CN108929422A - A kind of modified plastic rubber and preparation method thereof using nano silica foaming reinforcing material - Google Patents
A kind of modified plastic rubber and preparation method thereof using nano silica foaming reinforcing material Download PDFInfo
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- CN108929422A CN108929422A CN201810964916.7A CN201810964916A CN108929422A CN 108929422 A CN108929422 A CN 108929422A CN 201810964916 A CN201810964916 A CN 201810964916A CN 108929422 A CN108929422 A CN 108929422A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The present invention relates to a kind of modified plastic rubbers and preparation method thereof using nano silica foaming reinforcing material, plastic cement includes isocyanates 6-12%, polyether polyol 30-55%, nano silica 5-50%, 0.01 to 1.0 micron of nano silicon dioxide particles diameter, 20 to 30 meters squared per gram of specific surface area.Nano silica forms loose type scintilla unity structure through more than half encryptions processing, and it is 300-500 kilograms per cubic meter that scintilla, which rolls into a ball density,.The present invention uses nano-silicon dioxide modified polyurethane plastic, has not only facilitated the foaming of material, but also can play humidification, and polyurethane generates the bubble of uniform densification, improves intensity, drawing force, wearability, ageing-resistant and anti-ultraviolet property.The present invention can reduce the material quantity and weight of plastic cement race track, enhance the intensity and elasticity of plastic cement race track, and shock-absorbing effect is more preferable, so as to reduce sport injury, the safety and health of effective protection sporter.
Description
Technical field
The present invention relates to modified plastic rubber technical fields, especially a kind of to be used as foaming and strengthening material using nano silica
The preparation method of the modified plastic rubber of material and the modified plastic rubber.
Background technique
The plastic cement race track that the place such as existing sports ground, school playground and park is laid with, typically polyurethane synthesize
Material, these plastic cement race tracks are designed and are constructed according to old plant at present, and the intensity and elasticity of plastic cement race track are undesirable,
Service life is shorter, and the generally existing secondary pollution of while constructing.There are individual construction parties once to reduce cost, used inferior materials and turned out substandard goods,
Adulterate, mated formation plastic cement race track using inferior or even toxic, harmful raw material, to the health harm of school teachers and students compared with
Greatly, social influence is severe.
In May, 2018, the Ministry of Education of the state and related scientific research mechanism, which combine, has put into effect the new national standard of plastic cement race track:
GB36246-2018 " middle and primary schools' synthetic material surface layer sports ground " mandatory national standards, what which used plastic cement race track
Material and construction further standardize, and increase substantially associated specifications, will the formal implementation on November 1st, 2018.
Currently, fretting map plastic cement race track usually carries out foaming operation at the construction field (site), foaming operation is usually direct
A small amount of water is added or chemical foaming agent is added.By taking the plastic cement race track of 13mm thickness as an example, every square metre of material quantity in 13kg
More than, complicated construction technique, to be usually divided into 4 procedures could complete.The construction of requirement when to(for) weather and environmental condition is high,
Especially temperature and humidity are affected to the foaming of plastic cement race track, tend to cause bubble excessive, or foaming is not exclusively,
And very high to the technical requirements of construction personnel, Site quality control is very difficult, and the quality that plastic cement race track is laid with is extremely difficult to
Associated specifications.In addition, the surface layer spraying of plastic cement race track is also to construct at the scene, when construction, also wants wind direction
Ask, strong wind weather cannot construct, against the wind when cannot construct, difficulty of construction is big in a word, if misoperation, can not only pollute ring
Border, but also construction personnel can be damaged, meanwhile, the construction quality and construction speed of plastic cement race track cannot all obtain effectively
It ensures.
Summary of the invention
For the new state compulsory standard of plastic cement race track, how to accomplish not only to have met new national standard, but also do not increase throwing
Money cost, applicant have been invented a kind of be used as using nano silica and foamed on the basis of research for many years and repetition test
With the preparation method of the modified plastic rubber of reinforcing material and the modified plastic rubber.Low in cost, easy construction of the invention, can subtract
The secondary pollution of few plastic cement race track construction.
The object of the present invention is to provide a kind of modified plastic rubber using nano silica foaming reinforcing material and its preparations
Method.Using silica modified polyurethane synthetic material, the foaming of material was not only facilitated, but also humidification can be played, had been used for
Athletic ground is mated formation, and the health and sports safety of human body can not only be effectively ensured, and improves the intensity of plastic cement race track
And elasticity, it prolongs its service life.
The purpose of the present invention is what is realized by using following technical scheme:
A kind of modified plastic rubber using nano silica foaming reinforcing material, including but not limited to following weight percent
Component:
As the preferred technical solution of the present invention, the foaming reinforcing material further includes following components in weight percent:
Age resister 0.1-0.5%.
As the preferred technical solution of the present invention, the foaming reinforcing material further includes following components in weight percent: silicon
Alkane coupling agent 0.5-1.0%.
As the preferred technical solution of the present invention, the foaming reinforcing material further includes following components in weight percent: face
Expect 0.5-2.5%.
As the preferred technical solution of the present invention, the filler is talcum powder or calcium carbonate；The plasticizer is that synthesis is planted
Object ester plasticiser.
As the preferred technical solution of the present invention, the nano silica is granular structure, and the diameter of particle is
0.01 micron to 1.0 microns, specific surface area is 20 to 30 meters squared per grams.
As the preferred technical solution of the present invention, the nano silica forms loose type differential through more than half encryptions processing
The density of sub- unity structure, the scintilla group is 300-500 kilograms per cubic meter；Titanium dioxide in the nano-silica powder
Silicone content is more than or equal to 90%.
A kind of modified plastic rubber preparation method using nano silica foaming reinforcing material, comprising the following steps:
(1) by the polyether polyol weighed according to weight percent, plasticizer, filler, reaction kettle is added at normal temperature, rises
Temperature arrives 100-120 DEG C, and heating while is stirred；
(2) aforesaid reaction vessel is vacuumized, when temperature of reaction kettle being waited to drop to room temperature, nano silica is added and carries out
Stirring；
(3) after the temperature of reaction kettle drops to room temperature, isocyanates is added, reaction kettle is warming up to 70-90 DEG C, makes reaction kettle
Interior raw material reacts 1-2 hours, catalyst is then added, the reaction was continued 1-2 hours；
(4) it is separately added into age resister, pigment, amino silicane coupling agent in reaction kettle, is sufficiently stirred, forms institute after cooling
State modified plastic rubber paste；
(5) the modified plastic rubber paste that above-mentioned steps obtain is injected into particular manufacturing craft or designated position, is formed after solidification
Plastic block or plastic cement race track.
As the preferred technical solution of the present invention, the step (1) further includes dehydration, and dewatering time is controlled 0.5
To 1.5 hours.
As the preferred technical solution of the present invention, the diameter of the nano silicon dioxide particles is 0.01 micron to 1.0 micro-
Rice, specific surface area are 20 to 30 meters squared per grams；Also, the nano silica processes to form pine through more than half encryption technologies
Type scintilla unity structure is dissipated, the density of the scintilla group is 300-500 kilograms per cubic meter.
The beneficial effects of the present invention are: compared with the existing technology, the present invention solves existing plastic cement race track, and difficulty of construction is big,
At high cost, quality control is unstable, is also easy to produce secondary environmental pollution, and be extremely difficult to asking for new state compulsory standard
Topic, the technical solution provided through the invention can be good at solving the above problems.
The plastic cement race track mated formation using polyurethane synthetic material of the present invention and technique is compared with existing traditional plastic cement race track, tool
It has the advantage that
1, the invention uses foaming and reinforcing material of the nano silica as modified polyurethane plastic cement, existing
Help the foaming of material, and humidification can be played, the bubble of uniform densification is generated after polyurethane addition silica, is improved
The intensity and drawing force of polyurethane synthetic plastic improve wearability, ageing-resistant and anti-ultraviolet property, so as to reduce plastic cement
The material quantity and weight of runway, while enhancing the intensity and elasticity of plastic cement race track.
2, advantage of lower cost of the present invention, easy construction, quality control are stablized, and the secondary dirt of construction can be effectively reduced
Dye.There is high resiliency using the athletic ground that material of the present invention and technique are mated formation, super abrasive, structural strength is high, and meets ring
Guaranteed request, thickness needed for can completing plastic cement race track with one-time laying, complies fully with " GB46236-2018 national standard ".
3, plastic cement race track elasticity of the present invention is more preferable, intensity is higher, and saves material, and polyurethane material adds silica
Its internal structure can generate biggish variation afterwards, and intensity increases substantially, plastic cement race track mat formation face formed from top to bottom it is numerous close
It closes and mutually independent air bag, section shape of the air bag diameter generally between 0.1 to 1.5 millimeter, close to 2 to 3 millimeters of upper surface
At densification, the lesser micro- air bag of diameter, so that plastic cement race track elasticity is more preferable, pulling force is stronger, and raw material usage more saves.With
Traditional plastic cement race track of 13 mm of thickness compares measuring and calculating, and the present invention only needs to be laid with 8 to 10 millimeters of thickness, that is, is able to satisfy
The requirement of runway associated technical parameters, reaches identical technical performance and effect, saves 3 to 5 millimeters compared to traditional plastic cement race track
The raw material of thickness significantly improve economic benefit so that manufacture and the construction cost of plastic cement race track be greatly lowered.
4, the structure sheaf of plastic cement race track is made of numerous air bags not of uniform size, and elasticity and shock-absorbing effect are more preferable, so as to
Enough reduce sport injury, the safety and health of effective protection sporter.
5, field sampling detection, detection data are carried out by the plastic cement race track finished product being laid with to polyurethane material of the present invention
It is as follows: vertical deformation 2.2mm, new national standard 0.6-3.0mm；Impact absorbing rate 41%, new national standard 35-50%；Tensile strength
0.78MPa, new national standard are >=0.4MPa；Elongation rate of tensile failure is 150%, and new national standard is >=40%.All detection datas of the present invention
It is all satisfied and is more than the requirement of state compulsory standard.
Specific embodiment
The present invention is further explained in the light of specific embodiments:
A kind of modified plastic rubber using nano silica foaming reinforcing material, including but not limited to following weight percent
Component:
Surplus is filler.
In the present embodiment, the foaming reinforcing material further includes following components in weight percent:
Age resister 0.1-0.5%.
Silane coupling agent 0.5-1.0%.
Pigment 0.5-2.5%.
Filler described in the present embodiment is talcum powder or calcium carbonate；The plasticizer is that environment-friendly type synthesizes plant ester plasticiser.
Isocyanates abbreviation MDI, the preferential raw material for selecting the Production in Chemical Plant such as ten thousand China or BASF.Polyether polyol preferentially selects mountain
The big chemical industry of Dong Dong or the N330 of China LanXing group production are as raw material.
The diameter of the nano silicon dioxide particles is 0.01 micron to 1.0 microns, and specific surface area is 20 to 30 squares
Rice/gram.Nano silica forms loose type scintilla unity structure through more than half encryptions processing, and the density of the scintilla group is
300-500 kilograms per cubic meter.
Nano silica is mineral hot furnace byproduct, the silicon dioxide molecules group obtained by half encryption technology, surface
It is active strong, make nanometer titanium dioxide since it uses half encryption technology as the reinforcing agent of compound polyurethane material in the present invention
Silicon forms numerous scintilla groups, therefore plays the role of strength foaming agent again in the present invention, with nano silica additive amount
Increase, gas release is also more, and foam distribution it is more uniform, the bubble diameter formed after foaming is generally in 0.1mm-
Between 1.5mm, the additive amount of the present embodiment nano silica is preferably 40%.
A kind of modified plastic rubber preparation method using nano silica foaming reinforcing material, comprising the following steps:
(1) by the polyether polyol weighed according to weight percent, plasticizer, filler, reaction kettle is added at normal temperature, rises
Temperature arrives 100-120 DEG C, and heating while is stirred；
(2) aforesaid reaction vessel is vacuumized, when temperature of reaction kettle being waited to drop to room temperature, nano silica is added and carries out
Stirring；
(3) after the temperature of reaction kettle drops to room temperature, isocyanates is added, reaction kettle is warming up to 70-90 DEG C, makes reaction kettle
Interior raw material reacts 1-2 hours, catalyst is then added, the reaction was continued 1-2 hours；
(4) it is separately added into age resister, pigment, amino silicane coupling agent in reaction kettle, is sufficiently stirred, forms institute after cooling
State modified plastic rubber paste；
(5) the modified plastic rubber paste that above-mentioned steps obtain is injected into particular manufacturing craft or designated position, is formed after solidification
Plastic block or plastic cement race track.
In the present embodiment, the step (1) further includes dehydration, and dewatering time was controlled at 0.5 to 1.5 hour.It is described
The diameter of nano silicon dioxide particles is 0.01 micron to 1.0 microns, and specific surface area is 20 to 30 meters squared per grams；Also, institute
It states nano silica to process to form loose type scintilla unity structure through more than half encryption technologies, the density of the scintilla group is
300-500 kilograms per cubic meter.
Nano silica can as compound polyurethane material reinforcing agent and play the role of strength foaming agent.
When construction, it can will be divided into twice the step of nano silica is added, for the first time, a small amount of nano silica first be added, or
Person is used as additional amount for the first time according to the 5-35% that nano silica total weight should be added, and is stirred, this nanometer two
What silica was reacted primarily as reinforcing agent；Remaining nano silica is added for the second time, this nanometer
What silica was reacted primarily as foaming agent.Gas release is directly proportional to the additive amount of nano silica, and
The distribution of foaming is more uniform, and for the bubble diameter of formation generally between 0.1mm-1.5mm, the present embodiment nano silica is total
Additive amount be preferably 40%.
Nano silica is obtained silica scintilla group by the production of half encryption technologie using pelletizer by the present invention,
Contain a certain amount of water in silica scintilla group, surface-active is strong, with the polyethers performed polymer in single dual-component polyurethane
It chemically reacts, the carbon dioxide gas of generation forms numerous closed and mutually independent small-sized gas inside polyurethane material
Capsule.Meanwhile silica can also improve the intensity and drawing force of polyurethane synthetic material, improve wearability, ageing-resistant and anti-purple
Outside line performance reduces the material quantity and weight of plastic cement, enhances the intensity and elasticity of plastic cement, so that plastic cement products be greatly lowered
Manufacture and construction cost, significantly improve the quality and economic benefit of plastic cement products.
Above-described embodiment is only limitted to illustrate design and technical characteristic of the invention, and its object is to allow those skilled in the art
Member understands the technical solution and embodiment of invention, can not limit the scope of the invention accordingly.It is all according to the present invention
Equivalent replacement or equivalence changes made by technical solution should all cover within the protection scope of claims of the present invention.
Claims (10)
1. a kind of modified plastic rubber using nano silica foaming reinforcing material, it is characterized in that: including but not limited to following heavy
Measure percentage component:
2. the modified plastic rubber according to claim 1 using nano silica foaming reinforcing material, it is characterized in that: described
The reinforcing material that foams further includes following components in weight percent:
Age resister 0.1-0.5%.
3. the modified plastic rubber according to claim 1 using nano silica foaming reinforcing material, it is characterized in that: described
The reinforcing material that foams further includes following components in weight percent:
Silane coupling agent 0.5-1.0%.
4. the modified plastic rubber according to claim 1 using nano silica foaming reinforcing material, it is characterized in that: described
The reinforcing material that foams further includes following components in weight percent:
Pigment 0.5-2.5%.
5. the modified plastic rubber according to claim 1 using nano silica foaming reinforcing material, it is characterized in that: described
Filler is talcum powder or calcium carbonate；The plasticizer is synthesis plant ester plasticiser.
6. the modified plastic rubber according to any one of claims 1 to 5 using nano silica foaming reinforcing material, special
Sign is: the nano silica is granular structure, and the diameter of particle is 0.01 micron to 1.0 microns, and specific surface area is
20 to 30 meters squared per grams.
7. the modified plastic rubber according to claim 6 using nano silica foaming reinforcing material, it is characterized in that: described
Nano silica forms loose type scintilla unity structure through more than half encryptions processing, and the density of the scintilla group is 300-500
Kilograms per cubic meter；Dioxide-containing silica in the nano-silica powder is more than or equal to 90%.
8. a kind of such as the modified plastic rubber system described in any one of claim 1 to 5 using nano silica foaming reinforcing material
Preparation Method, it is characterized in that the following steps are included:
(1) by the polyether polyol weighed according to weight percent, plasticizer, filler, reaction kettle is added at normal temperature, is warming up to
100-120 DEG C, heating while, is stirred；
(2) aforesaid reaction vessel is vacuumized, when temperature of reaction kettle being waited to drop to room temperature, nano silica is added and is stirred
It mixes；
(3) after the temperature of reaction kettle drops to room temperature, isocyanates is added, reaction kettle is warming up to 70-90 DEG C, makes former in reaction kettle
Material reaction 1-2 hours, is then added catalyst, the reaction was continued 1-2 hours；
(4) it is separately added into age resister, pigment, amino silicane coupling agent in reaction kettle, is sufficiently stirred, changes described in formation after cooling
Property plastic cement paste；
(5) the modified plastic rubber paste that above-mentioned steps obtain is injected into particular manufacturing craft or designated position, forms plastic cement after solidification
Block or plastic cement race track.
9. the modified plastic rubber preparation method according to claim 8 using nano silica foaming reinforcing material, special
Sign is: the step (1) further includes dehydration, and dewatering time was controlled at 0.5 to 1.5 hour.
10. the modified plastic rubber preparation method using nano silica foaming reinforcing material according to claim 8 or claim 9,
It is characterized in that: the diameter of the nano silicon dioxide particles is 0.01 micron to 1.0 microns, specific surface area is 20 to 30 squares
Rice/gram；Also, the nano silica processes to form loose type scintilla unity structure, the differential through more than half encryption technologies
The density of son group is 300-500 kilograms per cubic meter.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810964916.7A CN108929422A (en) | 2018-08-23 | 2018-08-23 | A kind of modified plastic rubber and preparation method thereof using nano silica foaming reinforcing material |
| PCT/CN2018/120762 WO2020037892A1 (en) | 2018-08-23 | 2018-12-13 | Modified plastic using nano-silicon dioxide reinforced foam material, and preparation method therefor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810964916.7A CN108929422A (en) | 2018-08-23 | 2018-08-23 | A kind of modified plastic rubber and preparation method thereof using nano silica foaming reinforcing material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020037892A1 (en) * | 2018-08-23 | 2020-02-27 | 田友斌 | Modified plastic using nano-silicon dioxide reinforced foam material, and preparation method therefor |
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| WO2020037892A1 (en) | 2020-02-27 |
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