CN1594471A - Nano composite paving material and its preparation method - Google Patents
Nano composite paving material and its preparation method Download PDFInfo
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- CN1594471A CN1594471A CN 200410027946 CN200410027946A CN1594471A CN 1594471 A CN1594471 A CN 1594471A CN 200410027946 CN200410027946 CN 200410027946 CN 200410027946 A CN200410027946 A CN 200410027946A CN 1594471 A CN1594471 A CN 1594471A
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Abstract
The invention discloses a nano composite paving material and its preparation method, wherein the composite paving material comprises polyurethane performed polymer, color paste and rare earth composite drier (REC), wherein the weight ratio of the polyurethane performed polymer and color paste 1:2-20, the content of rare earth composite drier is 0.5-20 wt% of the total weight.
Description
Technical field
The present invention relates to a kind of compound surfacing material and production method thereof.
Background technology
Urethane (PU) surfacing material (claiming pavement material again) has good wear-resisting, oil resistant, fire-retardant, Weather-resistant, elasticity is suitable, shock-absorbing performance is good, durometer level is wide, smooth, anti-skidding, characteristics such as color is attractive in appearance, is widely used in laying all kinds of sports place (as polyurethane plastic runway, plastic net court, plastic cement basketball court, plastic cement court, plastic cement table tennis court etc.) and various floor (floors such as railway carriage, automobile bodies, production plant, laboratory).
1961 Minnesota ,USA mining company (3M company) at first laid the 200m race track with polyurethane material, laid the track and field runway in 1963 again.Because result of use is good, is subjected to various countries and payes attention to.The laying of polyurethane runway improves constantly athletic games results, improves 0.2-0.35s than on cinder track as 100m dash achievement, and long jump result can improve 20-30cm, and clearance can improve 0.5-1cm.The runway (Tartan runway) that nineteen sixty-eight has adopted the urethane surfacing material of 3M company to lay in the 19th olympic game that Mexico holds, after this International Olympic Committee just formally is decided to be plastic cement race track one of essential condition of international competition, and lay unexpectedly mutually countries in the world.At present, plastic cement race track also becomes an an integral part of modern sports.
The research of China's urethane surfacing material starts from 1972, and gymnasium, Beijing in September, 1979 indoor track at first adopts this material-paving, and area is 4500m2.The eighties, national each province has all laid plastic cement race track basically.Occurred urethane vollyball, table tennis, basketball, shuttlecock and tennis court afterwards in succession, even the football field is used in research also.The nineties urethane surfacing material also enters occasions such as swimming pool, hotel, restaurant, office and communal facility except the fast development of sport field application facet.
The TDI-MOCA-heavy metal catalyst system among the similar Chinese invention patent prospectus CN1033639A is all continued to use in the production three of this surfacing material during the last ten years, its prescription generally is made of two-pack: a component is a base polyurethane prepolymer for use as, and another component is mill base (including catalyzer).Its basic production technology is: produce base polyurethane prepolymer for use as and mill base in advance by factory; when constructing at the scene; with two components mixing (need add sometimes a certain amount of regenerated damaged tire micelle (black micelle) by a certain percentage); carry out cast-in-site; sprinkle anti-skidding micelle (EPDM micelle or urethane micelle etc.); solidify, become product.
At present, problem aspect two below this material exists in production and use:
One, environmental pollution and murder by poisoning problem
Base polyurethane prepolymer for use as is generally formed with multiple polyether glycol and auxiliary agent reaction by TDI (two kinds of isomer are arranged).Wherein TDI has the noxious chemical that high vapour pressure (25 ℃ of about 1.33Pa) is easy performance, not only make polyurethane plastic athletic ground irritating smell big, lasting, and easy and protein bound, the TDI steam that sucks high density can cause bronchitis, pneumonia and pulmonary edema; After the Long contact time, also can cause hepatic disease; Contact liq can cause skin and eyes permanent damage.Its LD50 (mouth is gone into mld) is 5.8g/kg, and TLV (toxic reaction liminal value) is 0.14mg/m
3, maximum allowable concentration 0.2mg/m in workshop air
3(health ministerial standard TJ36-79).It is reported that the surfacing material of producing with TDI can discharge toxic gas under sweltering heat or high light; The student just once took place when the plastic cement sports field of newly rebuilding is had physical education in the middle school, Taipei County, Taiwan Province, owing to suck 15 students of this poison gas incident of PI simultaneously.Countries such as Japan, Germany have banned use of TDI to lay the sports field of school at present.IST (international movement runway technology association) proposed the suggestion of " not accepting to use the polyurethane sport runway that contains monomer TDI composition " as far back as 1994.
Another component mill base in the surfacing material prescription generally is made up of vulcanizing agent (claim not only linking agent or chainextender), catalyzer (but also claiming siccative), processing aid (clorafin, stearic acid, dioctyl phthalate (DOP) etc.), filler (potter's clay, talcum powder, lime carbonate, kaolin etc.), thixotropic agent (gas-phase silica etc.), colorant (red iron oxide, Phthalocyanine Green G, Fast Yellow G etc.), other auxiliary agents (uv-absorbing agent, antiaging agent etc.), polyether glycol (one or more) etc.Wherein vulcanizing agent generally uses MOCA, its LD
50Be 5.0g/kg.Recent study shows: by breathe with contact MOCA can be carcinogenic, the Japan and the U.S. classify MOCA as the special management material, and require the user of service to carry out health to register, registry form need be preserved 30 years (be 15-20 the latent period of bladder cancer).Another main ingredient in the mill base is a catalyzer, generally uses organometallics, as isocaprylic acid lead, isocaprylic acid zinc, Phenylmercuric Acetate, stannous octoate, dibutyl tin laurate etc.With lead is example, the per kilogram lead tolerance is 1340mg in the polyurethane sport place surfacing material of being laid at present, regulation one-level among the existing standard GB 5618-1995 (soil environment quality standard), secondary, three grades of soil environment quality values are respectively that per kilogram soil lead tolerance is not more than 35,300,500mg, and the grade III Standard value that lead content surpasses GB in the present polyurethane sport place of laying is respectively: 38 times, 4.5 times, 2.7 times.In addition, the harm of mercury is self-evident.
In a word, the environmental pollution that is brought in traditional urethane surfacing material production process and the harm of HUMAN HEALTH be can not be ignored, this also is can't the go abroad places of the bottleneck that takes part in international competition of China's relevant industries.
Two, expensive problem
This point has two aspect implications, and the one, the cost height, two are to use and maintenance expense height.
From the type in the polyurethane sport place of present international sport match usefulness, mainly contain four kinds of full-plastic, double deck type, mixed type and folded forms.Except that folded form, other basic units of three types all are similarly, mainly are that the glue surface layer of laying is had any different, and need decide the laying of glue surface layer with agonistic requirement and cost of material situation.The double deck type that accounts for the overwhelming majority with present laying is an example, lays 400 meters (8 runway) stadium of track and fields of a standard, and the place, center is a natural grass, and required whole expense approximately is 5,000,000 yuan; If central field is an artificial grass, cost has reached 7,000,000 yuan.The China field is 5 years through association the regulation plastic cement race track warranty period, it is reported, the plastic cement race track that Germany lays can reach 10 years work-ing life.After completed in the place, the annual unit of laying also will bear no small expenses such as maintenance, maintenance.With central field is that the standard plastic cement stadium of track and field of natural grass is an example, and annual maintenance, maintenance cost reach about 50,000 yuan.Most of school of having laid plastic sports ground opens the playground to the student during normal physical education, extracurricular athletics; other times all are to lock in the gate; a principal once said: " school has spent so much money, has laid plastic cement, how at will to allow the student run chaotically in the above! ".Because cost, use and maintenance are too high, have limited it and have promoted the use of.
Expensive major cause is the expense of raw materials height, and for example 1 ton of MOCA is more than 30,000 yuan, and prior reason is that the mill base part that contains cheap mineral filler can not add at high proportion, otherwise can cause product performance not reach the GB requirement.
Nineteen thirty-seven, Germany professor Otto Bayer (founder of polyurethane industrial) at first utilizes isocyanic ester and polyvalent alcohol generation polyaddition reaction to make urethane resin.Early sixties, pavement materials such as urethane pavement material and paracril, ACRYLIC EMULSION, EVA class, polyethylene kind, nylon-type, after introducing to the market in the mode of competition, because the quality of urethane pavement material is good, other polymer pavement materials progressively are eliminated.
With regard to the environmental protection aspect, Sun Qingfeng etc. (development of MDI type two component polyurethane plastic cement race track slurry. polyurethane industrial .2003,18 (3): 22-24) studied MDI-MOCA-heavy metal catalyst system, thought and compare with traditional TDI system, smell is little, and over-all properties is superior.Ceng Fanjie etc. (the Chinese invention patent prospectus. publication number CN1352214A) application MDI-DA (diethylamide)-heavy metal catalyst patent of invention, but DA also has big toxicity.In addition, Wu Shuzhen etc. (reduce the research of the extravagant material isocaprylic acid of two component polyurethane zinc consumption. polyurethane industrial .2000,15 (4): 25-27), Fan Zuotong etc. (reduce the experiment of amine commissure system plastic cement race track sizing material cost. rubber industry .1991,38 (1): 14-15) carried out respectively reducing heavy metal consumption (especially plumbous), reduce the research of MOCA (costing an arm and a leg) consumption.The development of the substitute of carrying out MOCA is also arranged, promptly utilize hypotoxic synthetics to replace highly toxic MOCA, for example the Caytur-21 of the Baytec-1604 of Bayer AG, E.I.Du Pont Company (polyurethane plastic rubber paving material. Beijing: the .2003 of Chemical Industry Press, 45).The rare earth catalyst that the inventor just successfully utilizes the patent of invention technology (patent No. ZL98113249.9) of oneself to produce replaces the whole heavy metal catalysts in the urethane surfacing material, application of result has also been applied for national inventing patent (publication number 02134527.9) in plastic sports ground is produced; And successfully developed the MDI-MOCA-rare earth catalyst system, applied for patent of invention.In fact, the present invention carries out on these bases just.
With regard to the research of urethane/Nano composite material of montmorillonite, the high performance research means of urethane mainly was included in progressively in the past and regulates its molecular chain structure and add inorganic filling material in the polymerization process.In general, when introducing the packing material modification in PU, can't reach enhancing and toughness reinforcing purpose simultaneously, and can only look after performance index wherein, its toughness-elongation at break generally all can descend when improving PU intensity.The PLS nano composite material of utilizing intercalation technique to prepare the PU matrix is the effective way that addresses this problem.
Polynite belongs to 2: 1 type stratiforms or sheet silicate.Each unit cell is carried a silica octahedron secretly by two tetrahedrons and is constituted, and connects with shared Sauerstoffatom between the two, and every layer thickness is 1nm, has very high rigidity; Interlamellar spacing is about 1nm, exists Van der Waals force to interact between the crystal layer, and interlayer is easy glide not; Tetrahedral sheet in the crystal layer and octahedral sheet can be substituted by extensive isomorph, as the Si in the tetrahedron
4+By Al
3+, Fe
3+Substitute the Al in the octahedron
3+By Mg
2+, Fe
2+, Ni
2+, Zn
2+, Mn
2+Substitute, make a layer inner layer sheet wear negative charge.So hydrated cation (Na
2+, K
+, Ca
2+, Mg
2+) can occupy interlamination region with the superfluous negative charge that neutralizes.Polynite has very strong ion-exchange capacity, and loading capacity (CEC) is generally between 80-150mmol/100g.When preparation PLSN nano composite material, the normal organic cation that adopts is to imvite modified, pass through ion exchange reaction, the interlamellar spacing of polynite is increased, the crystal layer surface tension reduces, and becomes lipophilicity by wetting ability, thereby has improved the consistency of itself and polymeric matrix, be beneficial to monomer and polymkeric substance and insert between cheating engaging layer, form PLSN.And organic cation can have various official's functional groups, and these official's functional groups can react with polymkeric substance, thereby improves the bonding effect between inorganics and the organic polymer matrix.
(Adv Master.1999,11 (1): 49-52) specific tensile strength and elongation at break are improved Zilg etc. simultaneously mutually for the nano composite material of a kind of fluorine mica being introduced the polyurethane matrix preparation and polyurethane matrix.(Polymer Chemistry.1999,37:2225-2233 such as Chen; Polymer.2000,41:1345-1353; Polymer.2001,42 (7): 3213) utilize the method for introducing poly-hydroxyl caprolactone/polynite to synthesize novel PU/ Nano composite material of montmorillonite, the introducing of poly-hydroxyl caprolactone/polynite can make the over-all properties of PU/ Nano composite material of montmorillonite increase substantially on a small quantity.Ma Jisheng, QiZongNeng etc. have carried out a series of research (Chinese invention patent prospectus, publication number 1375524A to urethane/Nano composite material of montmorillonite; Synthetic, the structure of composite polyurethane elastomer/montmorillonoid nano-material and performance. polymer journal .2001,3,325-328; The nano composite polymer/laminated silicate material theory and practice. Beijing: the .2002 of Chemical Industry Press), they use the polynite of a kind of quaternary ammonium alkyl salt pair to carry out intercalation processing and obtain organo montmorillonite, utilize in-situ inserted polymeric method to prepare the PU/ Nano composite material of montmorillonite of excellent combination property then.Kong Kejian (the Chinese invention patent prospectus. publication number 1376749A; The Chinese invention patent prospectus. publication number 1376748A) making good try aspect the compound surfacing material of polyurethane/nano, add organo montmorillonite, organic hydrotalcite in MDI-MOCA-heavy metal catalyst, MDI-mphenylenediamine-heavy metal catalyst system respectively, though just in surfacing material, form simple nano-dispersed, bigger raising its performance.Because mphenylenediamine toxicity is very big, in fact this not environmental protection of product.
Generally speaking, no matter still domestic abroad, all are odd, systems not to the research of urethane surfacing material, base polyurethane prepolymer for use as, mill base, catalyzer are not paid attention to as an organic whole.The present invention is exactly the Dialectic Relationship from above three, has developed the MDI-OMMT-REC system, thoroughly solves the environmental protection and the cost problem of urethane surfacing material.
Summary of the invention
The object of the present invention is to provide the nano combined surfacing material of a kind of low cost, environmental protection.
Another object of the present invention is to provide a kind of production method of above-mentioned nano combined surfacing material.
Nano combined surfacing material of the present invention is made up of base polyurethane prepolymer for use as, mill base, rare earth composite drier, and wherein base polyurethane prepolymer for use as and mill base weight ratio are 1: 2～20, and the rare earth composite drier is a gross weight 0.5～20%.Wherein, base polyurethane prepolymer for use as is made up of 20～40 weight percent MDI and 60～80 weight percent polyether glycols; Mill base is made up of 20～50 weight percent fillers, 1～10 weight percent organo montmorillonite, 5～25 weight percent polyether glycols, 30～60 weight percent processing aids, 0.1～5 weight percent pigment, 0.1～5 weight percent antiaging agent, 0.1～5 weight percent UV light absorber, 0.1～5 weight percent organic yellow and 0.1～5 weight percent mould inhibitor; The rare earth composite drier is urged by 30～70 weight percent rare earths
Polyether glycol is N-210, N-220, N-2028, N-403, N-3035, the composition of one or more among the N-330.
Organo montmorillonite is prepared by following method: with concentration is 5wt% sodium-polynite aqueous solution drips excessive alkyl alcoholamine under 80 ℃ of whipped states aqueous hydrochloric acid, suction filtration behind the 1-3h, and wash with water to no Cl
-, vacuum-drying to constant weight also grinds the powder into about 50-90 μ m.Alkyl alcoholamine is 3-amino-1-propyl alcohol, 3-amino-1,2-propylene glycol or Pehanorm.
Filler is one or more the composition in talcum powder, potter's clay, clay, the lime carbonate; Processing aid is a clorafin, stearic acid, the composition of one or more in dibutyl phthalate, the dioctyl phthalate (DOP); Pigment is ferric oxide, iron oxide yellow, the composition of one or more in the husky Huang of the Chinese, Phthalocyanine Green G, the Fast Yellow G; UV light absorber is one or more the composition among UV531, UV-9, UV-327, the Tinuvin292; Antiaging agent is one or more the composition in antioxidant 1010,7501, the anti-aging agent-264.
Rare earth drier is a naphthenic acid rare earth, isooctoate of rare earth metal, and the composition of one or more in the fatty acid rare earth, zinc drier are zinc naphthenate, isocaprylic acid zinc, the composition of one or more in the fatty acid zinc.
Mould inhibitor is one or more the composition in oxine, oxine ketone, pentachlorophenol, sodium pentachlorophenate, tetrachloro 4-(methylsulfonyl) pyridine, the salicylanilide.
The production method of the nano combined surfacing material of the present invention, take the two step method synthetic route: promptly first synthesis of polyurethane performed polymer, mill base, synthetic then surfacing material, at normal temperatures promptly, the organo montmorillonite in base polyurethane prepolymer for use as and the mill base carries out in-situ inserted polyreaction and solidifies obtaining under the rare earth catalyst effect.
Base polyurethane prepolymer for use as synthetic taked following technological line: with polyether glycol, drop into reactor and carry out vacuum hydro-extraction (vacuum tightness is 4-6kPa), when the massfraction of water is lowered the temperature when following 0.05%, the MDI of Jia Ruing then, after the reacting by heating, cooling discharge becomes performed polymer.
Mill base synthetic technological line is: with organo montmorillonite, filler, processing aid, pigment, anti-aging agent, antioxidant, uv-absorbing agent, polyether glycol etc., mix, after the processing of high speed shear, on shredder, grind, require particle diameter＜70 μ m, vacuum hydro-extraction to moisture massfraction is lower than 0.05% (vacuum tightness is 4-6kPa), gets the mill base finished product.
The present invention compared with prior art,
1) proposes first to replace carcinogenic amine cross linking agent (especially MOCA) fully with the organo montmorillonite of alkyl alcoholamine intercalation;
2) propose first in surfacing material is synthetic that organo montmorillonite and performed polymer carry out the method that in-situ inserted polyreaction is produced nano composite material under normal temperature, rare earth composite catalyst effect, and the premium properties that utilizes nano composite material improves the ratio of low-cost mill base, and reduces the cost of this material by a relatively large margin;
3) in polyurethane sport place surfacing material is produced, the toxicity of synchronism eliminates TDI, MOCA, heavy metal catalyst and to the pollution of environment with to the harm of human body makes it to become cleaner production, and widens the range of application of the abundant rare earth resources of China's standing stock.
In addition, such environment-friendly type surfacing material not only can be used to lay all kinds of sports place, and can be used for various floors, walkway, chinampa, and also can be used for fields such as water-proof material, jointing material, sealing material, coating and decorating material, tackiness agent, coating, market outlook are particularly bright.
Embodiment
Below in conjunction with embodiment urethane surfacing material of the present invention is further described, helps those of ordinary skill in the art further to understand the present invention, but do not limit the present invention in any form.
Embodiment 1
Produce base polyurethane prepolymer for use as, mill base, rare earth composite drier by following prescription (each component content be weight percentage content) respectively.
Base polyurethane prepolymer for use as mill base rare earth composite drier
MDI:29.1 organo montmorillonite: 4.7 isooctoate of rare earth metal: 61.2
N-210:31.7 talcum powder: 30.3 isocaprylic acid zinc: 38.8
N-220:39.2 potter's clay: 11.1
White carbon black: 3.5
N-403：2.1
N-330：13.3
Clorafin: 33.6
Phthalocyanine Green G: 1.0
1010：0.1
UV-531：0.1
Organic yellow: 0.1
Oxine: 0.1
When constructing at the scene, according to base polyurethane prepolymer for use as: mill base: rare earth composite drier=1: 5.0: 0.3 weight ratio mixing, mat formation, spread anti-skidding micelle, dry getting final product.
Embodiment 2
Produce base polyurethane prepolymer for use as, mill base, composite drier by following prescription (each component content be weight percentage content) respectively:
Base polyurethane prepolymer for use as mill base rare earth composite drier
MDI:30.0 organo montmorillonite: 4.2 isooctoate of rare earth metal: 75.0
N-2028:70.0 N-403:1.4 isocaprylic acid zinc: 25.0
N-330：18.1
Talcum powder: 31.3
Kaolin: 12.4
Lime carbonate: 9.6
Ferric oxide: 0.8
Stearic acid: 21.8
Organic yellow: 0.1
T501：0.1
UV-9：0.1
Sodium pentachlorophenate: 0.1
At the scene in the construction, according to base polyurethane prepolymer for use as: mill base: rare earth composite drier=1: 10.0: 0.4 weight ratio mixing, mat formation, spread anti-skidding micelle, dry getting final product.
The nano combined surfacing material of embodiment 1,2 carries out various Mechanics Performance Testings according to the requirement of GB after 14 days.Product meets State Standard of the People's Republic of China GB/T 14833-93 (plastic cement race track): hardness (Shao A) (degree): 45-60, tensile strength (MPa) 〉=0.7, elongation rate of tensile failure (%) 〉=90, compression recovery rate (%) 〉=95, rebound value (%) 〉=20, flame retardant resistance (level): 1.
Claims (10)
1, a kind of nano combined surfacing material is made up of base polyurethane prepolymer for use as, mill base, rare earth composite drier, and wherein base polyurethane prepolymer for use as and mill base weight ratio are 1: 2～20, and the rare earth composite drier is a gross weight 0.5～20%.
2, nano combined surfacing material as claimed in claim 1 is characterized in that base polyurethane prepolymer for use as is made up of 20～40 weight percent MDI and 60～80 weight percent polyether glycols.
3, nano combined surfacing material as claimed in claim 1 is characterized in that mill base is made up of 20～50 weight percent fillers, 1～10 weight percent organo montmorillonite, 5～25 weight percent polyether glycols, 30～60 weight percent processing aids, 0.1～5 weight percent pigment, 0.1～5 weight percent antiaging agent, 0.1～5 weight percent UV light absorber, 0.1～5 weight percent organic yellow and 0.1～5 weight percent mould inhibitor.
4, nano combined surfacing material as claimed in claim 1 is characterized in that the rare earth composite drier is made up of 30～70 weight percent rare earth driers and 30～70 weight percent zinc driers.
5,, it is characterized in that polyether glycol is N-210, N-220, N-2028, N-403, N-3035, the composition of one or more among the N-330 as claim 2 or 3 described nano combined surfacing materials.
6, nano combined surfacing material as claimed in claim 3, it is characterized in that organo montmorillonite is prepared by following method: with concentration is 5wt% sodium-polynite aqueous solution drips excessive alkyl alcoholamine down in 80 ℃ of whipped states aqueous hydrochloric acid, suction filtration behind the 1-3h, and wash with water to no Cl
-, vacuum-drying to constant weight also grinds the powder into about 50-90 μ m.
7, nano combined surfacing material as claimed in claim 6 is characterized in that alkyl alcoholamine is 3-amino-1-propyl alcohol, 3-amino-1,2-propylene glycol or Pehanorm.
8, nano combined surfacing material as claimed in claim 3 is characterized in that filler is one or more the composition in talcum powder, potter's clay, clay, the lime carbonate; Processing aid is a clorafin, stearic acid, the composition of one or more in dibutyl phthalate, the dioctyl phthalate (DOP); Pigment is ferric oxide, iron oxide yellow, the composition of one or more in the husky Huang of the Chinese, Phthalocyanine Green G, the Fast Yellow G; UV light absorber is one or more the composition among UV531, UV-9, UV-327, the Tinuvin292; Antiaging agent is one or more the composition in antioxidant 1010,7501, the anti-aging agent-264.
9, nano combined surfacing material as claimed in claim 1 is characterized in that rare earth drier is a naphthenic acid rare earth, isooctoate of rare earth metal, the composition of one or more in the fatty acid rare earth, zinc drier is a zinc naphthenate, isocaprylic acid zinc, the composition of one or more in the fatty acid zinc.
10, nano combined surfacing material as claimed in claim 1, take the two step method synthetic route: promptly first synthesis of polyurethane performed polymer, mill base, synthetic then surfacing material, it is characterized in that at normal temperatures the organo montmorillonite in base polyurethane prepolymer for use as and the mill base carries out in-situ inserted polyreaction and solidify obtaining under the rare earth catalyst effect.
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| CNB2004100279463A CN100506933C (en) | 2004-07-06 | 2004-07-06 | Nano composite paving material and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093704A (en) * | 2010-12-31 | 2011-06-15 | 内蒙古普力司达体育设施工程有限公司 | Rare earth carboxylate modified polyurethane floor paving material and preparation method thereof |
| CN106188489A (en) * | 2016-08-08 | 2016-12-07 | 上海微谱化工技术服务有限公司 | A kind of runway rubber compositions and goods thereof |
| CN106977679A (en) * | 2017-03-28 | 2017-07-25 | 江苏耐斯坦铺装材料有限公司 | A kind of composite catalyst and plastic cement race track adhesive based on based on organic RE material |
| CN107216800A (en) * | 2017-06-28 | 2017-09-29 | 吕超 | A kind of hydrophobically modified nano barium sulfate fills the preparation method of aqueous polyurethane coating |
| CN108457153A (en) * | 2018-04-08 | 2018-08-28 | 福州大学 | A kind of campus flagstone path is laid with spacing and determines method |
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| US5059671A (en) * | 1988-12-28 | 1991-10-22 | Mitsui Toatsu Chemicals, Inc. | Manufacturing process of spray urethane elastomer |
| JP3343078B2 (en) * | 1998-07-29 | 2002-11-11 | 三井化学株式会社 | Elastic pavement material and elastic pavement method |
| CN1200061C (en) * | 2003-06-25 | 2005-05-04 | 广东药学院 | Environmental-protection type polyurethane paving material for sports ground |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102093704A (en) * | 2010-12-31 | 2011-06-15 | 内蒙古普力司达体育设施工程有限公司 | Rare earth carboxylate modified polyurethane floor paving material and preparation method thereof |
| CN102093704B (en) * | 2010-12-31 | 2013-01-02 | 内蒙古普力司达体育设施工程有限公司 | Rare earth carboxylate modified polyurethane floor paving material and preparation method thereof |
| CN106188489A (en) * | 2016-08-08 | 2016-12-07 | 上海微谱化工技术服务有限公司 | A kind of runway rubber compositions and goods thereof |
| CN106977679A (en) * | 2017-03-28 | 2017-07-25 | 江苏耐斯坦铺装材料有限公司 | A kind of composite catalyst and plastic cement race track adhesive based on based on organic RE material |
| CN106977679B (en) * | 2017-03-28 | 2021-03-19 | 江苏耐斯坦建设有限公司 | Composite catalyst based on organic rare earth material and adhesive for plastic track |
| CN107216800A (en) * | 2017-06-28 | 2017-09-29 | 吕超 | A kind of hydrophobically modified nano barium sulfate fills the preparation method of aqueous polyurethane coating |
| CN108457153A (en) * | 2018-04-08 | 2018-08-28 | 福州大学 | A kind of campus flagstone path is laid with spacing and determines method |
| CN109265977A (en) * | 2018-09-07 | 2019-01-25 | 江苏叙然信息科技有限公司 | A kind of athletic ground surface material and preparation process |
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| CN100506933C (en) | 2009-07-01 |
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