CN107814898A - A kind of mine flame retardant polyurethane enclosed material - Google Patents
A kind of mine flame retardant polyurethane enclosed material Download PDFInfo
- Publication number
- CN107814898A CN107814898A CN201711089403.8A CN201711089403A CN107814898A CN 107814898 A CN107814898 A CN 107814898A CN 201711089403 A CN201711089403 A CN 201711089403A CN 107814898 A CN107814898 A CN 107814898A
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- CN
- China
- Prior art keywords
- enclosed material
- flame retardant
- mine
- parts
- polyurethane
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Classifications
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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
-
- 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
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
Abstract
The invention discloses a kind of mine flame retardant polyurethane enclosed material, include the raw material of following parts by weight：3~6 parts of isocyanates, 13~17 parts of PPG, 0~2 part of dimethicone, it may expand 1~9 part of type graphite, 1~9 part of sodium metasilicate.Polyurethane enclosed material proposed by the present invention, light weight, human and material resources consumption is few during use, with good seal and anti-flammability, reach the service index of mine sealing material, and the inflatable type graphite added has the effect of cooperative flame retardant with borax, can improve the flame-retarding characteristic of polyurethane enclosed material, make material nonflammable, and fire retardant degree is reached, the intensity and elasticity of material are improved to a certain extent, increase the air-tightness of mine wall, it is cost-effective, reduce the duration.
Description
Technical field
The present invention relates to shaft production field of material technology, more particularly to a kind of closed material of mine flame retardant polyurethane
Material.
Background technology
Shaft production belongs to underground mining operations, is typically subject to the harm of extraneous water, gas, coal dust and fire, exploited
Most of perils in journey are all as caused by the fire in gas explosion and mine, have brought huge property
Loss, seriously endanger the precious life of workpeople.In rationally disposal accident most the most important thing is needing recovery ventilating system
The pernicious gas of underground is excluded, needs quickly to accomplish comburant being isolated from the outside out when fire occurs.Many feelings
Need to use enclosed material under condition to completely cut off hazardous area, in order to create the condition of work of safety to worker.Usual people
Custom does enclosed material with the material of masonry, stone sand, timber etc, but so does that time loss is more, physical demands is big, closed effect
Fruit is undesirable, and in the case where high temperature dense smoke and concentration of toxic gases are higher, casualty accident easily occurs.
Flexible polyurethane foams are a kind of materials easily to foam in a short time, its can quickly filling cracks and crackle,
So as to play a part of closed effect and quick isolation combustion zone, therefore can apply in mine.Flexible polyurethane foams
Surface after expansion have the characteristics that it is fine and close, smooth, and flexible polyurethane foams light weight, density are low, construction is very convenient, ratio
Intensity is big, and thermal conductivity is low, rebound degree is low, but the fire resistance of this kind of flexible polyurethane foams is undesirable, easy firing, easily
Cause fire incident.Based on above statement, the present invention proposes a kind of mine flame retardant polyurethane enclosed material.
The content of the invention
The invention aims to solve, time present in prior art and physical demands are big, seal is poor, fire-retardant
The shortcomings that performance is undesirable, and a kind of mine flame retardant polyurethane enclosed material proposed.
A kind of mine flame retardant polyurethane enclosed material, include the raw material of following parts by weight：3~6 parts of isocyanates, polyethers
13~17 parts of polyalcohol, 0~2 part of dimethicone, it may expand 1~9 part of type graphite, 1~9 part of sodium metasilicate.
Preferably, the mine includes the raw material of following parts by weight with flame retardant polyurethane enclosed material：5 parts of isocyanates,
15 parts of PPG, 0.5 part of dimethicone, it may expand 4 parts of type graphite, 1 part of sodium metasilicate.
Preferably, the mass ratio of the inflatable type graphite and sodium metasilicate is 1~6: 1.
Preferably, the mass ratio of the inflatable type graphite and sodium metasilicate is 4: 1.
Preferably, the mass ratio of the isocyanates and PPG is 1: 3.
The invention also provides a kind of mine preparation method of flame retardant polyurethane enclosed material, comprise the following steps：Claim
Take the PPG of corresponding parts by weight to be placed in reaction bulb, sequentially add the dimethicone of corresponding parts by weight, may expand
Type graphite, sodium metasilicate and isocyanates, stir, static to produce mine flame retardant polyurethane enclosed material to foaming completely.
Preferably, the mixing speed is 150~400r/min, and mixing time control is 10~30min.
Preferably, the mine is divided into three phases with the preparation process of flame retardant polyurethane enclosed material：
First stage, synthesis of polyurethane enclosed material performed polymer：PPG carries out reaction conjunction with isocyanate-monomer
Generating polyurethane enclosed material performed polymer, reaction equation are as follows
Second stage, the formation of bubble and chain extension：Terminal isocyanate groups and water reaction generation carbamic acid, carbamic acid is not
Stable to be further decomposed into terminal hydroxy group and carbon dioxide, the carbon dioxide of releasing forms bubble in the polymer, and generates
Amino End Group polymer can carry out chain extending reaction with base polyurethane prepolymer for use as, reaction equation is as follows
Phase III, crosslinking curing：Active hydrogen on free NCO and urea groups reacts, and sends out strand
Life is cross-linked to form network structure, obtains polyurethane enclosed material, reaction equation is as follows
Polyurethane enclosed material proposed by the present invention, fire retardant, dimethicone are used as using expanded graphites and sodium metasilicate
As defoamer, make polyurethane enclosed material light weight, human and material resources consumption is few during use, and with good seal and
Anti-flammability, reach the service index of mine sealing material；Adding rational proportion dimethicone in polyurethane enclosed material can
To play the generation for substantially reducing bubble, the quantity of stomata is reduced, increases gas seal；The inflatable type graphite added has ring
Protect, be nontoxic, the characteristics of flame retardant effect is obvious, it can be expanded during burning, and the graphite of expansion can make polyurethane close
Close material and the oxygen in the external world is kept apart, polyurethane enclosed material will be gradual because of oxygen deficiency after oxygen is lost
Extinguish, while the charcoal ash generated can be covered in the surface of polyurethane enclosed material, equally can also make polyurethane enclosed material with it is outer
The oxygen on boundary, which is kept apart, causes polyurethane enclosed material to burn, and sodium metasilicate can be taken away largely when losing the crystallization water
Heat, it can play a part of diluting fuel gas, material caused by them can be covered in material surface, so as to obtain well
Flame retardant effect, and the inflatable type graphite of rational proportion has the effect of cooperative flame retardant with sodium metasilicate, can improve polyurethane
The flame-retarding characteristic of enclosed material, material is burnt, and reach fire retardant degree, improve material to a certain extent
Intensity and elasticity, increase the air-tightness of mine wall, it is cost-effective, reduce the duration, and can be very good as the close of mine
Material is closed to use.
Embodiment
The present invention is made with reference to specific embodiment further to explain.
Embodiment, the parts by weight that raw material is corresponded to according to following table are more to the isocyanates in embodiment 21, polyethers to embodiment 1
First alcohol, dimethicone, expansile graphite and sodium metasilicate are sampled respectively, and respectively according to polyurethane proposed by the present invention
The preparation method of enclosed material carries out preparing polyurethane enclosed material, and concrete operations are as follows：The polyethers for weighing corresponding parts by weight is more
First alcohol is placed in reaction bulb, sequentially adds the dimethicone of corresponding parts by weight, inflatable type graphite, sodium metasilicate and isocyanic acid
Ester, stirred with 150~400r/min speed, mixing time control be 10~30min, it is static to foam completely produce it is poly-
Urethane enclosed material.Then performance test is carried out to the polyurethane enclosed material of preparation.
1st, influence of the dimethicone to polyurethane enclosed material
To embodiment 1 to embodiment 5 prepare polyurethane enclosed material carry out oxygen index (OI) test, and observe bubble situation,
Pore opening and airtight implementations are as a result as follows：
Test result is shown：The oxygen index (OI) of embodiment 1 is 17.0, and bubble is more during generation, stomata is larger, airtight
Property is bad, and embodiment 2 adds dimethicone into embodiment 5, and oxygen index (OI) increased, and with dimethicone
Addition increase, oxygen index (OI) is into growth trend, in addition, after adding dimethicone, the gas of polyurethane enclosed material
Bubble is significantly reduced, stomata is obviously reduced, air-tightness is obviously improved, and the nature difference of embodiment 2 to embodiment 5 is little, shows：
The addition of dimethicone can substantially reduce the generation of bubble in polyurethane enclosed material, reduce the quantity of stomata, increase gas
Seal.
2nd, it may expand influence of the type graphite to polyurethane enclosed material oxygen index (OI)
Oxygen index (OI) test is carried out respectively to embodiment 6, embodiment 8, embodiment 12, embodiment 17 and embodiment 23, as a result
It is as follows：
| Embodiment | Oxygen index (OI) 1 | Oxygen index (OI) 2 | Oxygen index (OI) 3 | Oxygen index (OI) average |
| 1 | 17.0 | 17.1 | 16.8 | 17.0 |
| 6 | 18.5 | 18.6 | 18.6 | 18.6 |
| 8 | 20.7 | 20.6 | 20.8 | 20.6 |
| 12 | 22.3 | 22.4 | 22.6 | 22.4 |
| 17 | 24.5 | 24.5 | 24.4 | 24.5 |
| 23 | 25.9 | 26.0 | 26.2 | 26.0 |
Test result is shown：Oxygen index (OI) with the increase polyurethane enclosed material of inflatable type quantity of graphite is also increasing,
And cutting edge aligned change is presented, illustrate that inflatable type graphite is increased more, its flame retardant effect also can be better, shows：It is inflatable
The addition of type graphite can improve the oxygen index (OI) of polyurethane enclosed material, improve fire resistance.
3rd, influence of the sodium metasilicate to polyurethane enclosed material oxygen index (OI)
Oxygen index (OI) test is carried out respectively to embodiment 7, embodiment 9, embodiment 13, embodiment 18 and embodiment 24, as a result
It is as follows：
| Embodiment | Oxygen index (OI) 1 | Oxygen index (OI) 2 | Oxygen index (OI) 3 | Oxygen index (OI) average |
| 1 | 17.0 | 17.1 | 16.8 | 17.0 |
| 7 | 17.2 | 17.1 | 17.3 | 17.2 |
| 9 | 18.1 | 18.2 | 18.2 | 18.2 |
| 13 | 18.4 | 18.5 | 18.5 | 18.5 |
| 18 | 19.0 | 18.9 | 19.1 | 19.0 |
| 24 | 19.5 | 19.4 | 19.5 | 19.5 |
Test result is shown：With can the oxygen index (OI) of increase polyurethane enclosed material of sodium metasilicate amount also increasing, explanation
The incrementss of sodium metasilicate are more, and its flame retardant effect is more obvious, shows：The addition of sodium metasilicate can improve polyurethane enclosed material
Oxygen index (OI), fire resistance is improved, but the flame retardant effect of the not inflatable type graphene of effect is notable.
4th, it may expand influence of the additional proportion of type graphite and sodium metasilicate to polyurethane enclosed material oxygen index (OI)
To embodiment 10, embodiment 11, embodiment 14, embodiment 15, embodiment 16, embodiment 19, embodiment 20, implementation
Example 21 and embodiment 22 carry out oxygen index (OI) test respectively, as a result as follows：
Test result is shown：Inflatable type graphite is added with sodium metasilicate with certain proportion, than independent inflatable type graphite
Or be individually added into oxygen index (OI) raising of the sodium metasilicate to polyurethane enclosed material and want big, and the oxygen index (OI) increase of embodiment 14 is maximum,
27.4 can be reached, shown：It is inflatable that there is synergy well between type graphite and sodium metasilicate, on the basis that dosage is constant
On add the flame retardant effect of polyurethane enclosed material, when in same oxygen index value, there is the inflatable type stone of synergy
Dosage when ink/sodium metasilicate is than being used alone is few.
5th, it may expand influence of the additional proportion of type graphite and sodium metasilicate to other performances of polyurethane enclosed material
Carry out tension test, thermogravimetric test respectively to polyurethane enclosed material prepared by embodiment 13 to embodiment 17, remain
Carbon rate is tested, activation energy is tested,
Test result indicates that：Adding inflatable type graphite and sodium metasilicate simultaneously can be such that polyurethane enclosed material has well
Mechanical property, can raise Second Inflexion Point temperature, remain the increase of carbon rate, activation energy rise.
In summary, polyurethane enclosed material proposed by the present invention, sending out polyurethane by adding a small amount of defoamer
A small amount of bubble is produced during bubble, increased the compactness of material, while inflatable the type graphite and silicic acid added
Sodium has good synergy, and flame retardant effect is notable when both are used cooperatively, and so adds not only flexibel polyurethane close
Also improve the fire retardancy of material while envelope property, fire retardant of the addition with synergy has polyurethane enclosed material
There is good mechanical property, raise Second Inflexion Point temperature, remain the increase of carbon rate, activation energy rise, exhaust smoke level lowers, and process is fire-retardant
Modified polyurethane enclosed material can be very good to use as the enclosed material of mine.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (8)
1. a kind of mine flame retardant polyurethane enclosed material, it is characterised in that include the raw material of following parts by weight：Isocyanates 3
~6 parts, 13~17 parts of PPG, 0.5~2 part of dimethicone, it may expand 1~9 part of type graphite, 1~9 part of sodium metasilicate.
A kind of 2. mine flame retardant polyurethane enclosed material according to claim 1, it is characterised in that the mine resistance
Flame-retardant polyurethane enclosed material includes the raw material of following parts by weight：5 parts of isocyanates, 15 parts of PPG, dimethicone 0.5
Part, it may expand 4 parts of type graphite, 1 part of sodium metasilicate.
A kind of 3. mine flame retardant polyurethane enclosed material according to claim 1, it is characterised in that the inflatable type
The mass ratio of graphite and sodium metasilicate is 1~6: 1.
A kind of 4. mine flame retardant polyurethane enclosed material according to claim 1, it is characterised in that the inflatable type
The mass ratio of graphite and sodium metasilicate is 4: 1.
A kind of 5. mine flame retardant polyurethane enclosed material according to claim 1, it is characterised in that the isocyanates
Mass ratio with PPG is 1: 3.
A kind of 6. mine flame retardant polyurethane enclosed material according to claim 1, it is characterised in that its preparation method bag
Include following steps：The PPG for weighing corresponding parts by weight is placed in reaction bulb, sequentially adds the diformazan of corresponding parts by weight
Base silicone oil, inflatable type graphite, sodium metasilicate and isocyanates, stir, static to produce mine to foaming completely and gathered with fire-retardant
Urethane enclosed material.
A kind of 7. preparation method of mine flame retardant polyurethane enclosed material according to claim 6, it is characterised in that institute
It is 150~400r/min to state mixing speed, and mixing time control is 10~30min.
A kind of 8. mine flame retardant polyurethane enclosed material according to claim 1, it is characterised in that its preparation process point
For three phases：
First stage, synthesis of polyurethane enclosed material performed polymer：PPG carries out reaction synthesis with isocyanate-monomer and gathered
Urethane enclosed material performed polymer, reaction equation are as follows
Second stage, the formation of bubble and chain extension：Terminal isocyanate groups and water reaction generation carbamic acid, carbamic acid are unstable
It is further decomposed into terminal hydroxy group and carbon dioxide, the carbon dioxide of releasing forms bubble in the polymer, and the end generated
Amino polymer can carry out chain extending reaction with base polyurethane prepolymer for use as, and reaction equation is as follows
Phase III, crosslinking curing：Active hydrogen on free NCO and urea groups reacts, and hands over strand
Connection forms network structure, obtains polyurethane enclosed material, reaction equation is as follows
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711089403.8A CN107814898A (en) | 2017-10-27 | 2017-10-27 | A kind of mine flame retardant polyurethane enclosed material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711089403.8A CN107814898A (en) | 2017-10-27 | 2017-10-27 | A kind of mine flame retardant polyurethane enclosed material |
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| CN107814898A true CN107814898A (en) | 2018-03-20 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111925498A (en) * | 2020-08-30 | 2020-11-13 | 宁波耀众模塑科技有限公司 | Flame-retardant expanded graphite material for polyurethane foam product |
| CN115353601A (en) * | 2022-08-31 | 2022-11-18 | 山东宙雨消防科技股份有限公司 | Polyurethane flame-retardant manufacturing method |
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Application publication date: 20180320 |