CN1295288C - Sports ground paving material prepared with nanometer montmorillonite and polyurethane plastic and its prepn process - Google Patents
Sports ground paving material prepared with nanometer montmorillonite and polyurethane plastic and its prepn process Download PDFInfo
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- CN1295288C CN1295288C CNB2004100464996A CN200410046499A CN1295288C CN 1295288 C CN1295288 C CN 1295288C CN B2004100464996 A CNB2004100464996 A CN B2004100464996A CN 200410046499 A CN200410046499 A CN 200410046499A CN 1295288 C CN1295288 C CN 1295288C
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Abstract
The present invention belongs to the field of high molecular materials, and particularly to an environment protection nanometer type sports field paving material prepared from polyurethane elastomer by a dry method, and a preparation method thereof. The environment protection nanometer type sports field paving material of the present invention is prepared from a component A, a component B, black rubber particles and metal carboxylate through mixing, stirring, polymerization and solidification, wherein the component A is prepared by reactions caused by adding diphenylmethane diisocyanate to dehydrated polyether dihydric alcohol; the component B is prepared by the steps of adding manometer montmorillonite prepared by a dry method to polyether polyhydric alcohol for modification reactions to enhance the product performances, mixing the reaction products with a filling material for further reactions and vacuum pumping. Not using stimulative and harmful TDI and heavy metal Pb, the present invention is favorable to production, construction and environment protection. Meanwhile, the present invention utilizes the modification function of nanometer materials to enhance the product performances, and as a result, the service life of a sports field is prolonged.
Description
Technical field
The invention belongs to polymeric material field, particularly because paving material for sports field of method nanometer/environment protection type polyurethane elastomer preparation 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 Glycols and organic thinner and makes base polyurethane prepolymer for use as, (being generally called the A component); Butyleneglycol, binary ammonia MOCA (two methylmethanes of 3,3 '-two chloro-, 4,4 ' diamino) 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 Press, 1 edition P262 was pointed in 1966, 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.Thus, International Track and Field Association's proposal does not use this chemical substance to produce paving material for sports field.
Summary of the invention
One of purpose of the present invention is to overcome because the conventional urethane elastomerics uses the injury to human body, the hidden danger that TDI brought, and the paving material for sports field by the preparation of nano montmorillonite/polyurethane plastic cement of environment-friendly type 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, provide a kind of TDI and heavy metal of not using, the preparation method of the paving material for sports field for preparing with the nano imvite and the polyurethane plastic of dried preparation.
Paving material for sports field by the preparation of nano montmorillonite/polyurethane plastic cement 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 polyurethane elastomer A component and B component is 1: 3～1: 4, the content of black rubber grain is 20～25% of A component and B component weight summation, and the content of metal carboxylates catalysts is 0.1～0.3% of A component and B component weight summation;
The composition of A component and weight percent are:
Diphenylmethanediisocyanate 36～48%
Polyether Glycols 52～64%
The composition of B component and weight percent are:
Polyether-tribasic alcohol 10～20%
Polyether Glycols 5～15%
3,3 '-two chloro-4,4 '-diaminodiphenyl-methane 4～8%
Nano imvite 3～5%
Clorafin 30～37%
Silicon dioxide powder 1～3%
Talcum powder 30～40%
Iron oxide red (Fe
2O
3) or lemon illiteracy Huang-phthalocyanine green mixture 1.5～3.0%
Described metal carboxylates catalysts comprises iron naphthenate, zinc naphthenate, isocaprylic acid zinc, isocaprylic acid iron or their any mixture etc.
Described black particle can be waste rubber grain or tire micelle etc.
Described diphenylmethanediisocyanate is that MDI-50 is 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate or their mixture etc.
Described polyether-tribasic alcohol comprises glycerol polyethers propylene ether, and its molecular weight is 3000.
Described polyether Glycols comprises propylene glycol polyethers propylene ether, and its molecular weight is 400～2000.
Described silicon dioxide powder, talcum powder are mineral fillers.Clorafin and talcum powder are technical grades; Silicon dioxide powder is gas phase or precipitated silica.
The preparation method of the paving material for sports field by nano montmorillonite/polyurethane plastic cement preparation of the present invention may further comprise the steps, by weight percentage:
(1), A component preparation: will join in the reactor based on the polyether Glycols 52～64% of A component total amount, stir down at 80 ℃～100 ℃, vacuumize the dehydration degassing 1～2 hour, be cooled to 40 ℃～60 ℃, add diphenylmethanediisocyanate 36～48%, 75 ℃～85 ℃ down reactions about 2 hours, it is standby to be cooled to room temperature;
(2), B component preparation: will join in the reactor based on the nano imvite 3～5% and polyether-tribasic alcohol 10～20%, the polyether Glycols 5～15% that obtain by dried preparation of B component total amount, stir down at 80 ℃～100 ℃, vacuumize the dehydration degassing 1～2 hour, add 3,3 '-two chloro-4 again, 4 '-diaminodiphenyl-methane 4～8%, clorafin 30～37%, talcum powder 30～40%, silicon dioxide powder 1～3%, iron oxide red (Fe
2O
3) or lemon cover Huang-phthalocyanine green mixture 1.5～3.0% and mix, be warming up to 85 ℃ ± 5 ℃ and vacuumize, dehumidification gas is about 2 hours, 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: 3～1: 4, add-on is 20～25% a black rubber grain of A and B component weight summation then, mixing the back add-on is 0.1～0.3% metal carboxylates catalysts of A and B component weight summation, stir polymerizing curable, prepare the paving material for sports field of nano montmorillonite/polyurethane plastic cement.
The used nano imvite of the present invention is obtained by dried preparation, can buy from market.It is different that dried preparation nano imvite and wet method prepare nano imvite.One, the nano imvite of dry production its by the effect of intercalation good than with wet production, so its superior performance is in the nano imvite of the production of wet method; Two, with the nano imvite of dry production to more obvious than with the production of wet method of the performance that changes goods; Three, dry production process non-environmental-pollution helps environmental protection; The sewage that the wet production process is discharged contains Toxic matter and is unfavorable for environmental protection.Because dry method polynite production cost is low than the wet production cost, so the present invention provides possibility to reducing production costs.
The used nano level 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 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.After carrying 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 just is much improved to the organic macromolecule mechanical property like this.
When the present invention uses the prescription of glue in change conventional urethane elastic sports place, adopt the nano imvite that obtains by dried preparation emphatically, not only improved elastomeric mechanical property, obtained prolongation work-ing life, and reduced production cost.The more important thing is and overcome injury and the hidden danger that traditional use TDI and heavy metal lead bring human body.It is the paving material for sports field of MDI-MOCA system that the paving material for sports field of preparing is referred to as dry method nano environmental protection I type.
Below in conjunction with embodiment technical scheme of the present invention is further described.
Embodiment
Embodiment 1: by the ball place of the environment-friendly type pavement material of nano montmorillonite/polyurethane plastic elastomeric preparation
1), A component preparation: will be based on A component total amount, its molecular weight is that 1000 and 2000 polyether Glycols 58% joins in the reactor, stir down at 85 ℃ ± 5 ℃, vacuumize the dehydration degassing about 2 hours, be cooled to 50 ℃～60 ℃, add diphenylmethanediisocyanate 42%, 85 ℃ ± 5 ℃ reactions about 2 hours down, it is standby to be cooled to room temperature;
2), B component preparation: will be that 3000 glycerol polyethenoxy ether 15.5%, molecular weight are that 2000 propanediol polyoxypropylene ether 8% joins in the reactor and mixes based on the nano imvite 4.0% that obtains by dried preparation of B component total amount and its molecular weight, vacuumizing the dehydration degassing about 2 hours under 85 ℃ ± 5 ℃, add 3 again, 3 '-two chloro-4,4 '-diaminodiphenyl-methane 7.0%, clorafin 32%, silicon dioxide powder 1%, talcum powder 30%, iron oxide red (Fe
2O
3) 2.5% mix, 85 ℃ ± 5 ℃ reactions about 2 hours down, 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 summation then, mixing the back add-on is 0.2% isocaprylic acid zinc catalyst of A and B component weight summation, stir, polymerizing curable is prepared paving material for sports field.
The performance test of court of the present invention glue is tested result such as table 1 by national sports articles for use quality supervision and test center.
Embodiment 2: by the environment-friendly type runway place pavement material of nano montmorillonite/polyurethane plastic elastomeric preparation
1), A component preparation: will be based on A component total amount, its molecular weight is that 1000 and 2000 polyether Glycols 60% 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 40%, 85 ℃ ± 5 ℃ down reactions about 2 hours, it is standby to be cooled to room temperature;
2), B component preparation: will be 3000 glycerol polyethenoxy ether 16% based on the nano imvite 3.0% that obtains by dried preparation of B component total amount and its molecular weight, molecular weight is that 2000 propanediol polyoxypropylene ether 8% joins in the reactor and mixes, vacuumizing the dehydration degassing about 2 hours under 85 ℃ ± 5 ℃, add 3 again, 3 '-two chloro-4,4 '-diaminodiphenyl-methane 4.0%, clorafin 33%, silicon dioxide powder 1%, talcum powder 32.5%, lemon covers Huang-phthalocyanine green mixture 2.5% and mixes, 85 ℃ ± 5 ℃ down reactions about 2 hours, 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: 4, add-on is 20% a black rubber grain of A and B component weight summation then, mixing the back add-on is 0.2% isocaprylic acid zinc catalyst of A and B component weight summation, stir, polymerizing curable is prepared paving material for sports field.
The performance test of runway rubber of the present invention is to test result such as table 2 by national sports articles for use quality supervision and test center.
Embodiment 3: by the ball place of the environment-friendly type pavement material of nano montmorillonite/polyurethane plastic elastomeric preparation
1), A component preparation: will be based on A component total amount, its molecular weight is that 1000 polyether Glycols 58% joins in the reactor, stir down at 85 ℃ ± 5 ℃, vacuumize the dehydration degassing about 2 hours, be cooled to 50 ℃～60 ℃, add diphenylmethanediisocyanate 42%, 85 ℃ ± 5 ℃ reactions about 2 hours down, it is standby to be cooled to room temperature;
2), B component preparation: will be that 3000 glycerol polyethenoxy ether 15.5%, molecular weight are that 2000 propanediol polyoxypropylene ether 8% joins in the reactor and mixes based on the nano imvite 4.0% that obtains by dried preparation of B component total amount and its molecular weight, vacuumizing the dehydration degassing about 2 hours under 85 ℃ ± 5 ℃, add 3 again, 3 '-two chloro-4,4 '-diaminodiphenyl-methane 7.0%, clorafin 32%, silicon dioxide powder 1%, talcum powder 30%, iron oxide red (Fe
2O
3) 2.5% mix, 85 ℃ ± 5 ℃ reactions about 2 hours down, 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 summation then, mix the mixed catalyst of the arbitrary proportion of 0.2% isocaprylic acid zinc that the back add-on is A and B component weight summation and isocaprylic acid iron, stir, polymerizing curable is prepared paving material for sports field.
The performance test of court of the present invention glue is tested result such as table 3 by national sports articles for use quality supervision and test center.
Embodiment 2: by the environment-friendly type runway place pavement material of nano montmorillonite/polyurethane plastic elastomeric preparation
1), A component preparation: will be based on A component total amount, its molecular weight is that 400～1000 polyether Glycols 60% 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 40%, 85 ℃ ± 5 ℃ down reactions about 2 hours, it is standby to be cooled to room temperature;
2), B component preparation: will be 3000 glycerol polyethenoxy ether 16% based on the nano imvite 3.0% that obtains by dried preparation of B component total amount and its molecular weight, molecular weight is that 2000 propanediol polyoxypropylene ether 8% joins in the reactor and mixes, vacuumizing the dehydration degassing about 2 hours under 85 ℃ ± 5 ℃, add 3 again, 3 '-two chloro-4,4 '-diaminodiphenyl-methane 4.0%, clorafin 33%, silicon dioxide powder 1%, talcum powder 32.5%, lemon covers Huang-phthalocyanine green mixture 2.5% and mixes, 85 ℃ ± 5 ℃ down reactions about 2 hours, 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: 4, add-on is 20% a black rubber grain of A and B component weight summation then, mix the blended catalyzer of the arbitrary proportion of 0.2% zinc naphthenate that the back add-on is A and B component weight summation and iron naphthenate, stir, polymerizing curable is prepared paving material for sports field.
The performance test of runway rubber of the present invention is tested result such as table 4 by national sports articles for use quality supervision and test center.
Polyurethane elastomer leading indicator test of the present invention is:
1, hardness is insulted the durometer LX-A type that instrument plant produces with Shanghai six;
2, tensile strength and elongation at break etc. are tested by standard GB/T14833-93 method;
3, specimen preparation is by standard GB/T538-92 method.
Runway rubber, court glue and the Chinese invention patent CN1033693 of the present invention's preparation relatively lists in table 1,2,3,4 by the runway rubber performance of TDI-MOCA system preparation.
Table 1:
| Interventions Requested | Requirement 1 | TDI-MOCA 2 | Embodiment 1 |
| Hardness (Shao Shi A), degree | 65-78 | 71 | 73 |
| Rebound value, % | ≥20 | 31 | 32 |
| The compression recovery rate, % | ≥95 | 98 | 99 |
| Tensile strength, Mpa | ≥0.7 | 1.14 | 3.5 |
| Tensile yield, % | ≥150 | 169 | 305 |
| Fire-retardant, level | 1 | 1 | 1 |
Table 2
| Interventions Requested | Requirement 1 | TDI-MOCA 2 | Embodiment 2 |
| Hardness (Shao Shi A), degree | 45-60 | 48 | 55 |
| Rebound value, % | ≥20 | 31 | 33 |
| The compression recovery rate, % | ≥95 | 98 | 99 |
| Tensile strength, Mpa | ≥0.7 | 1.14 | 1.9 |
| Tensile yield, % | ≥90 | 105 | 131 |
| Fire-retardant, level | 1 | 1 | 1 |
Table 3:
| Interventions Requested | Requirement 1 | TDI-MOCA 2 | Embodiment 3 |
| Hardness (Shao Shi A), degree | 65-78 | 73 | 75 |
| Rebound value, % | ≥20 | 30 | 30 |
| The compression recovery rate, % | ≥95 | 98 | 97 |
| Tensile strength, Mpa | ≥0.7 | 1.14 | 3.6 |
| Tensile yield, % | ≥150 | 170 | 303 |
| Fire-retardant, level | 1 | 1 | 1 |
Table 4:
| Interventions Requested | Requirement 1 | TDI-MOCA 2 | Embodiment 4 |
| Hardness (Shao Shi A), degree | 45-60 | 48 | 57 |
| Rebound value, % | ≥20 | 31 | 31 |
| The compression recovery rate, % | ≥95 | 98 | 98 |
| Tensile strength, Mpa | ≥0.7 | 1.14 | 1.8 |
| Tensile yield, % | ≥90 | 105 | 133 |
| Fire-retardant, level | 1 | 1 | 1 |
Claims (8)
1. paving material for sports field by nano montmorillonite/polyurethane plastic cement preparation, it is characterized in that: form by elastomerics A component, B component, black rubber grain and metal carboxylates catalysts, wherein, the weight ratio of polyurethane elastomer A component and B component is 1: 3～1: 4, the content of black rubber grain is 20～25% of A component and B component weight summation, and the content of metal carboxylates catalysts is 0.1～0.3% of A component and B component weight summation;
The composition of A component and weight percent are:
Diphenylmethanediisocyanate 36～48%
Polyether Glycols 52～64%
The composition of B component and weight percent are:
Polyether-tribasic alcohol 10～20%
Polyether Glycols 5～15%
3,3 '-two chloro-4,4 '-diaminodiphenyl-methane 4～8%
Nano imvite 3～5%
Clorafin 30～37%
Silicon dioxide powder 1～3%
Talcum powder 30～40%
Iron oxide red or lemon cover Huang-phthalocyanine green mixture 1.5～3.0%
Described metal carboxylates catalysts is iron naphthenate, zinc naphthenate, isocaprylic acid zinc, isocaprylic acid iron or their any mixture.
2. material according to claim 1 is characterized in that: described diphenylmethanediisocyanate is 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate or their mixture.
3. material according to claim 1 is characterized in that: described polyether-tribasic alcohol is a glycerol polyethers propylene ether.
4. material according to claim 1 is characterized in that: described polyether Glycols is a propylene glycol polyethers propylene ether.
5. material according to claim 1 is characterized in that: described nano imvite is obtained by dried preparation.
6. one kind according to each described preparation methods of claim 1～5, and it is characterized in that: described preparation method may further comprise the steps, by weight percentage:
(1), A component preparation: will join in the reactor based on the polyether Glycols 52～64% of A component total amount, stir down at 80 ℃～100 ℃, vacuumize the dehydration degassing, be cooled to 40 ℃～60 ℃, add diphenylmethanediisocyanate 36～48%, 75 ℃～85 ℃ down reactions, it is standby to be cooled to room temperature;
(2), B component preparation: will be based on the nano imvite 3～5% and the polyether-tribasic alcohol 10～20% that obtain by dried preparation of B component total amount, polyether Glycols 5～15% joins in the reactor, stir down at 80 ℃～100 ℃, vacuumize the dehydration degassing, add 3 again, 3 '-two chloro-4,4 '-diaminodiphenyl-methane 4～8%, clorafin 30～37%, talcum powder 30～40%, silicon dioxide powder 1～3%, iron oxide red or lemon cover Huang-phthalocyanine green mixture 1.5～3.0% and mix, and are warming up to 85 ℃ ± 5 ℃ and vacuumize, about dehumidification gas 2 hours, 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: 3～1: 4, add-on is 20～25% a black rubber grain of A and B component weight summation then, mixing the back add-on is 0.1～0.3% metal carboxylates catalysts of A and B component weight summation, stir polymerizing curable, prepare the paving material for sports field of nano montmorillonite/polyurethane plastic cement;
Described metal carboxylates catalysts is iron naphthenate, zinc naphthenate, isocaprylic acid zinc, isocaprylic acid iron or their any mixture.
7. method according to claim 6 is characterized in that: described diphenylmethanediisocyanate is 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate or their mixture.
8. method according to claim 6 is characterized in that: described polyether-tribasic alcohol is the glycerol polyethenoxy ether; Described polyether Glycols is a propanediol polyoxypropylene ether.
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|---|---|---|---|
| CNB2004100464996A CN1295288C (en) | 2004-06-10 | 2004-06-10 | Sports ground paving material prepared with nanometer montmorillonite and polyurethane plastic and its prepn process |
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|---|---|---|---|
| CNB2004100464996A CN1295288C (en) | 2004-06-10 | 2004-06-10 | Sports ground paving material prepared with nanometer montmorillonite and polyurethane plastic and its prepn process |
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| CN1295288C true CN1295288C (en) | 2007-01-17 |
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| CN100365066C (en) * | 2006-01-20 | 2008-01-30 | 浙江大学 | Method for preparing nano silicon dioxide reinforced polyurethane road crack filling material |
| CN100398607C (en) * | 2006-04-26 | 2008-07-02 | 浙江大学 | Method for preparing nano montmorillonite reinforced polyurethane road joint filling material |
| CN104945586A (en) * | 2015-06-17 | 2015-09-30 | 商丘师范学院 | Abrasion-resistant and environment-friendly polyurethane sports ground material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05106204A (en) * | 1991-10-16 | 1993-04-27 | Mizuno Corp | Work executing method for polyurethane pavement, and polyurethane paving material |
| CN1386815A (en) * | 2002-06-07 | 2002-12-25 | 丛树枫 | Preparing process and application of wet-solidifying single-component polyurethane adhesive |
| CN1706902A (en) * | 2004-06-10 | 2005-12-14 | 北京宝利通纳米橡塑材料有限公司 | Sports ground paving material prepared with nanometer montmorillonite and polyurethane plastic and its prepn process |
-
2004
- 2004-06-10 CN CNB2004100464996A patent/CN1295288C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05106204A (en) * | 1991-10-16 | 1993-04-27 | Mizuno Corp | Work executing method for polyurethane pavement, and polyurethane paving material |
| CN1386815A (en) * | 2002-06-07 | 2002-12-25 | 丛树枫 | Preparing process and application of wet-solidifying single-component polyurethane adhesive |
| CN1706902A (en) * | 2004-06-10 | 2005-12-14 | 北京宝利通纳米橡塑材料有限公司 | Sports ground paving material prepared with nanometer montmorillonite and polyurethane plastic and its prepn process |
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