CN106700920A - Reaction type polysiloxane flame-retardant coating and preparation method thereof - Google Patents
Reaction type polysiloxane flame-retardant coating and preparation method thereof Download PDFInfo
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- CN106700920A CN106700920A CN201710045703.XA CN201710045703A CN106700920A CN 106700920 A CN106700920 A CN 106700920A CN 201710045703 A CN201710045703 A CN 201710045703A CN 106700920 A CN106700920 A CN 106700920A
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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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- 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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- 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
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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- 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
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
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- 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
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/395—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing phosphorus
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- 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
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a reaction type polysiloxane flame-retardant coating and a preparation method thereof, and belongs to the technical field of flame-retardant coatings. The reaction type polysiloxane flame-retardant coating consists of a silane coupling agent, ammonium polyphosphate, a film-forming agent, a polysiloxane flame retardant, a wetting agent and ethanol. The film-forming agent and the silane coupling agent of the reaction type polysiloxane flame-retardant coating have the function of film forming simultaneously, the silane coupling agent and the synthesized polysiloxane flame retardant can be also acted with each other, and the silane coupling agent and the flame retardant can implement microencapsulation on the ammonium polyphosphate, and can be also reacted, so that the reaction type polysiloxane flame-retardant coating of a spatial cross-linked net structure can be prepared, the coating adopts ethanol as a solvent, and the raw materials of the whole system are environmental-friendly reagents which can do no harm to the environment and operators; the coating is a reaction type coating, is high in flame retardancy efficiency, and can be deformed together with a substrate without dropping, the limit oxygen index LOI of polypropylene can be up to 31.3% and can be qualified in UL-94 V0 tests, and the mechanical property of the substrate can be barely affected.
Description
Technical field
The present invention relates to a kind of response type polysiloxanes flame retardant coating and preparation method thereof, belong to flame retardant coating technology neck
Domain.
Background technology
In the modern life, because the fire that is improper and causing that controls of fire happens occasionally, which results in huge life
With property loss.However, a large amount of common used materials are all inflammable, therefore these Flame Retardancies are assigned to reduce fire generation
Probability is imperative.
Under normal circumstances, in flame retardant treatment mode, fire retardant is blended with matrix, prepares intrinsic fire-retardant high polymer, applied
With high polymeric fire-retardant coating etc..Intrinsic high polymer is difficult to prepare, and species is smaller, using limited.Addition type needs very big addition
Amount just has flame retardant effect, and this will bring following problem：First, fire retardant is migrated to top layer so that composition after a period of time
It is uneven；Second, the combination of addition type and matrix is more fragile, and this understands the mechanical property for producing tender spots in the base and reducing matrix
Energy.
It is a kind of preferable method that fire-retardant purpose is reached by the way of flame retardant coating, is also current research hot topic.With
Other two ways are compared, and the internal structure of the surface without destruction matrix of polymeric matrix is attached to due to flame retardant coating,
Therefore harmful effect will not be produced to mechanical property of matrix etc., maintains original performance of matrix material.In addition, it is fire-retardant
Coating can be dissolved among some solvents, reach the purpose for recycling matrix.But, rarely have flame retardant coating application at present
To the report of macromolecule engineering frosting.Main cause has following two：It is firstly because the surface of macromolecule engineering plastics
Polarity is relatively low, hydrophobicity is higher, causes the adhesion reduction of coating and matrix, easily comes off, and does not reach good flame retardant effect,
And weatherability, poor durability；Next to that the pliability of coating is not enough, it is difficult to be adapted with some macromolecule engineering plastics, such as apply
Layer is easy to be broken and come off in the state of polypropylene bends.Therefore, to solve macromolecule engineering plastics with the mode of coating
Inflammable problem, it is necessary to coating/matrix after considering the adhesion of the anti-flammability of coating, coating and matrix, imposing coating
Pliability.
China Patent Publication No. a kind of " high fire-retardance nonhazardous fabric coating material and preparation for CN104862970A is disclosed
The step of method ", the method is to prepare sodium chloride complex first, and cement composite powder is prepared afterwards, is then prepared compound
Water-base resin, finally prepares coating.The method low production cost, suitable application area is wide, but its preparation process is cumbersome and anti-flammability
Can be limited, it is not specified that influence of the coating to matrix properties.
China Patent Publication No. discloses " a kind of the light for architecture curing composite coating and its preparation side for CN105419607A
The step of method ", the method, includes the following steps：(1) by o-cresol formaldehyde epoxy acrylate, water soluble anion polyurethane, first
Base acrylic acid -2- hydroxyl ethyl esters, two propiophenones, polydimethylsiloxane uniformly mix, and add deionized water stirring, are made emulsion；(2)
PH adjusting agent butylethanolamine, cresyl diphenyl phosphate are added in emulsion in dispersed with stirring 30min, Zhi Houfang at 30 DEG C
Half an hour obtains composite coating in entering 50 DEG C of baking ovens；(3) by composite coating, 30-40s completes solidification under ultraviolet lighting.In patent
The flame-retardant nature of the flame retardant coating is not referred to, and the coating need to be such as applied on building, timber base material, also need to be modified
Treatment, paint solidification needs to be completed under ultraviolet light, cumbersome, using being restricted.
Document " Jimenez, M.; Duquesne, S.; Bourbigot, S., Fire protection of
polypropylene and polycarbonate by intumescent coatings. Polymers for
Advanced Technologies 2012,23 (1), 130-135. " is disclosed using expansion type flame-retardant coatings to polypropylene
Flame-proof treatment is carried out with makrolon.After by top finish, the anti-flammability of two kinds of high polymers has significantly to be improved,
The flame retardant coating is intumescent polish lacquer, does not refer to whether the coating has good mechanical property and coating to matrix in document
The influence of mechanical property.
China Patent Publication No. discloses " organosilane coating compositions and its application ", the combination for CN101925660A
The preparation process of thing includes：(1) in the presence of a catalyst, organosilan is hydrolyzed；(2) chela is carried out to Organometallic precursor
Close；(3) silane through hydrolyzing is mixed with the Organometallic precursor through chelating；(4) by the organosilan-organic
Metal precursor mixture is hydrolyzed.The patent describes preparation method and its application of composition in detail, and coating is reasonable in design, effect
Fruit is significantly.But if it is applied to flame retardant area, the adhesion with polymeric matrix is weaker, easily departs from and peels off, it is impossible to plays good
Good protective effect.
China Patent Publication No. discloses a kind of " metal surface silicon containing HMPA for CN103059727A
Alkane inorganic agent and preparation method thereof ", can improve the decay resistance of metal after the inorganic agent treatment metal of the invention.It is special with this
The similar patent of profit also has many, is much by silane coupler or contains-Si-O-CH2CH3, silicone hydroxyl material introduce apply
Layer, is connected through other compositions with metal surface so as to implement protection to reach corrosion resistant purpose to metal.And by silane
Coupling agent is incorporated into coating and is applied to rare in the flame-proof treatment of high polymer, and this is probably due to metal surface and polymer table
The polarity in face, wetability and roughness difference it is larger caused by.The coating that many is applied to anticorrosive metal is not directly applicable
High polymer implements fire-retardant, because to consider the factors such as adhesion, coating composition between coating and polymeric matrix.
China Patent Publication No. discloses " a kind of Wood plastic boards for applying silicon flame retardant coating ", coating for CN102218883A
Silicon flame retardant coating have the advantages that small density, high mechanical strength, air-breathing gas permeability be low, heat-resisting and fire resistance, but it is thick
Degree is much greater compared to thickness in this patent.Additionally, not referring to flame retardant coating to the mechanical property of wood in the patent
Influence, the adhesion between coating and timber.
The content of the invention
The present invention is intended to provide a kind of response type polysiloxanes flame retardant coating and preparation method thereof, in system between coating composition
Can be reacted to each other when during standby with heat, the coating production is simple, with good anti-flammability and pliability.
The invention provides a kind of response type polysiloxanes flame retardant coating, it is characterised in that：Its space structure is：
And the structural formula of polysiloxanes fire retardant is：
Wherein, m>0, n>0, x >=0；M, n are positive integer, and x is nonnegative integer；
R1With R2Respectively H, CH3Or the one kind in OH；
R3It is CH2CH(CH2OH)-P(=O)-O-C12H8、CH2CH(OH)-CH2-P(=O)-O-C12H8、CH2-CH(OH)-CH2-P(=
O)-(C6H5)2、CH2-CH(CH2OH)-P(=O)-(C6H5)2、CH(OH)-CH2-P(=O)(OH)2、CH(OH)-CH2-P(=O)2Or
CH(OH)-CH2One kind in-P (=O) (OH) H；
R4It is (CH2)3-Si-(O-CH2CH3)3、(CH2)3-Si-(O-CH3)3、 ((CH3)2)Si-NCO、
((CH3)2)Si-NHC(=O)-(CH3)Si(-O-L)-R1Or ((CH3)2)Si-NHC(=O)-(CH3)Si(-O-L)-R2In
One kind；Wherein R1With R2Ibid, L represents the-Si-O-Si- main chains in molecule.
Described response type polysiloxanes flame retardant coating, is made up of the raw material of following weight portion：
Film forming agent 5-7 parts；
APP 3-5 parts；
2-6 parts of polysiloxanes fire retardant；
Silane coupler 10-30 parts；
Wetting agent 1-2 parts；
Ethanol 50-150 parts；
Obtained flame-retardant coating cohesive force is strong, is firmly combined with matrix；
Wherein described polysiloxanes fire retardant is prepared from the following raw materials in parts by weight：
Containing hydrogen silicone oil 5-10 parts；
Allyl glycidyl ether 30-50 parts；
Isocyanatosilanes 5-20 parts；
Phosphorous active matter 30-50 parts；
In course of reaction, the consumption of catalyst is：1.8004*10-1-4.501*10-1Part；The consumption of solvent is：160-280 parts；
The consumption of cleaning solvent is：80-150 parts.
Further, the film forming agent is polyvinyl formal acetal, polyvinyl alcohol, polyalkenylalcohols acetal, polyvinyl alcohol
One or more of butyral or polyvinyl formal；When from both, the mass ratio of the two is 1:1.
Further, described wetting agent is lauryl sodium sulfate, xylitol acid anhydride fatty acid ester, polyoxyethylene (20) mistake
One or two in water sorbitol monooleate, polyoxyethylene fatty acid esters or polyethylene glycol oxide alkyl phenyl ether；Choose
At two kinds, quality proportioning is 1:1.
Further, described silane coupler is γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-methyl-prop
Alkene acryloxypropylethoxysilane trimethoxy silane, APTES, isocyanatopropyl triethoxysilane, urea propyl group
Triethoxysilane, N- aminoethyls-γ-aminopropyltrimethoxysilane, diethylenetriamine base propyl trimethoxy silicane or two
One or two in the isocyanatosilanes of methyl two；When choosing two kinds, mol ratio is 1:1.
Further, during the catalyst is Speier catalyst, Karstdet catalyst, triphenylphosphine or triethanolamine
Two kinds；
The containing hydrogen silicone oil is polymethyl hydrogen siloxane, poly- (methyl hydrogen siloxane-dimethylsiloxane copolymer), 1,3,5,7-
One kind in tetramethyl-ring tetrasiloxane or hydrogen end-blocking dimethyl silicone polymer；
The isocyanatosilanes are 3- NCOs propyl trimethoxy silicane, isocyanatopropyl triethoxysilane or two
One kind in the isocyanatosilanes of methyl two；
The phosphorous active matter be the miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 9,10- dihydro-9-oxies, phosphoric acid, phosphorous acid, metaphosphoric acid,
One kind in pyrophosphoric acid, dialkyl phosphite or diphenyl phosphorus oxygen；
Described solvent is isopropanol, absolute ethyl alcohol, toluene, benzene, acetone, dichloromethane, chloroform, N, N- dimethyl formyls
One or two in amine；When using two kinds, the volume ratio of two kinds of solvents is 1:1；
Described cleaning solvent is one or two in acetone, absolute ethyl alcohol, deionized water, N,N-dimethylformamide；When
During using two kinds, the volume ratio of the two is 1:1.
Described response type polysiloxanes flame retardant coating, the matrix that it is applicable can be polypropylene, polyethylene, polyphenyl second
Alkene or polyester plastics, while it is also applied for the protection of paper, timber or metal material.
The invention provides the preparation method of above-mentioned response type polysiloxanes flame retardant coating, comprise the following steps：
（1）Ethanol is added in beaker, controls mixing speed for 800-1000r/min, be subsequently adding film forming agent, continued after adding
Stirring 20-40min；
（2）APP is added under same rotating speed, 10-30min is persistently stirred；
（3）In room temperature at a temperature of 70 DEG C, to adding silane coupler, constant temperature stirring 10-30min in above-mentioned solution；
（4）To step（3）Polysiloxanes fire retardant is added in the mixing liquid of gained, 20-40min is sufficiently stirred for；
（5）Again to step（4）Middle addition wetting agent, the situation that low whipping speed is 400-600r/min, temperature is 80-100 DEG C
Under, make ethanol evaporation, until stopping heating during viscous pasty state.
In the above method, the preparation method of the polysiloxanes fire retardant is comprised the following steps：
（1）Containing hydrogen silicone oil, catalyst and 50-70 a part solvent are added to equipped with reflux condensing tube, thermometer and magnetic agitation, lazy
Property atmosphere four-hole boiling flask in, after being warming up to 60-80 DEG C constant temperature stirring 10-30min；
（2）After being warming up to 90-110 DEG C, in 2-4h by the isocyanate group siloxanes in constant pressure funnel and 10-30 parts of solvent dropwise
It is added in four-hole boiling flask, isothermal reaction 6-12h；
（3）The allyl glycidyl ether in constant pressure funnel and 20-40 parts of solvent are added dropwise to four-hole boiling flask in 1-3h
In, isothermal reaction 4-10h；
（4）Solvent and unreacting substance are removed by vacuum distillation, flame retardant intermediate API is obtained；
（5）By step（4）Flame retardant intermediate API, phosphorous active matter, catalyst and the 80-140 parts of solvent for obtaining are added to four
In mouth flask, configuration reflux condensing tube, thermometer and magnetic agitation are passed through nitrogen, isothermal reaction 10- after being warming up to 90-110 DEG C
24h；
（6）Above-mentioned solution is obtained into product by vacuum distillation, is repeatedly washed with cleaning solvent, afterwards at 80-100 DEG C
12-24h is dried, nitrogenous, phosphorus, the polysiloxanes fire retardant of silicon is obtained.
Further, the catalyst is added in reaction system at twice, step（1）The middle catalyst that uses is
One kind in Speier catalyst and Karstdet catalyst, step（5）The middle catalyst for using is triphenylphosphine and three ethanol
One kind in amine；In course of reaction, the consumption of both front and back catalyst is respectively 4*10-5-10-4Part, 0.18-0.45 parts.
Coating in the present invention is selected by reasonable composition, preparation flow rationally design has obtained that adhesion is strong, anti-flammability
The excellent reactive coatings of energy.Reaction principle is：Film forming agent plays filming function simultaneously with silane coupler, and silane coupler is again
Can be interacted with synthesized polysiloxanes fire retardant, silane coupler can both be implemented with fire retardant to APP
Microencapsulation can be reacted under uniform temperature and ethanol effect again, obtain space cross-linked structure, and heat endurance is higher；
So that producing preferable adhesion between coating and matrix, adhesion test can reach 5B（5B is adhesion rank, according to
The parameter that ASTM D3359-09 are obtained using the test of 3M adhesive tape cohesive forces method of testing）, fire resistance is good.This coating is reaction
Type coating, reacting can be carried out in coating preparation process with thermal histories, and especially when being heated, reaction is carried out more completely,
So as to play good fire retardation；Meanwhile, silane coupler can be replaced by other and contain-Si-O-CH in flame retardant coating2CH3
Or-Si-OH materials, APP can also be changed to other excellent materials, so as to obtain the polyfunctional reactant with ideal performance
Type coating.
Beneficial effects of the present invention：
（1）Flame retardant coating in the present invention is reactive coatings, and can be replaced by other any for silane coupler in flame retardant coating
Containing-Si-O-CH2CH3The material of group and-Si-OH, and APP can also be changed to the material of other good properties, so that
Obtain the polyfunctional reactant type coating with desirable properties；
（2）The coating has good flame retardant effect, and microencapsulation structure causes coating with space cross-linked structure in coating
Good flame retardant effect still can be obtained in the case of addition very little；
（3）The coating has good cohesive force, can be firmly adhered to plastics such as polypropylene, polyethylene, polystyrene, poly-
The surface of the materials such as ester etc. and paper, metal, with good ageing-resistant property such as water resistance, ultra-violet resistance matter；
（4）The coating does not have any bad influence to the mechanical property of matrix, and flame retardant coating have pliability higher with
Adhesion, can deform upon when matrix deforms together with matrix, will not be come off because of fracture；
（5）The coating obtained during from the low polypropylene of surface energy as matrix material is still smooth, with certain
Aesthetic feeling；
（6）With ethanol as solvent in the coating preparation process, while flame retardant coating can be dissolved in ethanol, so as to realize matrix with
Fire retardant is separately recovered recycling, does not have any harm to environment；
（7）The coating preparation process is simple and easy to apply, is only needed to when being applied to matrix surface in oven for drying, it is not necessary to ultraviolet
Solidification, preparation method is simple, it is easy to accomplish industrialized production.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of the gained polysiloxanes fire retardant of embodiment 1.
Fig. 2 is the thermogravimetric spectrogram of the gained polysiloxanes fire retardant of embodiment 1.
Fig. 3 is the contact angle schematic diagram of the gained polysiloxanes fire retardant of embodiment 1.
Fig. 4 is the test of the gained polysiloxanes flame retardant coating of embodiment 1 and polyacrylic surface adhesion.
Fig. 5 is the gained PP/ polysiloxanes flame retardant coatings of embodiment 1, and under different coating layer thicknesses, its oxygen refers to various sample
Several change curves.
Fig. 6 is the gained PP/ polysiloxanes flame retardant coatings of embodiment 1, and various sample is under different coating layer thicknesses, and its is vertical
The fire-retardant rank figure of burning.
Fig. 7 is the gained PP/ polysiloxanes flame retardant coatings of embodiment 1, under identical coating layer thickness, the change of its tensile strength
Curve.
Specific embodiment
The present invention is further illustrated below by embodiment, but embodiments described below is only one of the invention
Divide embodiment, the invention is not limited in following examples.Based on the embodiment in the present invention, the researcher in this area exists
The embodiment that creative experiments are obtained is not carried out, all should be within the scope of protection of the invention.
Embodiment 1
By 5 parts of poly- (methyl hydrogen siloxane-dimethylsiloxane copolymer), 6*10-5Part Karstdet catalyst and 50 parts of isopropyls
Alcohol is added to equipped with reflux condensing tube, thermometer and magnetic agitation, the four-hole boiling flask of inert atmosphere, constant temperature after being warming up to 70 DEG C
Stirring 15min；After being warming up to 100 DEG C, by 15 parts of isocyanatopropyl triethoxysilanes in constant pressure funnel and 15 parts in 3h
Isopropanol is added dropwise in four-hole boiling flask, continues isothermal reaction 6h；By 35 parts of allyl glycidyls in constant pressure funnel in 2h
Glycerin ether and 20 parts of isopropanols are added dropwise in four-hole boiling flask, continue isothermal reaction 6h；By vacuum distillation remove solvent with
And unreacting substance, obtain flame retardant intermediate API；All flame retardant intermediate API that previous step is obtained, 40 part two
Phenyl phosphorus oxygen, 0.29 part of triphenylphosphine and 100 parts of isopropanols are added to four-hole boiling flask, configuration reflux condensing tube, thermometer and magnetic
Power is stirred, and is passed through nitrogen, isothermal reaction 12h after being warming up to 100 DEG C；Above-mentioned solution is obtained into product by vacuum distillation, with 80
(volume ratio is 1 to part acetone with absolute ethyl alcohol:1) washed, dried 24h at 80 DEG C afterwards, obtained polysiloxanes fire retardant.
50 parts of ethanol is added in beaker, 7 parts of film forming agent, respectively polyethylene are added under the stirring condition of 900r/min
Alcohol contracting the first and second aldehyde and polyvinyl formal（The two mass ratio 1：1）, continue to stir 30min after adding；Under same rotating speed
5 parts of APPs are added, 25min is persistently stirred；At 50 DEG C, to 20 parts of silane couplers of addition in above-mentioned solution：N- ammonia second
Base-γ-aminopropyltrimethoxysilane and APTES（The two mol ratio 1：1）, constant temperature stirring
20min；To 6 parts of above-mentioned polysiloxanes fire retardants are added in the mixing liquid of gained, 30min is sufficiently stirred for；400r/min's
To 1 part of wetting agent is added in above solution under stirring condition, in the case where temperature is 80 DEG C, make ethanol evaporation, until sticky
Stop heating during state.
First polypropylene batten is impregnated into thick liquid, after through czochralski method, finally dry, just can prepare the poly- silicon of coating
The polypropylene of oxygen alkane coating/polysiloxane coating composite, the coating layer thickness being related in the present invention is 40 μm -200 μm.It is logical
The thickness of lifting number of times control coating is crossed so as to obtain the polypropylene/polysiloxane coating composite of different-thickness.The method
It also is adapted in the frosting prepares coating such as metal and polyethylene, polystyrene, polyester.
Every part represents 1g in the embodiment of the present invention.
In above-mentioned experimentation, the infrared spectrum of polysiloxanes fire retardant is as shown in Figure 1.It is apparent that phosphorous active matter
2384cm is located in matter-1- PH stretching vibration peak, be wholly absent in APID；Positioned at 909cm-1The peak of the epoxy radicals at place by
- PH in phosphorous active material substantially disappears with epoxy reaction, such as 1288cm of the characteristic peak in phosphorous active material-1
- P=O, the 1118cm at place-1The P-O-Ph peaks at place can find in APID, in 3430 cm-1Occur in that the feature of carbon hydroxyl
Peak, this phosphorous active material of explanation is already engaged in reaction, and grafting is on the side chain of APID.In addition 1639,1540,
3430cm-1New peak is occurred in that, is respectively the peak of-C=O ,-NH ,-NHCO, and be located at 2168cm-1With 906cm-1- SiH the peaks at place are complete
Mistake is totally disappeared, this explanation-SiH can obtain carbon-silane amides under Speier catalyst actions with isocyanatosilanes reaction, and
It is identical with target product structure and-SiH can react completely under the present conditions.And in 3430 cm-1Place occurs in that intensity very
Big peak, this is caused by the carbon hydroxyl that-NHCO and-PH due to containing in APID are generated with epoxide group reaction overlaps.More than
Evidence illustrates that preferable fire retardant APID has been successfully prepared.
Prepared polysiloxanes fire retardant and the thermogravimetric curve of the active phosphorus containg substances of raw material are as shown in Fig. 2 polysiloxanes
The temperature of initial decomposition of fire retardant is 237 DEG C, can meet the processing temperature of macromolecular material, and when temperature reaches 800 DEG C
When, the residual of the polysiloxanes fire retardant of synthesis has weighed 45.30%, illustrates that the carbon forming agent has preferable heat endurance and into charcoal
Property.
The contact angle schematic diagram of prepared polysiloxanes fire retardant is as shown in figure 3, the polysiloxanes fire retardant of synthesis
Contact angle has reached 118 °, in hydrophobicity, can be obviously improved the compatibility with polymer matrix.
Cohesive force test, normative reference ASTM D3359-09 are carried out to the present embodiment gained PP/ polysiloxanes flame retardant coating
Using 3M adhesive tape cohesive force methods of testing, the adhesion between coating and matrix is tested, as a result as shown in Figure 4.(a) is in Fig. 4
Photo before flame retardant coating test, and (b) is the photo after test.As can be seen from the figure the edge of otch all ten light splitting
Sliding, neither one lattice comes off, therefore the adhesiveness of the flame retardant coating can reach 5B ranks.Flame retardant coating can be firmly attached
In polypropylene surface, the flame-retardant nature of PP composite material can be significantly improved.
During above-mentioned prepares coating, under identical preparation condition, change the adding proportion of polysiloxanes fire retardant,
Sample 1-4 is obtained.Polysiloxanes flame retardant agent content is 4% wherein in sample 1, and polysiloxanes flame retardant agent content is in sample 2
6%, polysiloxanes flame retardant agent content is 8% in sample 3, and polysiloxanes flame retardant agent content is 10% in sample 4.Enter for sample 1-4
Different performance tests are gone, as shown in Fig. 5 ~ 7.
Fig. 5 be gained PP/ polysiloxanes flame retardant coatings, four kinds of samples of the above under different coating layer thicknesses, its oxygen index (OI)
Change curve.It can be seen that when coating composition is identical, oxygen index (OI) increases with the increase of thickness；Work as coating
When thickness is identical, oxygen index (OI) increases as polysiloxanes fire retardant ratio increases.When polysiloxanes flame retardant agent content 10%,
Oxygen index (OI) has reached 31.3%, and the polysiloxane coating being indicated above in the present invention has good anti-flammability.
Fig. 6 be gained PP/ polysiloxanes flame retardant coatings, four kinds of samples of the above under different coating layer thicknesses, its vertical combustion
Burn the change curve of data.
Fig. 7 is gained PP/ polysiloxanes flame retardant coatings, under identical coating layer thickness, its Tensile strength data figure.From figure
In as can be seen that four tensile strength of sample are approached with the tensile strength of virgin pp, in 34.5MPa or so, this shows
Flame retardant coating does not have any influence for the mechanical property of matrix.
Embodiment 2
By 10 parts of 1,3,5,7- tetramethyl-ring tetrasiloxanes, 4*10-5Part Speier catalyst and 60 parts of toluene solvants are added to and match somebody with somebody
Have in the four-hole boiling flask of reflux condensing tube, thermometer and magnetic agitation, inert atmosphere, constant temperature stirs 10min after being warming up to 70 DEG C；
After being warming up to 95 DEG C, 10 parts of isocyanatopropyl triethoxysilanes in constant pressure funnel and 15 parts of toluene are added dropwise in 3h
To in four-hole boiling flask, continue isothermal reaction 8h；By the 30 parts of allyl glycidyl ethers and 35 parts of first in constant pressure funnel in 2h
Benzene is added dropwise in four-hole boiling flask, continues isothermal reaction 7h；Solvent and unreacting substance are removed by vacuum distillation, is obtained
Flame retardant intermediate API；All of flame retardant intermediate API that previous step is obtained, 35 parts of 9,10- dihydro-9-oxies be miscellaneous-
10- phospho hetero phenanthrene -10- oxides, 1.8*10-1Part triethanolamine catalyst and 110 parts of toluene solvants are added to four-hole boiling flask, configure
Reflux condensing tube, thermometer and magnetic agitation, are passed through nitrogen, isothermal reaction 15h after being warming up to 105 DEG C；Above-mentioned solution is passed through
Vacuum distillation obtains product, with 120 parts of acetone and absolute ethyl alcohol（Volume ratio is 1:1）Washed, dried at 90 DEG C afterwards
24h, obtains polysiloxanes fire retardant.
100 parts of ethanol is added in beaker, 5 parts of polyvinyl formal is added under the stirring condition of 800r/min, plus
Continue to stir 40min after complete；3 parts of APPs are added under same rotating speed, 10min is persistently stirred；At 40 DEG C, to above-mentioned
25 parts of silane couplers are added in solution：APTES and urea propyl-triethoxysilicane（The two mole
Than being 1：1）, constant temperature stirring 10min；To 5 parts of polysiloxanes fire retardants are added in the mixing liquid of gained, 25min is sufficiently stirred for；
Under the stirring condition of 600r/min to above solution in add 2 parts of wetting agents, temperature be 90 DEG C in the case of, steam ethanol
Hair, until stopping heating during viscous pasty state.
First polyester batten is impregnated into thick liquid, after through czochralski method, finally dry, just can prepare the poly- silica of coating
The polyester of alkane coating/polysiloxane coating composite, the thickness of coating is controlled so as to obtain different-thickness by lifting number of times
（30μm-400μm）Polyester/polysiloxane coating composite.
Embodiment 3
By 6 parts of polymethyl hydrogen siloxanes, 7*10-5Part Speier catalyst and 70 parts of toluene solvants are added to equipped with reflux condensation mode
In pipe, thermometer and magnetic agitation, the four-hole boiling flask of inert atmosphere, constant temperature stirring 10min after being warming up to 70 DEG C；It is warming up to 100
After DEG C, 10 parts of 3- NCOs propyl trimethoxy silicanes in constant pressure funnel and 15 parts of toluene are added dropwise in 4h
In four-hole boiling flask, continue isothermal reaction 7h；By the 50 parts of allyl glycidyl ethers and 20 parts of toluene in constant pressure funnel in 3h
It is added dropwise in four-hole boiling flask, continues isothermal reaction 5h；Solvent and unreacting substance are removed by vacuum distillation, is hindered
Combustion agent intermediate A PI；All flame retardant intermediate API, 30 parts of phosphoric acid, the 4.0*10 that previous step is obtained-1Part triphenylphosphine
Catalyst and 105 parts of acetone are added to four-hole boiling flask, prepare reflux condensing tube, thermometer and magnetic agitation, are passed through nitrogen, heat up
Isothermal reaction 12h after to 105 DEG C；Above-mentioned solution is obtained into product by vacuum distillation, is washed with 90 parts of acetone, Zhi Hou
12h is dried at 80 DEG C, polysiloxanes fire retardant is obtained.
80 parts of ethanol is added in beaker, 6 parts of polyvinyl formal acetal is added under the stirring condition of 900r/min, plus
Continue to stir 30min after complete；5 parts of APPs are added under same rotating speed, 20min is persistently stirred；In the above conditions, to
30 parts of silane couplers are added in above-mentioned solution：γ-glycidyl ether oxygen propyl trimethoxy silicane and urea propyl triethoxy
Silane（The two mol ratio 1：1）, constant temperature stirring 30min；To 2 parts of polysiloxanes fire retardants are added in the mixing liquid of gained, fill
Divide stirring 40min；Under the stirring condition of 550r/min to above solution in add 1 part of wetting agent, in the feelings that temperature is 100 DEG C
Under condition, make ethanol evaporation, until stopping heating during viscous pasty state.
First by metal impregnation to thick liquid, after through czochralski method, then dry, just can be 5 μm -80 μm with prepares coating thickness
Metal/polysiloxane coating composite.Can also by thick liquid, equably Tu, in metal surface, then passes through using brush
Drying, obtains metal/polysiloxane coating composite.
Embodiment 4
By 5 parts of polymethyl hydrogen siloxanes, 6*10-5Part Speier catalyst and 50 parts of benzene solvents be added to equipped with reflux condensing tube,
In thermometer and magnetic agitation, the four-hole boiling flask of inert atmosphere, constant temperature stirring 10min after being warming up to 70 DEG C；After being warming up to 90 DEG C,
The 20 parts of isocyanatopropyl triethoxysilanes and 30 parts of benzene solvents in constant pressure funnel are added dropwise to four-hole boiling flask in 3h
In, continue isothermal reaction 12h；35 parts of allyl glycidyl ethers in constant pressure funnel and 40 parts of benzene solvents are dropwise added in 2h
Enter in four-hole boiling flask, continue isothermal reaction 9h；Solvent and unreacting substance are removed by vacuum distillation, in obtaining fire retardant
Mesosome API；All flame retardant intermediate API, 30 parts of phosphorous acid, the 3.0*10 that previous step is obtained-1Triethanolamine catalyst
Four-hole boiling flask is added to 120 parts of benzene solvents, reflux condensing tube, thermometer and magnetic agitation is prepared, nitrogen is passed through, 90 are warming up to
Isothermal reaction 18h after DEG C；Above-mentioned solution is obtained into product by vacuum distillation, with 100 parts of acetone and absolute ethyl alcohol（Volume ratio is
1:1）Washed, dried 12h at 80 DEG C afterwards, obtained polysiloxanes fire retardant.
100 parts of ethanol is added in beaker, 5 parts of film forming agents are added under the stirring condition of 1000r/min：Polyvinyl alcohol contracts
First and second aldehyde and polyvinyl butyral resin（The two mass ratio 1：1）, continue to stir 30min after adding；3 are added under same rotating speed
Part APP, persistently stirs 10min；At 60 DEG C, to 30 parts of silane coupler 3- aminopropyls three of addition in above-mentioned solution
Ethoxysilane, constant temperature stirring 20min；To 6 parts of polysiloxanes fire retardants are added in the mixing liquid of gained, divide stirring 30min；
Under the stirring condition of 400r/min to above solution in add 2 parts of wetting agents, temperature be 100 DEG C in the case of, make ethanol
Evaporation, until stopping heating during viscous pasty state.
Thick liquid is uniformly brushed above timber along the longitudinal direction of timber with brush after thick liquid is stirred,
Coating layer thickness is reached 100 μm of -0.3mm, obtain timber/polysiloxane coating composite.
Embodiment 5
By 4 parts of poly- (methyl hydrogen siloxane-dimethylsiloxane copolymer), 8*10-5Part Speier catalyst and 70 parts of toluene are molten
Agent is added to equipped with reflux condensing tube, thermometer and magnetic agitation, the four-hole boiling flask of inert atmosphere, constant temperature after being warming up to 75 DEG C
Stirring 15min；After being warming up to 110 DEG C, by the 5 parts of isocyanatosilanes of dimethyl two and 10 parts of toluene in constant pressure funnel in 3h
It is added dropwise in four-hole boiling flask, continues isothermal reaction 8h；By 40 parts of allyl glycidyl ethers in constant pressure funnel in 2h
It is added dropwise in four-hole boiling flask with 20 parts of toluene, continues isothermal reaction 8h；Solvent and unreacted are removed by vacuum distillation
Material, obtains flame retardant intermediate API；All flame retardant intermediate API that previous step is obtained, 30 parts of diphenyl phosphorus oxygens,
4.4*10-1Part triphenylphosphine catalysis are added to four-hole boiling flask with 100 parts of toluene solvants, prepare reflux condensing tube, thermometer and
Magnetic agitation, is passed through nitrogen, isothermal reaction 12h after being warming up to 100 DEG C；Above-mentioned solution is obtained into product by vacuum distillation, is used
80 parts of absolute ethyl alcohols are washed, and dry 15h at 80 DEG C afterwards, obtain polysiloxanes fire retardant.
150 parts of ethanol is added in beaker, 6 parts of film forming agents are added under the stirring condition of 950r/min：Polyvinyl alcohol contracts
Formaldehyde and polyvinyl butyral resin（The two mass ratio 1：1）, continue to stir 20min after adding；4 parts are added under same rotating speed
APP, persistently stirs 30min；At 70 DEG C, to 10 parts of silane couplers of addition in above-mentioned solution：The second of 3- aminopropyls three
TMOS and isocyanatopropyl triethoxysilane（The two mol ratio 1：1）, constant temperature stirring 30min；To the mixed liquor of gained
5 parts of polysiloxanes fire retardants are added in body, 20min is sufficiently stirred for；Under the stirring condition of 600r/min to above solution in plus
Enter 1 part of wetting agent, in the case where temperature is 80 DEG C, make ethanol evaporation, until stopping heating during viscous pasty state.
During paper impregnated in into thick liquid, unnecessary thick liquid is removed by extruding afterwards, then by drying, from
And paper/polysiloxanes fire retardant coating is obtained, coating layer thickness is 1 μm -15 μm.Coating layer thickness can be by adjusting squeezing parameter
To regulate and control.
Claims (10)
1. a kind of response type polysiloxanes flame retardant coating, it is characterised in that：Its space structure is：
And the structural formula of polysiloxanes fire retardant is：
Wherein, m>0, n>0, x >=0；M, n are positive integer, and x is nonnegative integer；
R1With R2Respectively H, CH3Or the one kind in OH；
R3It is CH2CH(CH2OH)-P(=O)-O-C12H8、CH2CH(OH)-CH2-P(=O)-O-C12H8、CH2-CH(OH)-CH2-P(=
O)-(C6H5)2、CH2-CH(CH2OH)-P(=O)-(C6H5)2、CH(OH)-CH2-P(=O)(OH)2、CH(OH)-CH2-P(=O)2Or
CH(OH)-CH2One kind in-P (=O) (OH) H；
R4It is (CH2)3-Si-(O-CH2CH3)3、(CH2)3-Si-(O-CH3)3、 ((CH3)2)Si-NCO、
((CH3)2)Si-NHC(=O)-(CH3)Si(-O-L)-R1Or ((CH3)2)Si-NHC(=O)-(CH3)Si(-O-L)-R2In
It is a kind of；Wherein R1With R2Ibid, L represents the-Si-O-Si- main chains in molecule.
2. a kind of response type polysiloxanes flame retardant coating according to claim 1, it is characterised in that by following weight portion
Raw material is made：
Film forming agent 5-7 parts；
APP 3-5 parts；
2-6 parts of polysiloxanes fire retardant；
Silane coupler 10-30 parts；
Wetting agent 1-2 parts；
Ethanol 50-150 parts；
Obtained flame-retardant coating cohesive force is strong, is firmly combined with matrix；
Wherein described polysiloxanes fire retardant is prepared from the following raw materials in parts by weight：
Containing hydrogen silicone oil 5-10 parts；
Allyl glycidyl ether 30-50 parts；
Isocyanatosilanes 5-20 parts；
Phosphorous active matter 30-50 parts；
In course of reaction, the consumption of catalyst is：1.8004*10-1-4.501*10-1Part；The consumption of solvent is：160-280 parts；
The consumption of cleaning solvent is：80-150 parts.
3. response type polysiloxanes flame retardant coating according to claim 1, it is characterised in that the film forming agent is polyethylene
Alcohol contract the first and second aldehyde, polyvinyl alcohol, polyalkenylalcohols acetal, polyvinyl butyral resin or polyvinyl formal one or two；
When from both, the mass ratio of the two is 1:1.
4. response type polysiloxanes flame retardant coating according to claim 1, it is characterised in that described wetting agent is 12
Sodium alkyl sulfate, xylitol acid anhydride fatty acid ester, polyoxyethylene (20) sorbitan monooleate, polyoxyethylene fatty acid esters
Or one or two in polyethylene glycol oxide alkyl phenyl ether；When choosing two kinds, quality proportioning is 1:1.
5. response type polysiloxanes flame retardant coating according to claim 1, it is characterised in that described silane coupler is
γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, 3- aminopropyls
Triethoxysilane, isocyanatopropyl triethoxysilane, urea propyl-triethoxysilicane, N- aminoethyls-γ-aminopropyl front three
One or two in TMOS, diethylenetriamine base propyl trimethoxy silicane or the isocyanatosilanes of dimethyl two；Choosing
When taking two kinds, mol ratio is 1:1.
6. response type polysiloxanes flame retardant coating according to claim 1, it is characterised in that the catalyst is Speier
Two kinds in catalyst, Karstdet catalyst, triphenylphosphine or triethanolamine；
The containing hydrogen silicone oil is polymethyl hydrogen siloxane, poly- (methyl hydrogen siloxane-dimethylsiloxane copolymer), 1,3,5,7-
One kind in tetramethyl-ring tetrasiloxane or hydrogen end-blocking dimethyl silicone polymer；
The isocyanatosilanes are 3- NCOs propyl trimethoxy silicane, isocyanatopropyl triethoxysilane or two
One kind in the isocyanatosilanes of methyl two；
The phosphorous active matter be the miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 9,10- dihydro-9-oxies, phosphoric acid, phosphorous acid, metaphosphoric acid,
One kind in pyrophosphoric acid, dialkyl phosphite or diphenyl phosphorus oxygen；
Described solvent is isopropanol, absolute ethyl alcohol, toluene, benzene, acetone, dichloromethane, chloroform, N, N- dimethyl formyls
One or two in amine；When using two kinds, the volume ratio of two kinds of solvents is 1:1；
Described cleaning solvent is one or two in acetone, absolute ethyl alcohol, deionized water, N,N-dimethylformamide；When
During using two kinds, the volume ratio of the two is 1:1.
7. response type polysiloxanes flame retardant coating according to claim 1, it is characterised in that described matrix be polypropylene,
One kind in one kind in polyethylene, polystyrene, polyester plastics, or paper, timber, metal material.
8. the preparation method of the response type polysiloxanes flame retardant coating described in a kind of any one of claim 1 ~ 7, it is characterised in that
Comprise the following steps：
（1）Ethanol is added in beaker, controls mixing speed for 800-1000r/min, be subsequently adding film forming agent, continued after adding
Stirring 20-40min；
（2）APP is added under same rotating speed, 10-30min is persistently stirred；
（3）In room temperature at a temperature of 70 DEG C, to adding silane coupler, constant temperature stirring 10-30min in above-mentioned solution；
（4）To step（3）Polysiloxanes fire retardant is added in the mixing liquid of gained, 20-40min is sufficiently stirred for；
（5）Again to step（4）Middle addition wetting agent, the situation that low whipping speed is 400-600r/min, temperature is 80-100 DEG C
Under, make ethanol evaporation, until stopping heating during viscous pasty state.
9. the preparation method of response type polysiloxanes flame retardant coating according to claim 8, it is characterised in that the poly- silicon
The preparation method of oxygen alkane fire retardant is comprised the following steps：
（1）Containing hydrogen silicone oil, catalyst and 50-70 a part solvent are added to equipped with reflux condensing tube, thermometer and magnetic agitation, lazy
Property atmosphere four-hole boiling flask in, after being warming up to 60-80 DEG C constant temperature stirring 10-30min；
（2）After being warming up to 90-110 DEG C, in 2-4h by the isocyanate group siloxanes in constant pressure funnel and 10-30 parts of solvent dropwise
It is added in four-hole boiling flask, isothermal reaction 6-12h；
（3）The allyl glycidyl ether in constant pressure funnel and 20-40 parts of solvent are added dropwise to four-hole boiling flask in 1-3h
In, isothermal reaction 4-10h；
（4）Solvent and unreacting substance are removed by vacuum distillation, flame retardant intermediate API is obtained；
（5）By step（4）Flame retardant intermediate API, phosphorous active matter, catalyst and the 80-140 parts of solvent for obtaining are added to four
In mouth flask, configuration reflux condensing tube, thermometer and magnetic agitation are passed through nitrogen, isothermal reaction 10- after being warming up to 90-110 DEG C
24h；
（6）Above-mentioned solution is obtained into product by vacuum distillation, is repeatedly washed with cleaning solvent, afterwards at 80-100 DEG C
12-24h is dried, nitrogenous, phosphorus, the polysiloxanes fire retardant of silicon is obtained.
10. the preparation method of response type polysiloxanes flame retardant coating according to claim 9, it is characterised in that：It is described to urge
Agent is added in reaction system at twice, step（1）The middle catalyst for using is that Speier catalyst is catalyzed with Karstdet
One kind in agent, step（5）The middle catalyst that uses be triphenylphosphine with triethanolamine in one kind；It is front and rear in course of reaction
The consumption of two kinds of catalyst is respectively 4*10-5-10-4Part, 0.18-0.45 parts.
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| CN109233290B (en) * | 2018-09-17 | 2021-05-28 | 苏州沃尔兴电子科技有限公司 | Preparation method of phosphorus-containing intrinsic flame-retardant silicone rubber |
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| CN110042652A (en) * | 2019-04-14 | 2019-07-23 | 太原理工大学 | A kind of expandable flame retardant coating solution and its application |
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| CN110359168A (en) * | 2019-08-14 | 2019-10-22 | 苏州百进纺织有限公司 | A kind of scribbled and fabric of flame-retardant viscose fiber and acrylic fibers fire resistance fibre |
| CN110606990A (en) * | 2019-09-11 | 2019-12-24 | 东华大学 | Hyperbranched polysiloxane-coated ammonium polyphosphate flame retardant and preparation method thereof |
| CN115125758A (en) * | 2021-03-26 | 2022-09-30 | 齐鲁工业大学 | Modified gelatin for paper fireproof flame-retardant coating and preparation method and application thereof |
| CN115125759A (en) * | 2021-03-26 | 2022-09-30 | 齐鲁工业大学 | Modified gelatin for paper fire-resistant flame-retardant coating and preparation method and application thereof |
| CN115125759B (en) * | 2021-03-26 | 2023-06-23 | 齐鲁工业大学 | Modified gelatin for paper fireproof flame-retardant coating and preparation method and application thereof |
| CN115785757A (en) * | 2022-10-28 | 2023-03-14 | 贵州电网有限责任公司 | Insulating coating with low interface adhesion and preparation method thereof |
| CN115781843A (en) * | 2022-11-24 | 2023-03-14 | 贵州洪乘宇科技有限责任公司 | Water-based flame-retardant treating agent and preparation method thereof |
| CN115781843B (en) * | 2022-11-24 | 2023-11-10 | 贵州洪乘宇科技有限责任公司 | Water-based flame retardant treating agent and preparation method thereof |
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