CN107641221B - A kind of hydroxide-modified expansible graphite fire retardant and preparation method thereof - Google Patents
A kind of hydroxide-modified expansible graphite fire retardant and preparation method thereof Download PDFInfo
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- CN107641221B CN107641221B CN201610583436.7A CN201610583436A CN107641221B CN 107641221 B CN107641221 B CN 107641221B CN 201610583436 A CN201610583436 A CN 201610583436A CN 107641221 B CN107641221 B CN 107641221B
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Abstract
The invention discloses a kind of hydroxide-modified expansible graphite fire retardants, and raw material mainly includes inorganic hydroxide, expansible graphite, silane coupling agent and reaction dissolvent.The lesser hydroxide of particle is dispersed using silane coupling agent and is bridged at the biggish expansible graphite surface of particle by the present invention, inorganic hydroxide is using expansible graphite as carrier, it can avoid the reunion of hydroxide particles, and improve the dispersion effect of fire retardant in the base, so that the intensity that can significantly improve matrix is blended with matrix for fire retardant, compatibilization of the expansible graphite for hydroxide simultaneously, the hydroxide content in matrix can be improved, to increase flame retardant effect, matrix strength greatly improves instead while so that matrix is kept preferable flame retardant effect.
Description
Technical field
The present invention relates to a kind of hydroxide-modified expansible graphite fire retardants and preparation method thereof, belong to fire retardant neck
Domain.
Background technique
With the development of synthetic material industry and the continuous expansion of application field, fire retardant chemical building material, electronic apparatus,
It is had a vast market foreground in the every field such as communications and transportation, space flight and aviation, household furniture, interior decoration, clothing, food, lodging and transportion -- basic necessities of life.This
Outside, the fields such as coalfield, oil field, forest extinguishing also promote fire-retardant, the faster development of extinguishing chemical production.It is most common in fire retardant
Although halogenated flame retardant has the unrivaled high efficiency of other fire retardants series, it is to the harm of environment and people can not
Ignore.Environmental issue is auxiliary agent development and application quotient's focus of attention, so adjusting the product of fire retardant always both at home and abroad
Structure increases the exploitation of Efficient environment-friendlyflame flame retardant.
Since halogen flame releases a large amount of cigarette and toxic gas in burning, developed country is used for having done
Stringent regulation is gone out.With the development of society, requirement of the people to safety and environmental protection also correspondingly improves.In order to reduce resistance
The harmful side effect of agent is fired, each state all is concentrating strength on developing high-performance inorganic fire retardant.In the regular period from now on, efficiently to hinder
Combustion, suppression cigarette, additive amount be few, on materials'use performance influence it is small, safe, environmentally friendly for the purpose of, miniaturize with nanoscale, table
The inorganic hydroxide fire retardant of more technologies synthesis such as face is modified, microencapsulation and composite synergistic will be rapidly developed and extensively
General use.
The inorganic hydroxides such as aluminium hydroxide and magnesium hydroxide component the releasable crystallization water and takes away heat in combustion
Amount, playing oxygen and cooling effect, the gasification of the crystallization water near dilution organic matter surface also can promote fire-retardant carbon-coating shape
At expansion structure, the heat-proof quality of fire-retardant carbon-coating is improved, heat is prevented to transmit to combustible intrinsic silicon.However it is traditional inorganic
Hydroxide will reach certain flame retardant effect, and content will reach 50% in the base, greatly reduce the intensity of basis material.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of hydroxide in view of the deficiency of the prior art
The modified expansible graphite fire retardant and preparation method thereof of object, expansible graphite have compatibilization for hydroxide, can change
Hydroxide content fruit in kind matrix, makes matrix keep preferable flame retardant effect, while greatly improving the intensity of matrix.
The present invention be solve the problems, such as it is set forth above used by technical solution are as follows:
A kind of expansible graphite fire retardant, uses inorganic hydroxide as modifying agent.
A kind of hydroxide-modified expansible graphite fire retardant, raw material mainly include inorganic hydroxide, may expand
Graphite, silane coupling agent and reaction dissolvent；Wherein, solid material proportion is calculated as on the basis of expansible graphite parts by weight: can be swollen
100 parts of swollen graphite, 100-1000 parts of inorganic hydroxide, 0.1-10 parts of silane coupling agent.
According to the above scheme, one or more of described silane coupling agent model KH550, KH560, KH570 etc.
Mixing.
According to the above scheme, the granularity of the expansible graphite is 10-200 μm.
According to the above scheme, the hydroxide is mainly one in the inorganic hydroxides such as aluminium hydroxide, magnesium hydroxide
Kind or several mixtures in any proportion.
According to the above scheme, the granularity of the hydroxide is 10nm-10 μm.
According to the above scheme, the reaction dissolvent is water, ethyl alcohol, ethyl acetate, tetrahydrofuran, toluene, acetone, N, N- bis-
The mixture of one or more of methylformamide etc. in any proportion.
The preparation method of above-mentioned hydroxide-modified expansible graphite fire retardant is: according to the ratio, by starting material inorganic hydrogen-oxygen
Compound, expansible graphite, silane coupling agent and reaction dissolvent after mixing, are stirred to react, and obtained solid product is hydrogen-oxygen
The modified expansible graphite fire retardant of compound.
The preparation method of above-mentioned hydroxide-modified expansible graphite fire retardant, key step are as follows:
1) raw material is weighed in parts by weight, is calculated as on the basis of expansible graphite parts by weight: 100 parts of expansible graphite, nothing
100-1000 parts of machine hydroxide, 0.1-10 parts of silane coupling agent, 10-200 parts of reaction dissolvent.:
2) expansible graphite, inorganic hydroxide and silane coupling agent are added to boil in reaction dissolvent and are stirred to react 1-
3h, reaction obtained solid product is hydroxide-modified expansible graphite fire retardant.
It according to the above scheme, further include the purifications step such as obtained solid product suction filtration, washing, centrifugation, vacuum drying in step 2)
Suddenly, to obtain purer product.Wherein, washing is using acetone, water, ethyl alcohol etc..
According to the above scheme, the content of hydroxide-modified expansible graphite fire retardant of the present invention in the base is
30%, the opposite content for being far below traditional inorganic hydroxide fire retardant and wanting 50% or more in the base.The base
Body can be hard-foam polyurethane, EPS sheet material etc..
Basic principle of the invention: the lesser hydroxide of particle is dispersed and is bridged at using silane coupling agent by the present invention
The biggish expansible graphite surface of particle, inorganic hydroxide can avoid hydroxide particles using expansible graphite as carrier
Reunite, and improves the dispersion effect of hydroxide in the base；Moreover, being bridged with silane coupling agent inflatable after hydroxide
Graphite and polymeric matrix have preferable compatibility, can effectively improve hydroxide bridge at it is compound with matrix behind its surface.
Meanwhile silane coupling agent bridge it is hydroxide-modified after expansible graphite in expansion process of getting angry, due to expansible graphite
Interlayer gap is blocked by the silane coupling agent of participation β-cyclodextrin, hydroxide object, and expanded by heating multiplying power will further improve, shape
At expansion carbon-coating can reach better heat-insulated oxygen-impermeable flame retardant effect；Moreover, hydroxide have certain alkalinity, can with can
The expanded graphite sour gas reaction released in expansion process of getting angry neutralizes, eliminate it is fire-retardant during the sour gas pair that discharges
The harm of human body.
Compared with prior art, the beneficial effects of the present invention are:
1, expansible graphite has high intensity in fire retardant of the present invention, so that fire retardant is blended with matrix significantly to be changed
The intensity of kind matrix, while expansible graphite has compatibilization for hydroxide, the hydroxide that can improve in matrix contains
Amount, to increase flame retardant effect, matrix strength greatly improves instead while so that matrix is kept preferable flame retardant effect；
2, it after the present invention is to expansible graphite β-cyclodextrin, gets angry in expansion process in graphite, due to expansible graphite layer
Between gap be bonded modifier closure, expansion multiplying power will further improve, to increase expansion carbon layers having thicknesses, can reach preferably
Heat-insulated oxygen-impermeable flame retardant effect；
3, the expansible graphite in fire retardant of the present invention can completely cut off thermal energy radiation, have the function of reflecting infrared ray,
Therefore the pyroconductivity that substrate can be reduced, plays synergistic effect to fire retardation.
The present invention is halogen-free as a kind of New-type halide-free efficient flame-retarding agent, and use process is environmentally protective, is had sustainable
It is expansionary, it can be used for water-based emulsion, extruded polystyrene foam, the compounds such as hard polyurethane foams are modified, and it is fire-retardant building,
Heat preservation, energy conservation, environment protection field have significant application prospect.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Reaction principle of the invention is: silane coupling agent is a kind of in the molecule while containing there are two types of different chemical property bases
The organo-silicon compound of group, due to this special construction, having simultaneously in the molecule thereof can be with inanimate matter material (such as glass, silicon
Sand, metal etc.) chemically combined reactive group and with organic material (synthetic resin etc.) chemically combined reactive group, can be with
For being surface-treated.The present invention is grafted by the hydroxy or carboxy on silane coupling agent one end and expansible graphite, the other end with
Inorganic hydroxide is connected.
Embodiment 1
A kind of hydroxide-modified expansible graphite fire retardant, raw material include aluminium-hydroxide powder, expansible graphite,
Silane coupling agent and reaction dissolvent ethyl alcohol；Wherein, solid material proportion is calculated as on the basis of expansible graphite parts by weight: inflatable
100 parts of graphite, 900 parts of aluminium hydroxide, 5 parts of silane coupling agent；Reaction dissolvent is ethyl alcohol.Wherein, expansible graphite granularity is 200
μm, aluminium-hydroxide powder granularity 10nm.
The preparation method of above-mentioned hydroxide-modified expansible graphite fire retardant, carries out according to the following steps:
It takes 0.1g expansible graphite, 0.9g aluminium-hydroxide powder to be distributed in 100mL ethyl alcohol, is subsequently poured into tri- mouthfuls of 250mL
In bottle, 0.005gKH550 silane coupling agent is added, mechanical stirring mixes at 500RPM, boils reaction 2h；It filters out wherein solid
Body product is repeatedly washed with ethyl alcohol, and vacuum drying is at 40 DEG C to get hydroxide-modified expansible graphite fire retardant.
Using: the hydroxide-modified expansible graphite fire retardant that the present embodiment is obtained is added by 30% mass ratio
Into EPS particle, it is uniformly mixed, sheet coupon is made, oxygen index (OI) reaches 30.17；Blank EPS oxygen index (OI) is only 18.It compares
For, hydroxide-modified expansible graphite is for improving 67.6% than blank EPS sample oxygen index (OI) in EPS sample.
When unmodified expansible graphite is added in EPS particle by 30% mass ratio, made EPS sheet material sample
Oxygen index (OI) reach maximum value 27.8.In comparison, hydroxide-modified expansible graphite flame retardant effect is than non-modified
Expansible graphite flame retardant effect to get well.
Meanwhile when with Horizontal Bridgman Method and normal beam technique measurement combustibility, the examination of the EPS sheet material made of fire retardant of the present invention
There is continuous flaming combustion in sample, but flame front is less than 100mm graticule, and 7.41s of the individual sample after fire source removes is put out
It goes out, vertical combustion grade reaches V0 grades, and horizontal firing grade reaches HB grades；Also, the pull strength of EPS drops to 0.22Mpa,
The requirement of 0.1MPa, no security risk need to be greater than considerably beyond pull strength specified in standard JG149-2003.
Embodiment 2
A kind of hydroxide-modified expansible graphite fire retardant, raw material include magnesium hydroxide powder, expansible graphite,
Silane coupling agent and reaction dissolvent water；Wherein, solid material proportion is calculated as on the basis of expansible graphite parts by weight: inflatable stone
100 parts, 600 parts of aluminium hydroxide, 10 parts of silane coupling agent of ink；Reaction dissolvent is water.Wherein, expansible graphite granularity be 200 μm,
Aluminium-hydroxide powder granularity 10nm.
The preparation method of above-mentioned hydroxide-modified expansible graphite fire retardant, carries out according to the following steps:
It takes 0.1g expansible graphite, 0.6g magnesium hydroxide powder to be distributed in 100mL deionized water, is subsequently poured into 250mL
In there-necked flask, 0.01gKH560 silane coupling agent is added, mechanical stirring mixes at 500RPM, boils reaction 1h；Filter out it
Middle solid product is repeatedly washed with deionized water, is dried in vacuo at 40 DEG C fire-retardant to get hydroxide-modified expansible graphite
Agent.
Using: the hydroxide-modified expansible graphite fire retardant that the present embodiment is obtained is added by 30% mass ratio
Into EPS particle, it is uniformly mixed, sheet coupon is made, oxygen index (OI) reaches 31.35；Blank EPS oxygen index (OI) is only 18.It compares
For, hydroxide-modified expansible graphite is for improving 74.1% than blank EPS sample oxygen index (OI) in EPS sample.
When unmodified expansible graphite is added in EPS particle by 30% mass ratio, made EPS sheet material sample
Oxygen index (OI) reach maximum value 27.8.In comparison, hydroxide-modified expansible graphite flame retardant effect is than non-modified
Expansible graphite flame retardant effect to get well.
Meanwhile when with Horizontal Bridgman Method and normal beam technique measurement combustibility, the examination of the EPS sheet material made of fire retardant of the present invention
There is continuous flaming combustion in sample, but flame front is less than 100mm graticule, and 3.87s of the individual sample after fire source removes is put out
It goes out, vertical combustion grade reaches V0 grades, and horizontal firing grade reaches HB grades；Also, the pull strength of EPS drops to 0.23Mpa,
The requirement of 0.1MPa, no security risk need to be greater than considerably beyond pull strength specified in standard JG149-2003.
Embodiment 3
A kind of hydroxide-modified expansible graphite fire retardant, raw material include aluminium-hydroxide powder, expansible graphite,
Silane coupling agent and reaction dissolvent water；Wherein, solid material proportion is calculated as on the basis of expansible graphite parts by weight: inflatable stone
100 parts, 800 parts of aluminium hydroxide, 1 part of silane coupling agent of ink；Reaction dissolvent is water.Wherein, expansible graphite granularity be 200 μm,
Aluminium-hydroxide powder granularity 10nm.
The preparation method of above-mentioned hydroxide-modified expansible graphite fire retardant, carries out according to the following steps:
It takes 0.1g expansible graphite, 0.8g aluminium-hydroxide powder to be distributed in 100mL ethyl alcohol, is subsequently poured into tri- mouthfuls of 250mL
In bottle, 0.001gKH570 silane coupling agent is added, mechanical stirring mixes at 500RPM, boils reaction 2h；It filters out wherein solid
Body product is repeatedly washed with ethyl alcohol, and vacuum drying is at 40 DEG C to get hydroxide-modified expansible graphite fire retardant.
Using: the hydroxide-modified expansible graphite fire retardant that the present embodiment is obtained is added by 30% mass ratio
Into EPS particle, it is uniformly mixed, sheet coupon is made, oxygen index (OI) reaches 29.82；Blank EPS oxygen index (OI) is only 18.It compares
For, hydroxide-modified expansible graphite is for improving 65.7% than blank EPS sample oxygen index (OI) in EPS sample.
When unmodified expansible graphite is added in EPS particle by 30% mass ratio, made EPS sheet material sample
Oxygen index (OI) reach maximum value 27.8.In comparison, hydroxide-modified expansible graphite flame retardant effect is than non-modified
Expansible graphite flame retardant effect to get well.
Meanwhile when with Horizontal Bridgman Method and normal beam technique measurement combustibility, the examination of the EPS sheet material made of fire retardant of the present invention
There is continuous flaming combustion in sample, but flame front is less than 100mm graticule, and 8.67s of the individual sample after fire source removes is put out
It goes out, vertical combustion grade reaches V0 grades, and horizontal firing grade reaches HB grades；Also, the pull strength of EPS drops to 0.22Mpa,
The requirement of 0.1MPa, no security risk need to be greater than considerably beyond pull strength specified in standard JG149-2003.
Embodiment 4
The present embodiment and embodiment 3 the difference is that: 300 parts of magnesium hydroxide, 0.5 part of silane coupling agent.
Using: the hydroxide-modified expansible graphite fire retardant that the present embodiment is obtained is added by 30% mass ratio
Into EPS particle, it is uniformly mixed, sheet coupon is made, oxygen index (OI) reaches 28.68.Meanwhile it being fired with Horizontal Bridgman Method and normal beam technique measurement
When burning performance, there is continuous flaming combustion in the EPS sheet material sample made of fire retardant of the present invention, but flame front does not surpass
100mm graticule is crossed, 9.13s of the individual sample after fire source removes extinguishes, and vertical combustion grade reaches V0 grades, horizontal firing grade
Reach HB grades；Also, the pull strength of EPS drops to 0.23Mpa, strong considerably beyond drawing specified in standard JG149-2003
Degree need to be greater than the requirement of 0.1MPa, no security risk.
In conclusion the content of hydroxide-modified expansible graphite fire retardant of the present invention in the base is 30%
When, in 28.68-31.35, intensity reaches pull strength specified in JG149-2003 to be wanted greater than 0.1MPa oxygen index (OI)
It asks, matrix strength also substantially increases while so that matrix is kept preferable flame retardant effect, no security risk.
The above is only a preferred embodiment of the present invention, it is noted that come for those of ordinary skill in the art
It says, without departing from the concept of the premise of the invention, several modifications and variations can also be made, these belong to of the invention
Protection scope.
Claims (6)
1. a kind of preparation method of hydroxide-modified expansible graphite fire retardant, it is characterised in that key step is as follows:
1) raw material is weighed in parts by weight, is calculated as on the basis of expansible graphite parts by weight: 100 parts of expansible graphite, inorganic hydrogen
100-1000 parts of oxide, 0.1-10 parts of silane coupling agent, 10-200 parts of reaction dissolvent:
2) expansible graphite, inorganic hydroxide and silane coupling agent are added in reaction dissolvent, boil and is stirred to react 1-3h,
Reacting obtained solid product is hydroxide-modified expansible graphite fire retardant.
2. the preparation method of the hydroxide-modified expansible graphite fire retardant of one kind according to claim 1, feature
It is the mixing of silane coupling agent the model KH550, KH560, one or more of KH570.
3. the preparation method of the hydroxide-modified expansible graphite fire retardant of one kind according to claim 1, feature
The granularity for being the expansible graphite is 10-200 μm.
4. the preparation method of the hydroxide-modified expansible graphite fire retardant of one kind according to claim 1, feature
Be the hydroxide be mainly one or more of aluminium hydroxide, magnesium hydroxide, calcium hydroxide in any proportion
Mixture.
5. the preparation method of the hydroxide-modified expansible graphite fire retardant of one kind according to claim 1, feature
The granularity for being the hydroxide is 10nm-10 μm.
6. the preparation method of the hydroxide-modified expansible graphite fire retardant of one kind according to claim 1, feature
It is the reaction dissolvent in water, ethyl alcohol, ethyl acetate, tetrahydrofuran, toluene, acetone, N,N-dimethylformamide
One or more of mixtures in any proportion.
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| CN108963895A (en) * | 2018-06-08 | 2018-12-07 | 江苏中讯电力科技有限公司 | A kind of highly-breathable tray type cable bridge |
| CN109111617B (en) * | 2018-06-11 | 2023-01-10 | 台州市佳信新材料科技有限公司 | Flame-retardant core layer of aluminum-plastic plate and aluminum-plastic plate |
| CN110317365A (en) * | 2019-07-09 | 2019-10-11 | 兰州大学 | A kind of preparation method of smokeless expansible graphite fire retardant |
| CN112375257B (en) * | 2020-11-12 | 2022-08-23 | 上海湘新阻燃材料有限公司 | Efficient environment-friendly composite flame retardant and preparation method thereof |
| CN114015116A (en) * | 2021-11-10 | 2022-02-08 | 哈尔滨工程大学 | Preparation method of aluminum hydroxide surface modified expandable graphite flame retardant and method for preparing flame-retardant polyurethane foam plastic by using same |
| CN115651257A (en) * | 2022-11-09 | 2023-01-31 | 安徽昊源化工集团有限公司 | Polystyrene synthesis process |
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| CN103318873B (en) * | 2013-05-14 | 2015-02-25 | 北京理工大学 | Modification method for expandable graphite |
| CN103333370B (en) * | 2013-07-25 | 2015-05-13 | 北京市建筑工程研究院有限责任公司 | Organic and inorganic microcapsule coating expansible graphite preparation method |
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