CN112457545A - Color rubber floor tile and preparation method thereof - Google Patents
Color rubber floor tile and preparation method thereof Download PDFInfo
- Publication number
- CN112457545A CN112457545A CN202011236449.XA CN202011236449A CN112457545A CN 112457545 A CN112457545 A CN 112457545A CN 202011236449 A CN202011236449 A CN 202011236449A CN 112457545 A CN112457545 A CN 112457545A
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- polyurethane
- rubber
- floor tile
- waste
- excess
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L19/00—Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
- C08L19/003—Precrosslinked rubber; Scrap rubber; Used vulcanised rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a color rubber floor tile and a preparation method thereof, belonging to the field of recycling of excess materials of two high polymer material processing products. The color rubber floor tile comprises polymer material excess, an adhesive component and water serving as a curing agent; the polymer material residual comprises: one or more of ethylene propylene rubber particles, waste strips after rubber vulcanization, polyurethane elastomer waste strips, polyurethane shockproof material waste particles and waste rubber particles; the adhesive component comprises: polyisocyanate, polyether diol and polyether triol. The invention takes the waste rubber particles as the filling material, thereby reducing the cost without reducing the performance; rubber particles are adopted completely, so that water permeation is facilitated; the MDI is used and has lower toxicity than TDI, and the prepared adhesive is a solvent-free product, has no VOC emission and is more environment-friendly in production and use.
Description
Technical Field
The invention relates to a colored rubber floor tile and a preparation method thereof, belongs to the field of recycling of remainders of two processed high polymer materials, and particularly relates to recycling of rubber, a polyurethane elastomer and a polyurethane shockproof material, in particular to recycling of remainders after rubber vulcanization, polyurethane elastomer leftover materials and the polyurethane shockproof material.
Background
In the manufacturing process of the rubber product, in order to fill the mold, excessive rubber is generally required to be added, the excessive rubber is usually 1-5%, and the rubber is changed from a thermoplastic material to a thermosetting material after vulcanization. The performance of the vulcanized rubber excess material is consistent with that of a rubber product, but the shape and the color limit the continuous use of the rubber excess material and only can be treated as waste materials: desulfurizing to obtain regenerated rubber powder; cutting into granules to be used as other filling materials; as garbage, landfill treatment; and incinerating the waste liquid as fuel.
The polyurethane elastomer and the polyurethane shockproof material are prepared by reacting polyisocyanate with polyol to generate polyurethane prepolymer, mixing the prepolymer with chain extender, vulcanizing to form polyurethane elastomer, adding foaming agent and foam stabilizer during chain extension of polyurethane to form foamed polyurethane, which can be used as shockproof material. During the synthesis of the polyurethane prepolymer, the triol is added, so the polyurethane elastomer and the polyurethane shockproof material are also thermosetting materials. The elastomer excess materials in the polyurethane forming process are used as garbage and landfill treatment, other treatment modes are researched a lot, and the practical application is few. The problem of recycling the high polymer material is how to fully utilize the waste materials with good performance but unsatisfactory shape and color.
At present, in international and domestic special sports grounds, most of ground paving materials are prepared by mixing polyurethane pure glue or adding a small amount of waste rubber particles, wherein the used polyurethane materials are mostly double-component polyurethane casting glue, the ground paving materials are paved by adopting a field mixing mode, the sports protection and anti-skid functions of the ground paving materials are greatly superior to those of the traditional ground paving materials, the mixing ration is inaccurate by using a double-component adhesive, and the commonly used MOCA in a curing agent has carcinogenic possibility. The color rubber floor tile is produced with waste rubber grain, pigment, polyurethane or other adhesive, stuffing, curing agent, antiwear agent, antiager, etc. and through heating and pressurizing in special mold, and has the following demerits: poor appearance, no water resistance, low service life, and fading, edge warping and deformation in three years or less (Chinese patent CN 200520080362.2).
Disclosure of Invention
The invention aims to provide a colored rubber floor tile and a preparation method thereof, which mainly uses polymer material remainders as rubber floor tiles by bonding the polymer material remainders together by a polymer adhesive through simple physical cutting, embodies the maximum use value of the rubber floor tiles, reasonably allocates resources and changes waste into valuable.
The invention aims to adopt new vulcanized finished rubber, a polyurethane elastomer with wear resistance, a polyurethane shockproof material with elasticity (namely, the performance of a qualified product is achieved, but the shape of the polyurethane elastomer cannot meet the use requirement), and an environment-friendly solvent-free polyurethane prepolymer reacts with water to form polyurea, the polyurea is bonded together, and colored ethylene propylene rubber particles are bonded on the surface of the polyurea to prepare the environment-friendly colored rubber floor tile. The defects of short service life, poor performance and the like caused by the use of materials such as waste rubber particles, a filling agent, a curing agent, an anti-wear agent, an anti-aging agent and the like are overcome, VOC emission caused by the use of a solvent-type bi-component polyurethane adhesive is also overcome, and 3,3 '-dichloro-4, 4' -diaminodiphenylmethane (MOCA) has carcinogenic risk. The obtained product is the colorful rubber floor tile with long service life, strong mechanical property, adjustable hardness and gorgeous appearance.
The present invention is achieved by a method of,
the invention provides a color rubber floor tile: comprises polymer material remainder, adhesive component and water as curing agent; the polymer material residual comprises: one or more of ethylene propylene rubber particles, waste strips after rubber vulcanization, polyurethane elastomer waste strips, polyurethane shockproof material waste particles and waste rubber particles; the adhesive component comprises: polyisocyanate, polyether diol and polyether triol.
The polymer material elastomer: a polyurethane prepolymer: the mass ratio of the water is 87-91: 8-12: 1.
The invention provides a preparation method of a color rubber floor tile, which comprises the steps of firstly synthesizing a polyurethane adhesive, and then bonding the polyurethane adhesive with a residual material of a high polymer material to prepare the rubber floor tile.
The polymer material excess comprises one of rubber vulcanized excess, polyurethane elastomer excess and polyurethane shockproof material excess.
The preparation process of the polyurethane adhesive comprises the following steps: the raw material is polyether diol PPG-220, the hydroxyl value is 56, and the relative molecular weight is 2000; the polyether trihydric alcohol PPG-330 has a hydroxyl value of 56 and a relative molecular weight of 3000; the production process of the mixture (MDI-50) of 2, 4-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate comprises the steps of adding polyether diol and polyether triol into a reaction bottle according to the mass ratio of 1:5, heating to 90-95 ℃, carrying out vacuum dehydration for 2 hours, cooling to 50 +/-5 ℃, dropwise adding weighed MDI-50 under stirring according to the ratio of isocyanate groups to hydroxyl groups (NCO/OH) =1.4, heating to 80 +/-5 ℃, maintaining the temperature, and reacting for 2.5 hours to obtain the polyurethane adhesive.
The excess material after rubber vulcanization is rubber which overflows from a mold after synthetic or natural rubber is molded and vulcanized. The polyurethane elastomer excess material refers to excess material cut after mixing and vulcanizing the polyurethane prepolymer and the chain extender, and the polyurethane shockproof material excess material refers to a material handle (excess material between an injection port and a mold) when the polyurethane prepolymer and the chain extender are mixed and filled with a mold without filling the polyurethane material of the mold in the molding process.
When the rubber shockproof material is used, the remainders after rubber vulcanization and the remainders of the polyurethane elastomers are cut into strips with the width of 2-3 cm and the length of 10-15 cm, and the remainders of the polyurethane shockproof materials are cut into particles with the width of 10-15 mm and waste rubber particles with the length of 2-3 mm for later use.
The invention has the beneficial effects that: because the surface adopts the colored rubber, the color is brighter than that of the colored polyurethane adhesive; the performance of the residual material after the rubber vulcanization is better than that of the waste rubber, and the service life is long; the excess material after rubber vulcanization is added as a long strip to play a role of a reinforcing rib, so that the rubber brick is not easy to break and has high strength; the waste rubber particles are used as filling materials, so that the cost is reduced without reducing the performance; rubber particles are adopted completely, so that water permeation is facilitated; the MDI is used and has lower toxicity than TDI, and the prepared adhesive is a solvent-free product, has no VOC emission and is more environment-friendly in production and use.
Detailed Description
The embodiments of the present invention are described below with reference to specific experimental cases as examples, and it should be understood that the embodiments described herein are only for explaining the present invention and are not intended to limit the present invention.
A color rubber floor tile: comprises a rubber component and an adhesive component, wherein the rubber component comprises: ethylene propylene rubber particles, rubber vulcanized waste strips, polyurethane elastomer waste strips, polyurethane shockproof material waste particles and waste rubber particles; the adhesive component comprises: a polyurethane prepolymer formed by polymerizing polyisocyanate, polyether diol and polyether triol and water used as a curing agent.
The following are specific examples in which the invention may be practiced for further illustration.
Example one:
1. preparing a polyurethane prepolymer: adding 56g of polyether glycol PPG-220 and 11.2g of PPG-330 into a three-neck flask, uniformly stirring, sealing, vacuumizing to 0.6Mpa, heating to 110 ℃, keeping the temperature and the vacuum degree for two hours, recovering the normal pressure, cooling to 50 ℃, stirring, slowly adding 10.9g of MDI-50 into the three-neck flask, heating to 80 ℃, keeping the temperature at 80 +/-5 ℃ and continuously reacting for 2 hours to obtain the polyurethane prepolymer with the NCO content of 4%.
2. Preparing a mould: coating silicon oil release agent on the inner side, the upper template and the lower template of the mold;
3. preparing rubber particles: removing impurities from 2-3 mm of waste rubber particles, and weighing and preparing;
4. preparing materials: weighing the synthesized polyurethane prepolymer, uniformly mixing the waste rubber particle polyurethane prepolymer, adding water accounting for 10% of the mass of the polyurethane prepolymer, and uniformly mixing;
5. filling a mold: placing a mould on a bottom plate, and adding a mixture of waste rubber particles, polyurethane prepolymer and water into the mould;
6. molding: covering a template, pressurizing to 0.2Mpa, heating to 120 ℃ for 40 minutes, and demolding;
7. the ratio of all the materials is as follows: waste rubber particles: a polyurethane prepolymer: water =89:10: 1.
The proportions referred to in the examples are mass ratios.
Example two:
the polyurethane prepolymer and the forming process are the same as the example I, the used high polymer material elastomers are colored ethylene propylene rubber particles and waste rubber particles, the ratio of the two materials is 2:8, and the components are respectively mixed according to the following ratio of the high polymer material elastomers: a polyurethane prepolymer: water =91:8: 1;
when filling the mold, firstly spreading a mixture of the color ethylene propylene rubber particles, the polyurethane prepolymer and water, and then spreading a mixture of the waste rubber particles, the polyurethane prepolymer and water.
Example three:
the polyurethane prepolymer and the forming process are the same as in the first example, the used high polymer material elastomers are colored ethylene propylene rubber particles, waste rubber particles and residual strips after rubber vulcanization, and the proportion of the three materials is 2: 4:4, during compounding, according to the weight ratio of the high polymer material elastomer: a polyurethane prepolymer: water =89:10: 1; mixing the color ethylene propylene rubber particles, the polyurethane prepolymer and water separately, and mixing the other treatments together; when filling the mold, firstly spreading a mixture of the color ethylene propylene rubber particles, the polyurethane prepolymer and water, and then spreading a mixture of the waste rubber particles, the residual strips after rubber vulcanization, the polyurethane prepolymer and water.
Example four:
the polyurethane prepolymer and the forming process are the same as in the first embodiment, the used high polymer material elastomers are colorful ethylene propylene rubber particles, waste rubber particles, excess strips after rubber vulcanization and excess particles of polyurethane shockproof materials, and the proportion of the four materials is 2: 3:2:3, during compounding, according to the weight ratio of the high polymer material elastomer: a polyurethane prepolymer: water =89:10: 1; mixing the color ethylene propylene rubber particles, the polyurethane prepolymer and water separately, and mixing the other treatments together;
when filling the mold, firstly spreading a mixture of the color ethylene propylene rubber particles, the polyurethane prepolymer and water, and then spreading a mixture of the waste rubber particles, the residual strips after rubber vulcanization, the residual particles of the polyurethane shockproof material, the polyurethane prepolymer and water.
Example five:
the polyurethane prepolymer and the forming process are the same as in the first embodiment, the used high polymer material elastomers are colored ethylene propylene rubber particles, waste rubber particles, excess strips after rubber vulcanization, excess polyurethane shockproof material particles and excess polyurethane elastomer, the proportion of the five materials is 2: 3:2:1: 2, during material preparation, according to the following polymer material elastomer: a polyurethane prepolymer: water =89:10: 1; mixing the color ethylene propylene rubber particles, the polyurethane prepolymer and water separately, and mixing the other treatments together;
when filling the mold, firstly spreading a mixture of the color ethylene propylene rubber particles, the polyurethane prepolymer and water, and then spreading a mixture of the waste rubber particles, the residual strips after rubber vulcanization, the residual particles of the polyurethane shockproof material, the polyurethane prepolymer and water.
Example six:
the ingredients and the process are the same as the fifth example
Pressurizing to 0.2Mpa during molding, heating to room temperature for 0.5 hr, and demolding.
Example seven:
the process is the same as the example one
Waste rubber particles: a polyurethane prepolymer: water =84:15: 1. Pressurizing to 0.2Mpa during molding, heating to room temperature for 0.5 hr, and demolding.
Example eight:
the process is the same as the second example
Colored rubber particles: waste rubber particles =1: 1.
And (3) comparing the performances:
Claims (8)
1. a color rubber floor tile is characterized in that: comprises polymer material remainder, adhesive component and water as curing agent; the polymer material residual comprises: one or more of ethylene propylene rubber particles, waste strips after rubber vulcanization, polyurethane elastomer waste strips, polyurethane shockproof material waste particles and waste rubber particles; the adhesive component comprises: polyisocyanate, polyether diol and polyether triol.
2. The colored rubber floor tile according to claim 1, wherein: elastomer of high molecular material: a polyurethane prepolymer: the mass ratio of the water is 87-91: 8-12: 1.
3. The method for preparing the colored rubber floor tile according to claim 1 or 2, wherein the method comprises the following steps: firstly, a polyurethane adhesive is synthesized, and then the polyurethane adhesive is bonded with the residual materials of the high polymer material to prepare the rubber floor tile.
4. The method for preparing the colored rubber floor tile according to claim 3, wherein the method comprises the following steps: the polymer material excess comprises one of rubber vulcanized excess, polyurethane elastomer excess and polyurethane shockproof material excess.
5. The method for preparing the colored rubber floor tile according to claim 4, wherein the method comprises the following steps: the excess material after rubber vulcanization refers to rubber which overflows from a mold after synthetic or natural rubber is molded and vulcanized.
6. The method for preparing the colored rubber floor tile according to claim 4, wherein the method comprises the following steps: the polyurethane elastomer excess material refers to excess material cut after mixing the polyurethane prepolymer and the chain extender and vulcanizing and molding, and the polyurethane shockproof material excess material refers to a material handle when the polyurethane prepolymer and the chain extender are mixed and filled with a mold in the molding process without filling the mold with the polyurethane material.
7. The method for preparing the colored rubber floor tile according to claim 4, wherein the method comprises the following steps: cutting the remainder of the vulcanized rubber and the remainder of the polyurethane elastomer into strips with the width of 2-3 cm and the length of 10-15 cm, and cutting the remainder of the polyurethane shockproof material into particles with the width of 10-15 mm and waste rubber particles with the width of 2-3 mm for later use.
8. The method for preparing the colored rubber floor tile according to claim 3, wherein the method comprises the following steps: the preparation process of the polyurethane adhesive comprises the following steps: the raw material is polyether diol PPG-220, the hydroxyl value is 56, and the relative molecular weight is 2000; the polyether trihydric alcohol PPG-330 has a hydroxyl value of 56 and a relative molecular weight of 3000; the production process of the mixture of 2, 4-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate comprises the steps of adding polyether diol and polyether triol into a reaction bottle according to the mass ratio of 1:5, heating to 90-95 ℃, carrying out vacuum dehydration for 2 h, cooling to 50 +/-5 ℃, stirring, dropwise adding weighed MDI-50 according to the ratio of isocyanate groups to hydroxyl groups (NCO/OH) =1.4, heating to 80 +/-5 ℃, and maintaining the temperature for reaction for 2.5h to obtain the polyurethane adhesive.
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| CN202011236449.XA CN112457545A (en) | 2020-11-09 | 2020-11-09 | Color rubber floor tile and preparation method thereof |
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| CN202011236449.XA CN112457545A (en) | 2020-11-09 | 2020-11-09 | Color rubber floor tile and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU209863U1 (en) * | 2021-11-11 | 2022-03-23 | Общество с ограниченной ответственностью «РТ ТЕХНОЛОГИИ» | GRID DECKING |
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| US5397825A (en) * | 1993-05-19 | 1995-03-14 | Segrest; Neal | Rubber recycling process and product |
| JP2001187841A (en) * | 1999-12-24 | 2001-07-10 | Bayer Ag | Rubber mixture based on noncrosslinked rubber, crosslinked rubber particle and multifunctional isocyanate |
| CN1373257A (en) * | 2002-04-15 | 2002-10-09 | 孟哲 | Elastic color composite rubber floor tile |
| US20030203208A1 (en) * | 2002-04-29 | 2003-10-30 | Peter Kvesic | Recycled rubber products |
| US20110024021A1 (en) * | 2007-08-27 | 2011-02-03 | Joerg Heinz Hueneke | Process for producing rubber sheets, rubber mats or similar rubber products from rubber granules |
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2020
- 2020-11-09 CN CN202011236449.XA patent/CN112457545A/en active Pending
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| US5397825A (en) * | 1993-05-19 | 1995-03-14 | Segrest; Neal | Rubber recycling process and product |
| JP2001187841A (en) * | 1999-12-24 | 2001-07-10 | Bayer Ag | Rubber mixture based on noncrosslinked rubber, crosslinked rubber particle and multifunctional isocyanate |
| CN1373257A (en) * | 2002-04-15 | 2002-10-09 | 孟哲 | Elastic color composite rubber floor tile |
| US20030203208A1 (en) * | 2002-04-29 | 2003-10-30 | Peter Kvesic | Recycled rubber products |
| US20110024021A1 (en) * | 2007-08-27 | 2011-02-03 | Joerg Heinz Hueneke | Process for producing rubber sheets, rubber mats or similar rubber products from rubber granules |
| CN107141545A (en) * | 2017-06-22 | 2017-09-08 | 合肥易美特建材有限公司 | A kind of rubber floor covering and preparation method using waste-tyre rubber-powder as raw material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU209863U1 (en) * | 2021-11-11 | 2022-03-23 | Общество с ограниченной ответственностью «РТ ТЕХНОЛОГИИ» | GRID DECKING |
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