CN105601965B - A kind of method for preparing polyurethane-poly-isocyanurate film functionally gradient material (FGM) - Google Patents
A kind of method for preparing polyurethane-poly-isocyanurate film functionally gradient material (FGM) Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1816—Catalysts containing secondary or tertiary amines or salts thereof having carbocyclic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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Abstract
The invention discloses a kind of methods for preparing polyurethane polyureas isocyanuric acid ester film functionally gradient material (FGM), this method is using aromatic diisocyanate, oligomer diol as raw material, organotin, blue the Sudan are catalyst, polyurethane polyureas isocyanuric acid ester cross-linked network is made by urethane formation reaction and polycyclotrimerization reaction, the solution containing reactant and catalyst then is poured into curing on hydrophobic mold obtains such film.The present invention matches different reaction mixture solutions and is poured on a horizontal hydrophobic surface, it can make one surface elastic modulus height of obtained gradient film, and another surface elastic modulus is low, graded is presented from a surface to another surface for elasticity modulus on film thickness direction, and there is no interfaces, macro manifestations go out on prepared film through-thickness from soft rubber to duroplasts graded, brittleness, the fragility of plastic film can be overcome, can also solve the characteristic that rubber film elasticity modulus changes with the variation of strain.
Description
Technical field
The present invention relates to a kind of methods for preparing polyurethane-poly-isocyanurate film functionally gradient material (FGM), belong to thin-film material
Preparation field.
Background technology
People are due to aerospace earliest since metal and alloy to the synthesis of functionally gradient material (FGM) and performance study
The needs of field development, Japanese Scientists are formal in 1984 to propose functionally graded material this concept, is flown with solving space flight
Machine engine chamber wall one side must bear to be more than 2000 DEG C of high temperature, and opposite side is subjected to ultralow temperature liquid hydrogen and cools down this to ask
Topic.Functionally graded material basic thought is according to specific requirement, selects two kinds of materials with different performance, passes through company
Change composition, structure or combining form of two kinds of materials etc. continuously, the internal interface of composite material is made to disappear, so as to obtain function
The gradual heterogeneous material corresponding to the variation of the Nomenclature Composition and Structure of Complexes, to reduce and overcome the performance of engaging portion to mismatch factor.
The material is noteworthy characterized by component structure transitivity parameter on one-dimensional, two-dimentional or three-dimensional all in consecutive variations, and
The comprehensive performance of material in the corresponding direction also in consecutive variations, this allow for functionally gradient material (FGM) can preferably adapt to varying environment with
Meet some special needs.
This concept of functionally gradient material (FGM) introduces polymer arts and there was only short more than the 20 years time, in recent years polymer gradient material
Expect that (PGM) development is very rapid.Without such as apparent interface of double layer material, they have compositions of consecutive variations, show PGM
It is ripe to go out the remarkable ability for the resisting juxtaposition metamorphose and damage and crazing extension institute that behaves, particularly the relaxation property of PGM and its
Its polymer phase is than significantly different.In this case, the cyclically-varying of Young's modulus can hinder crazing to extend.Therefore, PGM
It is the influence for being not susceptible to radial stress, this is the advantages of it is main compared with double layer material.This phenomenon can also explain PGM
The raising of middle dissipative stress.Specifically, the experiment of stress/strain, which has been reacted, can enhance breaking strain using PGM and improve
Vibration damping characteristic.
Polyurethane elastomer is the high molecular synthetic material between rubber and plastics, is a kind of Soft hard segment structure alternating
The block polymer of composition, wherein soft segment in elastomeric state, can generate very big stretcher strain at room temperature, and hard section is soft
The elongation and deformation of section provide node.As a kind of good material of preparing, exploitation and the research of film are increasingly taken seriously,
The field of application also progressively expands.But pure polyurethane film is since property is relatively single, relatively more limited in application aspect.In recent years
Come as market is to the increase of the demand of novel film materials and the development of membrane technology, the research to the modification of polyurethane film
Also gradually deeply, polyurethane inorganic particulate composite membrane is made or with such as vinegar in addition inorganic particulate such as in polyurethane film
Sour fiber (CA), it is poly- sough (PS), the polymer such as polyacrylonitrile (PAN) and polyurethane are into blend film.These gather by modified
Urethane film is all expected to become the new membrane material with some specific functions.
Polymer gradient material prepared by existing method can not make elasticity modulus that can not disappear in a broad range
Except the viscoplasticity of rubber and plastic transition region.
The content of the invention
Goal of the invention：In order to overcome the deficiencies in the prior art, present invention proposition is a kind of to prepare polyurethane-poly- isocyanide
The method of urea acid esters film functionally gradient material (FGM), the film of preparation has preferable thermal stability and dielectric properties, and overcomes modeling
Expect major defect-fragility of film.
Technical solution：In order to solve the above technical problems, the present invention's prepares polyurethane-poly-isocyanurate film gradient material
The method of material, comprises the following steps：
(1) oligomer diol stirring is warming up to 100-110 DEG C, and 2-3 is carried out dehydrating under -0.3~-0.1MPa
Hour；
(2) temperature of object glycol to be oligomerized is reduced to 50-60 DEG C, and the aromatic series two for adding in 2-2.2 times of the amount of its substance is different
Polyisocyanate reactant 30-40 minutes after being warming up to 75-85 DEG C of reaction 1h, adds in the 0.05- compared with oligomer dihydric alcohol quality
When 0.1wt% organotin catalysts the reaction was continued 1-2 is small, then to above-mentioned mixed system vacuumizing and defoaming, obtains end NCO bases and gather
Urethane performed polymer；
(3) anhydrous solvent that 60~80wt% of performed polymer quality fraction is added in the performed polymer into step (2) fully stirs
It mixes to reduce system viscosity, the diisocyanate of 0~90wt% of performed polymer quality is then added in, compared with performed polymer quality
Cyclotrimerization occurs in the presence of 1wt%~2.5wt% the Sudan indigo plant catalyst, when this process time 1-2 is small, makes in the system
Generation part cyclotrimerization makes its molecular weight and after solution viscosity reaches certain value, and the large-sized polymers generated at this time are still
The linear structure for being can be dissolved in solvent, this is unlikely to collapse when being and forming a film in hydrophobic substrates to be next cast in,
Film forming can be stablized；
(4) solution after above-mentioned deaeration being cast in a horizontal hydrophobic substrates, film passes through after soft drying,
The reaction of body polycyclotrimerization occurs under progressively heating condition for ladder-elevating temperature in the range of 60 DEG C -120 DEG C, the film of formation until anti-
It should be properly completed, form fully crosslinked polyurethane-poly-isocyanurate film.
Preferably, the oligomer diol in the step (1) is THF-PO copolymer glycol or end hydroxyl
Base polybutadiene, THF-PO copolymer glycol, between 60-70mgKOH/g, number-average molecular weight exists hydroxyl value
Between 1600-2000；End hydroxy butadiene, hydroxyl value between 50-60mgKOH/g, number-average molecular weight 1800-2400 it
Between.
Preferably, the diisocyanate is 2,4- toluene di-isocyanate(TDI)s (2,4-TDI), 2,4- diphenyl methanes two
One kind in the mixture of isocyanates or 4,4'- methyl diphenylene diisocyanate (MDI-50).
Preferably, the organotin catalysts in the step (2) are dibutyl tin laurate or stannous octoate, the Sudan
Blue catalyst is 1- methylamino -4- to phenylamino anthraquinone (the Sudan indigo plant G).
Preferably, the anhydrous solvent in the step (3) is acetone, cyclohexanone or ethyl acetate.
Preferably, the ladder-elevating temperature in the step (4) is 60 DEG C of heat preservation a period of times, it is warming up to 80 DEG C and keeps the temperature one section
Time is warming up to 100 DEG C of heat preservation a period of times, is finally warming up to 120 DEG C of heat preservation a period of times.
The reaction equation of two-step method is figure below in the present invention：The isocyanuric acid ester three-membered ring that is drawn in figure with dotted line and its it is connected
Aromatic rings play the role of crosslinking points, be film rigid structure；And the Rn being connected in by urethano between crosslinking points is played
The effect of flexible chain is the flexible structure of film.
The first step:Base polyurethane prepolymer for use as synthesis urethane forms reaction
Wherein R is:
R' is
Second step:Film hardening --- polycyclotrimerization reacts
The present invention has synthesized polyurethane-poly-isocyanurate network, this material by theoretical calculation with CAD
For material in -60-140 DEG C of temperature ranges, the transformation from glassy state to rubbery state is a progressive smooth process, i.e. elasticity modulus
It is a progressive smooth process from the variation of peak to peak, in transition region and so.Therefore tradition is improved
Polymer is in rubber and plastic transition region due to viscoelastic presence so that larger deformation, and temperature can occurs in it under external force
Lifting elasticity modulus by a small margin, which occurs, for degree can occur variation drastically, it is impossible to the defects of as high-performance engineering material.Simultaneously
This material contains a large amount of isocyanurate rings, therefore with preferable thermal stability and dielectric properties.
In view of the highly cross-linked rigid network structure of frosting, it may be considered that being prepared by functionally gradient material (FGM)
Technology, we can prepare film by highly cross-linked polymer, and overcome major defect-fragility of plastic film.
The design concept of gradient film can solve the problems, such as another of rubbery state film.All rubber materials all have
So-called S types stress strain curve (load-deformation curve), this means that the elastic modulus E (E=δ/ε) of rubber material is not one
A constant, but change with the variation of strain., it is necessary to prepare load-deformation curve in broad range in rubber engineering
For the material of linear relationship, it can be designed by gradient technology of preparing and prepare this material.
Contain in the polyurethane synthesized by aromatic diisocyanate and oligomer diol-poly-isocyanurate cross-linked polymer
There is substantial amounts of isocyanurate ring, this polymer network has rigid structure.Therefore, by these polymers film very
It is crisp, it easily cracks, there is fragility.This defect can be eliminated by designing film of the preparation with hardness gradient,
So that seamlessly transitting from plastics state to rubbery state occurs from one side to opposite side in the gradient film, showing a surface has
High elastic modulus, a surface has low elastic modulus, according to the elasticity modulus of the different polymer of film thickness and other property
Graded can be presented from a surface to another surface, and any boundary layer and glue are not present on film thickness direction
Connect layer.The solution for matching different reaction mixtures is poured into a horizontal hydrophobic substrates, such film can be obtained.It should
The mechanical performance of film can be regulated and controled by the ratio for the different chemical structures for during the reaction changing polymer, be led to simultaneously
It crosses and designs different film thicknesses, it is possible to obtain the gradient film of arbitrary modulus.
Advantageous effect：The method for preparing polyurethane-poly-isocyanurate film functionally gradient material (FGM) of the present invention has following excellent
Point：
(1) single thin-film material is made elasticity modulus and other performance along film thickness direction gradual change by the present invention
Gradient-structure is designed into highly cross-linked polymer network structure, wherein rigid isocyanurate ring is as large volume
Crosslinking points, oligomer polyol play the role of flexible chain, then, can also be in cross-linked network even if being added without plasticizer and filler
The ratio for changing rigid structure and flexible structure by adjusting rate of charge in the process is complexed into, so as to fulfill elasticity modulus same
One material internal consecutive variations, material macroscopically show as the change from soft rubber to duroplasts.It can be handed over simultaneously by changing
The chemical constitution and length of flexible chain between connection point further expand the performance range of polyurethane-poly-isocyanurate film；
(2) the present invention overcomes brittleness, the fragility of traditional conventional plastic film, traditional rubbery state thin flexible film modulus with
The variation of strain and change, realize seamlessly transitting from rubber to plastics on film thickness direction, and can be by designing not
Same film thickness, can obtain the gradient film that elasticity modulus arbitrarily changes in the range of 2-3 to 2800MPa.In the present invention,
We can arbitrarily control the elasticity modulus of gained film, make it that smooth continuous change occur in a larger scope,
And without interface.Simultaneously because the presence of a large amount of isocyanurate rings so that the film has preferable thermal stability and dielectric
Performance.Therefore material can be used as damper, silencer to use；Radio electronics industry and instrument and equipment neck can also be widely used in
Domain.
Specific embodiment
Embodiment 1
The THF-PO copolymer glycol (PF-OP-151700) of 85.00g (0.05mol) is added to
In 500ml three-necked flasks, stirring is warming up to 105 DEG C, the vacuum dehydration 2h under -0.1MPa, when temperature is reduced to 60 DEG C or so,
2, the 4- toluene di-isocyanate(TDI)s (2,4-TDI) of 17.40g (0.1mol) are added in three-necked flask, natural reaction 40min
Afterwards, 80 DEG C are to slowly warm up to the reaction was continued 1h, add in 0.05g (THF-PO copolymer glycol quality
0.05wt%) dibutyltin dilaurate catalyst the reaction was continued 1.5 it is small when, then above-mentioned mixed system vacuumizing and defoaming is obtained
To 102.4g ends NCO based polyurethanes performed polymers；
The anhydrous propanone that 81.92g (80wt%) is added in into above-mentioned performed polymer is sufficiently stirred to reduce system viscosity, then
Cyclotrimerization occurs in the presence of the Sudan's indigo plant G catalyst of addition 1.54g (1.5%), when this process time 2 is small, makes in the body
Part cyclotrimerization occurs in system, makes its molecular weight and after solution viscosity reaches certain value, the large scale polymerization generated at this time
The linear structure that object is still can be dissolved in solvent, be cast on a Teflon mold, in vacuum drying chamber deaeration and continue this
Precursor reactant, film pass through after soft drying, (60 DEG C/2h+80 DEG C/3h+100 DEG C/2h of ladder-elevating temperature in the range of 60 DEG C -120 DEG C
+ 120 DEG C/2h), 60 DEG C/2h+80 DEG C/3h+100 DEG C/2h+120 DEG C/2h is：Two hours are kept the temperature at 60 DEG C, is warming up to 80 DEG C
Heat preservation three hours is warming up to 100 DEG C and keeps the temperature two hours, is finally warming up to 120 DEG C and keeps the temperature two hours, and the film of formation is progressively adding
Cyclotrimerization occurs under heat condition to be properly completed until reacting, forms fully crosslinked cured polyurethane-poly-isocyanurate
Film.
Show raw material PF-OP-15 in 3540cm performed polymer infrared analysis-1The characteristic peak for locating hydroxyl disappears；2,4-TDI is mono-
Body is in 2270cm-1The antisymmetric stretching vibration absworption peak of place's isocyanate group weakens with prepolymerization reaction, in 1615cm-1、
1578cm-1、1525cm-1The feature skeletal vibration of phenyl ring at 3 as reaction carries out decrease disappearance, illustrates that two kinds of raw materials occur
Urethane forms reaction, generates terminal isocyanate group base polyurethane prepolymer for use as.Polyurethane-poly-isocyanurate film is carried out infrared
Analysis shows that in 1720cm-1、1420cm-1、760cm-1Occur the characteristic absorption peak of isocyanuric acid ester at 3, illustrate main in product
It is the trimerization product of the six-membered cyclic structure containing isocyanuric acid ester ,-NCO group stretching vibration absworption peak disappears, illustrates to add in substantially
TDI monomers and performed polymer substantially completely react, NCO group content is extremely low.3348cm-1And 1542cm-1Neighbouring absworption peak is then
Show the presence of ammonia ester bond.It was therefore concluded that the prepolymerization reaction of oligomer diol and isocyanates is given birth in the first step
Into the base polyurethane prepolymer for use as of end NCO bases, in the presence of the Sudan's indigo plant G catalyst cyclotrimerization occurs for second step, by progressively
It is heating and curing to obtain the film with isocyanurate ring.Thermogravimetric analysis shows that this film has 3 thermal decomposition stages:150~
It is mainly the fracture of ammonia ester bond between 300 DEG C, has regenerated the reactants such as TDI and alcohol and some micromolecular compounds, mainly
Caused by the interface phase decomposition between the soft segment area of material and stiffness region, since the presence of isocyanurate ring stiffening ring reduces
The stability for the amino-formate bond being connected with soft segment, while form crosslinking with TDI again dimerization generation carbodiimides
The side reactions such as structure；It is mainly the decomposition of isocyanurate ring between 300~420 DEG C；For in film in the range of 420~470 DEG C
Soft segment molecular backbone fast decoupled.Carbon yield is 12% or so.
Performance test：Vulcanize the measure of rubber or thermoplastic elastomer tensile stress-strain performance by GB/T 528-2009, treat
Sample is dumbbell shape, total length 100mm, and narrow length is 25mm, and narrow parallel width is 5mm, the drawing of test sample
Stretch intensity, elongation at break, elasticity modulus；Shore hardness is tested by GB/T 531.1-2008.Test result is shown in Table 1.
Embodiment 2
The THF-PO copolymer glycol (PF-OP-151700) of 85.00g (0.05mol) is added to
In 500ml three-necked flasks, stirring is warming up to 100 DEG C, the vacuum dehydration 2h under -0.3MPa, when temperature is reduced to 50 DEG C or so,
2, the 4- toluene di-isocyanate(TDI)s (2,4-TDI) of 17.40g (0.1mol) are added in three-necked flask, natural reaction 40min
Afterwards, 85 DEG C are to slowly warm up to the reaction was continued 1h, adding in 0.05g (0.05wt%) dibutyltin dilaurate catalyst, the reaction was continued
1.5 it is small when, then to above-mentioned mixed system vacuumizing and defoaming, obtain end NCO based polyurethanes performed polymers.
The anhydrous propanone that 81.92g (80wt%) is added in into above-mentioned performed polymer is sufficiently stirred to reduce system viscosity, then
5.12g (5wt% of performed polymer quality) 2,4-TDI is added in, the Sudan indigo plant G of 1.62g (1.5%) is stirring evenly and then adding into, is urging
Cyclotrimerization occurs in the presence of agent, when this process time 2 is small, then is cast in a horizontal hydrophobic substrates, in vacuum
Simultaneously bulk polymerization occurs for drying box deaeration, drying box (60 DEG C/2h+80 DEG C/3h of ladder-elevating temperature in the range of 60 DEG C -120 DEG C
+ 100 DEG C/2h+120 DEG C/2h), cyclotrimerization occurs under progressively heating condition and is properly completed until reacting for the film of formation,
Form fully crosslinked cured polyurethane-poly-isocyanurate film.
Infrared analysis is carried out to this film and is shown in 1720cm-1、1420cm-1、760cm-1Occurs isocyanuric acid ester at 3
Characteristic absorption peak, illustrate in product be mainly the six-membered cyclic structure containing isocyanuric acid ester trimerization product ,-NCO base stretching vibrations
Absworption peak disappears substantially, illustrates that the TDI monomers added in and performed polymer substantially completely react ,-NCO base contents are extremely low.3348cm-1With
1542cm-1Neighbouring absworption peak then shows the presence of ammonia ester bond.Thermogravimetric analysis shows that this film starting heat decomposition temperature is 165
DEG C, maximum heat decomposition temperature is 352 DEG C, carbon yield 15%.
Its performance test methods the results are shown in Table 1 with embodiment 1.
Embodiment 3
The THF-PO copolymer glycol (PF-OP-151700) of 85.00g (0.05mol) is added to
In 500ml three-necked flasks, stirring is warming up to 105 DEG C, the vacuum dehydration 2h under -0.1MPa, when temperature is reduced to 55 DEG C or so,
2, the 4- toluene di-isocyanate(TDI)s (2,4-TDI) of 17.40g (0.1mol) are added in three-necked flask, natural reaction 40min
Afterwards, 80 DEG C are to slowly warm up to the reaction was continued 1h, add in 0.1g (0.1wt%) dibutyltin dilaurate catalyst the reaction was continued 2
Hour, then to above-mentioned mixed system vacuumizing and defoaming, obtain end NCO based polyurethanes performed polymers.
The anhydrous propanone that 61.44g (60wt%) is added in into above-mentioned performed polymer is sufficiently stirred to reduce system viscosity, then
10.24g (10wt% of performed polymer quality) 2,4-TDI is added in, is stirring evenly and then adding into the Sudan indigo plant G of 1.72g (1.5%), body
Cyclotrimerization occurs in the presence of a catalyst for system, when this process time 1 is small, is then cast in a horizontal hydrophobic substrates again
On, in vacuum drying chamber deaeration and (60 DEG C/2h+80 DEG C/3h+100 DEG C/2h+120 of ladder-elevating temperature in the range of 60 DEG C -120 DEG C
DEG C/2h), cyclotrimerization occurs under progressively heating condition for the film of formation until reaction is properly completed, and formation is fully crosslinked
Cured polyurethane-poly-isocyanurate film.
Infrared analysis is carried out to this film and is shown in 1720cm-1、1420cm-1、760cm-1Occurs isocyanuric acid ester at 3
Characteristic absorption peak, illustrate in product be mainly the six-membered cyclic structure containing isocyanuric acid ester trimerization product ,-NCO base stretching vibrations
Absworption peak disappears substantially, illustrates that the TDI monomers added in and performed polymer substantially completely react ,-NCO base contents are extremely low.3348cm-1With
1542cm-1Neighbouring absworption peak then shows the presence of ammonia ester bond.Thermogravimetric analysis shows that this film starting heat decomposition temperature is 165
DEG C, maximum heat decomposition temperature is 352 DEG C, carbon yield 16%.
Its performance test methods the results are shown in Table 1 with embodiment 1.
Embodiment 4
The THF-PO copolymer glycol (PF-OP-151700) of 85.00g (0.05mol) is added to
In 500ml three-necked flasks, stirring is warming up to 100 DEG C, the vacuum dehydration 2h under -0.1MPa, when temperature is reduced to 60 DEG C or so,
2, the 4- toluene di-isocyanate(TDI)s (2,4-TDI) of 19.14g (0.11mol) are added in three-necked flask, natural reaction 40min
Afterwards, 80 DEG C are to slowly warm up to the reaction was continued 1h, adding in 0.05g (0.05wt%) dibutyltin dilaurate catalyst, the reaction was continued
1.5 it is small when, then to above-mentioned mixed system vacuumizing and defoaming, obtain end NCO based polyurethanes performed polymers.
The anhydrous propanone that 72.9g (70wt%) is added in into above-mentioned performed polymer is sufficiently stirred to reduce system viscosity, then
20.83g (20wt% of performed polymer quality) 2,4-TDI is added in, is stirring evenly and then adding into the Sudan indigo plant G of 2.02g (1.5%), body
Cyclotrimerization occurs in the presence of a catalyst for system, when this process time 2 is small, is then cast in a horizontal hydrophobic substrates again
On, in vacuum drying chamber deaeration and (60 DEG C/2h+80 DEG C/3h+100 DEG C/2h+120 of ladder-elevating temperature in the range of 60 DEG C -120 DEG C
DEG C/2h), cyclotrimerization occurs under progressively heating condition for the film of formation until reaction is properly completed, and formation is fully crosslinked
Cured polyurethane-poly-isocyanurate film.
Infrared analysis is carried out to this film and is shown in 1720cm-1、1420cm-1、760cm-1Occurs isocyanuric acid ester at 3
Characteristic absorption peak, illustrate in product be mainly the six-membered cyclic structure containing isocyanuric acid ester trimerization product ,-NCO base stretching vibrations
Absworption peak disappears substantially, illustrates that the TDI monomers added in and performed polymer substantially completely react ,-NCO base contents are extremely low.3348cm-1With
1542cm-1Neighbouring absworption peak then shows the presence of ammonia ester bond.Thermogravimetric analysis shows that this film starting heat decomposition temperature is 165
DEG C, maximum heat decomposition temperature is 352 DEG C, carbon yield 20%.
Its performance test methods the results are shown in Table 1 with embodiment 1.
Embodiment 5
The THF-PO copolymer glycol (PF-OP-151700) of 85.00g (0.05mol) is added to
In 500ml three-necked flasks, stirring is warming up to 105 DEG C, the vacuum dehydration 2h under -0.1MPa, when temperature is reduced to 60 DEG C or so,
2, the 4- toluene di-isocyanate(TDI)s (2,4-TDI) of 17.40g (0.1mol) are added in three-necked flask, natural reaction 40min
Afterwards, 80 DEG C are to slowly warm up to the reaction was continued 1h, adding in 0.05g (0.05wt%) dibutyltin dilaurate catalyst, the reaction was continued
1.5 it is small when, then to above-mentioned mixed system vacuumizing and defoaming, obtain end NCO based polyurethanes performed polymers.
The anhydrous propanone that 81.92g (80wt%) is added in into above-mentioned performed polymer is sufficiently stirred to reduce system viscosity, then
40.96g (40wt% of performed polymer quality) 2,4-TDI is added in, is stirring evenly and then adding into the Sudan indigo plant G of 2.25g (1.5%), body
Cyclotrimerization occurs in the presence of a catalyst for system, when this process time 2 is small, is then cast in a horizontal hydrophobic substrates again
On, be placed in vacuum drying chamber deaeration and in the range of 60 DEG C -120 DEG C staged heating (60 DEG C/2h+80 DEG C/3h+100 DEG C/
2h+120 DEG C/2h), cyclotrimerization occurs under progressively heating condition and is properly completed until reacting for the film of formation, has been formed
Polyurethane-poly-isocyanurate film of full crosslinking curing.
Infrared analysis is carried out to this film and is shown in 1720cm-1、1420cm-1、760cm-1Occurs isocyanuric acid ester at 3
Characteristic absorption peak, illustrate in product be mainly the six-membered cyclic structure containing isocyanuric acid ester trimerization product ,-NCO base stretching vibrations
Absworption peak disappears substantially, illustrates that the TDI monomers added in and performed polymer substantially completely react ,-NCO base contents are extremely low.3348cm-1With
1542cm-1Neighbouring absworption peak then shows the presence of ammonia ester bond.Thermogravimetric analysis shows that this film starting heat decomposition temperature is 175
DEG C, maximum heat decomposition temperature is 357 DEG C, carbon yield 24%.
Performance test：By the tensile strength of GB/T 1040.3-2006 test samples, elongation at break, elasticity modulus；Shao
Family name's hardness is pressedGB/T 2411-2008 are tested.Test result is shown in Table 1.
Embodiment 6
The THF-PO copolymer glycol (PF-OP-151700) of 85.00g (0.05mol) is added to
In 500ml three-necked flasks, stirring is warming up to 105 DEG C, the vacuum dehydration 2h under -0.1MPa, when temperature is reduced to 60 DEG C or so,
2, the 4- toluene di-isocyanate(TDI)s (2,4-TDI) of 17.40g (0.1mol) are added in three-necked flask, natural reaction 40min
Afterwards, 80 DEG C are to slowly warm up to the reaction was continued 1h, adding in 0.05g (0.05wt%) dibutyltin dilaurate catalyst, the reaction was continued
1.5 it is small when, then to above-mentioned mixed system vacuumizing and defoaming, obtain end NCO based polyurethanes performed polymers.Add into above-mentioned performed polymer
The anhydrous propanone for entering 81.92g (80wt%) is sufficiently stirred to reduce system viscosity, then add in 61.44g (performed polymer quality
60wt%) 2,4-TDI, it is stirring evenly and then adding into the Sudan indigo plant G of 2.46g (1.5%), system initial ring three in the presence of a catalyst
Poly- reaction, when this process time 2 is small, is then cast in a horizontal hydrophobic substrates, is placed in deaeration in vacuum drying chamber again
And staged heating (60 DEG C/2h+80 DEG C/3h+100 DEG C/2h+120 DEG C/2h), the film of formation in the range of 60 DEG C -120 DEG C
Cyclotrimerization occurs under progressively heating condition to be properly completed until reacting, the fully crosslinked cured polyurethane of formation-poly- different
Cyanurate film.
Infrared analysis is carried out to this film and is shown in 1720cm-1、1420cm-1、760cm-1Occurs isocyanuric acid ester at 3
Characteristic absorption peak, illustrate in product be mainly the six-membered cyclic structure containing isocyanuric acid ester trimerization product ,-NCO base stretching vibrations
Absworption peak disappears substantially, illustrates that the TDI monomers added in and performed polymer substantially completely react ,-NCO base contents are extremely low.3348cm-1With
1542cm-1Neighbouring absworption peak then shows the presence of ammonia ester bond.Thermogravimetric analysis shows that this film starting heat decomposition temperature is 175
DEG C, maximum heat decomposition temperature is 360 DEG C, carbon yield 25%.
Its performance test methods the results are shown in Table 1 with embodiment 5.
Embodiment 7
The THF-PO copolymer glycol (PF-OP-151700) of 85.00g (0.05mol) is added to
In 500ml three-necked flasks, stirring is warming up to 105 DEG C, the vacuum dehydration 2h under -0.1MPa, when temperature is reduced to 60 DEG C or so,
2, the 4- toluene di-isocyanate(TDI)s (2,4-TDI) of 17.40g (0.1mol) are added in three-necked flask, natural reaction 40min
Afterwards, 80 DEG C are to slowly warm up to the reaction was continued 1h, adding in 0.05g (0.05wt%) dibutyltin dilaurate catalyst, the reaction was continued
1.5 it is small when, then to above-mentioned mixed system vacuumizing and defoaming, obtain end NCO based polyurethanes performed polymers.Add into above-mentioned performed polymer
The anhydrous propanone for entering 81.92g (80wt%) is sufficiently stirred to reduce system viscosity, then add in 81.92g (performed polymer quality
80wt%) 2,4-TDI, it is stirring evenly and then adding into the Sudan indigo plant G of 2.82g (1.5%), system initial ring three in the presence of a catalyst
Poly- reaction, when this process time 2 is small, is then cast in a horizontal hydrophobic substrates, is placed in deaeration in vacuum drying chamber again
And staged heating (60 DEG C/2h+80 DEG C/3h+100 DEG C/2h+120 DEG C/2h), the film of formation in the range of 60 DEG C -120 DEG C
Cyclotrimerization occurs under progressively heating condition to be properly completed until reacting, the fully crosslinked cured polyurethane of formation-poly- different
Cyanurate film.
Infrared analysis is carried out to this film and is shown in 1720cm-1、1420cm-1、760cm-1Occurs isocyanuric acid ester at 3
Characteristic absorption peak, illustrate in product be mainly the six-membered cyclic structure containing isocyanuric acid ester trimerization product ,-NCO base stretching vibrations
Absworption peak disappears substantially, illustrates that the TDI monomers added in and performed polymer substantially completely react ,-NCO base contents are extremely low.3348cm-1With
1542cm-1Neighbouring absworption peak then shows the presence of ammonia ester bond.Thermogravimetric analysis shows that this film starting heat decomposition temperature is 175
DEG C, maximum heat decomposition temperature is 365 DEG C, carbon yield 28%.
Its performance test methods the results are shown in Table 1 with embodiment 5.
Embodiment 8
The end hydroxy butadiene (HTPB 2000) of 100.00g (0.05mol) is added in 500ml three-necked flasks,
110 DEG C, vacuum dehydration 2h under -0.1MPa, when temperature is reduced to 60 DEG C or so, by 2, the 4- toluene two of 17.40g (0.1mol)
Isocyanates (2,4-TDI) is added in three-necked flask, after natural reaction 40min, is to slowly warm up to 80 DEG C the reaction was continued 1h, add
Enter 0.05g (0.05wt%) dibutyltin dilaurate catalyst the reaction was continued 1.5 it is small when, then above-mentioned mixed system is taken out true
Empty deaeration obtains end NCO based polyurethanes performed polymers.The anhydrous propanone that 93.92g (80wt%) is added in into above-mentioned performed polymer is abundant
Then stirring adds in 23.48g (20wt% of performed polymer quality) 2,4-TDI, is stirring evenly and then adding into reduce system viscosity
Cyclotrimerization occurs in the presence of a catalyst for the Sudan indigo plant G of 2.11g (1.5%), system, when this process time 2 is small, Ran Houzai
It is cast in a horizontal hydrophobic substrates, deaeration and the staged heating in the range of 60 DEG C -120 DEG C in vacuum drying chamber
Under progressively heating condition cyclotrimerization occurs for (60 DEG C/2h+80 DEG C/3h+100 DEG C/2h+120 DEG C/2h), the film of formation
Until reaction is properly completed, fully crosslinked cured polyurethane-poly-isocyanurate film is formed.
Infrared analysis is carried out to this film, display product is in 3540cm-1Hydroxyl characteristic peak disappear, in 2280cm-1's
The characteristic peak of isocyanate group disappears, and illustrates that two kinds of raw materials react completely；In 760cm-1And 1420cm-1There is isocyanic acid
The corresponding characteristic peak of ester ring, 3348cm-1Locate characteristic peak, the 1740cm of ammonia key-1Locate characteristic peak, the 1180cm of carbonyl-1Locate aryl oxide key
Characteristic peak illustrate the formation of ammonia ester bond and isocyanates ring, that is, urethane has occurred and forms reaction and cyclotrimerization.It therefore can
To draw a conclusion, prepared by two-step method and polyurethane-poly-isocyanurate film is formed by isocyanates ring.Thermogravimetric point
Analysis shows that this film starting heat decomposition temperature is 165 DEG C, and maximum heat decomposition temperature is 356 DEG C, carbon yield 15%.
Its performance test methods the results are shown in Table 1 with embodiment 1.
Embodiment 9
The end hydroxy butadiene (HTPB 2000) of 100.00g (0.05mol) is added in 500ml three-necked flasks,
110 DEG C, vacuum dehydration 2h under -0.1MPa, when temperature is reduced to 60 DEG C or so, by 2, the 4- toluene two of 17.40g (0.1mol)
Isocyanates (2,4-TDI) is added in three-necked flask, after natural reaction 40min, is to slowly warm up to 80 DEG C the reaction was continued 1h, add
Enter 0.05g (0.05wt%) dibutyltin dilaurate catalyst the reaction was continued 1.5 it is small when, then above-mentioned mixed system is taken out true
Empty deaeration obtains end NCO based polyurethanes performed polymers.The anhydrous propanone that 93.92g (80wt%) is added in into above-mentioned performed polymer is abundant
Then stirring adds in 46.96g (40wt% of performed polymer quality) 2,4-TDI, is stirring evenly and then adding into reduce system viscosity
Cyclotrimerization occurs in the presence of a catalyst for the Sudan indigo plant G of 2.67g (1.5%), system, when this process time 2 is small, Ran Houzai
It is cast in a horizontal hydrophobic substrates, deaeration and the staged heating in the range of 60 DEG C -120 DEG C in vacuum drying chamber
Under progressively heating condition cyclotrimerization occurs for (60 DEG C/2h+80 DEG C/3h+100 DEG C/2h+120 DEG C/2h), the film of formation
Until reaction is properly completed, fully crosslinked cured polyurethane-poly-isocyanurate film is formed.Infrared point is carried out to this film
Analysis, display product is in 3540cm-1Hydroxyl characteristic peak disappear, in 2280cm-1Isocyanate group characteristic peak disappear, say
Understand that two kinds of raw materials react completely；In 760cm-1And 1420cm-1There is the corresponding characteristic peak of isocyanates ring, 3348cm-1Place
Characteristic peak, the 1740cm of ammonia key-1Locate characteristic peak, the 1180cm of carbonyl-1The characteristic peak of place's aryl oxide key illustrates ammonia ester bond and isocyanic acid
The formation of ester ring has occurred urethane and forms reaction and cyclotrimerization.Therefore it may be concluded that being prepared by two-step method
Polyurethane-poly-isocyanurate film formed by isocyanates ring.Thermogravimetric analysis shows that this film originates heat decomposition temperature
For 165 DEG C, maximum heat decomposition temperature is 356 DEG C, carbon yield 17%.
Test method the results are shown in Table 1 with embodiment 5.
Embodiment 10
The end hydroxy butadiene (HTPB 2000) of 100.00g (0.05mol) is added in 500ml three-necked flasks,
110 DEG C, vacuum dehydration 2h under -0.1MPa, when temperature is reduced to 60 DEG C or so, by 2, the 4- toluene two of 17.40g (0.1mol)
Isocyanates (2,4-TDI) is added in three-necked flask, after natural reaction 40min, is to slowly warm up to 80 DEG C the reaction was continued 1h, add
Enter 0.05g (0.05wt%) dibutyltin dilaurate catalyst the reaction was continued 1.5 it is small when, then above-mentioned mixed system is taken out true
Empty deaeration obtains end NCO based polyurethanes performed polymers.The anhydrous propanone that 93.92g (80wt%) is added in into above-mentioned performed polymer is abundant
Then stirring adds in 158.5g (90wt% of performed polymer quality) 2,4-TDI, is stirring evenly and then adding into reduce system viscosity
Cyclotrimerization occurs in the presence of a catalyst for the Sudan indigo plant G of 3.26g (1.5%), system, when this process time 2 is small, Ran Houzai
It is cast in a horizontal hydrophobic substrates, deaeration and the staged heating in the range of 60 DEG C -120 DEG C in vacuum drying chamber
Under progressively heating condition cyclotrimerization occurs for (60 DEG C/2h+80 DEG C/3h+100 DEG C/2h+120 DEG C/2h), the film of formation
Until reaction is properly completed, fully crosslinked cured polyurethane-poly-isocyanurate film is formed.Infrared point is carried out to this film
Analysis, display product is in 3540cm-1Hydroxyl characteristic peak disappear, in 2280cm-1Isocyanate group characteristic peak disappear, say
Understand that two kinds of raw materials react completely；In 760cm-1And 1420cm-1There is the corresponding characteristic peak of isocyanates ring, 3348cm-1Place
Characteristic peak, the 1740cm of ammonia key-1Locate characteristic peak, the 1180cm of carbonyl-1The characteristic peak of place's aryl oxide key illustrates ammonia ester bond and isocyanic acid
The formation of ester ring has occurred urethane and forms reaction and cyclotrimerization.Therefore it may be concluded that being prepared by two-step method
Polyurethane-poly-isocyanurate film formed by isocyanates ring.Thermogravimetric analysis shows that this film originates heat decomposition temperature
For 165 DEG C, maximum heat decomposition temperature is 362 DEG C, carbon yield 21%.
Its performance test methods the results are shown in Table 1 with embodiment 5.
The performance of polyurethane-poly-isocyanurate film obtained by 1 each embodiment of table
The above is only the preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (5)
1. prepare the method for polyurethane-poly-isocyanurate film functionally gradient material (FGM), which is characterized in that comprise the following steps：
（1）Oligomer diol stirring is warming up to 100-110 DEG C, and be carried out dehydrating under -0.3 ~ -0.1MPa 2-3 it is small when；
（2）The temperature of object glycol to be oligomerized is reduced to 50-60 DEG C, adds in the aromatic diisocyanates of 2-2.2 times of the amount of its substance
Ester reacts 30-40 minutes, after being warming up to 75-85 DEG C of reaction 1h, adds in the 0.05-0.1wt% compared with oligomer dihydric alcohol quality
When organotin catalysts the reaction was continued 1-2 is small, then to above-mentioned mixed system vacuumizing and defoaming, it is pre- to obtain end NCO based polyurethanes
Aggressiveness；
（3）To step（2）In performed polymer in add in the anhydrous solvent of performed polymer quality fraction 60 ~ 80wt% and be sufficiently stirred, then
The diisocyanate of 0 ~ 90wt% of performed polymer quality is added in, in 1wt% ~ 2.5wt% the Sudan indigo plant catalyst compared with performed polymer quality
In the presence of occur cyclotrimerization, cyclotrimerization continue time 1-2 it is small when；
（4）Above-mentioned solution is cast in a horizontal positioned hydrophobic substrates, carry out deaeration, film by it is soft it is dry it
Afterwards, the reaction of body polycyclotrimerization occurs under progressively heating condition for the ladder-elevating temperature in the range of 60 DEG C -120 DEG C, the film of formation
Until reaction is properly completed, fully crosslinked polyurethane-poly-isocyanurate film is formed；
The step（1）In oligomer diol be THF-PO copolymer glycol or end hydroxy butadiene, four
Hydrogen furans-propylene oxide copolyethers glycol, hydroxyl value is between 60-70mgKOH/g, and number-average molecular weight is between 1600-2000；End
Hydroxyl polybutadiene, hydroxyl value is between 50-60mgKOH/g, and number-average molecular weight is between 1800-2400.
2. the method according to claim 1 for preparing polyurethane-poly-isocyanurate film functionally gradient material (FGM), feature exist
In：The diisocyanate is 2,4- toluene di-isocyanate(TDI)s, 2,4- methyl diphenylene diisocyanates or 4,4'- diphenyl
One kind in the mixture of methane diisocyanate.
3. the method according to claim 1 for preparing polyurethane-poly-isocyanurate film functionally gradient material (FGM), feature exist
In：The step（2）In organotin catalysts for dibutyl tin laurate or stannous octoate, the Sudan's indigo plant catalyst is 1- first
Amino -4- is to phenylamino anthraquinone.
4. the method according to claim 1 for preparing polyurethane-poly-isocyanurate film functionally gradient material (FGM), feature exist
In：The step（3）In anhydrous solvent be acetone, cyclohexanone or ethyl acetate.
5. the method according to claim 1 for preparing polyurethane-poly-isocyanurate film functionally gradient material (FGM), feature exist
In：The step（4）In ladder-elevating temperature for 60 DEG C heat preservation a period of time, be warming up to 80 DEG C heat preservation a period of time, be warming up to 100
DEG C heat preservation a period of time, be finally warming up to 120 DEG C heat preservation a period of time.
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