CN1706902A - 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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- CN1706902A CN1706902A CN 200410046498 CN200410046498A CN1706902A CN 1706902 A CN1706902 A CN 1706902A CN 200410046498 CN200410046498 CN 200410046498 CN 200410046498 A CN200410046498 A CN 200410046498A CN 1706902 A CN1706902 A CN 1706902A
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- diphenylmethanediisocyanate
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Abstract
The present invention belongs to the field of polymer material, and is especially sports ground paving material prepared with nanometer montmorillonite and polyurethane and its preparation process. The preparation process includes the following steps: dewatering polyether diol, adding diphenylmethane diisocyanate and further reaction to prepare component A; adding dry nanometer montmorillonite into polyether polyol to modify, adding stuffing and vacuum pumping to prepare component B; mixing component A, component B, black rubber grain and metal carboxylate; and stirring to polymerize, cure and obtain the green sports ground paving material. The green sports ground paving material has high performance and long service life.
Description
Technical field
The invention belongs to polymeric material field, particularly environment-friendly type paving material for sports field for preparing by the nano montmorillonite/polyurethane plastic cement 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; 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 the conventional urethane elastomerics uses the injury to human body, the hidden danger that TDI and MOCA brought, and a kind of 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 MOCA and heavy metal of not using, by the preparation method of the paving material for sports field of the nano imvite of dried preparation and polyurethane plastic 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, 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 34～46%
Polyether Glycols 54～66%
The composition of B component and weight percent are:
Polyether-tribasic alcohol 10～20%
Polyether Glycols 5～15%
3,5-diformazan sulfenyl tolylene diamine 3～6%
TriMethylolPropane(TMP) 0.4～2%
Nano imvite 3～5%
Clorafin 25～35%
Silicon dioxide powder 1～3%
Talcum powder 15～30%
Potter's clay (kaolin) 10～20%
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 rubber grain can be waste rubber grain or tire micelle etc.
Described diphenylmethanediisocyanate (MDI-50) is a kind of water white, not volatile organic compound of the utmost point, and its volatility is at 45～54 ℃.Comprise 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate or their mixture etc.
3 of the present invention's use, 5-diformazan alkyl tolylene diamine is a kind of faint yellow, slightly bitter organic compound that does not contain poisonous composition.
Described polyether-tribasic alcohol comprises the glycerol polyethenoxy ether, and its molecular weight is 3000.
Described polyether Glycols comprises propanediol polyoxypropylene ether, and its molecular weight is 400～2000.
Described silicon dioxide powder, potter's clay (kaolin), talcum powder are mineral fillers.Silicon dioxide powder is gas phase or precipitated silica; Clorafin and talcum powder are technical grades.
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 54～66% of A component total amount, stir down at 80 ℃～100 ℃, vacuumize the dehydration degassing 1～2 hour, be cooled to 40 ℃～60 ℃, add diphenylmethanediisocyanate 34～46%, 70 ℃～90 ℃ 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 again, 5-diformazan sulfenyl tolylene diamine 3～6%, TriMethylolPropane(TMP) 0.4～2.0%, clorafin 25～35%, silicon dioxide powder 1～3%, talcum powder 15～30%, potter's clay (kaolin) 10～20%, iron oxide red (Fe
2O
3) or lemon cover Huang-phthalocyanine green mixture 1.5～3.0%, 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 at 1: 3, add-on is 20～25% a black rubber grain of A and B component weight summation then, mixing the back add-on is 0.10～0.30% 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 level polynite 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.Montmorillonite intercalation was thorough when one, the nano imvite of dry production was owing to production process, so it is than using the better of wet production; Two, the nano imvite of dry production to the performance change of goods than increasing with wet production; 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 dried preparation nano imvite production cost is low than the wet production cost, so the present invention provides possibility to reducing production costs.
The used nano imvite 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 polynite that generation organises, 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 the elastomeric mechanical property of product, 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 MOCA bring human body.The paving material for sports field of preparing is referred to as the paving material for sports field of dry method nano environmental protection II type MDI-E300 system.
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 2000 propanediol polyoxypropylene ether 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 that 3000 glycerol polyethenoxy ether 12.5%, molecular weight are that 2000 propanediol polyoxypropylene ether 12% joins in the reactor and mixes based on the nano imvite 4.5% 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, 5-diformazan sulfenyl tolylene diamine 4%, TriMethylolPropane(TMP) 0.6%, clorafin 35%, silicon dioxide powder 1%, talcum powder 17.9%, kaolin 10%, 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 2000 propanediol polyoxypropylene ether 62% 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 38%, 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 polynite 4.0% that obtains by dried preparation of B component total amount and its molecular weight, molecular weight is that 2000 propanediol polyoxypropylene ether 15% joins in the reactor and mixes, vacuumizing the dehydration degassing about 2 hours under 85 ℃ ± 5 ℃, add 3 again, 5-diformazan sulfenyl tolylene diamine 3%, TriMethylolPropane(TMP) 0.4%, clorafin 30%, silicon dioxide powder 1%, talcum powder 18.1%, kaolin 10%, lemon covers Huang-phthalocyanine green mixture 2.5% and mixes, and 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 runway rubber of the present invention is to be tested by national sports articles for use quality supervision and test center.Its result such as table 2
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 propanediol polyoxypropylene ether 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 that 3000 glycerol polyethenoxy ether 12.5%, molecular weight are that 2000 propanediol polyoxypropylene ether 12% joins in the reactor and mixes based on the nano imvite 4.5% 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, 5-diformazan sulfenyl tolylene diamine 4%, TriMethylolPropane(TMP) 0.6%, clorafin 35%, silicon dioxide powder 1%, talcum powder 17.9%, kaolin 10%, 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 A and the isocaprylic acid zinc of B component weight summation 0.2% and the arbitrary proportion mixed catalyst of 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 4: 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 the propanediol polyoxypropylene ether 62% of 400-1000 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 38%, 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 polynite 4.0% that obtains by dried preparation of B component total amount and its molecular weight, molecular weight is that 2000 propanediol polyoxypropylene ether 15% joins in the reactor and mixes, vacuumizing the dehydration degassing about 2 hours under 85 ℃ ± 5 ℃, add 3 again, 5-diformazan sulfenyl tolylene diamine 3%, TriMethylolPropane(TMP) 0.4%, clorafin 30%, silicon dioxide powder 1%, talcum powder 18.1%, kaolin 10%, lemon covers Huang-phthalocyanine green mixture 2.5% and mixes, and 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 A and the isocaprylic acid zinc of B component weight summation 0.2% and the arbitrary proportion mixed catalyst of zinc 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 strengths and elongation at break etc. are tested by standard GB/T14833-93 method;
3 specimen preparations are 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 | ??72 | ?75 |
| Rebound value, % | ??≥20 | ??30 | ?32 |
| The compression recovery rate, % | ??≥95 | ??98 | ?99 |
| Tensile strength, Mpa | ??≥0.7 | ??1.14 | ?4.5 |
| Tensile yield, % | ??≥150 | ??175 | ?300 |
| 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 | ?54 |
| Rebound value, % | ??≥20 | ??31 | ?34 |
| The compression recovery rate, % | ??≥95 | ??98 | ?99 |
| Tensile strength, Mpa | ??≥0.7 | ??1.14 | ?1.8 |
| Tensile yield, % | ??≥90 | ??105 | ?121 |
| Fire-retardant, level | ??1 | ??1 | ?1 |
Table 3:
| Interventions Requested | Requirement 1 | ??TDI-MOCA 2 | Embodiment 3 |
| Hardness (Shao Shi A), degree | ??65-78 | ??72 | ?73 |
| Rebound value, % | ??≥20 | ??30 | ?31 |
| The compression recovery rate, % | ??≥95 | ??98 | ?99 |
| Tensile strength, Mpa | ??≥0.7 | ??1.14 | ?4.4 |
| Tensile yield, % | ??≥150 | ??175 | ?305 |
| 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 | ?54 |
| Rebound value, % | ??≥20 | ??31 | ?34 |
| The compression recovery rate, % | ??≥95 | ??98 | ?99 |
| Tensile strength, Mpa | ??≥0.7 | ??1.14 | ?1.8 |
| Tensile yield, % | ??≥90 | ??105 | ?121 |
| Fire-retardant, level | ??1 | ??1 | ?1 |
Claims (10)
1. paving material for sports field by nano montmorillonite/polyurethane plastic cement preparation, 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 polyurethane elastomer A component and B component is 1: 3, 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 34～46%
Polyether Glycols 54～66%
The composition of B component and weight percent are:
Polyether-tribasic alcohol 10～20%
Polyether Glycols 5～15%
3,5-diformazan sulfenyl tolylene diamine 3～6%
TriMethylolPropane(TMP) 0.4～2%
Nano imvite 3～5%
Clorafin 25～35%
Silicon dioxide powder 1～3%
Talcum powder 15～30%
Potter's clay 10～20%
Iron oxide red or lemon cover Huang-phthalocyanine green mixture 1.5～3.0%.
2. material according to claim 1 is characterized in that: described metal carboxylates catalysts comprises iron naphthenate, zinc naphthenate, isocaprylic acid zinc, isocaprylic acid iron or their any mixture.
3. material according to claim 1 is characterized in that: described diphenylmethanediisocyanate is 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate or their mixture.
4. material according to claim 1 is characterized in that: described polyether-tribasic alcohol is the glycerol polyethenoxy ether.
5. material according to claim 1 is characterized in that: described polyether Glycols is a propanediol polyoxypropylene ether.
6. material according to claim 1 is characterized in that: described nano imvite is obtained by dried preparation.
7. one kind according to each described material preparation method of claim 1～6, 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 54～66% of A component total amount, stir down at 80 ℃～100 ℃, vacuumize the dehydration degassing, be cooled to 40 ℃～60 ℃, add diphenylmethanediisocyanate 34～46%, 70 ℃～90 ℃ 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, 5-diformazan sulfenyl tolylene diamine 3～6%, TriMethylolPropane(TMP) 0.4～2.0%, clorafin 25～35%, silicon dioxide powder 1～3%, talcum powder 15～30%, potter's clay 10～20%, iron oxide red or lemon cover Huang-phthalocyanine green mixture 1.5～3.0%, mix, and are warming up to 85 ℃ ± 5 ℃ and vacuumize, 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 at 1: 3, 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.
8. method according to claim 7 is characterized in that: described metal carboxylates catalysts comprises iron naphthenate, zinc naphthenate, isocaprylic acid zinc, isocaprylic acid iron or their any mixture.
9. method according to claim 7 is characterized in that: described diphenylmethanediisocyanate is 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate or their mixture.
10. method according to claim 7 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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|---|---|---|---|
| CN 200410046498 CN1706902A (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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|---|---|---|---|
| CN 200410046498 CN1706902A (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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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295288C (en) * | 2004-06-10 | 2007-01-17 | 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 |
| CN100408610C (en) * | 2006-08-17 | 2008-08-06 | 浙江大学 | Horniness polyurethane foam ternary composite material and preparation method thereof |
| CN101307129B (en) * | 2007-05-17 | 2011-05-11 | 宁波星箭航天机械厂 | Polyurethane/organic montmorillonite nano composite material and method for preparing same |
-
2004
- 2004-06-10 CN CN 200410046498 patent/CN1706902A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295288C (en) * | 2004-06-10 | 2007-01-17 | 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 |
| CN100408610C (en) * | 2006-08-17 | 2008-08-06 | 浙江大学 | Horniness polyurethane foam ternary composite material and preparation method thereof |
| CN101307129B (en) * | 2007-05-17 | 2011-05-11 | 宁波星箭航天机械厂 | Polyurethane/organic montmorillonite nano composite material and method for preparing same |
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