CN1580162A - Stadium paving material prepared from nano polyurethane elastomer and its preparing method - Google Patents
Stadium paving material prepared from nano polyurethane elastomer and its preparing method Download PDFInfo
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- CN1580162A CN1580162A CN 03149973 CN03149973A CN1580162A CN 1580162 A CN1580162 A CN 1580162A CN 03149973 CN03149973 CN 03149973 CN 03149973 A CN03149973 A CN 03149973A CN 1580162 A CN1580162 A CN 1580162A
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- polyurethane elastomer
- diphenylmethanediisocyanate
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Abstract
The invention belongs to macromole material, Used for beautification of palaestra with nanometer environmental polyurethane elastomer. The preparation method follows such process. Dehydrate polyther diatomic alcohol, add diphenylmethane and 2-isocynani ester, A part is prepared after reaction. Add polyether polyalcohol to montmorillonite as to improve the manufacture's capability, add brasque and mix them, B part is prepared. Mix A part, B part, prill of black basic hydrocarbon and metal hydroxide-ac-salt in the weight ratio 1:3, agitate, converge and solidif them, so the invention is produced the invention don't use the exciative and harmful TDL, so it is propitious to the construction and protecting environment.
Description
Technical field
The invention belongs to polymeric material field, particularly by paving material for sports field of nano-environment protection type polyurethane elastomer production and preparation method thereof.
Background technology
The polyurethane elastomer of the track and field runway of modern stadium and ball game place pavement material is known that earlier with tolylene diisocyanate TDI and polyether glycol and organic thinner and makes base polyurethane prepolymer for use as, (being generally called the A component); Butyleneglycol, diamine MOCA (3,3 '-two chloro-, 4,4 ' diaminodiphenyl-methane) and filler (common name B component) with A component and chain extension-cross linking agent polyether glycol, dibasic alcohol mixes again, again the polyurethane elastomer made from the catalyst action polymerization.So far, each manufacturer production of China is as the prescription of the polyurethane elastomer of paving material for sports field, and all continuing to use the Chinese invention patent publication number is the disclosed TDI-MOCA system of CN1033639A.
As " pharmaceutical chemicals fire-fighting and first aid handbook, chemical industry slice version society, 1 edition P262 was pointed in 1996, tolylene diisocyanate belongs to Hazardous Chemical Substances, its steam and air can form explosive mixture, thermal degradation give off poisonous gas, and particularly skin and the eyes to the people have strong stimulation effect and allergenic effect; MOCA is a carcinogenic substance.Thus, International Track and Field Association's proposal does not use these two kinds of chemical substances to produce paving material for sports field.
Summary of the invention
One of purpose of the present invention is to overcome because traditional polyurethane elastomer uses the injury to human body, the hidden danger that TDI and MOCA brought, and the paving material for sports field by the nano-polyurethane elastomer production is provided.
Another object of the present invention is to overcome the defective that the every physical index of environment protection type polyurethane elastomer is low and work-ing life is short with the usual way preparation, a kind of TDI and MOCA and heavy metal of not using is provided, with the preparation method of the paving material for sports field of the polyurethane elastomer of nano modification preparation, be referred to as the paving material for sports field of nano-environment protection type in order to manufacturing.
Paving material for sports field by the nano-polyurethane elastomer production of the present invention is made up of elastomerics A component, B component, black rubber grain and metal carboxylates catalysts, wherein, the weight ratio of A component and B component is 1: 2～1: 3 in the polyurethane elastomer, the content of black rubber grain is 20～25% of A component and B component weight summation, and metal carboxylates catalysts is 0.10～0.30% of A component and a B component weight summation;
The composition of A component and weight percent are:
Diphenylmethanediisocyanate 35～45%
Polyether Glycols 55～65%
The composition of B component and weight percent are:
Polyether-tribasic alcohol 20～35%
3,5-diformazan sulfenyl tolylene diamine 3～6%
Polynite 3～5%
Clorafin 26～36%
Silicon dioxide powder 1～3%
Talcum powder 20～30%
Kaolin 10～20%
Iron oxide red (Fe
2O
3) or lemon yellow-phthalocyanine green mixture 1.5～3.0%
Described metal carboxylates catalysts comprises iron naphthenate, zinc naphthenate, isocaprylic acid zinc or different zincic acid iron; Described black rubber grain can be waste rubber grain or tire micelle; Described diphenylmethanediisocyanate is that MDI-50 is 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate or their mixture; Described polyether-tribasic alcohol comprises the glycerol polyethenoxy ether, and its molecular weight is 3000; Described polyether Glycols comprises propanediol polyoxypropylene ether, its molecular weight 400-2000; Described silicon dioxide powder, kaolin, talcum powder are mineral fillers.Clorafin and talcum powder are technical grades; Silicon dioxide powder is gas phase or precipitated silica.Pigment is iron oxide red (Fe
2O
3) or lemon yellow-phthalocyanine green mixture.
Paving material for sports field by the nano-polyurethane elastomer production of the present invention is that the step of this method comprises by weight percentage:
(1) .A component preparation: will join in the reactor based on the polyether Glycols 55～65% of A component total amount, stir down at 80 ℃～100 ℃, vacuumize the dehydration degassing 1～3 hour, be cooled to 40 ℃～60 ℃, add diphenylmethanediisocyanate 35～45%, 70 ℃～90 ℃ down reactions after 2～3 hours, it is standby to be cooled to room temperature;
(2) .B component preparation: will join in the reactor based on the polynite 3～5% and the polyether-tribasic alcohol 20～35% of B component total amount, stir down at 80 ℃～100 ℃, vacuumize the dehydration degassing 1～3 hour, add 3 again, 5-diformazan sulfenyl tolylene diamine 3～6%, clorafin 26～36%, silicon dioxide powder 1～3%, talcum powder 20～30%, kaolin 10～20%, iron oxide red (Fe
2O
3) or lemon yellow-phthalocyanine green mixture 1.5～3.0%, mix, be warming up to 85 ℃ ± 5 ℃ and vacuumize, dehumidification gas 1～2 hour, it is standby to be cooled to room temperature;
(3). the preparation of polyurethane elastomer: by the A component in the polyurethane elastomer and the weight ratio of B component is to mix A and B component in 1: 2～1: 3, add-on is 20～25% a black rubber grain of A and B component weight sum total then, mix the back add-on and be 0.10～0.30% metal carboxylates catalysts of A and B component weight sum total, stir, polymerizing curable is prepared the paving material for sports field by the nano-polyurethane elastomer production.
The used polynite of the present invention can be buied from market, nano imvite can obtain with following preparation method: polynite 5% (W/W) aqueous solution, its cation exchange capacity CEC9-10mmol/g, under 80 ℃, dropwise add 16-octadecyl ammonium chloride, its amount is by 〉=9-10mmol/g, stirring reaction one hour, suction strainer is washed to no cl
-(AgNO
3), oven dry is pulverized.
The used polynite of the present invention is a kind of layered silicate, about 1 nanometer of its structure lamella (1nm).One alumina octahedral subgrade is arranged in its laminate structure, and it is connected by shared Sauerstoffatom with the subgrade of two silicon-oxy tetrahedrons therein, because the aluminium atom of the alumina layer of intermediate course is by the low price ion, as Na
+, Ca
++Deng replacement, lamella thereby negative charge is arranged exchanges with alkyl quaternary ammonium salts or other organic cation easily, the generation organic montmorillonoid, thereby have lipophilicity.So, it can mix with the organic polymer monomer, also may enter by the interlayer that enlarges because of the alkyl quaternary ammonium salts exchange by monomer.Carry out macromolecular polymerization reaction, the nano effect (as high surface energy etc.) that it not only has nano-scale to provide, and polymer molecule exists in the structure lamella, and crystalline structure improves greatly to the organic macromolecule mechanical property like this, thereby has prolonged work-ing life.
Paving material for sports field leading indicator test by the nano-polyurethane elastomer production of the present invention is:
1. hardness is insulted the durometer LX-A type that instrument plant produces with Shanghai six;
2. draw and stretch intensity and elongation rate of tensile failure, measure, test by standard GB/T14833-93 method with Britain Instorn 1122 section bar material trier;
3. specimen preparation is by standard GB/T538-92 method.
Can find out from embodiments of the invention, paving material for sports field by the nano-polyurethane elastomer production of the present invention does not use tolylene diisocyanate TDI and 3,3 '-two chloro-4,4 ' diaminodiphenyl-methane MOCA and heavy metal lead, its component and Chinese invention patent publication number are that CN1033639A also makes a world of difference.The made paving material for sports field salient features test result by the nano-polyurethane elastomer production of the embodiment of the invention is listed in the table below.
| Embodiment | Title | Hardness (Shao Shi A) degree | Tensile strength Mpa | Elongation at break % | The flame retardant resistance level |
| ??1 | Runway | ?50-58 | ??1.8±0.07 | ??120±8 | ????1 |
| ??2 | The court | ?65-75 | ??4.0±0.07 | ??300±3 | ????1 |
Therefore the present invention has changed the prescription of conventional urethane elastic sports place with glue, production safety, owing to do not use pungency, and nocuous TDI, thereby can be not again working-yard workman's eyes not be damaged and cause allergic, and help environmental protection.
The runway rubber performance that track and field runway rubber that the present invention makes and Chinese invention patent CN1033693 are made by the TDI-MOCA system relatively is listed in the table below.
| Interventions Requested | Requirement 1 | The TDI---MOCA system 2 | The MDI-E300 system 3 |
| Hardness (Shao Shi A), degree | 45-60 | 48 | ?55 |
| Rebound value, % | ≥20 | 31 | ?32 |
| The compression recovery rate, % | ≥95 | 98 | ?99 |
| Tensile strength, Mpa | ≥0.7 | 1.14 | ?1.8 |
| Tensile yield, % | ≥90 | 105 | ?120 |
| Fire-retardant, level | 1 | 1 | ?1 |
1, standard GB/T14833-93
2, the Chinese invention patent publication number is the report data of CN1033639A
3, nano-environment protection type polyurethane elastomerics runway rubber test result of the present invention, national sports articles for use quality supervision and test center.
Below in conjunction with embodiment technical scheme of the present invention is further described.
Embodiment
Embodiment 1: by the runway place pavement material of nano-polyurethane elastomer production
(1) preparation of .A component: will be based on A component total amount, its molecular weight is that 1000 and 2000 polyether Glycols 60% joins in the reactor, stirs down at 85 ℃ ± 5 ℃.Vacuumizing the dehydration degassing about 2 hours, and being cooled to 50 ℃～60 ℃, adding 4,4 '-diphenylmethanediisocyanate and 2, the mixture of 4 '-diphenylmethanediisocyanate (MDI-50) 40%, 85 ℃ of reactions about 2 hours down, it is standby to be cooled to room temperature;
(2) preparation of .B component: will be glycerol polyoxy third rare ether 23% of 3000 based on the nano imvite 4% of B component total amount and its molecular weight, join in the reactor and mix, vacuumizing the dehydration degassing about 1 hour under 85 ℃ ± 5 ℃, add 3 again, 5-diformazan sulfenyl tolylene diamine (E300) 3.5%, clorafin 36%, talcum powder 20%, silicon dioxide powder 1%, kaolin 10%, iron oxide red 2.5% mix, being warming up to 85 ℃ vacuumizes, dehumidification gas 1～2 hour, it is standby to be cooled to room temperature;
(3). the preparation of polyurethane elastomer: by the A component in the polyurethane elastomer and the weight ratio of B component is to mix A and B component at 1: 3, add-on is 20% a black rubber grain of A and B component weight sum total then, mix the back add-on and be 0.14% isocaprylic acid zinc catalyst of A and B component weight sum total, stir, polymerizing curable is prepared the polyurethane elastomer that paving material for sports field is used.
Embodiment 2: by the ball place pavement material of nano-polyurethane elastomer production
(1) .A component preparation: will be based on A component total amount, its molecular weight is that 1000 and 2000 polyether Glycols 55% joins in the reactor, stir down at 85 ℃ ± 5 ℃, vacuumize the dehydration degassing about 2 hours, be cooled to 50 ℃～60 ℃, add 4,4 '-diphenylmethanediisocyanate 45%, 85 ℃ ± 5 ℃ down reactions about 2 hours, it is standby to be cooled to room temperature;
(2) .B component preparation: will be that 3000 glycerol polyethenoxy ether 27% joins in the reactor and mixes based on the nano imvite 4.5% of B component total amount and its molecular weight, vacuumizing the dehydration degassing about 1 hour under 85 ℃ ± 5 ℃, add 3 again, 5-diformazan sulfenyl tolylene diamine (E300) 5.5%, clorafin 26%, silicon dioxide powder 1%, iron oxide red 2%, kaolin 12%, talcum powder 22% mixes, at 85 ℃ ± 5 ℃ following vacuum dehumidification gas about 1 hour, it is standby to be cooled to room temperature;
(3). the preparation of polyurethane elastomer: by the A component in the polyurethane elastomer and the weight ratio of B component is to mix A and B component at 1: 3, add-on is 20% a black rubber grain of A and B component weight sum total then, mix the back add-on and be 0.2% isocaprylic acid zinc catalyst of A and B component weight sum total, stir, polymerizing curable is prepared the nano-environment protection type polyurethane elastomerics that paving material for sports field is used.
Claims (10)
1. paving material for sports field by the nano-polyurethane elastomer production, it is characterized in that: described material is made up of elastomerics A component, B component, black rubber grain and metal carboxylates catalysts, wherein, the weight ratio of A component and B component is 1: 2～1: 3 in the polyurethane elastomer, the content of black rubber grain is 20～25% of A component and B component weight summation, and metal carboxylates catalysts is 0.10～0.30% of A component and a B component weight summation;
The composition of A component and weight percent are:
Diphenylmethanediisocyanate 35～45%
Polyether Glycols 55～65%
The composition of B component and weight percent are:
Polyether-tribasic alcohol 20～35%
3,5-diformazan sulfenyl tolylene diamine 3～6%
Polynite 3～5%
Clorafin 26～36%
Silicon dioxide powder 1～3%
Talcum powder 20～30%
Kaolin 10～20%
Iron oxide red or lemon yellow-phthalocyanine green mixture 1.5～3.0%.
2. material as claimed in claim 1 is characterized in that: described metal carboxylates catalysts comprises iron naphthenate, zinc naphthenate, isocaprylic acid zinc or different zincic acid iron.
3. material as claimed in claim 1 is characterized in that: described diphenylmethanediisocyanate is 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate or their mixture.
4. material as claimed in claim 1 is characterized in that: described polyether-tribasic alcohol is the glycerol polyethenoxy ether.
5. material as claimed in claim 1 is characterized in that: described polyether Glycols is a propanediol polyoxypropylene ether.
6. one kind as each described preparation methods of claim 1～5, it is characterized in that: be that the step of this method comprises by weight percentage:
(1) .A component preparation: will join in the reactor based on the polyether Glycols 55～65% of A component total amount, stir down, vacuumize the dehydration degassing at 80 ℃～100 ℃, cooling, add diphenylmethanediisocyanate 35～45%, 70 ℃～90 ℃ reactions down, it is standby to be cooled to room temperature;
(2) .B component preparation: will join in the reactor based on the polynite 3～5% and the polyether-tribasic alcohol 20～35% of B component total amount, stir down at 80 ℃～100 ℃, vacuumize the dehydration degassing, add 3 again, 5-diformazan sulfenyl tolylene diamine 3～6%, clorafin 26～36%, silicon dioxide powder 1～3%, talcum powder 20～30%, kaolin 10～20%, iron oxide red or lemon yellow-phthalocyanine green mixture 1.5～3.0%, mix, being warming up to 85 ℃ ± 5 ℃ vacuumizes, dehumidification gas, it is standby to be cooled to room temperature;
(3). the preparation of polyurethane elastomer: by the A component in the polyurethane elastomer and the weight ratio of B component is to mix A and B component in 1: 2～1: 3, add-on is 20～25% a black rubber grain of A and B component weight sum total then, mix the back add-on and be 0.10～0.30% metal carboxylates catalysts of A and B component weight sum total, stir, polymerizing curable is prepared the paving material for sports field by the nano-polyurethane elastomer production.
7. method as claimed in claim 6 is characterized in that: described metal carboxylates catalysts comprises iron naphthenate, zinc naphthenate, isocaprylic acid zinc or different zincic acid iron.
8. method as claimed in claim 6 is characterized in that: described diphenylmethanediisocyanate is 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate or their mixture.
9. the method for claim 1, it is characterized in that: described polyether-tribasic alcohol is the glycerol polyethenoxy ether.
10. the method for claim 1, it is characterized in that: described polyether Glycols is a propanediol polyoxypropylene ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03149973 CN1254494C (en) | 2003-08-01 | 2003-08-01 | Stadium paving material prepared from nano polyurethane elastomer and its preparing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03149973 CN1254494C (en) | 2003-08-01 | 2003-08-01 | Stadium paving material prepared from nano polyurethane elastomer and its preparing method |
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| Publication Number | Publication Date |
|---|---|
| CN1580162A true CN1580162A (en) | 2005-02-16 |
| CN1254494C CN1254494C (en) | 2006-05-03 |
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|---|---|---|---|
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|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100365066C (en) * | 2006-01-20 | 2008-01-30 | 浙江大学 | Method for preparing nano silicon dioxide reinforced polyurethane road crack filling material |
| CN100408610C (en) * | 2006-08-17 | 2008-08-06 | 浙江大学 | Horniness polyurethane foam ternary composite material and preparation method thereof |
| CN101289574B (en) * | 2008-06-06 | 2010-09-29 | 上海世鹏聚氨酯科技发展有限公司 | Wear resistant elastic material of polyurethane modified by nano-steel slag |
| CN103980458A (en) * | 2014-05-05 | 2014-08-13 | 北京新世纪纳米塑胶材料有限公司 | Sports ground wearing layer material prepared from polyurethane elastomer and preparation method thereof |
| CN108948310A (en) * | 2018-07-21 | 2018-12-07 | 济宁市伟松环保产品有限公司 | A kind of silicon PU sports ground pavement material and its manufacturing 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 |
| CN110804151A (en) * | 2019-11-15 | 2020-02-18 | 武汉奥体家体育材料有限公司 | Preparation method of solvent-free polyurethane plastic ball field material |
| 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 |
-
2003
- 2003-08-01 CN CN 03149973 patent/CN1254494C/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100365066C (en) * | 2006-01-20 | 2008-01-30 | 浙江大学 | Method for preparing nano silicon dioxide reinforced polyurethane road crack filling material |
| CN100408610C (en) * | 2006-08-17 | 2008-08-06 | 浙江大学 | Horniness polyurethane foam ternary composite material and preparation method thereof |
| CN101289574B (en) * | 2008-06-06 | 2010-09-29 | 上海世鹏聚氨酯科技发展有限公司 | Wear resistant elastic material of polyurethane modified by nano-steel slag |
| CN103980458A (en) * | 2014-05-05 | 2014-08-13 | 北京新世纪纳米塑胶材料有限公司 | Sports ground wearing layer material prepared from polyurethane elastomer and preparation method thereof |
| CN103980458B (en) * | 2014-05-05 | 2016-03-09 | 北京新世纪纳米塑胶材料有限公司 | Sports field wearing layer material prepared by polyurethane elastomer and preparation method thereof |
| CN108948310A (en) * | 2018-07-21 | 2018-12-07 | 济宁市伟松环保产品有限公司 | A kind of silicon PU sports ground pavement material and its manufacturing 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 |
| CN110804151A (en) * | 2019-11-15 | 2020-02-18 | 武汉奥体家体育材料有限公司 | Preparation method of solvent-free polyurethane plastic ball field material |
| 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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| Publication number | Publication date |
|---|---|
| CN1254494C (en) | 2006-05-03 |
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