CN109563703A - Flexible light weight fire barrier - Google Patents
Flexible light weight fire barrier Download PDFInfo
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- CN109563703A CN109563703A CN201680087973.0A CN201680087973A CN109563703A CN 109563703 A CN109563703 A CN 109563703A CN 201680087973 A CN201680087973 A CN 201680087973A CN 109563703 A CN109563703 A CN 109563703A
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- flexible base
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- 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
- C09K21/00—Fireproofing materials
- C09K21/02—Inorganic materials
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- 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
- C09K21/00—Fireproofing materials
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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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
- C08K3/02—Elements
- C08K3/04—Carbon
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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
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
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Abstract
A kind of light fire-proof partition, the fire barrier include the refractory coating containing expansible graphite.The fire barrier has improved fire resistance and is flexible, without undesirable layering.When band coating surface direction fire, which will not be burnt, and keep flexible without cracking after 10 minutes fire exposures.
Description
Technical field
The present invention relates to the light fire-proof partitions including refractory coating.
Background technique
In many cases, such as urgent military and fireman cover, public transport, especially aircraft exist
For the needs of light-weight refractory partition.The U.S. Patent number 6,322,022 of Fay et al. discloses resistance to burn-through system.Tomkins and
The U.S. Patent number 6,670,291 of Vogel-Martin describes a kind of laminate sheet material for fire barrier application.
The U.S. Patent number 8,292,027 and 8,387,748 of Richardson and Knoff discloses one kind to contain inorganic laminar layer
The composite laminate of the thermoacoustic barrier of (flame retardant coating).The shortcomings that pervious solution-composite laminate is heavy, usual tool
There is 150-300g/m2Base weight and high rigidity (non-flexible), close covering cannot be provided for non-flat surface, and depositing
Forbid folding when storage.
Therefore, it is desirable to provided with as most light as possible material have the fire resistant flexible of outstanding fire resistance every
Plate.
Summary of the invention
The fire barrier for the resistance to burn-through resistance with improvement that the present invention provides a kind of, the fire barrier include:
The flexible base board being made of polyimides, and
Refractory coating containing expansible graphite,
Wherein
The coating composition of the refractory coating derived from curable, which includes:
(a) expansible graphite of about 10-50 weight %, and
(b) elastomer silicone of about 50-90 weight %,
Wherein weight % is the total weight based on the curable coating composition；And
The refractory coating is present at least one surface of the flexible base board.
The present invention also provides a kind of methods for being used to prepare fire barrier as described above, this method comprises:
I., flexible base board and curable coating composition are provided；
Ii. the curable coating composition is applied at least one surface of the flexible base board；
Iii. the fire barrier is obtained by heating or radiating the coated substrate come curing schedule ii；
Wherein
Based on the total weight of the curable coating composition, which includes:
(a) expansible graphite of about 10-50 weight %, and
(b) elastomer silicone of about 50-90 weight %.
Specific embodiment
Unless otherwise stated, all publications, patent application mentioned by this paper, patent and other bibliography, for
All purposes is whole clearly in conjunction with here, as fully expounded with it by reference.
Unless otherwise defined, all technical and scientific terms used herein all have and fields of the present invention
The normally understood identical meanings of those of ordinary skill institute.In the case of a conflict, then with this specification, including subject to definition.
Unless otherwise stated, all percentage, number, ratio etc. are by weight.
As used herein, term " by ... be made " it is synonymous with "comprising".As used herein, term " includes
(comprises) ", " include (comprising) ", " including (includes) ", " including (including) ", " have
(has) ", " having (having) ", " containing (contain) " or " containing (containing) " or its equal purport of any other modification
Covering non-exclusive inclusion.E.g., including composition, technique, method, product or the equipment of element list are not necessarily limited to
Those elements, but may include not expressly listed or such composition, technique, method, product or equipment intrinsic other
Element.
Conjunctive phrase " Consists of " excludes any element that do not point out, step or ingredient.If in the claims,
Such phrase will make claim closed, so that it is not included the material in addition to the material of those descriptions, but associated therewith
Customary impurities except.In the clause that phrase " Consists of " appears in the main body of claim, rather than immediately preamble when,
Only it is limited in the element mentioned in the clause；Other elements are excluded from the claim not as entirety.
Conjunctive phrase "consisting essentially of ..." further includes material, step other than those of literal discussion for limiting
Suddenly, the composition of feature, component or element, method or equipment, on condition that these additional materials, step, feature, component,
Or element will not the claimed invention of materially affect one or more essential characteristics and novel feature.Term is " substantially
By ... form " it occupy among "comprising" and " Consists of ".
Term "comprising" is intended to include the embodiment that term "consisting essentially of ..." and " Consists of " are covered.It is similar
Ground, term "consisting essentially of ..." are intended to include the embodiment covered by term " Consists of ".
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When choosing value provides, this be should be understood as specifically disclosing by any range limit or preferred value and any range lower limit or preferably
Any pairing of value is formed by all ranges, regardless of whether the range is separately disclosed.For example, when the model for enumerating " 1 to 5 "
When enclosing, cited range be should be interpreted that including the models such as " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to 5 ", " 1 to 3 and 5 "
It encloses.When enumerating numberical range herein, unless otherwise stated, otherwise the range be intended to include its endpoint and this within the scope of
All integers and score.
When term " about " description range value or endpoint in use, the disclosure should be read to include the spy being mentioned
Definite value or endpoint.
In addition, unless expressly stated to the contrary, otherwise "or" refers to the "or" of inclusive, exclusive without referring to
"or".For example, any one of following condition A "or" B:A that is all satisfied is that very (or presence) and B are false (or being not present), A is false
(or being not present) and B are true (or presence) and A and B is true (or presence).
" mole (Mole) % " or " mole (Mol) % " refers to molar percentage.
When describing and/or the claimed present invention, term " homopolymer " refers to the polymerization derived from single repetitive unit
Polymer；Term " copolymer " refers to the polymer by two kinds or the copolymerization more than two kinds of repetitive units.
As it is used herein, term " fiber " is defined as having high length and width on the cross section perpendicular to its length
The relative flexibility of ratio, elongated main body.The fibre section can be any shape, such as round, pancake or rectangle, but allusion quotation
It is type round.The fibre section can be it is solid or hollow, it is preferably solid.
As it is used herein, term " nanofiber ", which refers to, to be had less than 1000nm, even less than 800nm, even exists
The fiber of number average diameter between about 50nm and 500nm and even between about 100 and 400nm.It is received in non-circular cross sections
In the case where rice fiber, as it is used herein, term " diameter " refers to maximum cross sectional dimensions.
It, can be with if the embodiment of the present invention described in summary of the invention includes any other embodiments described herein
Any mode mutually merges, and the description in embodiment for variable is directed not only to composite laminate of the invention, but also relates to
And product as made from it.
The present invention is described in detail below.
(a) flexible base board
According to the present invention, which is made of polyimides.Polyimides is a kind of heat-staple and non-combustible
Polymer, and commercially available polyimide film is flexible, thus the thickness with range from about 5 μm to about 150 μm makes
Obtain the elite clone of its flexible base board (a) for acting as fire barrier of the present invention.
From the perspective of the practical use of fire barrier of the present invention, the thickness of the flexible base board (a) is preferably about 5-
150 μm or about 10-130 μm or about 15-110 μm.
According to the disclosure, the base weight of the flexible base board (a) is preferably 10-50g/m2Or 12.5-40g/m2Or 15-
30g/m2。
Polyimides is typically derived from diamines and dianhydride or their precursor-tetrabasic carboxylic acid.When be suitable for polyimides or
When polyamic acid, term " all aromatic " means that it is aromatic that the monomer of polyamic acid is produced by it.The reality of aromatic diamine
Example including but not limited to 1,4- phenylenediamine (PPD), 1,3- phenylenediamine (MPD), 4,4 '-diaminodiphenyl ethers (ODA), 1,3- is bis-
(4- amino-benzene oxygen) benzene (RODA) and 3,3 '-methylene-dianil.The example of aromatic dianhydride is including but not limited to equal
Pyromellitic dianhydride (PMDA), 3,3 ', 4,4 '-xenyls-tetracarboxylic acid dianhydride (BPDA), 1,4,5,8- naphthalene-tetracarboxylic acid dianhydride
(NTDA), 4,4 '-oxydiphthalic acid dianhydrides (oxydiphtalic dianhydride) (ODPA) and 3,3 ', 4,
4 '-benzophenone tetracarboxylic dianhydrides (BTDA).
Aromatic diamine above-mentioned and aromatic dianhydride can be used alone to form polyimides homopolymer, or with two kinds
Or the form of the mixture of two or more monomeric units is used to form polyimide copolymer.It is copolymerized when using polyimides
When object, the aromatic dianhydride for constituting the copolymer can be by one or more selected from by PMDA, BPDA, NTDA, ODPA and BTDA
It is prepared by the compound of the group of composition.Alternatively, constitute the polyimide copolymer aromatic diamine can by a kind of or
It is prepared by a variety of compounds selected from the group being made of PPD, MPD, ODA, RODA and 3,3 '-methylene-dianil.
As it is used herein, these polyimides homopolymers or copolymer are indicated by repeated monomer unit, wherein " // "
For distinguishing one or more aromatic dianhydrides and one or more aromatic diamines, and "/" is for distinguishing same functional group
Monomer.For example, the polyimides homopolymer derived from PMDA and ODA can be designated as " PMDA//ODA "；It is derived from
The polyimide copolymer of the mixture of BPDA and PPD and MPD can be designated as " BPDA//PPD/MPD ".Polyimides
The main polymerisation unit of copolymer can exist with the amount of at least about 70mol% or about 80mol% or about 90mol% or more
In the copolymer.
In one embodiment, in fire barrier of the present invention, which includes to be selected from derived from least one
By PMDA, BPDA, NTDA, ODPA, BTDA, and combinations thereof the aromatic dianhydride of group that forms, and it is at least one selected from by
PPD, MPD, ODA, RODA, 3,3 '-methylene dianilines, and combinations thereof composition group aromatic diamine polyimides.
In another embodiment, in fire barrier of the present invention, the flexible base board (a) include derived from selected from by
The aromatic dianhydride of the group of PMDA, BPDA and combinations thereof composition, and selected from by ODA, RODA, and combinations thereof the virtue of group that forms
The all aromatic polyimides of fragrant race's diamines.
In a further embodiment, flexible base board (a) of the present invention includes the work derived from least 70mol% to 100mol%
For the polyimides of the monomeric unit of PMDA//ODA or BPDA//RODA.
Broad practice of process needs to be initially formed polyamic acid in polyimides synthesis.It is related to: making aforementioned fragrance race two
Any one of any one of acid anhydride and aforementioned fragrance race diamines react in polar non-solute, corresponding a kind of to generate
Or a variety of polyamic acids, the polyamic acid are polyimide precursor solutions.
The example of polar non-solute includes amide, such as n-methyl-2-pyrrolidone (NMP), N, N- dimethylacetamide
Amine (DMAc), N, N- diethyl acetamide, N,N-dimethylformamide (DMF), N, N- diethylformamide and hexamethyl sulphonyl
Amine；Sulfoxide, such as dimethyl sulfoxide and diethyl sulfoxide；And sulfone, such as dimethyl sulfone and diethyl sulfone.These solvents can individually make
With or in a joint manner use.
The amount (by mol) of these aromatic dianhydrides and aromatic diamine in any in aforementioned solvents is basic
The amount (by mol) of one of upper identical or these components is just over the amount of another component, and passes through so that reaction is mixed
Close object reaction preferably 100 DEG C or lower (more preferable 80 DEG C or lower) at a temperature of carry out about 0.2 to about 60 hour, to obtain
Obtain corresponding polyamic acid (PAA) solution, i.e. polyimide precursor solution.
In fire barrier of the present invention, which be can be with polyimide film or polyimide nano net
(nanoweb) form.
In view of the production method for the polyimide film or polyimide nano net, the PAA can be suitably determined
The total monomer concentration of solution.The polyimide film can pass through following acquisition: be poured PAA solution by means of such as mould (die)
Suitable support (for example, metallic roll, ceramic roller or plastic roller, metal tape or thereon provide metallic film band roller or
Band) surface on, the film with uniform thickness is consequently formed.
Then, by the film of the casting by range from about 100 DEG C to about 500 DEG C or about 150 DEG C to about 450 DEG C of temperature
The thermal cycle of degree is heated, until at least 90% amide acid functionality is converted into imide functionalities (i.e. imidizate),
In the thermal cycle can suitably be determined by one skilled in the art.The hot-imide can be filled by means of any heating
It sets, is carried out such as hot-blast stove or infrared furnace.Preferably, the flexible base board (a) be at least 90% or 95% or
The polyimide film of 99% or 100% imidizate degree (DOI).
Should " imidizate degree " (DOI) be defined herein as that acid imide C-N is flexible (to be usually located at or near 1375cm-1)
Infrared IR, which absorbs to stretch with aromatic C-NH, (is usually located at or near 1500cm-1) infrared IR absorb ratio.For appointing
To (repetitive unit), the method for measuring DOI involves the steps of what given monomer: operation and IR spectrum simultaneously establish these
The exact position of absorption.
Polyimide nano net can by by T.J.Dennes et al. in U.S. Patent Application Publication No. 2013/
It is prepared by the method be described in detail in 0005940.
It is such as suitable for the invention, term " nano net " refers to that by the fiber for being greater than 50% in net be nanofiber institute structure
The nano net made.Nano net of the invention also can have nanofiber greater than 70% or 90% or it can even include
100% nanofiber.
Term " non-woven " means the net of the fiber comprising multiple random orientations herein." random orientation " means these fibres
Dimension is without the recognizable long-range repetitive structure of naked eyes.These fibers can be bonded to one another, or can be non-adherent and twine
Knot is to assign intensity and integrality to the net.
PAA solution forms nano net by electroblowing, such as in U.S. Patent Application Publication No. 2013/0005940A1 in detail
Carefully describe.The electricity, which blows nano net, to be first calendered.The drying and the nano net of calendering then can be in range from about 200
DEG C at a temperature of about 500 DEG C by 5 seconds to the 10 minutes time of hot-imide.
Alternatively, the electricity blow nano net can range from about 200 DEG C to about 500 DEG C at a temperature of by hot-imide
5 seconds to 10 minutes time, and be then calendered.
" calendering " is the process for making Netcom cross the roll gap between two rollers.These rollers can be in contact with each other, or in roller surface
Between can have fixed or variable gap.Advantageously, in calender line, roll gap can between soft roller and hard roller shape
At.Should " soft roller " be that two rollers keep together the roller deformed under pressure applied in calender.Being somebody's turn to do " hard roller " is tool
There is the roller on following surface, wherein not occurring to the deformation that process or product have a significant impact under the pressure of the process." do not scheme
Case " roller be in the limit of power for manufacturing their process with smooth surface roller.Unlike bond roll,
When non-patterned roller passes through roll gap, point or pattern specially are not generated online.The calender line also can be used two
Hard roller.
Be thusly-formed polyamic acid nano net imidizate can be convenient by following progress: so that nano net is existed first
Solvent extraction is subjected in the vacuum drying oven with nitrogen purging at a temperature of about 100 DEG C；After extraction, then the baking oven is heated
To about 200 DEG C to about 500 DEG C of temperature, so that thus the nano net is heated at least 5 seconds or about 10 minutes or less, preferably 5
Minute or less, more preferable 2 minutes or less and even more preferably 1 minute or even 30 seconds or less, with abundant acid imide
Change the nano net.
In one embodiment, the polyimide nano net is substantially fine by the polyimide nano formed from monomeric unit
Dimension composition: pyromellitic acid anhydride (PMDA) and diaminodiphenyl ether (ODA).
Suitable polyimide film and polyimide nano net can be by commercial sources, such as from Delaware, USA prestige
Ming Dun E.I.Du Pont De Nemours and Co. (E.I.Du Pont de Nemours and Company) is with trade nameNH
It obtains.
Refractory coating
According to the disclosure, refractory coating (b) is derived from the curable painting comprising elastomer silicone and expansible graphite
Layer composition.
As it is used herein, " elastomer silicone " is silicon composition, when being then cured or vulcanizing, provide
Elastomer silicone or rubber.Organosilicon refers to containing independently selected from (R3SiO0.5)、(R2SiO)、(RSiO1.5) or (SiO2)
The organopolysiloxane of the siloxane unit of siloxy unit, wherein R can be any organic group.These siloxy lists
Member can be combined in different ways to form the structure of ring, straight chain or branch.It can be used for curable coating composition
Elastomer silicone can be selected from any elastomer silicone known in the art, such as be considered as that of high-consistency silicon rubber
A bit.Elastomer silicone may be derived from being considered as those of " liquid silastic " (LSR).
LSR is typically made of the methyl hydrogen siloxane as crosslinking agent and the organosilicon polymer containing vinyl,
Solidify under the catalysis of noble metal catalyst (such as Pt (0) complex) generally by means of hydrosilylation reactions.LSR may include
The inhibitor of hydrosilylation reactions, especially by those of the catalyst based on platinum, such as alkynol, such as 3- methyl-1-fourth
Alkynes -3- alcohol, 3,5- dimethyl -1- hexin -3- alcohol, 1- acetenyl -1- cyclohexanol and phenylbutynol；Yne compounds, such as
3- methyl-pirylene and 3,5- dimethyl -3- hexene -1- alkynes；- four hexenyl cyclotetrasiloxane of tetramethyl；And benzene
And triazole.Hydrosilylation reactions inhibitor preferably be enough to ensure that the curing of coatings of generation it is sufficiently fast and allow with can be swollen
The swollen well-mixed ratio of graphite is present in LSR configuration product.
Commercially available LSR is usually with the sale of two parts preparation, and the preparation is after two parts are with specified ratio mixing
There can be specific viscosity.Organosilicon polymer (for example, alkenyl organopolysiloxane) and precious metal catalyst containing vinyl
Agent is usually comprised in the first part of the preparation, and organohydrogensiloxanes and/or hydrosilylation reactions inhibitor
It is comprised in second part.What the LSR of commercial source would generally suggest the weight ratio between two parts may range from 10:1
To 1:1.Preferably, elastomer silicone is the liquid silastic suitable for fabric coating.
Exemplary SLR in 2 part preparations is from Daukangnin GmbH (Dow Corning Co.) with trade nameIt is commercially available.
According to the disclosure, used in curable coating composition to form the expansible graphite of refractory coating (b),
With about 20-300 μm or about 50-150 μm of average grain diameter (d50).The average grain diameter is for example, by laser diffraction/scattering grain
Distribution measurement instrument is spent to measure.Also, according to the disclosure, expansible graphite used herein is substantially free of sulphur.That is,
Expansible graphite used herein has the sulfur content less than 200ppm horizontal.
Suitable expansible graphite for example can win ancient cooking vessel effect Carbon Co., Ltd (Boading Action from Hebei China
Carbon Co.Ltd.) commercially obtain.
Curable coating composition can by by two parts of desired amount of expansible graphite and LSR preparation simultaneously
Mixing is to prepare.Alternatively, expansible graphite can be mixed with the first part of the preparation, and by the of the preparation
Two parts are subsequently added in mixture.
Amount of the expansible graphite in curable coating composition can be about 20-70 weight % or about 20-60 weight
Measure the level of % or about 25-50 weight %, the total weight based on the curable coating composition.Including with such amount should
The curable coating composition of expansible graphite still can be easily applied on flexible base board (a), be maintained simultaneously
The excellent flexibility of machine silicone elastomer.
No matter preparation process be simultaneously mixing or sequence mix, curable coating composition should have be suitable for it is specific
Using, suitable for the viscosity for the machine being applied on flexible base board (a), but generally at 25 DEG C, it is the model in 2-120Pas
In enclosing.Preferred curable coating composition has the viscosity within the scope of 5-40Pas at 25 DEG C, and can be
Solidify within half a minute at a temperature of 150 DEG C -200 DEG C to provide elastomer at least one surface of flexible base board (a) and apply
Layer.According to the present invention, when less than about 40 DEG C at a temperature of save when, which should be able to be maintained at can
Operating viscosity continues at least 3-6 hours.
The curable coating composition can be applied on flexible base board (a) by following any coating technique: packet
Include intaglio printing, blade coating and transfer coated technology.Although some curable coating compositions can be consolidated at normal temperature
Change, but the solidification of curable coating composition is preferably carried out by heating or radiating.Heating is preferred method, and
Preferably in range from 100 DEG C to about 200 DEG C or from about 130 DEG C to about 170 DEG C at a temperature of.
One major advantage of the curable coating composition of the present invention is small from 30 seconds to one in range at about 150 DEG C
When, after general 1-30 minutes and typically 1-15 minutes of relatively short curing time, good adherency may be implemented
Property.The increase of solidification temperature is so that curing time shortening.
From the perspective of providing enough resistance to burn-through resistance without damaging lightweight and the flexible characteristic of fire barrier of the present invention,
The coating composition of derived from curable and be present in flexible base board (a) at least one surface refractory coating (b) thickness
Preferably 10-180 μm or 15-160 μm or 20-135 μm of degree.
From the perspective of the flexibility for preventing damage film, flexible base board (a) and fire barrier (that is, the flexible base board (a)
The summation of the thickness of thickness and the refractory coating (b)) thickness than be preferably 0.75 or lower or 0.50 or lower or
0.25 or lower.Special limitation is not forced to minimum thickness ratio, as long as not damaging effect of the invention.Flexible base board (a) with
The thickness of fire barrier is than being preferably 0.01 or bigger or 0.05 or bigger or 0.1 or bigger.
Although the desired use of fire barrier of the invention is included in electrical cable slot, burning line, steam and process duct
Pipe protection, steel structure fireproofing and refractory wall component etc. application in have it is flexible, prolong prolonged flame barrier, it should be understood that
It is to contemplate other final uses.Typical application include for example, as be sealed in for building structure (as urgent military and
Fireman cover) or the doors of the vehicles (such as aircraft, train, automobile or ship), wall or roof between or internal backing member
(liner), additional heat and flame can be provided by heat transmitting of slowing down to protect.Other purposes packets of fire barrier of the invention
Include for example for equipment cover, supporting member, circuit board, medical gas case and elevator-calling box protective cover；Or it is used for fuel
The wrappage of pipeline, jet chimney and process pipe and cable.
Without further elaborating, it is believed that those skilled in the art can utilize the present invention to it most using preceding description
Big degree.Therefore, following instance should be construed as illustrative only, and not limit the disclosure in any way.
Example
It abridges " E " representative " example ", and " CE " representative " comparison example ", it is anti-that digital representation behind wherein prepares heat
Protect the number of the example of clothes.Example and comparative example are prepared in a similar manner and are tested.
Material
Polyimide film (a1): with trade name50HN is commercially available from E.I.Du Pont De Nemours and Co., the U.S.
(E.I.du Pont de Nemours Co.).The polyimide film has about 18.8g/m2Base weight and 12.7 μm (0.5mil)
Thickness.
Polyimide nano net (a2): according to program system described in U.S. Patent Application Publication No. 2013/0005940
It is standby.First by the polyimide nano net imidizate, then roll to obtain the nano net with following item: about 17.0g/m2
Base weight, 25.6 μm of thickness, for 0.630 DOI, 40.7MPa tensile strength and 18.0% elongation at break.It should
It is 25mm and a length of 100mm that the tensile strength and elongation at break of nano net (a2), which are by the way that the nano net (a2) is cut into width,
Item measures.The test carries out on Instron5566 universal testing machine according to improved ASTM D882-12 method.Test
Gauge length be 50mm and crosshead speed (crosshead speed) is 100mm/min.
Polyimide nano net (a3): according to program system described in U.S. Patent Application Publication No. 2013/0005940
It is standby.The polyimide nano network pressure is prolonged first, then imidizate is to obtain the nano net with following item: about 23.8g/m2
Base weight, 72.5 μm of thickness, for 0.584 DOI, 19.0MPa tensile strength and 9.0% elongation at break.This is received
The tensile strength and elongation at break of rice net (a3) are measured according to the same procedure described above for nano net (a2).
Expansible graphite: it is commercially available from Hebei China and wins ancient cooking vessel action Carbon Co., Ltd.The expansible graphite is flat with 75 μm
Equal granularity.
Liquid silastic (b1): being commercially available from Daukangnin GmbH, by3600A (49.5 weight %),3600B (49.5 weight %) and solidification retarding agent-DowLC-9608 (1 weight %) composition.
Liquid silastic (b2): it is commercially available from Daukangnin GmbH, by 90.9%The portion 9151-200P
Divide A's and 9.1%The part 9151-200P B composition.
Prepare curable coating composition CC1-CC3
CC0: will3600A (49.5 parts by weight),3600B (49.5 parts by weight) and DowThe mixture of LC-9608 (1 parts by weight) is uniformly mixed, to obtain the comparison coatings combine for being free of expansible graphite
Object, such as CC0.
CC1: will3600A (49.5 parts by weight),3600B (49.5 parts by weight), DowThe mixture of LC-9608 (1 parts by weight) and expansible graphite (60 parts by weight) is uniformly mixed, to be contained
The curable coating composition of the expansible graphite of 37.5 weight %, such as CC1.It should be by freshly prepared curable coating group
Object is closed to be applied within 48 hours on specified flexible base board.
CC2: will3600A (49.5 parts by weight),3600B (49.5 parts by weight), DowThe mixture of LC-9608 (1 parts by weight) and expansible graphite (15 parts by weight) is uniformly mixed, and contains 13 to obtain
The curable coating composition of the expansible graphite of weight %, such as CC2.
CC3: willThe part 9151-200P A (91 parts by weight),The part 9151-200P B (9
Parts by weight) and the mixture of expansible graphite (26.7 parts by weight) be uniformly mixed, it is inflatable containing 21.1 weight % to obtain
The curable coating composition of graphite, such as CC3.
Prepare coated sample E1-E10 and CE1-CE7
Specified by table 1-3, which is uniformly spread over using knife
On the glass fabric of PTFE dipping, to cover out 18x18cm2Square area.Then, on curable coating composition
Place a piece of identical size, pre-weighed polyimide film or nano net in portion.To have that be clipped in PTFE fabric soft with polyimides
Property substrate between the assembling object of curable coating composition turn, and by removal now on the assembling object top
PTFE fabric, which is transferred on the polyimide flex substrate.By the coated polyamides
Imines flexible base board solidifies 4 minutes in an oven at 160 DEG C, and to provide sample, this is the embodiment of fire barrier of the present invention.
Test method
Base weight (g/m2): the weight of uncoated and coated sample is in METTLER TOLEDO precision balance mould
It is measured on type PR8002.The base weight is the area (m by weight (g) divided by uncoated or coated sample2) come
It calculates.
Thickness (μm): the thickness of polyimide film or nano net before coating and later is according to ASTM D1777 with directly
Presser feet (presser foot) and the pressure of 4.14kPa that diameter is 28.7mm measures.
Burn test: the test is by adjusting the propane flow of Bunsen burner (Bunsen burner) to provide such as from combustion
What the flame envelope for being 100 ± 2mm with the internal flame for being highly 70 ± 2mm and with height measured by burner head carried out.This is outer
The temperature of flame rose to 600 DEG C from 100 DEG C in 25 seconds, 700 DEG C was risen in 35 seconds, and 800 DEG C are risen in 47 seconds.It will examination
Part horizontal-clamping, wherein coated side has the exposed area of 10cm x 10cm towards the burner on bearing support.By burner
It is placed below sample, and is positioned with a vertical at 45 degree of angles, the tip for providing internal flame just connects with sample coatings
The flame of touching, so that it is guaranteed that being come into full contact with flame envelope.Being somebody's turn to do " burn through time " is that test starts until flame penetrates between sample
Duration is often produced with the sample in hole or crack.If sample holding is completely continued above 10 minutes, stop testing,
And by the sample record be " not burning ".
Flexible test: make to keep complete sample to be subjected to this test after burning test.By sample on combustion zone edge
One direction folds, and then vertically folds again, to form 4 foldings square, the square be original size four/
One.Pass through the sample of this test, if it can be folded and unfolded, shows crack or coating point without a part of sample
From, or a part of sample does not fall off from sample structure, then is marked with "○"；Otherwise it is marked as "×".
The result of above-mentioned test is reported in table 1-3.
Table 1
Table 2
Table 3
The test result of table 1-3 clearly illustrates the excellent flame retardancy of the fire barrier of (E1-E9) of the invention.
Compare burn-through test result, no expansible graphite comprising elastomer silicone sample (i.e. CE2, CE3, CE5 and
CE6 it) is quickly burnt in 2 minutes.In contrast, the sample of example 1-9 (embodiment of fire barrier i.e. of the invention) is logical
It crosses after 10 minutes fire exposures and keeps complete and show excellent anti-flammability.
Other advantages observed in the burn-through test process of fire barrier of the invention are: the sample of comparison example 1-7
Product generate a large amount of cigarette and disagreeable burning gases during the test and become brittle friable later；And example 1-9's is anti-
Fire screen plate keeps complete after burning test during the test without generating cigarette or gas.
Compared with the sample of comparison example 1-3, another advantage of flame barrier of the invention is: the fire prevention of example 1-9
Partition is more flexible, can be folded and be unfolded without showing crack.
Although illustrating and describing the present invention in an exemplary embodiment, be not intended to be limited to shown in details because
May there are various modifications and replacement without departing from spirit of the invention.Similarly, the modification of the present invention disclosed herein and equivalent
Routine experiment, which can be used only, by those skilled in the art in object occurs, and thinks that all such modifications and equivalent are in such as
In the spirit and scope of the present invention that following following claims limits.
Claims (10)
1. a kind of fire barrier of the resistance to burn-through resistance with improvement, the fire barrier include:
(a) flexible base board being made of polyimides, and
(b) containing the refractory coating of expansible graphite,
Wherein
The coating composition of the refractory coating derived from curable, which includes:
The expansible graphite of about 10-50 weight %, and
The elastomer silicone of about 50-90 weight %,
Wherein weight % is the total weight based on the curable coating composition；And
The refractory coating is present at least one surface of the flexible base board.
2. fire barrier as described in claim 1, wherein the fire barrier has about 20-200g/m2Or about 25-175g/
m2Or about 30-150g/m2Base weight.
3. fire barrier as described in claim 1, wherein the amount of the refractory coating is about 10-180g/m2Or about 15-160g/
m2Or about 20-135g/m2。
4. fire barrier as described in claim 1, wherein the fire barrier have about 45-550 μm or about 60-430 μm or
About 75-310 μm of overall thickness.
5. fire barrier as described in claim 1, wherein the flexible base board is polyimide nano net or polyimide film.
6. fire barrier as described in claim 1, wherein the flexible base board have about 5-150 μm or about 10-130 μm or
About 15-110 μm of thickness.
7. fire barrier as described in claim 1, wherein the thickness ratio of the flexible base board and the fire barrier is about 0.01-
0.75。
8. fire barrier as described in claim 1, wherein the elastomer silicone for including in the refractory coating is liquid silicon rubber
Glue.
9. a kind of method for being used to prepare fire barrier as described in claim 1, this method comprises:
I., the flexible base board being made of polyimides and curable coating composition are provided；
Ii. the curable coating composition is applied at least one surface of the flexible base board；
Iii. the fire barrier is obtained by heating or radiating the coated substrate come curing schedule ii；Wherein
Based on the total weight of the curable coating composition, which includes:
The expansible graphite of about 10-50 weight %, and
The elastomer silicone of about 50-90 weight %.
10. the purposes of fire barrier as described in claim 1, wherein the fire barrier is for building structure or traffic work
The backing member of the door of tool, wall or roof；For equipment cover, supporting member, circuit board, medical gas case and elevator-calling box guarantor
Shield；Or for burning line, jet chimney and process pipe and the wrappage of cable.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2016/092000 WO2018018483A1 (en) | 2016-07-28 | 2016-07-28 | Flexible lightweight fire barrier |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109563703A true CN109563703A (en) | 2019-04-02 |
Family
ID=61015339
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| CN201680087973.0A Pending CN109563703A (en) | 2016-07-28 | 2016-07-28 | Flexible light weight fire barrier |
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| Country | Link |
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| CN (1) | CN109563703A (en) |
| WO (1) | WO2018018483A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114222513A (en) * | 2019-08-13 | 2022-03-22 | Molo设计有限责任公司 | Flexible furniture with wooden panels and related methods |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020034117A1 (en) | 2018-08-15 | 2020-02-20 | 3M Innovative Properties Company | Silicone sealer compositions |
| EP4201665A1 (en) | 2021-12-21 | 2023-06-28 | Nolax AG | Composite material as heat, fire and/or smoke protection material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101903173A (en) * | 2007-10-24 | 2010-12-01 | 戈尔企业控股股份有限公司 | Thermally protective materials |
| CN102867599A (en) * | 2011-07-07 | 2013-01-09 | 日东电工株式会社 | Covering material, superconducting electric wire and electrical device |
| CN103692707A (en) * | 2013-12-17 | 2014-04-02 | 3M创新有限公司 | Fireproof film and electric equipment |
| WO2015161024A1 (en) * | 2014-04-18 | 2015-10-22 | Dow Global Technologies Llc | Panel with fire barrier |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201119826D0 (en) * | 2011-11-17 | 2011-12-28 | Dow Corning | Silicone resin |
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2016
- 2016-07-28 CN CN201680087973.0A patent/CN109563703A/en active Pending
- 2016-07-28 WO PCT/CN2016/092000 patent/WO2018018483A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101903173A (en) * | 2007-10-24 | 2010-12-01 | 戈尔企业控股股份有限公司 | Thermally protective materials |
| CN102867599A (en) * | 2011-07-07 | 2013-01-09 | 日东电工株式会社 | Covering material, superconducting electric wire and electrical device |
| CN103692707A (en) * | 2013-12-17 | 2014-04-02 | 3M创新有限公司 | Fireproof film and electric equipment |
| WO2015161024A1 (en) * | 2014-04-18 | 2015-10-22 | Dow Global Technologies Llc | Panel with fire barrier |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114222513A (en) * | 2019-08-13 | 2022-03-22 | Molo设计有限责任公司 | Flexible furniture with wooden panels and related methods |
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