CN1376748A - Environment protection type polyurethane elastomer/laminated nano composition and its preparing process - Google Patents
Environment protection type polyurethane elastomer/laminated nano composition and its preparing process Download PDFInfo
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Abstract
An environment protection type composite polyurethane elastomer/nano laminated material is prepared through vacuum heating of dihydroxy polyoxyacrylether, dewatering, adding the mixture (MDI-50) of 4,4'-and 2,4'-diphenylmethane diisocyanate, reacting to obtain component A, compounding organic laminated nano material with trihydroxy or dihydroxy polyoxyacrylether, mixing with metaphenyldiamine pigment, filler and plasticizer to obtain component B, proportionally mixing components A with B, and laminating polymerization reaction under catalysis of zinc naphthenate. Its advantages are no pollution on preparing and using it, high mechanical performance, and excellent flame-retarding and anti-mildew performance.
Description
Technical field
The invention belongs to the polymer composite field.Be particularly related to environment protection type polyurethane elastomer/nano composite material and preparation method thereof, be mainly used in the laying of sports field.
Background technology
About the laying of sports field, a race track was at first laid with polyurethane material by Minnesota Mining and Manufacturing Company in 1961; The urethane surfacing material that nineteen sixty-eight 19 Olympic Games, stadium runway formally adopt 3M company to produce is laid (being called " tower when " (Tartan) runway), now by internationally recognized be best competition area, and generally adopted.The last century the eighties, the stadium runway with the urethane laying has also appearred in China.All continuing to use over more than twenty year and being similar to the Chinese invention patent application publication number is the formula system that CN1033639A adopted, that is: so-called TDI (tolylene diisocyanate) (A component) and MOCA (3,3 '-two chloro-4,4 '-diaminodiphenylmethane) (B component) system.Performance is up to state standards (GB/T14833-93) (with reference to table 1) reluctantly.
1), only be 105% because of the main mechanical mechanics property of product, as elongation at break the several of main problems that this formula system exists is:, can not adapt to sports field because of generations such as frozen ground, the water logging bases stress that deformation produced such as rupture, swell, subside, cause the fracture of urethane paver; 2), the flame retardant properties of product is lower, in fact, the flame retardant properties of domestic most of products does not all reach fire-retardant primary standard at present; 3), for anti-aging, mildew-resistant, added anti UV agent, antioxidant and the mould inhibitor of multiple pricing costliness, improved cost greatly, but add-on reaches actual requirement again far away, effect is unsatisfactory.4), the TDI (tolylene diisocyanate) that uses in the prescription, its vapour pressure reaches 10.9Pa (30 ℃), and direct labor's eye and respiratory tract etc. are had strong impulse and allergenic effect; And chain extension-crosslinking agent MOCA (3,3 '-two chloro-4,4 '-diaminodiphenyl-methane) belong to halogen aromatic amines, be the carcinogenic raw material of avoiding usefulness in the chemical industry.Therefore, in order to overcome the above problems, improve mechanical mechanics property, flame retardant properties and anti-aging, the mildew-resistant sex change energy of urethane paver; Simultaneously, the sports field that the raw material of the non-TDI-MOCA system of advocating according to International Track and Field Association of use comes the production excellent property is with polyurethane elastomer etc., just is necessary to consider synthetic from newly carrying out molecular designing and formula adjustment and using of the new technology the excellent more sports field paver of obtained performance to polyurethane elastomer.
Summary of the invention
Purpose of the present invention just is to solve as above problem, provide a kind of novel, that performance is excellent more, that be safe from harm to human body, to environment sports field paver and manufacture method thereof, i.e. environment protection type polyurethane elastomer/laminated nano composition sports field paver and preparation method thereof.
At first, the present inventor attempts the mechanical property that the applying nano materials new technology strengthens polyurethane elastomer.Common ultra-fine granular nano material such as silicon-dioxide, titanium dioxide etc. were used in test once.But it is when mixing,, more outstanding because the effect of the powerful Van der Waals between nano molecular " agglomeration ", especially inorganic nano material takes place in organic phase with the elastomeric high polymer monomer of synthesis of polyurethane.Can't show the small-size effect of nano molecular etc., also just can't reach enhancement to former polyurethane elastomer mechanical property, even with organic molecule ultra-fine granular nano material such as silicon-dioxide etc. are given " coating " in advance, effect is also very little, does not have the substantive phenomenon that strengthens.
Test by analysis, the present invention has selected the polynite of inorganic laminated nano material such as silico-aluminate or the hydrotalcite of Mg aluminate for use, effectively organise handle after, can avoid the agglomeration of nano material, thereby can show all manifold effects of nano material, reach the effect that strengthens the polyurethane elastomer mechanical property.Polynite (MMT) has the alkali feature, its basic structural unit is natural nano silicate lamella, and each layer constitutes about 1 nanometer of interlamellar spacing size by containing an alumina octahedral in two silicon-oxy tetrahedrons, about 100 nanometers of length and width, the residual negative electric charge on the lamella is by positively charged ion that is positioned at interlayer such as Na
+, Ca
++Deng cation balance.Available like this organic cation carries out ion exchange reaction and generates organic montmorillonoid (OMMT).And hydrotalcite (LDHs) has acidic character, becomes monolithic layer by the octahedra shared prismatic of magnesia, and the interlamellar spacing size is about 20～60 nanometers, is positioned at the magnesium ion (Mg on the layer
++) can be within the specific limits by AL ion (Al
+++) isomorphous substitution makes laminate have positive charge, and the positive charge balance on tradable negatively charged ion and the laminate is arranged between laminate.Therefore, available organic anion is carried out ion exchange reaction and is generated the hydrotalcite (OLDHs) that organises.
The present invention makes full use of the intercalation compounding technology to this inorganic laminated nano material, insert different stratified nano materials with different objects after, can assemble the stratified nano materials that organises with different performance.They carry out macromolecular polymerization reaction after fusing with the organic molecule monomer of forming urethane again, have obtained the enhancing polyurethane elastomer.The sports field of laying with the polyurethane elastomer/laminated nano composition of this technology preparation has higher mechanical mechanics property and fire-retardant, anti-mold effect.
After organic molecule carries out intercalation to the laminated structure nano material, general organic molecule has to a certain degree winding effect to the main body flaggy, this effect comes down to organising to inorganic lamellar material, and degree that organises and effect can be decided with object kind quantity, therefore use different stratified nano materials, select different intercalation objects can obtain the ideal interfacial effect, and the latter's enhancing is the key that the macromolecular material mechanical property improves.Stratified nano materials has the obstructing capacity to the micromolecular compound migration, can avoid as the molecular migration of the used softening agent of polyurethane elastomer/laminated nano composition involved in the present invention.(promptly preventing " oil impregnate " phenomenon of above-mentioned materials).Because the good combination of polyurethane elastomer and stratified nano materials by the planar orientation of laminar nano, makes it polyurethane elastomer/laminated nano composition and shows good dimensional stability, barrier, thereby has fire-retardant self-gravitation.The special construction of the matrix material of this polymer and laminar nano has significant inhibitory effect to multiple microorganism and fungus grown, has antimildew function.
In addition, in the urethane polymerization reaction process, the acid-basicity of medium is bigger to the speed of response influence, especially being used for different sport fields ground under different weathers lays, more to select different acid-basicity stratified nano materials, show weakly alkaline as organic montmorillonoid, but accelerated reaction speed.On the contrary, the hydrotalcite that organises is slightly acidic, can reduce speed of response.In like manner, also can be influential as the acid-basicity of the stopping composition in the polyurethane elastomer/laminated nano composition to polymerization rate.Especially in the polymerization reaction system of stratified nano materials is arranged under the condition of system viscosity thickening, do not wish that too fast speed of response (especially when the hot weather construction surface temperature is higher) more do not wish to use weakly alkaline talcum powder, so select weakly acidic potter's clay for use.And the latter to the reinforcement of elastic polyurethane/laminated nano composition fruit also be better than the former.
Secondly, the present invention replaces TDI, MOCA with MDI-50 and non-halo diamines.MDI-50 is 4, the 4 ' body of two cyanate ester based ditanes and the mixture of 2,4 ' body, is liquid under the room temperature, vapour pressure only be ten thousand of TDI/, do not constituted harm to human body.But not halo aryl diamine-mphenylenediamine does not have any corrodibility, can think a kind of polymer composite of no environmental protection harm of excellent property.
The environment protection type polyurethane elastomer/laminated nano composition sports field paver of the present invention's first scheme is, by the MDI-50 that gives aggressiveness (A component) (two cyanate ester based ditans 4,4 ' body, 2,4 ' body mixture) with dihydroxyl polyoxytrimethylene ether reactant, in the system of forming with the mphenylenediamine of chain extension-crosslinking agent (B component), polyhydroxy polycarboxylic propylene oxide ether solvate and catalyzer, organic montmorillonoid (OMMT) or the hydrotalcite that organises (OLDHs) stratified nano materials have been added.
The environment protection type polyurethane elastomer/laminated nano composition sports field paver of alternative plan of the present invention is that it specifically consists of in above-mentioned first scheme:
The A component is formed (weight percent)
The mixture 30-50% of 4,4 ' body of two cyanate ester based ditans and 2,4 ' body
Dihydroxyl polyoxytrimethylene ether 40-55%
Clorafin 8-15%
The B component is formed (weight percent)
Stratified nano materials 2-6% organises
Mphenylenediamine 1.5-3%
Trihydroxy-polyoxytrimethylene ether 20-30%
Dihydroxyl polyoxytrimethylene ether 3-8%
Pigment 3-5%
Potter's clay 25-40%
Clorafin 25-38%
Wherein, the weight ratio of A component and B component is 1: 3.Catalyst consumption be A component and B composition weight and 0.10-0.50%.
The environment protection type polyurethane elastomer/laminated nano composition sports field paver of third party's case of the present invention is in above-mentioned alternative plan, adds the black rubber grain (the track and field runway is used) of 20～30 weight % of this composite system.
The manufacture method of the environment protection type polyurethane elastomer/laminated nano composition sports field paver of the cubic case of the present invention is may further comprise the steps:
1) prepare the stratified nano materials (organic montmorillonoid (OMMT) or the hydrotalcite that organises (OLDHs)) that organises, in advance,
2), preparation A component, dihydroxyl polyoxytrimethylene ether and chlorinated paraffin computation weigh are joined in the reactor, under 80-85 ℃ of temperature, evenly stir and be evacuated to the 0.002MPa dehydration after 2-2.5 hour, fill nitrogen and recover normal pressure, be cooled to 40-45 ℃.Normal pressure adds the MDI-50 of metering down, and under dry N2 gas shiled, reaction is 2.5 hours under 80-85 ℃ of temperature, is cooled to 50 ℃, and the barrelling sealing is standby under nitrogen protection.
3), preparation B component, organise stratified nano materials and trihydroxy-polyoxytrimethylene ether, dihydroxyl polyoxytrimethylene ether with metering stir in reactor, under 80-90 ℃ of temperature, are evacuated to 0.002MPa and dewater 2-3 hour.In another stirring tank, pigment and softening agent are puddled and ground to form mill base through colloidal mill, again with the chainextender mphenylenediamine, stopping composition potter's clay and mill base puddle in the lump, after colloidal mill grinds, squeeze in the reactor under 80-90 ℃ of temperature with toothed gear pump, stratified nano materials and hydroxyl polyoxytrimethylene ether solvate stir with organising, after vacuum hydro-extraction 2-3 hour, be cooled to 50 ℃, the barrelling sealing is standby under normal pressure
4), at the on-the-spot environment protection type polyurethane elastomer/laminated nano composition sports field paver of laying of sports field, with the standby A component of aforesaid barrelling sealing, the B component is 1: 3 computation weigh by weight, stir, catalyzer (the A component that adds calculated amount, the weight of B component and 0.10～0.50 weight %) stir rapidly, it is ready-made in advance to pave immediately, on the smooth basis, under 15-35 ℃ of condition, about 30-60 divides inner gel, solidify in 24 hours, can come into operation after the complete slaking on the 14th, and survey its various mechanical properties etc.
The manufacture method of the environment protection type polyurethane elastomer/laminated nano composition sports field paver of the present invention's the 5th scheme is in cubic case of the present invention, the method for preparing organic montmorillonoid (OMMT) is, in the water of 80 ℃ of 800ml, add the 5g caprolactam and the 4ml vitriol oil, fully hydrolysis, slowly be injected into again and contain 20g sodium-polynite (anion-exchange capacity=90-100mmol/100g, particle diameter 40-70 μ m) in the aqueous solution, with this mixed solution 80 ℃ fierce stir 3 hours after, cooling, centrifuging is washed to no SO
4 =(use BaCl
2Solution detects no white precipitate), drying at room temperature, vacuum-drying is to constant weight again, and grinding is into about the powder that is 50-90 μ m.It is 1nm that na montmorillonite is surveyed interlamellar spacing with the WAXD instrument.The cheating engaging layer spacing survey that organises through ion exchange method is 1.9nm.
The manufacture method of the environment protection type polyurethane elastomer/laminated nano composition sports field paver of the present invention's the 6th scheme is in cubic case of the present invention, the method for preparing the hydrotalcite (OLDHs) that organises is, in the water of 80 ℃ of 800ml, add hydrotalcite (Mg
6Al
2(OH)
16CO
34H
2O) 20g under agitation dropwise adds the about 12g of Witco 1298 Soft Acid, until solution is not seen CO
2Bubble is overflowed, fully stir 2 hours after, centrifuging is washed to pH6.Grind after the vacuum-drying and be powder.Hydrotalcite layers is apart from being 0.79nm, and organising back with ion exchange method is 1.56nm with WAXD instrument test layer spacing.
The manufacture method of the environment protection type polyurethane elastomer/laminated nano composition sports field paver of the present invention's the 7th scheme is in cubic case of the present invention, the 4th) stage adds the black rubber grain (track and field runway with) of 20～30 weight % of this composite system during on-the-spot the laying.
More than in each scheme, catalyzer uses zinc naphthenate gasoline solution.
More than the specification of employed raw material be: the mixture (MDI-50) of two cyanate ditane 4,4 ' bodies and 2,4 ' body, the ratio of its 4,4 ' body and 2,4 ' body is between 40-60%, this variation of ratio does not influence product property substantially; Dihydroxyl polyoxytrimethylene ether (N220, N210, N204) molecular-weight average be respectively=2000,1000,400; Trihydroxy-polyoxytrimethylene ether (N330), molecular-weight average=3000; M.p.62-66 ℃ of mphenylenediamine (m-PDA); Pigment: redness is red iron oxide Fe
2O
3Green being mixed in proportion by phthalocyanine green (Cu-Pr), lemon yellow (Y-Cr) and chrome green (G-Cr) formed; Clorafin (Cl-P) cl content 50-52%; Potter's clay (Clay): Al
2O
3.2SiO
2, mean particle size 2-10 μ m, pH 6.72, wherein impurity F e content≤0.1%.
The present invention has changed the prescription of traditional sports field with polyurethane material, except brand-new consideration molecular designing make its more reasonable, adopted stratified nano materials intercalation composite polymeric technology emphatically, the mechanical property that makes matrix material is such as tensile strength, elongation at break greatly strengthens, amplification 1 times to more than 2 times, flame retardant properties all reaches country-level standard, improved the quality of sports field greatly, longer service life.Simultaneously, do not jeopardize operator's health in the preparation, do not jeopardize environmental protection in use.
Concrete embodiment
By the following examples the present invention is described further.(below, environment protection type polyurethane elastomer/laminated nano composition is abbreviated as " glue ").
Embodiment 1 track and field runway is laid and is used glue
(1) A component preparation
Divide another name N220 312kg, N210 206Kg and Cl-P 118Kg add in the reactor, stir under 80-85 ℃ of temperature, are evacuated to the 0.002MPa dehydration after 2 hours, fill nitrogen and recover normal pressure, are cooled to 45 ℃.Under nitrogen protection, add MDI-50 360Kg again, reaction is 2.5 hours under 80-85 ℃ of temperature, is cooled to 50 ℃, and the barrelling sealing is standby under the N2 gas shiled.
(2) B component preparation
Divide another name OMMT 45Kg and N330 236Kg, N204 45Kg in adding reactor, to stir, under 80-90 ℃ of temperature, be evacuated to 0.002MPa dehydration 2.5 hours.In another stirring tank, weighing adds Fe2O3 45Kg, Cl-P 365Kg, through evenly stirring, colloidal mill adds m-PDA 20Kg after grinding and making mill base successively again, clay 244Kg stirs in the lump and behind the colloidal mill porphyrize, squeezes into reactor under 80-85 ℃ of temperature condition with toothed gear pump, with OMMT, N330, the N204 solvate stirs in the lump, and vacuum hydro-extraction is after 2.5 hours, be cooled to 50 ℃, the barrelling sealing is standby under normal pressure.
(3) lay track and field runway glue at the scene
A component and B component were by weight 1: 3 computation weigh, be about to A component 20Kg, after B component 60Kg puddles evenly, add black rubber grain (d3-4mm) 20Kg, continuing under the stirring condition, add catalyzer zinc naphthenate gasoline solution (concentration 3%) 7Kg that accounts for glue gross weight 7% again, stir rapidly, pave immediately then in advance ready-made, smooth track and field runway basis, automatic levelling, gel solidification becomes glue.Slaking can formally be used after 14 days under the external temperature, and test performance (seeing Table 1).
Embodiment 2 track and field runways are laid and are used glue
(1) A component preparation, identical with embodiment 1.
(2) B component preparation
Except that using OLDHs 45Kg to replace the OMMT 45Kg, all the other are identical with embodiment 1.
(3) lay track and field runway glue at the scene
Account for catalyzer zinc naphthenate gasoline solution (concentration 3%) 8Kg of glue weight 8% except that adding, all the other are identical with embodiment 1.
(net, orchid, row) uses glue in embodiment 3 courts
(1) A component preparation
Divide another name N220 276Kg, N210 204Kg, Cl-P 98Kg adds in the reactor, stirs under 80-85 ℃ of temperature, is evacuated to the 0.002MPa dehydration after 2 hours, fills nitrogen and recovers normal pressure, is cooled to 45 ℃.Under nitrogen protection, add MDI-50 422Kg again, under 80-85 ℃ of temperature condition, reacted 2.5 hours, be cooled to 50 ℃, the barrelling sealing is standby under the N2 gas shiled.
(2) B component preparation
Divide another name OMMT 30Kg and N330 256Kg, N204 80Kg stirs in the adding reactor, under 80-90 ℃ of temperature, is evacuated to 0.002MPa dehydration 2.5 hours.In another stirring tank, weighing adds following pigment: Cu-Pr 6Kg, Y-Cr 22Kg, G-Cr 12Kg and Cl-P 295Kg are after evenly stir, colloidal mill grinds and makes mill base, add m-PDA 21Kg clay 278Kg successively again, stir in the lump and behind the colloidal mill porphyrize, squeeze into reactor under 80-85 ℃ of temperature condition with toothed gear pump, with OMMT, N330, the N204 solvate stirs in the lump, after the vacuum hydro-extraction 2.5 hours, be cooled to 50 ℃, the barrelling sealing is standby under normal pressure.
(3) lay ball place glue at the scene
A component and B component were by weight 1: 3 ratio computation weigh.Be about to A component 25Kg, B component 75Kg, after puddling evenly, add catalyzer zinc naphthenate gasoline solution (concentration 3%) 6Kg of total glue weight 6% again, continue to stir, evenly pave then on the basis, court, automatic levelling, gel solidification becomes glue, and the external temperature slaking is after 14 days, can formally use, and test performance (seeing Table 1).
Embodiment 4 court glue
(1) A component preparation, identical with embodiment 3.
(2) B component preparation
Except that using OLDHs 30Kg to replace the OMMT 30Kg, all the other are identical with embodiment 3
(3) lay ball place glue at the scene, identical with embodiment 3.
Embodiment 5 track and field runway top layer pellet glue
(1) A component preparation
Divide another name N220 302Kg, N210 226Kg and Cl-P 98Kg add in the reactor, stir under 80-85 ℃ of temperature, are evacuated to the 0.002MPa dehydration after 2 hours, fill nitrogen and recover normal pressure, are cooled to 45 ℃.Under nitrogen protection, add MDI-50 374Kg again, under 80-85 ℃ of temperature, reacted 2.5 hours, be cooled to 50 ℃, the barrelling sealing is standby under nitrogen protection.
(2) B component preparation
Divide another name OMMT 35Kg, N330 246Kg, N204 48Kg stirs in the adding reactor, under 80-90 ℃ of temperature, is evacuated to 0.002MPa dehydration 2.5 hours.In another stirring tank, weighing adds Fe
2O
345Kg, Cl-P 360Kg is through evenly stirring, colloidal mill adds m-PDA 21Kg, clay 245Kg after grinding and making mill base successively, stir in the lump and behind the colloidal mill porphyrize, squeeze into reactor under 80-85 ℃ of temperature condition with toothed gear pump, with OMMT, N330, the N204 solvate stirs in the lump, after the vacuum hydro-extraction 2.5 hours, be cooled to 50 ℃, the barrelling sealing is standby under normal pressure.
(3) make pellet
A component and B component were in 1: 3 ratio computation weigh, be about to A component 25Kg, B component 75Kg, catalyzer zinc naphthenate gasoline solution (concentration 3%) 8Kg that adds total glue weight 8% after stirring again, continue to stir, on the polyethylene plastic film on ground grading of paving then, shakeout, gel solidification becomes glue, the next day after can be placed in 80 ℃ of drying rooms slaking 3 hours.The offset plate of slaking can break into particle (general diameter is 3-4mm), the offset plate testability energy (seeing Table 1) after the slaking on request on rubber crusher.
Embodiment 6 track and field runway top layer pellet glue
(1) A component preparation, identical with embodiment 5.
(2) B component preparation
Except that using OLDHs 35Kg to replace the OMMT 35Kg, all the other are identical with embodiment 5.
(3) make pellet, identical with embodiment 5.
Table 1 environment protection type polyurethane elastomer/laminated nano composition The performance test results
| Title | Standard GB/T-14833-93 | The track and field runway rubber | The track and field runway rubber | Court glue | Court glue | Court glue | Pellet glue |
| The characteristic test project | Polyurethane plastic track and field runway | Embodiment 1 A: B=1: 3 OMMT | Embodiment 2 A: B=1: 3 OLDHs | Embodiment 3 A: B=1: 3 OMMT | Embodiment 4 A: B=1: 3 OLDHs | Embodiment 5 A: B=1: 3 OMMT | Embodiment 6 A: B=1: 3 OLDHs |
| Tensile strength (Mpa) | ?????0.7 | ????1.4 | ????1.2 | ????3.5 | ????3.2 | ????1.45 | ????1.3 |
| Elongation at break (%) | ?????90 | ????165 | ????148 | ????405 | ????388 | ????200 | ????205 |
| Hardness (Shao Shi A) | ?????45-60 | ????58 | ????57 | ????75 Annotate | ????74 Annotate | ????67 Annotate | ????66 Annotate |
| Flame retardant resistance (level) | ?????1 | ????1 | ????1 | ????1 | ????1 | ????1 | ????1 |
| Rebound resilience (%) | ?????≥20 | ????32 | ????31 | ????32 | ????31 | ????30 | ????30 |
| Compression recovery rate (%) | ?????≥95 | ????98 | ????98 | ????99 | ????98 | ????98 | ????98 |
Annotate: court glue hardness requires 〉=75, and pellet glue hardness requires 〉=65.
Claims (9)
1, a kind of environment protection type polyurethane elastomer/laminated nano composition sports field paver, it is characterized in that: it is by the MDI-50 that gives aggressiveness (A component) (two cyanate ester based ditans 4,4 ' body, 2,4 ' body mixture) with dihydroxyl polyoxytrimethylene ether reactant, mphenylenediamine, polyhydroxy polycarboxylic propylene oxide ether solvate with chain extension-crosslinking agent (B component), and in the system of catalyzer composition, organic montmorillonoid (OMMT) or the hydrotalcite that organises (OLDHs) stratified nano materials have been added.
2, according to the environment protection type polyurethane elastomer/laminated nano composition sports field paver of claim 1, it is characterized in that it specifically consists of:
The A component is formed (weight percent)
The mixture 30-50% of 4,4 ' body of two cyanate ester based ditans and 2,4 ' body
Dihydroxyl polyoxytrimethylene ether 40-55%
Clorafin 8-15%
The B component is formed (weight percent)
Stratified nano materials 2-6% organises
Mphenylenediamine 1.5-3%
Trihydroxy-polyoxytrimethylene ether 20-30%
Dihydroxyl polyoxytrimethylene ether 3-8%
Pigment 3-5%
Potter's clay 25-40%
Chlorinated paraffin 25-38%
Wherein, the weight ratio of A component and B component is 1: 3.Catalyst consumption be A component and B composition weight and 0.10-0.50%.
3, according to the environment protection type polyurethane elastomer/laminated nano composition sports field paver of claim 2, it is characterized in that: the black rubber grain (the track and field runway is used) that adds 20～30 weight % of this composite system.
4, according to the environment protection type polyurethane elastomer/laminated nano composition sports field paver of claim 2 or 3, it is characterized in that: catalyzer uses zinc naphthenate gasoline solution
5, a kind of manufacture method of environment protection type polyurethane elastomer/laminated nano composition sports field paver is, it is characterized in that, may further comprise the steps:
1), give the stratified nano materials (organic montmorillonoid (OMMT) or the hydrotalcite that organises (OLDHs)) that organises of preparation earlier,
2), preparation A component, dihydroxyl polyoxytrimethylene ether and chlorinated paraffin computation weigh are joined in the reactor, under 80-85 ℃ of temperature, evenly stir and be evacuated to the 0.002MPa dehydration after 2-2.5 hour, fill nitrogen and recover normal pressure, be cooled to 40-45 ℃.Normal pressure adds the MDI-50 of metering down, and under the drying nitrogen protection, reaction is 2.5 hours under 80-85 ℃ of temperature, is cooled to 50 ℃, and the barrelling sealing is standby under the N2 nitrogen protection.
3), preparation B component, organise stratified nano materials and trihydroxy-polyoxytrimethylene ether, dihydroxyl polyoxytrimethylene ether with metering stir in reactor, under 80-90 ℃ of temperature, are evacuated to 0.002MPa and dewater 2-3 hour.In another stirring tank, pigment and softening agent are puddled and ground to form mill base through colloidal mill, again with the chainextender mphenylenediamine, stopping composition potter's clay and mill base puddle in the lump, after colloidal mill grinds, squeeze in the reactor under 80-90 ℃ of temperature with toothed gear pump, stratified nano materials and hydroxyl polyoxytrimethylene ether solvate stir with organising, after vacuum hydro-extraction 2-3 hour, be cooled to 50 ℃, the barrelling sealing is standby under normal pressure
4), at the on-the-spot environment protection type polyurethane elastomer/laminated nano composition sports field paver of laying of sports field, with the standby A component of aforesaid barrelling sealing, the B component is 1: 3 computation weigh by weight, stir, catalyzer (the A component that adds calculated amount, the weight of B component and 0.10～0.50 weight %) stir rapidly, it is ready-made in advance to pave immediately, on the smooth basis, under 15-35 ℃ of condition, about 30-60 divides inner gel, solidify in 24 hours, can come into operation after the complete slaking on the 14th, and survey its various mechanical properties etc.
6, according to the manufacture method of the environment protection type polyurethane elastomer/laminated nano composition sports field paver of claim 5, it is characterized in that:
The method for preparing organic montmorillonoid (OMMT) is, in the water of 80 ℃ of 800ml, add the 5g caprolactam and the 4ml vitriol oil, fully hydrolysis, slowly be injected into again and contain 20g sodium-polynite (anion-exchange capacity=90-100mmol/100g, particle diameter 40-70 μ m) in the aqueous solution, this mixed solution, is cooled off after 3 hours 80 ℃ of fierce stirrings, centrifuging is washed to no SO
4 =(use BaCl
2Solution detects no white precipitate), drying at room temperature, vacuum-drying is to constant weight again, and grinding is into about the powder that is 50-90 μ m.It is 1nm that na montmorillonite is surveyed interlamellar spacing with the WAXD instrument.The cheating engaging layer spacing survey that organises through ion exchange method is 1.9nm.
7, according to the manufacture method of the environment protection type polyurethane elastomer/laminated nano composition sports field paver of claim 5, it is characterized in that:
The method for preparing the hydrotalcite (OLDHs) that organises is in the water of 80 ℃ of 800ml, to add hydrotalcite (Mg
6Al
2(OH)
16CO
34H
2O) 20g under agitation dropwise adds the about 12g of Witco 1298 Soft Acid, until solution is not seen CO
2Bubble is overflowed, fully stir 2 hours after, centrifuging is washed to pH6.Grind after the vacuum-drying and be powder.Hydrotalcite layers is apart from being 0.79nm, and organising back with ion exchange method is 1.56nm with WAXD instrument test layer spacing.
8, according to the manufacture method of the environment protection type polyurethane elastomer/laminated nano composition sports field paver of claim 5, it is characterized in that: the 4th) stage adds the black rubber grain (track and field runway with) of 20～30 weight % of this composite system during on-the-spot the laying.
9, according to the manufacture method of the environment protection type polyurethane elastomer/laminated nano composition sports field paver of any one in the claim 5～8, it is characterized in that: catalyzer uses zinc naphthenate gasoline solution
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318454C (en) * | 2003-11-13 | 2007-05-30 | 北京化工大学 | Preparing nano sheet type polymer using LDHs as template and its preparing method |
| CN100575429C (en) * | 2004-01-22 | 2009-12-30 | 核动力工业树脂有限公司 | Stain blocking water borne coating composition |
| CN105219066A (en) * | 2015-10-09 | 2016-01-06 | 北京化工大学 | A kind of have polyurethane/nano hydrotalcite composite material of high damping, uv-absorbing and toughness reinforcing performance and preparation method thereof |
| CN105385103A (en) * | 2015-12-10 | 2016-03-09 | 朱晓燕 | Light weight porous melamine resin type border-crossing capturing material and preparation method thereof |
| CN106283265A (en) * | 2016-09-07 | 2017-01-04 | 浙江华峰氨纶股份有限公司 | A kind of preparation method of the microcosmic finely dispersed zirconium phosphate fire-retardant spandex of synergistic |
| CN110452611A (en) * | 2019-08-26 | 2019-11-15 | 武汉比邻科技发展有限公司 | A kind of nano modified polyurethane water-repellent paint and preparation method thereof |
| CN111171274A (en) * | 2020-03-30 | 2020-05-19 | 惠州市腾威新材料有限公司 | Method for manufacturing double-component polyurethane runway elastic material |
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- 2002-04-09 CN CNB021059241A patent/CN1158370C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318454C (en) * | 2003-11-13 | 2007-05-30 | 北京化工大学 | Preparing nano sheet type polymer using LDHs as template and its preparing method |
| CN100575429C (en) * | 2004-01-22 | 2009-12-30 | 核动力工业树脂有限公司 | Stain blocking water borne coating composition |
| CN105219066A (en) * | 2015-10-09 | 2016-01-06 | 北京化工大学 | A kind of have polyurethane/nano hydrotalcite composite material of high damping, uv-absorbing and toughness reinforcing performance and preparation method thereof |
| CN105219066B (en) * | 2015-10-09 | 2018-02-23 | 北京化工大学 | A kind of polyurethane/nano hydrotalcite composite material with high-damping, UV absorption and toughness reinforcing performance and preparation method thereof |
| CN105385103A (en) * | 2015-12-10 | 2016-03-09 | 朱晓燕 | Light weight porous melamine resin type border-crossing capturing material and preparation method thereof |
| CN105385103B (en) * | 2015-12-10 | 2017-12-19 | 朱晓燕 | A kind of light porous melamine resin class is crossed the border capture material and its preparation technology |
| CN106283265A (en) * | 2016-09-07 | 2017-01-04 | 浙江华峰氨纶股份有限公司 | A kind of preparation method of the microcosmic finely dispersed zirconium phosphate fire-retardant spandex of synergistic |
| CN106283265B (en) * | 2016-09-07 | 2018-06-26 | 浙江华峰氨纶股份有限公司 | A kind of preparation method of the microcosmic finely dispersed fire-retardant spandex of basic zirconium phosphate synergistic |
| CN110452611A (en) * | 2019-08-26 | 2019-11-15 | 武汉比邻科技发展有限公司 | A kind of nano modified polyurethane water-repellent paint and preparation method thereof |
| CN111171274A (en) * | 2020-03-30 | 2020-05-19 | 惠州市腾威新材料有限公司 | Method for manufacturing double-component polyurethane runway elastic material |
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| CN1158370C (en) | 2004-07-21 |
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