 or 2 or 3 described a kind of methods that prepare hexamethylene diisocyanate biuret solidifying agent, it is characterized in that: strainer (6) keeps the vacuum filtration state, and filter cloth (7) is 80～220 purposes.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643402A (en) * | 2012-05-14 | 2012-08-22 | 济南大学 | Method for preparing micro-sized monodisperse polyuria microspheres |
| CN102702476A (en) * | 2012-06-07 | 2012-10-03 | 华南理工大学 | Preparation method for hexamethylene diisocyanate biruet |
| CN102702470A (en) * | 2012-06-06 | 2012-10-03 | 济南大学 | Method for preparing micro-sized monodisperse polyurea microsphere in static condition |
| CN107703096A (en) * | 2017-09-30 | 2018-02-16 | 万华化学（宁波）有限公司 | The application of the method and its on-line monitoring of moisture and/or urea content in a kind of detection isocyanates |
| CN108659201A (en) * | 2018-06-08 | 2018-10-16 | 北京中煤矿山工程有限公司 | Anti- well drilling machine reaming construction broken formation gib material |
| CN115894302A (en) * | 2022-10-20 | 2023-04-04 | 山东新和成维生素有限公司 | Process for the preparation of biuret polyisocyanates |
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| CN102643402A (en) * | 2012-05-14 | 2012-08-22 | 济南大学 | Method for preparing micro-sized monodisperse polyuria microspheres |
| CN102643402B (en) * | 2012-05-14 | 2013-10-02 | 济南大学 | Method for preparing micro-sized monodisperse polyuria microspheres |
| CN102702470A (en) * | 2012-06-06 | 2012-10-03 | 济南大学 | Method for preparing micro-sized monodisperse polyurea microsphere in static condition |
| CN102702476A (en) * | 2012-06-07 | 2012-10-03 | 华南理工大学 | Preparation method for hexamethylene diisocyanate biruet |
| CN102702476B (en) * | 2012-06-07 | 2013-12-25 | 华南理工大学 | Preparation method for hexamethylene diisocyanate biruet |
| CN107703096A (en) * | 2017-09-30 | 2018-02-16 | 万华化学（宁波）有限公司 | The application of the method and its on-line monitoring of moisture and/or urea content in a kind of detection isocyanates |
| CN108659201A (en) * | 2018-06-08 | 2018-10-16 | 北京中煤矿山工程有限公司 | Anti- well drilling machine reaming construction broken formation gib material |
| CN115894302A (en) * | 2022-10-20 | 2023-04-04 | 山东新和成维生素有限公司 | Process for the preparation of biuret polyisocyanates |
| CN115894302B (en) * | 2022-10-20 | 2024-06-25 | 山东新和成维生素有限公司 | Process for preparing biuret polyisocyanates |
| CN116041224A (en) * | 2023-01-31 | 2023-05-02 | 美瑞新材料股份有限公司 | Preparation method of hexamethylene diisocyanate biuret curing agent |
| CN116041224B (en) * | 2023-01-31 | 2024-02-13 | 美瑞新材料股份有限公司 | Preparation method of hexamethylene diisocyanate biuret curing agent |
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