CN106700920B - A kind of response type polysiloxanes flame retardant coating and preparation method thereof - Google Patents
A kind of response type polysiloxanes flame retardant coating and preparation method thereof Download PDFInfo
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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
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- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
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- C08G77/04—Polysiloxanes
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- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
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Abstract
The invention discloses a kind of response type polysiloxanes flame retardant coatings and preparation method thereof, belong to flame retardant coating technical field.The coating composition is made of silane coupling agent, ammonium polyphosphate, film forming agent, polysiloxanes fire retardant, wetting agent and ethyl alcohol.Film forming agent and silane coupling agent of the invention plays filming function simultaneously, silane coupling agent can interact again with synthesized polysiloxanes fire retardant, silane coupling agent not only can implement microencapsulation to ammonium polyphosphate with fire retardant but also can react, obtain the response type polysiloxanes flame retardant coating of space cross-linked structure, the coating is using ethyl alcohol as solvent, and raw material is environmentally friendly reagent in whole system, non-hazardous with operator to environment；The coating is reactive coatings, and flame retarding efficiency is high, polyacrylic limit oxygen index LOI can be made to reach 31.3% and test by UL-94 V0, and do not influence the mechanical property of matrix completely, can not fallen off as matrix deforms together.
Description
Technical field
The present invention relates to a kind of response type polysiloxanes flame retardant coatings and preparation method thereof, belong to flame retardant coating technology neck
Domain.
Background technique
In the modern life, the fire due to caused by the control of fire is improper happens occasionally, and 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 conditions, in flame retardant treatment mode, there is fire retardant to be blended with matrix, prepare intrinsic fire-retardant high polymer, apply
With high polymeric fire-retardant coating etc..Intrinsic high polymer is difficult to prepare, and type is smaller, and application is limited.Addition type needs very big addition
Amount just has flame retardant effect, and this will bring following problem: firstly, fire retardant migrates to surface layer and makes ingredient after a period of time
Unevenly；Second, the combination of addition type and matrix is more fragile, this understands the mechanical property for generating tender spots in the base and reducing matrix
Energy.
Reaching fire-retardant purpose by the way of flame retardant coating is a kind of preferable method and current research hot topic.With
Other two ways are compared, since flame retardant coating is attached to internal structure of the surface of polymeric matrix without destroying matrix,
Therefore adverse effect will not be generated to mechanical property of matrix etc., maintains original performance of basis material.In addition to this, fire-retardant
Coating can be dissolved among certain solvents, achieve the purpose that recycle matrix.But rarely have at present by flame retardant coating application
To the report of macromolecule engineering frosting.Main cause has following two: being firstly because the surface of macromolecule engineering plastics
Polarity is lower, hydrophobicity is higher, leads to the reduction of the binding force of coating and matrix, is easy to fall off, good flame retardant effect is not achieved,
And weatherability, poor durability；The flexibility of followed by coating is inadequate, is difficult to be adapted with certain macromolecule engineering plastics, such as apply
Layer is easy to be broken and fall off in the state that polypropylene is bent.Therefore, to solve macromolecule engineering plastics with the mode of coating
Inflammable problem, need in view of coating anti-flammability, the binding force of coating and matrix, impose coating/matrix after coating
Flexibility.
China Patent Publication No. is that CN104862970A discloses a kind of " high fire-retardance nonhazardous fabric coating material and preparation
The step of method ", this method is to prepare sodium chloride complex first, prepares cement composite powder later, then prepares compound
Water-base resin finally prepares coating.This method production cost is low, and suitable application area is wide, but its preparation step is cumbersome and anti-flammability
It can be limited, it is not specified that influence of the coating to matrix properties.
China Patent Publication No. is that CN105419607A discloses " a kind of the light for architecture curing composite coating and its preparation side
The step of method ", this method includes the following steps: (1) by o-cresol formaldehyde epoxy acrylate, water soluble anion polyurethane, first
Base acrylic acid -2- hydroxyl ethyl ester, two propiophenones, polydimethylsiloxane uniformly mix, and deionized water stirring is added, lotion is made；(2)
PH adjusting agent butylethanolamine is added in lotion, cresyl diphenyl phosphate is dispersed with stirring 30min, Zhi Houfang at 30 DEG C
Entering half an hour in 50 DEG C of baking ovens obtains composite coating；(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 also needs to be modified if you need to be applied on the substrates such as building, timber
Processing, paint solidification needs are 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. " are disclosed using expansion type flame-retardant coatings to polypropylene
Flame-proof treatment is carried out with polycarbonate.After top finish, the anti-flammability of two kinds of high polymers has and significantly improves,
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. is that CN101925660A discloses " organosilane coating compositions and its application ", the combination
The preparation step of object include: (1) in the presence of a catalyst, organosilan is hydrolyzed；(2) chela is carried out to Organometallic precursor
It closes；(3) silane through hydrolyzing is mixed with the Organometallic precursor through chelating；(4) organosilan-is organic
Metal precursor mixture hydrolysis.The patent describes the preparation method and its application of composition in detail, and coating design rationally, is imitated
Fruit is significant.But if it applied to flame retardant area, weaker with the binding force of polymeric matrix, easily disengaging is peeled off, and cannot be played good
Good protective effect.
China Patent Publication No. is that CN103059727A discloses a kind of " metal surface silicon containing hexamethylphosphoramide
Alkane inorganic agent and preparation method thereof " can be improved the corrosion resistance of metal after the inorganic agent processing metal of the invention.Specially with this
There are many more the similar patents of benefit, is much by silane coupling agent or to contain-Si-O-CH2CH3, silicone hydroxyl substance introduce apply
Layer is connected through other compositions and metal surface to implement protection to metal to reach corrosion resistant purpose.And by silane
Coupling agent be introduced into coating applied to high polymer flame-proof treatment in it is rare, this may be 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 implementation is fire-retardant, because to consider the factors such as binding force, the coating composition between coating and polymeric matrix.
China Patent Publication No. is that CN102218883A discloses " a kind of Wood plastic boards for applying silicon flame retardant coating ", coating
Silicon flame retardant coating have many advantages, such as that small density, high mechanical strength, air-breathing gas permeability be low, heat-resisting and flame retardant property, but it is thick
Degree is much greater compared to the thickness in this patent.In addition, not referring to flame retardant coating to the mechanical property of wood in the patent
Influence, the adhesion strength between coating and timber.
Summary of the invention
The present invention is intended to provide a kind of response type polysiloxanes flame retardant coating and preparation method thereof, is making between coating composition
It can react to each other during standby with when heat, the coating production is simple, has good anti-flammability and flexibility.
The present invention provides a kind of response type polysiloxanes flame retardant coatings, it is characterised in that: its space structure are as follows:
And the structural formula of polysiloxanes fire retardant are as follows:
Wherein, m > 0, n > 0, x >=0；M, n is positive integer, and x is nonnegative integer；
R1With R2Respectively H, CH3Or one of OH；
R3For 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 of-P (=O) (OH) H；
R4For (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)-R2
One of；Wherein R1With R2Ibid, L represents the-Si-O-Si- main chain in molecule.
The response type polysiloxanes flame retardant coating, is made of raw material from the following weight:
5-7 parts of film forming agent；
3-5 parts of ammonium polyphosphate；
2-6 parts of polysiloxanes fire retardant；
10-30 parts of silane coupling agent；
1-2 parts of wetting agent；
50-150 parts of ethyl alcohol；
Obtained flame-retardant coating cohesive force is strong, is firmly combined with matrix；
Wherein the polysiloxanes fire retardant is prepared from the following raw materials in parts by weight:
5-10 parts of containing hydrogen silicone oil；
30-50 parts of allyl glycidyl ether；
5-20 parts of isocyanatosilanes；
Phosphorous active matter 30-50 parts；
In reaction process, the dosage of catalyst are as follows: 1.8004*10-1-4.501*10-1Part；The dosage of solvent are as follows: 160-
280 parts；The dosage of cleaning solvent are as follows: 80-150 parts.
Further, the film forming agent is polyvinyl formal acetal, polyvinyl alcohol, polyalkenylalcohols acetal, polyvinyl alcohol
Butyral or polyvinyl formal it is one or more；When selecting the two, the mass ratio of the two is 1:1.
Further, the wetting agent is lauryl sodium sulfate, xylitol acid anhydride aliphatic ester, polyoxyethylene (20) mistake
One or both of water sorbitol monooleate, polyoxyethylene fatty acid esters or polyethylene glycol oxide alkyl phenyl ether；It chooses
At two kinds, quality proportioning 1:1.
Further, the silane coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-methyl-prop
Alkene acryloxypropylethoxysilane trimethoxy silane, 3-aminopropyltriethoxysilane, isocyanatopropyl triethoxysilane, urea propyl
Triethoxysilane, N- aminoethyl-γ-aminopropyltrimethoxysilane, diethylenetriamine base propyl trimethoxy silicane or two
One or both of methyl diisocyanate base silane；When choosing two kinds, mol ratio 1:1.
Further, the catalyst is in 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,
One of 5,7- tetramethyl-ring tetrasiloxane or hydrogen sealing end dimethyl silicone polymer；
The isocyanatosilanes are 3- isocyanate group propyl trimethoxy silicane, isocyanatopropyl triethoxysilane
Or one of dimethyl diisocyanate base silane；
The phosphorous active matter is the miscellaneous -10- phospho hetero phenanthrene -10- oxide of 9,10- dihydro-9-oxy, phosphoric acid, phosphorous acid, inclined phosphorus
One of acid, pyrophosphoric acid, dialkyl phosphite or diphenyl phosphorus oxygen；
The solvent is isopropanol, dehydrated alcohol, toluene, benzene, acetone, methylene chloride, chloroform, N, N- dimethyl
One or both of formamide；When using two kinds, the volume ratio of two kinds of solvents is 1:1；
The cleaning solvent is one of acetone, dehydrated alcohol, deionized water, N,N-dimethylformamide or two
Kind；When using two kinds, the volume ratio of the two is 1:1.
The response type polysiloxanes flame retardant coating, the matrix being applicable in can be polypropylene, polyethylene, polyphenyl second
Alkene or polyester plastics, while its protection for being also applied for paper, timber or metal material.
The present invention provides the preparation methods of above-mentioned response type polysiloxanes flame retardant coating, comprising the following steps:
(1) ethyl alcohol is added in beaker, control mixing speed is 800-1000r/min, film forming agent is then added, after adding
Continue to stir 20-40min；
(2) ammonium polyphosphate is added under same revolving speed, persistently stirs 10-30min；
(3) at a temperature of room temperature is to 70 DEG C, silane coupling agent is added in Xiang Shangshu solution, constant temperature stirs 10-30min；
(4) polysiloxanes fire retardant is added into step (3) resulting mixing liquid, 20-40min is sufficiently stirred；
(5) wetting agent is added into step (4) again, low whipping speed 400-600r/min, temperature are 80-100 DEG C
In the case of, make ethanol evaporation, until stopping heating when viscous pasty state.
In the above method, the preparation method of the polysiloxanes fire retardant the following steps are included:
(1) containing hydrogen silicone oil, catalyst and 50-70 a part solvent are added to and are stirred equipped with reflux condensing tube, thermometer and magnetic force
It mixes, in the four-hole boiling flask of inert atmosphere, constant temperature stirs 10-30min after being warming up to 60-80 DEG C；
(2) after being warming up to 90-110 DEG C, by the isocyanate group siloxanes and 10-30 parts of solvents in constant pressure funnel in 2-4h
It is added dropwise in four-hole boiling flask, isothermal reaction 6-12h；
(3) allyl glycidyl ether in constant pressure funnel is added dropwise to four mouthfuls with 20-40 parts of solvents in 1-3h
In flask, isothermal reaction 4-10h；
(4) solvent and unreacting substance are removed by vacuum distillation, obtains flame retardant intermediate API；
(5) flame retardant intermediate API, phosphorous active matter, catalyst and the 80-140 parts of solvents obtained step (4) are added
Into four-hole boiling flask, configuration reflux condensing tube, thermometer and magnetic agitation are passed through nitrogen, constant temperature is anti-after being warming up to 90-110 DEG C
Answer 10-24h；
(6) above-mentioned solution is obtained into product by vacuum distillation, is repeatedly washed with cleaning solvent, later in 80-100
The polysiloxanes fire retardant of nitrogenous, phosphorus, silicon is made in dry 12-24h at DEG C.
Further, the catalyst is added in two portions in reaction system, and catalyst used in step (1) is
One of Speier catalyst and Karstdet catalyst, catalyst used in step (5) is triphenylphosphine and three ethyl alcohol
One of amine；In reaction process, the dosage of both front and back catalyst is respectively 4*10-5-10-4Part, 0.18-0.45 parts.
Coating in the present invention rationally designs to have obtained that adhesion strength is strong, anti-flammability by reasonable composition selection, preparation flow
The excellent reactive coatings of energy.Reaction principle are as follows: film forming agent and silane coupling agent play filming function simultaneously, and silane coupling agent is again
It can interact with synthesized polysiloxanes fire retardant, silane coupling agent and fire retardant can both be implemented ammonium polyphosphate
Microencapsulation can be reacted under certain temperature and ethyl alcohol effect again, obtain space cross-linked structure, thermal stability is higher；
To make to generate preferable binding force between coating and matrix, it is adhesion strength rank that adhesion strength test, which can achieve 5B(5B, according to
The parameter that ASTM D3359-09 uses 3M adhesive tape cohesive force method of testing to test), flame retardant property is good.This coating is reaction
Type coating, reaction in coating preparation process with can be carried out in thermal histories, especially when heated reaction progress it is more complete,
To play good fire retardation；Meanwhile silane coupling agent can be changed to other and contain-Si-O-CH in flame retardant coating2CH3
Or-Si-OH substance, ammonium polyphosphate can also be changed to other excellent substances, 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 silane coupling agent can be changed to other in flame retardant coating
It is any to contain-Si-O-CH2CH3The substance of group and-Si-OH, and ammonium polyphosphate can also be changed to the substance of other good properties,
To obtain the polyfunctional reactant type coating with desirable properties；
(2) coating has good flame retardant effect, and microencapsulation structure makes with space cross-linked structure in coating
Coating still can obtain good flame retardant effect in the case where additive amount very little；
(3) coating has good cohesive force, can be firmly adhered to plastics such as polypropylene, polyethylene, polyphenyl second
The surface of the materials such as alkene, polyester etc. and paper, metal has good ageing-resistant property such as water resistance, ultra-violet resistance matter；
(4) coating does not have any undesirable influence to the mechanical property of matrix, and flame retardant coating is with higher flexible
Property and adhesion strength, matrix deformation Shi Nengyu matrix deformation occurs together, will not fall off because of fracture；
(5) coating obtained is still smooth when the polypropylene for selecting surface energy low is as basis material, has one
Fixed aesthetic feeling；
(6) using ethyl alcohol as solvent in the coating preparation process, while flame retardant coating can be dissolved in ethyl alcohol, to realize base
Recycling is separately recovered in body and fire retardant, does not have any harm to environment；
(7) the coating preparation process is simple and easy, only needs to dry in baking oven when being applied to matrix surface, not need
Ultra-violet curing, preparation method are simple, it is easy to accomplish industrialized production.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of 1 gained polysiloxanes fire retardant of embodiment.
Fig. 2 is the thermogravimetric spectrogram of 1 gained polysiloxanes fire retardant of embodiment.
Fig. 3 is the contact angle schematic diagram of 1 gained polysiloxanes fire retardant of embodiment.
Fig. 4 is the test of embodiment 1 gained polysiloxanes flame retardant coating and polyacrylic surface adhesion.
Fig. 5 is 1 gained PP/ polysiloxanes flame retardant coating of embodiment, and under different coating layer thicknesses, oxygen refers to various sample
Several change curves.
Fig. 6 is 1 gained PP/ polysiloxanes flame retardant coating of embodiment, and various sample is vertical under different coating layer thicknesses
The fire-retardant rank figure of burning.
Fig. 7 is 1 gained PP/ polysiloxanes flame retardant coating of embodiment, under identical coating layer thickness, the variation of tensile strength
Curve.
Specific embodiment
The present invention is further illustrated below by embodiment, but embodiments described below is only of the invention one
Divide embodiment, the invention is not limited to following embodiments.Based on the embodiments of the present invention, the researcher in this field exists
Creative experiments embodiment obtained is not carried out, it 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
Isopropanol be added to equipped with reflux condensing tube, thermometer and magnetic agitation, inert atmosphere four-hole boiling flask in, after being warming up to 70 DEG C
Constant temperature stirs 15min；After being warming up to 100 DEG C, in 3h by constant pressure funnel 15 parts of isocyanatopropyl triethoxysilanes with
15 parts of isopropanols are added dropwise in four-hole boiling flask, continue isothermal reaction 6h；By 35 parts of allyls in constant pressure funnel in 2h
Glycidol ether and 20 parts of isopropanols are added dropwise in four-hole boiling flask, continue isothermal reaction 6h；It is removed by vacuum distillation molten
Agent and unreacting substance obtain flame retardant intermediate API；All flame retardant intermediate API that previous step is obtained, 40 parts
Diphenyl phosphorus oxygen, 0.29 part of triphenylphosphine and 100 parts of isopropanols are added to four-hole boiling flask, configuration reflux condensing tube, thermometer with
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 acetone are washed with dehydrated alcohol (volume ratio 1:1), and drying for 24 hours, it is fire-retardant to obtain polysiloxanes at 80 DEG C later
Agent.
50 parts of ethyl alcohol are added in beaker, 7 parts of film forming agent, respectively polyethylene are added under the stirring condition of 900r/min
Alcohol the first and second aldehyde of contracting and polyvinyl formal (the two mass ratio 1:1) continue to stir 30min after adding；Under same revolving speed
5 parts of ammonium polyphosphate are added, persistently stir 25min；At 50 DEG C, 20 parts of silane coupling agents: N- ammonia second are added in Xiang Shangshu solution
Base-γ-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane (the two molar ratio 1:1), constant temperature stirring
20min；6 parts of above-mentioned polysiloxanes fire retardants are added into resulting mixing liquid, 30min is sufficiently stirred；400r/min's
1 part of wetting agent is added under stirring condition into the above solution, in the case where temperature is 80 DEG C, makes ethanol evaporation, until sticky
Stop heating when state.
First polypropylene batten is impregnated into thick liquid, after through czochralski method, finally dry, the poly- silicon of coating can be prepared
The polypropylene of oxygen alkane coating/polysiloxane coating composite material, the coating layer thickness that is related to is 40 μm -200 μm in the present invention.It is logical
The thickness of lifting number control coating is crossed to obtain polypropylene/polysiloxane coating composite material of different-thickness.The method
Also it is suitble in the frostings prepares coating such as metal and polyethylene, polystyrene, polyester.
1g is represented for every part in the embodiment of the present invention.
In above-mentioned experimentation, the infrared spectroscopy of polysiloxanes fire retardant is as shown in Figure 1.It is apparent that phosphorous active matter
It is located at 2384cm in matter-1- PH stretching vibration peak, completely disappeared in APID；Positioned at 909cm-1The peak of the epoxy group 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 peak P-O-Ph at place can be found in APID, in 3430 cm-1There is the feature of carbon hydroxyl
Peak, this illustrates that phosphorous active material is already engaged in reaction, grafts on the side chain of APID.In addition to this 1639,1540,
3430cm-1There is new peak, be the peak of-C=O ,-NH ,-NHCO respectively, and is located at 2168cm-1With 906cm-1The peak-SiH at place is complete
Totally disappeared mistake, this explanation-SiH can react to obtain carbon-silane amides with isocyanatosilanes under Speier catalyst action, and
And-SiH can react completely under the present conditions, it is identical as target product structure.And in 3430 cm-1There is intensity very in place
Big peak, this is because caused by the-NHCO and-PH that contain in APID are overlapped with the carbon hydroxyl that epoxy group reaction generates.More than
Evidence explanation, ideal fire retardant APID have been successfully prepared.
The thermogravimetric curve of prepared polysiloxanes fire retardant and the active phosphorus containg substances of raw material is as shown in Fig. 2, polysiloxanes
The temperature of initial decomposition of fire retardant is 237 DEG C, can satisfy the processing temperature of high molecular 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 thermal stability and at 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 °, is in hydrophobicity, can be obviously improved the compatibility with polymer matrix.
Cohesive force test, reference standard ASTM D3359-09 are carried out to PP/ polysiloxanes flame retardant coating obtained by the present embodiment
Using 3M adhesive tape cohesive force method of testing, the adhesion strength between coating and matrix is tested, as a result as shown in Figure 4.(a) is in Fig. 4
Flame retardant coating test before photo, and (b) be test after photo.As can be seen from the figure the edge of notch all ten is divided
Sliding, none lattice falls off, therefore the adhesiveness of the flame retardant coating can achieve 5B rank.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.Wherein polysiloxanes flame retardant agent content is 4% 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.For sample 1-4 into
Different performance tests is gone, as shown in Fig. 5 ~ 7.
Fig. 5 is gained PP/ polysiloxanes flame retardant coating, and above four kinds of samples are under different coating layer thicknesses, oxygen index (OI)
Change curve.It can be seen from the figure that oxygen index (OI) increases with the increase of thickness when coating composition is identical；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 is gained PP/ polysiloxanes flame retardant coating, and above four kinds of samples are vertical to fire under different coating layer thicknesses
Burn the change curve of data.
Fig. 7 is gained PP/ polysiloxanes flame retardant coating, under identical coating layer thickness, Tensile strength data figure.From figure
In as can be seen that the tensile strength of four samples and the tensile strength of virgin pp are close, 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
Into the four-hole boiling flask equipped with reflux condensing tube, thermometer and magnetic agitation, inert atmosphere, constant temperature is stirred after being warming up to 70 DEG C
10min；After being warming up to 95 DEG C, in 3h by constant pressure funnel 10 parts of isocyanatopropyl triethoxysilanes and 15 parts of toluene by
It is added dropwise in four-hole boiling flask, continues isothermal reaction 8h；In 2h by constant pressure funnel 30 parts of allyl glycidyl ethers with
35 parts of toluene are added dropwise in four-hole boiling flask, continue isothermal reaction 7h；Solvent and unreacted reactant are removed by vacuum distillation
Matter obtains flame retardant intermediate API；All flame retardant intermediate API, the 35 parts of 9,10- dihydro -9- that previous step is obtained
Oxa- -10- phospho hetero phenanthrene -10- oxide, 1.8*10-1Part triethanolamine catalyst and 110 parts of toluene solvants are added to four mouthfuls of burnings
Bottle, configuration reflux condensing tube, thermometer and magnetic agitation, is passed through nitrogen, isothermal reaction 15h after being warming up to 105 DEG C；It will be above-mentioned molten
Liquid obtains product by vacuum distillation, is washed with 120 parts of acetone with dehydrated alcohol (volume ratio 1:1), later at 90 DEG C
Lower drying for 24 hours, obtains polysiloxanes fire retardant.
100 parts of ethyl alcohol are added in beaker, 5 parts of polyvinyl formal are added under the stirring condition of 800r/min, adds
Continue to stir 40min after complete；3 parts of ammonium polyphosphate are added under same revolving speed, persistently stir 10min；At 40 DEG C, Xiang Shangshu
25 parts of silane coupling agents: 3-aminopropyltriethoxysilane and urea propyl-triethoxysilicane (the two mole are added in solution
Than for 1:1), constant temperature stirs 10min；5 parts of polysiloxanes fire retardants are added into resulting mixing liquid, 25min is sufficiently stirred；
2 parts of wetting agents are added into the above solution under the stirring condition of 600r/min steams ethyl alcohol in situation at a temperature of 90 °C
Hair, until stopping heating when viscous pasty state.
First polyester batten is impregnated into thick liquid, after through czochralski method, finally dry, the poly- silicon oxygen of coating can be prepared
The polyester of alkane coating/polysiloxane coating composite material controls the thickness of coating by lifting number to obtain different-thickness
The polyester of (30 μm -400 μm)/polysiloxane coating composite material.
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 returned cold
Solidifying pipe, thermometer and magnetic agitation, inert atmosphere four-hole boiling flask in, constant temperature stirs 10min after being warming up to 70 DEG C；It is warming up to
After 100 DEG C, 10 parts of 3- isocyanate group propyl trimethoxy silicanes in constant pressure funnel are added dropwise with 15 parts of toluene in 4h
Enter into four-hole boiling flask, continues isothermal reaction 7h；In 3h by constant pressure funnel 50 parts of allyl glycidyl ethers and 20 parts
Toluene is added dropwise in four-hole boiling flask, continues isothermal reaction 5h；Solvent and unreacting substance are removed by vacuum distillation, is obtained
To flame retardant intermediate API；All flame retardant intermediate API, 30 parts of phosphoric acid, the 4.0*10 that previous step is obtained-1Part triphen
Base phosphine 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,
Isothermal reaction 12h after being warming up to 105 DEG C；Above-mentioned solution is obtained into product by vacuum distillation, is washed with 90 parts of acetone, it
The dry 12h at 80 DEG C afterwards, obtains polysiloxanes fire retardant.
80 parts of ethyl alcohol are added in beaker, 6 parts of polyvinyl formal acetal are added under the stirring condition of 900r/min, adds
Continue to stir 30min after complete；5 parts of ammonium polyphosphate are added under same revolving speed, persistently stir 20min；In the above conditions, to
30 parts of silane coupling agents: γ-glycidyl ether oxygen propyl trimethoxy silicane and urea propyl triethoxy are added in above-mentioned solution
Silane (the two molar ratio 1:1), constant temperature stir 30min；2 parts of polysiloxanes fire retardants are added into resulting mixing liquid, fill
Divide stirring 40min；1 part of wetting agent is added into the above solution under the stirring condition of 550r/min, the feelings for being 100 DEG C in temperature
Under condition, make ethanol evaporation, until stopping heating when viscous pasty state.
First by metal impregnation into thick liquid, after through czochralski method, then dry, can prepares coating with a thickness of 5 μm-
80 μm of metal/polysiloxane coating composite material.Can also use brush by thick liquid equably Tu in metal surface, then
By drying, metal/polysiloxane coating composite material is obtained.
Embodiment 4
By 5 parts of polymethyl hydrogen siloxanes, 6*10-5Part Speier catalyst and 50 parts of benzene solvents are added to equipped with reflux condensation mode
Pipe, thermometer and magnetic agitation, inert atmosphere four-hole boiling flask in, constant temperature stirs 10min after being warming up to 70 DEG C；It is warming up to 90 DEG C
Afterwards, in 3h by constant pressure funnel 20 parts of isocyanatopropyl triethoxysilanes and 30 parts of benzene solvents be added dropwise to four mouthfuls of burnings
In bottle, continue isothermal reaction 12h；In 2h by constant pressure funnel 35 parts of allyl glycidyl ethers and 40 parts of benzene solvents dropwise
It is added in four-hole boiling flask, continues isothermal reaction 9h；Solvent and unreacting substance are removed by vacuum distillation, obtains fire retardant
Intermediate A PI；All flame retardant intermediate API, 30 parts of phosphorous acid, the 3.0*10 that previous step is obtained-1Triethanolamine catalysis
Agent and 120 parts of benzene solvents are added to four-hole boiling flask, prepare reflux condensing tube, thermometer and magnetic agitation, are passed through nitrogen, are warming up to
Isothermal reaction 18h after 90 DEG C；Above-mentioned solution is obtained into product by vacuum distillation, with 100 parts of acetone and dehydrated alcohol (volume ratio
It is washed for 1:1), the dry 12h at 80 DEG C, obtains polysiloxanes fire retardant later.
100 parts of ethyl alcohol are added in beaker, 5 parts of film forming agents: polyvinyl alcohol contracting are added under the stirring condition of 1000r/min
First and second aldehyde and polyvinyl butyral (the two mass ratio 1:1) continue to stir 30min after adding；3 are added under same revolving speed
Part ammonium polyphosphate, persistently stirs 10min；At 60 DEG C, 30 parts of silane coupling agent 3- aminopropyls three are added in Xiang Shangshu solution
Ethoxysilane, constant temperature stir 20min；6 parts of polysiloxanes fire retardants are added into resulting mixing liquid, point stirring 30min；
2 parts of wetting agents are added into the above solution under the stirring condition of 400r/min, in the case where temperature is 100 DEG C, make ethyl alcohol
Evaporation, until stopping heating when viscous pasty state.
Thick liquid is uniformly brushed above timber along the longitudinal of timber with brush after thick liquid is stirred evenly,
So that coating layer thickness is reached 100 μm of -0.3mm, obtains timber/polysiloxane coating composite material.
Embodiment 5
By 4 parts of poly- (methyl hydrogen siloxane-dimethylsiloxane copolymer), 8*10-5Part Speier catalyst and 70 parts of first
Benzene solvent be added to equipped with reflux condensing tube, thermometer and magnetic agitation, inert atmosphere four-hole boiling flask in, after being warming up to 75 DEG C
Constant temperature stirs 15min；After being warming up to 110 DEG C, in 3h by constant pressure funnel 5 parts of dimethyl diisocyanate base silanes and 10 parts
Toluene is added dropwise in four-hole boiling flask, continues isothermal reaction 8h；It is in 2h that 40 parts of allyl glycidyls in constant pressure funnel are sweet
Oily ether and 20 parts of toluene are added dropwise in four-hole boiling flask, continue isothermal reaction 8h；By vacuum distillation removing solvent and not
Reactive material obtains flame retardant intermediate API；All flame retardant intermediate API, the 30 parts of diphenylphosphines that previous step is obtained
Oxygen, 4.4*10-1Part triphenylphosphine catalysis and 100 parts of toluene solvants are added to four-hole boiling flask, prepare reflux condensing tube, thermometer
With magnetic agitation, it 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,
It is washed with 80 parts of dehydrated alcohols, the dry 15h at 80 DEG C, obtains polysiloxanes fire retardant later.
150 parts of ethyl alcohol are added in beaker, 6 parts of film forming agents: polyvinyl alcohol contracting are added under the stirring condition of 950r/min
Formaldehyde and polyvinyl butyral (the two mass ratio 1:1) continue to stir 20min after adding；4 parts are added under same revolving speed
Ammonium polyphosphate persistently stirs 30min；At 70 DEG C, 10 parts of silane coupling agents: three second of 3- aminopropyl are added in Xiang Shangshu solution
Oxysilane and isocyanatopropyl triethoxysilane (the two molar ratio 1:1), constant temperature stir 30min；To resulting mixed liquor
5 parts of polysiloxanes fire retardants are added in body, 20min is sufficiently stirred；Add under the stirring condition of 600r/min into the above solution
Enter 1 part of wetting agent, in the case where temperature is 80 DEG C, make ethanol evaporation, until stopping heating when viscous pasty state.
Paper is impregnated in thick liquid, is later removed extra thick liquid by squeezing, using 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 (9)
1. a kind of response type polysiloxanes flame retardant coating, it is characterised in that: its space structure are as follows:
And the structural formula of polysiloxanes fire retardant are as follows:
Wherein, m > 0, n > 0, x >=0；M, n is positive integer, and x is nonnegative integer；
R1With R2Respectively H, CH3Or one of OH；
R3For 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 of-P (=O) (OH) H；
R4For (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 chain in molecule；
The response type polysiloxanes flame retardant coating, which is characterized in that be made of raw material from the following weight:
5-7 parts of film forming agent；
3-5 parts of ammonium polyphosphate；
2-6 parts of polysiloxanes fire retardant；
10-30 parts of silane coupling agent；
1-2 parts of wetting agent；
50-150 parts of ethyl alcohol；
Obtained flame-retardant coating cohesive force is strong, is firmly combined with matrix；
Wherein the polysiloxanes fire retardant is prepared from the following raw materials in parts by weight:
5-10 parts of containing hydrogen silicone oil；
30-50 parts of allyl glycidyl ether；
5-20 parts of isocyanatosilanes；
Phosphorous active matter 30-50 parts；
In reaction process, the dosage of catalyst are as follows: 1.8004 × 10-1-4.501× 10-1Part；The dosage of solvent are as follows: 160-280
Part；The dosage of cleaning solvent are as follows: 80-150 parts.
2. response type polysiloxanes flame retardant coating according to claim 1, which is characterized in that the film forming agent is polyethylene
The one or two of the first and second aldehyde of alcohol contracting, polyvinyl alcohol, polyalkenylalcohols acetal, polyvinyl butyral or polyvinyl formal；
When selecting the two, the mass ratio of the two is 1:1.
3. response type polysiloxanes flame retardant coating according to claim 1, which is characterized in that the wetting agent is 12
Sodium alkyl sulfate, xylitol acid anhydride aliphatic ester, 20 sorbitan monooleate of polyoxyethylene, polyoxyethylene fatty acid esters or
One or both of polyethylene glycol oxide alkyl phenyl ether；When choosing two kinds, quality proportioning 1:1.
4. response type polysiloxanes flame retardant coating according to claim 1, which is characterized in that the silane coupling agent is
γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, 3- aminopropyl
Triethoxysilane, isocyanatopropyl triethoxysilane, urea propyl-triethoxysilicane, N- aminoethyl-γ-aminopropyl front three
One or both of oxysilane, diethylenetriamine base propyl trimethoxy silicane or dimethyl diisocyanate base silane；Choosing
When taking two kinds, mol ratio 1:1.
5. response type polysiloxanes flame retardant coating according to claim 1, which is characterized 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 of tetramethyl-ring tetrasiloxane or hydrogen sealing end dimethyl silicone polymer；
The isocyanatosilanes are 3- isocyanate group propyl trimethoxy silicane, isocyanatopropyl triethoxysilane or two
One of methyl diisocyanate base silane；
The phosphorous active matter be the miscellaneous -10- phospho hetero phenanthrene -10- oxide of 9,10- dihydro-9-oxy, phosphoric acid, phosphorous acid, metaphosphoric acid,
One of pyrophosphoric acid, dialkyl phosphite or diphenyl phosphorus oxygen；
The solvent is isopropanol, dehydrated alcohol, toluene, benzene, acetone, methylene chloride, chloroform, N, N- dimethyl formyl
One or both of amine；When using two kinds, the volume ratio of two kinds of solvents is 1:1；
The cleaning solvent is one or both of acetone, dehydrated alcohol, deionized water, N,N-dimethylformamide；When
When using two kinds, the volume ratio of the two is 1:1.
6. response type polysiloxanes flame retardant coating according to claim 1, which is characterized in that described matrix be polypropylene,
One of polyethylene, polystyrene, polyester plastics or one of paper, timber, metal material.
7. a kind of preparation method of the described in any item response type polysiloxanes flame retardant coatings of claim 1 ~ 6, which is characterized in that
The following steps are included:
(1) ethyl alcohol is added in beaker, control mixing speed is 800-1000r/min, and film forming agent is then added, continues after adding
Stir 20-40min；
(2) ammonium polyphosphate is added under same revolving speed, persistently stirs 10-30min；
(3) at a temperature of room temperature is to 70 DEG C, silane coupling agent is added in Xiang Shangshu solution, constant temperature stirs 10-30min；
(4) polysiloxanes fire retardant is added into step (3) resulting mixing liquid, 20-40min is sufficiently stirred；
(5) again to wetting agent is added in step (4), the case where low whipping speed 400-600r/min, temperature are 80-100 DEG C
Under, make ethanol evaporation, until stopping heating when viscous pasty state.
8. the preparation method of response type polysiloxanes flame retardant coating according to claim 7, which is characterized in that the poly- silicon
The preparation method of oxygen alkane fire retardant the following steps are included:
(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 stir 10-30min；
(2) after being warming up to 90-110 DEG C, in 2-4h by constant pressure funnel isocyanate group siloxanes and 10-30 parts of solvents dropwise
It is added in four-hole boiling flask, isothermal reaction 6-12h；
(3) allyl glycidyl ether in constant pressure funnel is added dropwise to four-hole boiling flask with 20-40 parts of solvents in 1-3h
In, isothermal reaction 4-10h；
(4) solvent and unreacting substance are removed by vacuum distillation, obtains flame retardant intermediate API；
(5) flame retardant intermediate API, phosphorous active matter, catalyst and 80-140 parts of solvents that step (4) obtains 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, later at 80-100 DEG C
The polysiloxanes fire retardant of nitrogenous, phosphorus, silicon is made in dry 12-24h.
9. the preparation method of response type polysiloxanes flame retardant coating according to claim 8, it is characterised in that: the catalysis
Agent is added in two portions in reaction system, and catalyst used in step (1) is Speier catalyst and Karstdet catalyst
One of, catalyst used in step (5) is one of triphenylphosphine and triethanolamine；In reaction process, front and back two
The dosage of kind catalyst is respectively 4 × 10-5-10-4Part, 0.18-0.45 parts.
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| Title |
|---|
| An intumescent flame retardant polypropylene system with simultaneously improved flame retardancy and water resistance;Cheng-Liang Deng等;《Polymer Degradation and Stability》;20140614;第97-107页 |
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| Publication number | Publication date |
|---|---|
| CN106700920A (en) | 2017-05-24 |
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