CN105175780B - The acrylate as fire retarding agent and its flame retardant epoxy acrylate coatings preparation method of a kind of Nitrogen-and Phosphorus-containing silicon - Google Patents
The acrylate as fire retarding agent and its flame retardant epoxy acrylate coatings preparation method of a kind of Nitrogen-and Phosphorus-containing silicon Download PDFInfo
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Abstract
The invention discloses a kind of acrylate as fire retarding agent of Nitrogen-and Phosphorus-containing silicon and its flame retardant epoxy acrylate coatings preparation method, and the addition product of toluene di-isocyanate(TDI) hydroxy ethyl methacrylate half is synthesized with the diisocyanate of toluene 2,4 and hydroxy ethyl methacrylate；With phosphoric acid and glycidyl ether synthesis phosphoric acid GMA；The addition product of toluene di-isocyanate(TDI) hydroxy ethyl methacrylate half, phosphoric acid GMA and tri-methyl-chlorosilane are reacted again to obtain Nitrogen-and Phosphorus-containing silicon monomer THGT, the as acrylate as fire retarding agent of Nitrogen-and Phosphorus-containing silicon；After THGT uniformly mixes with epoxy acrylate, light trigger is added, even spread prepares coating, illumination curing, produces flame retardant epoxy acrylate coatings, its translucency, superior flame retardant property, excellent in mechanical performance, heat endurance is also improved.
Description
Technical field
The present invention relates to a kind of acrylate as fire retarding agent of Nitrogen-and Phosphorus-containing silicon and its flame retardant epoxy acrylate coatings preparation side
Method.
Background technology
Solvent in traditional coating is volatile, easily pollutes environment, health, in recent years is influenceed, with environmental consciousness
Continuous enhancing, people start gradually to recognize the harmfulness of these traditional coatings, have developed some low solvents even without molten
The new ultra-violet photocureable coating of agent, such coating have the advantages that curing rate is fast, operation temperature is low, and film quality is good, but
Monomer used in being it is often combustibles, and easily burning, there is certain potential safety hazard.In addition, modern society is for transparent
The use of coating is also more and more, and existing clear dope only has two kinds, and melmac and Lauxite is respectively adopted
For film forming agent, but melmac stability is poor, it is impossible to which long-term storage, coating are easy to crack.And Lauxite fire resisting, resistance to boiling
Water, ageing-resistant performance are very poor, also contain free formaldehyde, also environmental and human health impacts are had a certain impact.Therefore, research is a kind of
Transparent fire protection flame retarding photocureable coating, it is the demand of social development, it is also significant to field of fire-proof technology
The content of the invention
It is an object of the invention in place of overcome the deficiencies in the prior art, there is provided a kind of acrylate resistance of Nitrogen-and Phosphorus-containing silicon
Combustion agent and its flame retardant epoxy acrylate coatings preparation method, the flame retardant epoxy acrylate coatings being prepared have translucency
The advantages of high, fire resistance is by force, excellent in mechanical performance, heat endurance are good.
One of the technical solution adopted for the present invention to solve the technical problems is：
A kind of preparation method of the acrylate as fire retarding agent of Nitrogen-and Phosphorus-containing silicon, including：
1) synthesis of the addition product of toluene di-isocyanate(TDI)-hydroxy ethyl methacrylate half：- 5~5 DEG C, nitrogen protection under, to first
Hydroxy ethyl methacrylate is at the uniform velocity added dropwise with 2.5~3.5h in benzene -2,4- diisocyanate, 0.5~1.5h of stirring reaction, produces first
The addition product of phenylene diisocyanate-hydroxy ethyl methacrylate half；The Toluene-2,4-diisocyanate, 4- diisocyanate, hydroxy ethyl methacrylate it
Mol ratio is 0.8~1.2:0.8~1.2；
2) phosphoric acid GMA synthesis：At -5~5 DEG C, glycidyl ether is added dropwise into the mixture of phosphoric acid and acetone,
7~9h of reaction at 55~70 DEG C is placed in, produces phosphoric acid GMA；The mol ratio of the phosphoric acid and glycidyl ether for 0.8~
1.2:2.5~3.5；
3) Nitrogen-and Phosphorus-containing silicon monomer THGT synthesis：Toluene di-isocyanate(TDI)-the hydroxyethyl that will be obtained in step 1)
The addition product of ester half is diluted with the TMPGA of phase homogenous quantities, under normal temperature, nitrogen protection, the phosphoric acid GMA obtained in step 2) is added dropwise, stirs
3.5~4.5h of reaction is mixed, tri-methyl-chlorosilane is added dropwise, after reacting 3.5~4.5h, obtains Nitrogen-and Phosphorus-containing silicon monomer THGT, is
The acrylate as fire retarding agent of Nitrogen-and Phosphorus-containing silicon；The addition product of toluene di-isocyanate(TDI)-hydroxy ethyl methacrylate half, phosphoric acid GMA with
The mol ratio of tri-methyl-chlorosilane is 1.5~2.5:0.8~1.2:0.8~1.2.
The two of the technical solution adopted for the present invention to solve the technical problems are：
A kind of flame retardant epoxy acrylate coatings of acrylate as fire retarding agent using above-mentioned Nitrogen-and Phosphorus-containing silicon.
The three of the technical solution adopted for the present invention to solve the technical problems are：
The preparation method of above-mentioned flame retardant epoxy acrylate coatings, add into the acrylate as fire retarding agent of the Nitrogen-and Phosphorus-containing silicon
Enter epoxy acrylate, uniformly after mixing, add light trigger, obtain hybrid resin；The acrylate resistance of the Nitrogen-and Phosphorus-containing silicon
The mass ratio for firing agent, epoxy acrylate and light trigger is 0.8~8.5:1.5~7.5:0.3~0.5；By the compound tree
Fat is spread evenly across on coated carrier, illumination curing, produces described epoxy acrylate coatings.
In one embodiment：After the acrylate as fire retarding agent of the Nitrogen-and Phosphorus-containing silicon is disperseed with acrylic acid dilution, ring is added
Oxypropylene acid esters.
In one embodiment：The quality of the acrylate as fire retarding agent of the Nitrogen-and Phosphorus-containing silicon, epoxy acrylate and light trigger
Than for 0.9~1.1:6.8~7.2:0.35~0.45.
In one embodiment：The quality of the acrylate as fire retarding agent of the Nitrogen-and Phosphorus-containing silicon, epoxy acrylate and light trigger
Than for 1.8~2.2:6.8~7.2:0.35~0.45.
In one embodiment：The quality of the acrylate as fire retarding agent of the Nitrogen-and Phosphorus-containing silicon, epoxy acrylate and light trigger
Than for 2.8~3.2:6.8~7.2:0.35~0.45.
In one embodiment：The quality of the acrylate as fire retarding agent of the Nitrogen-and Phosphorus-containing silicon, epoxy acrylate and light trigger
Than for 3.8~4.2:6.8~7.2:0.35~0.45.
In one embodiment：The quality of the acrylate as fire retarding agent of the Nitrogen-and Phosphorus-containing silicon, epoxy acrylate and light trigger
Than for 4.8~5.2:4.8~5.2:0.35~0.45.
In one embodiment：The quality of the acrylate as fire retarding agent of the Nitrogen-and Phosphorus-containing silicon, epoxy acrylate and light trigger
Than for 5.8~6.2:3.8~4.2:0.35~0.45.
In one embodiment：The quality of the acrylate as fire retarding agent of the Nitrogen-and Phosphorus-containing silicon, epoxy acrylate and light trigger
Than for 7.8~8.2:1.8~2.2:0.35~0.45.
In one embodiment：The light trigger is light trigger 1173.
Reagent involved in the present invention, instrument, method etc., are this area routine techniques unless otherwise stated.
Compared with background technology, it has the following advantages that the technical program：
The present invention synthesizes Nitrogen-and Phosphorus-containing silicon by the addition products of HEA-TDI half, phosphoric acid GMA, tri-methyl-chlorosilane reaction first
Function monomer TGHT, as Nitrogen-and Phosphorus-containing silicon acrylate as fire retarding agent, and apply it in EA matrix resins, resistance is prepared
Fire epoxy acrylate coatings, its translucency, superior flame retardant property；Meanwhile mechanical property, shock resistance, the hardness of coating
Deng excellent performance, coating heat endurance is also improved.
Brief description of the drawings
The invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 is the Nitrogen-and Phosphorus-containing silicon monomer TGHT infrared spectrum spectrograms of the present invention.
Fig. 2 is the flame retardant epoxy acrylate coatings transmittance figure of the present invention.
Fig. 3 is the flame retardant epoxy acrylate coatings thermogravimetric analysis figure of the present invention.
Fig. 4 is flame retardant epoxy acrylate coatings REAL TIME INFRARED THERMAL IMAGE analysis chart in embodiment 4.
Fig. 5 is the flame retardant epoxy acrylate coatings HRR analysis chart of the present invention.
Fig. 6 is the carbon residue pattern schematic diagram after the flame retardant epoxy acrylate coatings burning obtained in embodiment 7.
Embodiment
Present disclosure is illustrated below by embodiment：
Embodiment 1~7
The preparation of epoxy acrylate coatings in embodiment 1~7 is carried out according to epoxy acrylate coating formula in table 1：
1) synthesis of the addition product of toluene di-isocyanate(TDI)-hydroxy ethyl methacrylate (TDI-HEA) half：At three mouthfuls of 250mL
Dropping funel, mechanical agitator are loaded onto on flask, ice bath keeps reaction temperature in -5~5 DEG C, is passed through nitrogen protection, to
0.1mol Toluene-2,4-diisocyanates, 4- diisocyanate (TDI) is interior, and 0.1mol hydroxy ethyl methacrylates (HEA) are at the uniform velocity added dropwise with 3h, and stirring is anti-
1h is answered, obtains milky white liquid, as the addition product of toluene di-isocyanate(TDI)-hydroxy ethyl methacrylate (TDI-HEA) half；Reaction equation
It is shown below：
2) phosphoric acid GMA synthesis：0.1mol phosphoric acid, 50mL acetone are added mechanical agitator is housed, the three of dropping funel
In mouth flask, ice bath keeps reaction temperature to be added dropwise in -5~5 DEG C into the mixture of above-mentioned 0.1mol phosphoric acid and 50mL acetone
0.3mol glycidyl ethers, reaction 8h in 60~65 DEG C of water-baths is placed in after being added dropwise, obtains transparency liquid, is
P thiodipropionic acid glycidol ether (phosphoric acid GMA)；Reaction equation is shown below：
3) Nitrogen-and Phosphorus-containing silicon monomer THGT synthesis：By the addition products of TDI-HEA half obtained in 0.1mol steps 1) with identical
Trimethylolpropane trimethacrylate (TMPGA) dilution of quality, is added in the three-necked flask equipped with dropping funel, normal temperature, nitrogen
Under gas shielded, the phosphoric acid GMA obtained in 0.05mol steps 2) is added dropwise, magnetic stirrer reaction 4h, 0.05mol tri- is added dropwise
The chlorosilane of methyl one, after reacting 4h, obtain viscous brown shape liquid, as Nitrogen-and Phosphorus-containing silicon monomer THGT (the poly- ammonia of silyl phosphate
Ester acrylate), the as acrylate as fire retarding agent of Nitrogen-and Phosphorus-containing silicon；Reaction equation is shown below：
4) prepared by coating：According to the ratio in table 1, the acrylate as fire retarding agent of the Nitrogen-and Phosphorus-containing silicon obtained into step 3) is i.e.
Epoxy acrylate (EA) is added in Nitrogen-and Phosphorus-containing silicon monomer THGT, uniformly to mix, addition light draws for ultrasonic vibration after stirring
Agent 1173 is sent out, obtains hybrid resin；As needed, after Nitrogen-and Phosphorus-containing silicon monomer THGT can be disperseed with acrylic acid (AA) dilution,
Add epoxy acrylate；The hybrid resin is spread evenly across coated carrier with spreader and cleans dry glass plate
On, being irradiated after ultraviolet lamp preheating 1min makes its solidification, produces the flame retardant epoxy acrylate coatings of Nitrogen-and Phosphorus-containing silicon；Can be according to need
Different shapes such as sample layer or sample strip are prepared into, the general thickness of sample layer is 80 μm, sample strip thickness about 3mm；Hardening time
The former is 80s, and the latter is about 20s, while according to the shade degree and solidification concrete condition of sample, can to particular sample
Appropriate hardening time is selected, basic principle is：Completion of cure, and non-degradable coating.
The preparation (being free of TGHT) of blank group：According to the ratio in table 1, epoxy acrylate is added into acrylic acid (AA)
(EA) ultrasonic vibration adds light trigger 1173, obtains hybrid resin uniformly to mix after, stirring；By the compound tree
Fat is spread evenly across coated carrier with spreader and cleaned on the glass plate of drying, and being irradiated after ultraviolet lamp preheating 1min makes it solid
Change, produce blank group coating.
The flame retardant epoxy acrylate coatings formula of table 1
Embodiment 8：The preparation of the acrylate as fire retarding agent of Nitrogen-and Phosphorus-containing silicon
1) synthesis of the addition product of toluene di-isocyanate(TDI)-hydroxy ethyl methacrylate (TDI-HEA) half：At three mouthfuls of 250mL
Dropping funel, mechanical agitator are loaded onto on flask, ice bath keeps reaction temperature in -5~5 DEG C, is passed through nitrogen protection, to
0.1mol Toluene-2,4-diisocyanates, 4- diisocyanate (TDI) is interior, and 0.1mol hydroxy ethyl methacrylates (HEA) are at the uniform velocity added dropwise with 3h, and stirring is anti-
1h is answered, obtains milky white liquid, as the addition product of toluene di-isocyanate(TDI)-hydroxy ethyl methacrylate (TDI-HEA) half；
2) phosphoric acid GMA synthesis：0.1mol phosphoric acid, 50mL acetone are added mechanical agitator is housed, the three of dropping funel
In mouth flask, ice bath keeps reaction temperature to be added dropwise in -5~5 DEG C into the mixture of above-mentioned 0.1mol phosphoric acid and 50mL acetone
0.3mol glycidyl ethers, reaction 8h in 60~65 DEG C of water-baths is placed in after being added dropwise, obtains transparency liquid, is
P thiodipropionic acid glycidol ether (phosphoric acid GMA)；
3) Nitrogen-and Phosphorus-containing silicon monomer THGT synthesis：By the addition products of TDI-HEA half obtained in 0.1mol steps 1) with identical
Trimethylolpropane trimethacrylate (TMPGA) dilution of quality, is added in the three-necked flask equipped with dropping funel, normal temperature, nitrogen
Under gas shielded, the phosphoric acid GMA obtained in 0.05mol steps 2) is added dropwise, magnetic stirrer reaction 4h, 0.05mol tri- is added dropwise
The chlorosilane of methyl one, after reacting 4h, obtain viscous brown shape liquid, as Nitrogen-and Phosphorus-containing silicon monomer THGT (the poly- ammonia of silyl phosphate
Ester acrylate), the as acrylate as fire retarding agent of Nitrogen-and Phosphorus-containing silicon.
The effect of following experimental examples can be achieved in above-described embodiment：
Experimental example 1：The acrylate as fire retarding agent infrared analysis of Nitrogen-and Phosphorus-containing silicon
IR Characterization is carried out to sample using German BRUKER company's Ts ENSOR27 types Fourier infrared spectrograph.Scan model
Enclose：500~4000cm-1.Take the acrylate as fire retarding agent i.e. Nitrogen-and Phosphorus-containing silicon monomer of the Nitrogen-and Phosphorus-containing silicon obtained in a small amount of embodiment 8
THGT and KBr is according to mass ratio 1：40 proportionings are ground uniformly, tabletting detection.
As shown in Figure 1,3337cm-1Locate as N-H symmetrical stretching vibration characteristic peaks, 1725cm-1Locate as P-OH key characteristic peaks,
Show to contain P element in new synthetic.1634cm-1The absworption peak at place is C=C double bond stretching vibration absworption peaks, shows newly to close
Into material contain double bond.1070cm-1Locate as Si-O key characteristic absorption peaks.Analysis understands same in synthetic THGT more than
Tri- kinds of Shi Hanyou N, P, Si elements.
Experimental example 2：Flame retardant epoxy acrylate coatings transmissivity is analyzed
The transmissivity analysis of coating, it is primarily used to characterize coating in absorption of the UV-vis light area to light and passes through feelings
Condition.The more high then coating transparency of transmitance is higher, and when as transparent flame-retardant coating, its effect is better.With ultraviolet/visible point
UV-vis of the light photometric determination coating in the range of 200~800nm absorbs transmitted spectrum.
As seen from Figure 2, the transmitance highest of embodiment 1, the transmitance of embodiment 5 is minimum, in the visible of 400~700nm
The region of light, coating transmittance is between 60% to 70%.
Experimental example 3：Flame retardant epoxy acrylate coatings mechanics property analysis
Coating hardness is tested：With the standard that GB/T 6739 is measure.Specifically method of testing is：Coating to be measured is fixed
On the horizontal level, then the pencil cut it is stuck on request on propeller, makes it with film be in 45° angle, shaking screw rod makes
Pencil is with about 1mms-1Speed promote, since most hard pencil, the pencil of each hardness level draws five, until five
Untill cut does not scratch film, the hardness of this pencil is to represent the hardness of surveyed coating.Chinese board pencil is selected in this test, firmly
Degree scope is 6B~6H, and wherein 6H is most hard, and 6B is most soft.
Coating adhesion is tested：This test is according to GB/T 9286-1998《The cross cut test of paint and varnish paint film》Measure
The adhesive force paint film adhesion determination method of hybridized film determines the adhesive force of film, experimental result point 1~7 etc. using scratch
Level, 1 grade of adhesion property is best, and 7 grades worst.
Impact resistance of coating is tested：Using the shock resistance of drop weight test method measure coating.
Table 2 is refer to, is the flame retardant epoxy acrylate coatings mechanics property analysis obtained in the embodiment of the present invention 1~7
Data.
The flame retardant epoxy acrylate coatings mechanics property analysis of table 2
As shown in Table 2, in embodiment 1~7, hardness, adhesive force and the impact strength of coating are with the increasing of TGHT contents
Add and reduce, in embodiment 1, when TGHT contents are 10%, hardness is up to 5H, and impact strength is up to 65kgcm, attached
Put forth effort as 1 grade.
Experimental example 4：Flame retardant epoxy acrylate coatings thermogravimetric analysis
The heat endurance of obtained solidify coating is studied by thermogravimetric analysis.In air atmosphere, using SDT-2960 types
Thermogravimetric analyzer carries out thermogravimetric analysis to sample.Temperature range be room temperature to 800 DEG C, heating rate is 10 DEG C of min-1。
Fig. 3, general provision are refer to, the temperature corresponding to 5% mass loss is the initial temperature that sample starts degraded.
In figure, blank group coating is primary structure coating, and it is 353 DEG C that it, which starts the initial temperature of degraded, but in high temperature, it is final residual
Charcoal amount is only 9.11%, and than relatively low, its flame retardant effect is poor.In embodiment 1, the incipient degradation temperature of the coating containing 10%THGT is
346 DEG C, final carbon yield is 30.38%.In embodiment 4, the coating containing 40% Nitrogen-and Phosphorus-containing silicon monomer THGT, it starts degraded temperature
To spend for 329 DEG C, final level of residue is 34.03%, improves 25.19%, after showing that addition contains P, N, Si monomer in system, its
Fire resistance is very significantly improved.And in embodiment 7, the incipient degradation temperature of the coating containing 80%THGT is 353 DEG C, finally
Carbon yield is 35.70%.Analysis is known more than：The final carbon left of coating containing P, N, Si is higher than blank group coating, i.e., its
High high-temp stability is preferable.
Experimental example 5：Flame retardant epoxy acrylate coatings REAL TIME INFRARED THERMAL IMAGE is analyzed
REAL TIME INFRARED THERMAL IMAGE can be used for condensed phase chemical constitution in epoxy acrylate coatings thermal degradation process prepared by research
Change.The infrared spectrum of coating thermal degradation process is in 500~4000cm of wavelength-1In the range of change.
Fig. 4 is refer to, is the flame retardant epoxy acrylate coatings REAL TIME INFRARED THERMAL IMAGE analysis chart obtained in embodiment 4,
3422cm-1The absworption peak at place is-OH stretching vibration absworption peak, has been disappeared at 350 DEG C；2926cm-1For methyl and methylene
The C-H of base characteristic peak, disappeared at 600 DEG C, shown that aliphatic chain has been degraded completely；In 1671cm-1The absworption peak at place is uncle
The characteristic peak of acid amides (C-O-N), it starts the temperature of degraded at 350 DEG C, and at 450 DEG C, characteristic peak has also disappeared, and shows tertiary acyl
Amine has been degraded completely；In 1735cm-1The characteristic absorption peak of the C=O keys at place has almost no change before 300 DEG C, and at 600 DEG C
When be almost wholly absent, illustrate coating before 300 DEG C be mainly P-O-C keys degrade；And in 1067cm-1Locate Si-
The vibration peak of O-C keys rapid decrease more than 400 DEG C, and 600 DEG C just degraded it is complete, so the coating in high temperature from it is fire-retardant
The mainly element silicon of effect.
Experimental example 6：Flame retardant epoxy acrylate coatings fire resistance
Coating limited oxygen index is tested：GB is pressed using Jiangning county's analytical instrument JF-3 digital display limited oxygen indexs instrument
2406-96 carries out limited oxygen index (LOI) test.The length of flame：About 10mm.The duration of ignition：30s；Criterion：Burning length：
40mm, that is, light a fire 30s, and batten can't burn, although the burning length that can burn in other words is less than 40mm, then it represents that oxygen is dense
Spend it is relatively low, must also toward eminence adjust；If batten can be lighted in 30s, and the burning length of batten is more than 40mm, then it represents that oxygen is dense
Spend high, it is necessary to turn down.So tested, until finding a critical oxygen concentration, i.e. the limit oxygen as the sample refers to
Number.
Vertical combustion rank UL-94 is tested：By GB 2408-80 standards on WC-5400 types horizontal vertical burning analyzer
Test.The combustion stage of material is determined by determining burning time of the sample being disposed vertically after burning things which may cause a fire disaster is removed untill self-extinguishment
Not.Test result is divided into Three Estate：V-0, V-1 and V-2 level.V-0 levels are the best ranks that material can reach.Batten size is
100×12.5×3mm3.Batten is fixed on the place of 30cm above flame.Sample starts to allow from below burning things which may cause a fire disaster continuous action 10s.
Remove after burning things which may cause a fire disaster if sample self-extinguishment, then act on 10s with burning things which may cause a fire disaster again.
Table 3 is refer to, is the flame retardant epoxy acrylate coatings fire resistance analysis obtained in the embodiment of the present invention 1~7
Data.
The flame retardant epoxy acrylate coatings mechanics property analysis of table 3
From table 3：The LOI of embodiment 3 and embodiment 5 is respectively 34,37, increases many, table than blank group coating
Understand that the fire resistance of prepared coating is significantly improved compared with the blank group coating for being not added with flame-retardant monomer.Ignition temperature compared with
When low, bound phosphate groups can degrade, and it is strong dehydrating agent that acidic materials, the polyphosphoric acids such as polyphosphoric acid are produced in coating, can be made
Contain hydroxylated material dehydration carbonization in coating, form porous layer of charcoal, oxygen barrier, heat-blocking action are played to coating, can be prevented
Burning.When in high temperature, the nitrogen in coating, which can degrade, produces some non-flame properties gases, and these gases are flammable in dilution
While gas concentration, layer of charcoal can be expanded, the layer of charcoal of expansion can play a part of heat-insulated, oxygen barrier, while can make combustion
Burn region imflammable gas to reduce, so as to reduce the combustibility of material, improve the LOI of coating；In addition, system is when heated
Si-O keys decompose, and because the surface energy of silicon is relatively low, silicon-containing material moves to material at slightly higher temperature caused by the decomposition
Surface, form effective protection aquiclude；And the high performance siliceous layer of charcoal ultimately formed can hinder heat transfer and imflammable gas
Diffusion, retarded combustion speed and hot rate of release, so as to improve the anti-flammability of cured film.
Experimental example 7：Flame retardant epoxy acrylate coatings HRR is analyzed
The peak value of HRR can be as an important indicator of evaluation fire degree.According to GB/T 16172-
2007 standards, the measure of HRR is carried out using JCZ-1 cone amounts instrument.
Fig. 5 is refer to, peak change can obtain in analysis chart：Blank group coating rapid burning, HRR peak after lighting
Sharply, it can reach 733KWm-2；In other coatings, embodiment 4 and the peak value of the HRR of embodiment 7 are respectively
313KW·m-2And 351KWm-2, 57.29% and 52.11% are reduced respectively, and reduction amplitude is big, and is added with function monomer
The increase of amount, the peak value of HRR are reduced；Because the phosphate ester structure in flame retardant epoxy acrylate coatings is relatively low
At a temperature of degraded can generate volatile small molecule compound, so its burning time is obviously prolonged, burning time shifts to an earlier date.
Experimental example 8：Flame retardant epoxy acrylate coatings carbon yield is analyzed
Carbon yield is tested：Take the sample of certain mass to burn under air, be quality m before burning1, it is quality m after burning2,
Then carbon yield is：
Table 4 is refer to, is that the flame retardant epoxy acrylate coatings carbon yield obtained in the embodiment of the present invention 1~7 analyzes number
According to.
The flame retardant epoxy acrylate coatings carbon yield of table 4 is analyzed
It is described above, only present pre-ferred embodiments, therefore the scope that the present invention is implemented can not be limited according to this, i.e., according to
The equivalent changes and modifications that the scope of the claims of the present invention and description are made, all should still it belong in the range of the present invention covers.
Claims (10)
- A kind of 1. preparation method of the acrylate as fire retarding agent of Nitrogen-and Phosphorus-containing silicon, it is characterised in that：Including：1) synthesis of the addition product of toluene di-isocyanate(TDI)-hydroxy ethyl methacrylate half：- 5~5 DEG C, nitrogen protection under, to toluene- Hydroxy ethyl methacrylate is at the uniform velocity added dropwise with 2.5~3.5h in 2,4- diisocyanate, 0.5~1.5h of stirring reaction, produces toluene The addition product of diisocyanate-hydroxy ethyl methacrylate half；The Toluene-2,4-diisocyanate, 4- diisocyanate, hydroxy ethyl methacrylate rub You are than being 0.8~1.2:0.8~1.2；2) phosphoric acid GMA synthesis：At -5~5 DEG C, glycidyl ether is added dropwise into the mixture of phosphoric acid and acetone, is placed in 7~9h is reacted at 55~70 DEG C, produces phosphoric acid GMA；The mol ratio of the phosphoric acid and glycidyl ether is 0.8~1.2: 2.5~3.5；3) Nitrogen-and Phosphorus-containing silicon monomer THGT synthesis：By the toluene di-isocyanate(TDI)-hydroxy ethyl methacrylate obtained in step 1) half Addition product is diluted with the trimethylolpropane trimethacrylate of phase homogenous quantities, under normal temperature, nitrogen protection, is added dropwise in step 2) and is obtained Phosphoric acid GMA, 3.5~4.5h of stirring reaction, be added dropwise tri-methyl-chlorosilane, react 3.5~4.5h after, obtain Nitrogen-and Phosphorus-containing silicon list Body THGT, as Nitrogen-and Phosphorus-containing silicon acrylate as fire retarding agent；The addition of toluene di-isocyanate(TDI)-hydroxy ethyl methacrylate half The mol ratio of thing, phosphoric acid GMA and tri-methyl-chlorosilane is 1.5~2.5:0.8~1.2:0.8~1.2.
- A kind of 2. flame retardant epoxy acrylate coatings of the acrylate as fire retarding agent of Nitrogen-and Phosphorus-containing silicon using described in claim 1.
- 3. the preparation method of flame retardant epoxy acrylate coatings according to claim 2, it is characterised in that：To described nitrogenous Epoxy acrylate is added in the acrylate as fire retarding agent of phosphorus silicon, uniformly after mixing, light trigger is added, obtains hybrid resin； The mass ratio of the acrylate as fire retarding agent of the Nitrogen-and Phosphorus-containing silicon, epoxy acrylate and light trigger is 0.8~8.5:1.5~ 7.5:0.3~0.5；The hybrid resin is spread evenly across on coated carrier, illumination curing, produces described epoxy acrylic Ester coating.
- 4. the preparation method of flame retardant epoxy acrylate coatings according to claim 3, it is characterised in that：Will be described nitrogenous After the acrylate as fire retarding agent of phosphorus silicon is disperseed with acrylic acid dilution, epoxy acrylate is added.
- 5. the preparation method of flame retardant epoxy acrylate coatings according to claim 3, it is characterised in that：The Nitrogen-and Phosphorus-containing The mass ratio of the acrylate as fire retarding agent of silicon, epoxy acrylate and light trigger is 0.9~1.1:6.8~7.2:0.35~ 0.45；Or：The mass ratio of the acrylate as fire retarding agent of the Nitrogen-and Phosphorus-containing silicon, epoxy acrylate and light trigger for 1.8~ 2.2:6.8~7.2:0.35~0.45.
- 6. the preparation method of flame retardant epoxy acrylate coatings according to claim 3, it is characterised in that：The Nitrogen-and Phosphorus-containing The mass ratio of the acrylate as fire retarding agent of silicon, epoxy acrylate and light trigger is 2.8~3.2:6.8~7.2:0.35~ 0.45；Or：The mass ratio of the acrylate as fire retarding agent of the Nitrogen-and Phosphorus-containing silicon, epoxy acrylate and light trigger for 3.8~ 4.2:6.8~7.2:0.35~0.45.
- 7. the preparation method of flame retardant epoxy acrylate coatings according to claim 3, it is characterised in that：The Nitrogen-and Phosphorus-containing The mass ratio of the acrylate as fire retarding agent of silicon, epoxy acrylate and light trigger is 4.8~5.2:4.8~5.2:0.35~ 0.45。
- 8. the preparation method of flame retardant epoxy acrylate coatings according to claim 3, it is characterised in that：The Nitrogen-and Phosphorus-containing The mass ratio of the acrylate as fire retarding agent of silicon, epoxy acrylate and light trigger is 5.8~6.2:3.8~4.2:0.35~ 0.45。
- 9. the preparation method of flame retardant epoxy acrylate coatings according to claim 3, it is characterised in that：The Nitrogen-and Phosphorus-containing The mass ratio of the acrylate as fire retarding agent of silicon, epoxy acrylate and light trigger is 7.8~8.2:1.8~2.2:0.35~ 0.45。
- 10. the preparation method of the flame retardant epoxy acrylate coatings according to any one of claim 3 to 9, its feature exist In：The light trigger is light trigger 1173.
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