CN104448237B - It is a kind of suitable for silicon nitrogen phosphorus cooperative flame retardant epoxy powder coating of steel pipe and preparation method thereof - Google Patents
It is a kind of suitable for silicon nitrogen phosphorus cooperative flame retardant epoxy powder coating of steel pipe and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of suitable for epoxy powder coating of silicon nitrogen phosphorus cooperative flame retardant of steel pipe and preparation method thereof.The coating is made up of 30~80wt% silicon P Modification epoxy resin base-material, the epoxy curing agent of the siliceous nitrogen of 2~10wt%, 5~15wt% carbon forming agents, 5~20wt% foaming agents, 5~20wt% char forming catalysts, 0.5~2wt% curing accelerators, 2~10 wt% color stuffings and 0.1~2wt% levelling agents.The coating is that epoxy resin base-material is first carried out into organosilicon, P Modification successively, then the epoxy curing agent with siliceous nitrogen, carbon forming agent, foaming agent, char forming catalyst, curing accelerator, color stuffing and levelling agent progress mix preparation and obtained.Epoxy resin oxygen index (OI) after the present invention is modified solidified is higher than 33.The present invention using electrostatic spray by powder paint on preheating steel, the fire resistance period under the conditions of 800~1000 DEG C of high temperature is longer than 2h.
Description
Technical field
The present invention relates to a kind of anti-flaming dope.More particularly, to a kind of silicon nitrogen phosphorus cooperative flame retardant ring suitable for steel pipe
Oxygen toner coating and preparation method thereof.
Background technology
After steel pipe is offline on steel plant's streamline, its surface corrosion resistance performance is poor, during storage and transport process and use very
Easily it is corroded, has a strong impact on its performance and used life.Once its surface is corroded, its subsequent processes is cumbersome, work
Amount is big.Meanwhile, mechanical property can decline rapidly steel pipe in high temperature environments, and No. 45 steel 0.5h under the conditions of 600 DEG C is opened as
Begin to soften.Therefore, safeguard measure is taken to these steel pipes, it is to avoid its direct calcination by thermal-flame, it is possible to subtract significantly
Few damage of the hot environment to steel pipe part.Using steel tube surface plating alloy in producing at present, the technique such as alramenting is to steel
Pipe is handled, and improves its antiseptic property.Compared with other surfaces anticorrosion treatment technology, painting anticorrosion erosion coating formation coating is protected
Nurse's skill has the incomparable advantage of some other materials such as simple to operation, excellent performance and economic benefit height, meanwhile, resistance
Combustion coating can further enhance the security of steel pipe at high temperature.
Powdery paints has without solvent, reduces the advantages, tool such as environmental pollution, the saving energy, storage stabilization, convenient transportation
There is good economy and social effect.Wherein, Flame Retardant Powder Coatings can be divided into intumescent and the class of non-expansion type two, and non-expansion type is prevented
Fiery coating realizes fireproof purpose by the high flame retardancy of itself, but its heat insulating function needs thicker coating layer thickness real
It is existing；Intumescent coating is then to form honeycomb charring layer and isolate hot environment by meeting fire to realize fire-retardant, thus its thickness can be more
It is thin, cost is advantageously reduced with reducing load-bearing.But, current existing steel tube surface coating played a part of it is more single, it is comprehensive
Poor performance is closed, most importantly fire resistance needs very big raising.
Epoxy resin is widely used in the industries such as semiconductor packages, bonding, coating, the requirement with these industries to security
Increasingly increase, the requirement to the heat-proof combustion-resistant performance of epoxy resin is also constantly being improved.However, traditional additive-based fire-retardant nothing
Method meet fire-retardant, insulation, excellent in mechanical performance and with the composite request such as matrix compatibility is good.Using reactive flame retardant, i.e.,
By ignition-proof element, such as chlorine, bromine, phosphorus element are introduced into epoxy resin-base, can effectively improve the oxygen index (OI) of epoxy resin, but
Be halogenated flame retardant in burning be that can release the materials such as poisonous hydrogen halides, halogenation dibenzodioxin English, and it is discarded after to ring
Border pollution it is larger, thus application be restricted.Phosphorus inherent flame retardant system can improve the hygroscopicity and reduction mechanical property of system, and
Due to the particularity of its structure, the phosphorus contents of most of phosphorous epoxy resin systems is no more than 10%, fire resistance increase rate by
It is therefore, significant using a variety of harmless element cooperative flame retardants to limitation.At present also it is proposed that the collaboration resistance of silicon nitrogen phosphorus
Epoxy resin is fired, is limited by preparation thinking and technique, though its fire resistance improves, but fire resistance
And combination property is still not fully up to expectations.
Accordingly, it is contemplated that develop a kind of fire resistance more preferably, with good adhesive force, weatherability, corrosion resistance,
The outer surface of steel tube anti-corrosion flame retardant coating of the high comprehensive performances such as resistance to elevated temperatures.
The content of the invention
The technical problems to be solved by the invention are that the defect and deficiency for overcoming existing steel tube surface coating have there is provided one kind
There is the outer surface of steel tube anti-corrosion flame retardant coating of good adhesive force, high comprehensive performance.Epoxy resin of the present invention is applied
Material be using the epoxy resin of organosilicon and P Modification as base-material, with reference to the curing agent of siliceous nitrogen, in base-material add carbon forming agent,
Foaming agent, char forming catalyst, curing accelerator etc., effectively improve the fire resistance of coating.
It is an object of the invention to provide a kind of silicon nitrogen phosphorus cooperative flame retardant epoxy powder coating suitable for steel pipe.
Another object of the present invention is to provide the preparation method of the silicon nitrogen phosphorus cooperative flame retardant epoxy powder coating.
Still a further object of the present invention is to provide application and the user of the silicon nitrogen phosphorus cooperative flame retardant epoxy powder coating
Method.
Above-mentioned purpose of the present invention is achieved through the following technical solutions：
It is specifically first successively to epoxy resin present invention firstly provides a kind of method for improving ethoxyline resin antiflaming performance
Silicon, P Modification is carried out to obtain silicon P Modification epoxy resin base-material, then with the epoxy curing agent of siliceous nitrogen solidified；It is described
The epoxy curing agent of siliceous nitrogen has following molecular structural formula：
Wherein, n=1~2500, R is the substituent containing organic amine.
It is with silicon P Modification epoxy resin the invention provides a kind of epoxy powder coating of silicon nitrogen phosphorus cooperative flame retardant
Base-material coordinates the epoxy curing agent of siliceous nitrogen, then with carbon forming agent, foaming agent, char forming catalyst, curing accelerator, color stuffing
Mixed, be prepared from levelling agent.
Preferably, the epoxy powder coating of the silicon nitrogen phosphorus cooperative flame retardant is made up of following component：30~80wt% silicon
P Modification epoxy resin base-material, the epoxy curing agent of the siliceous nitrogen of 2~10wt%, 5~15wt% carbon forming agents, 5~20wt% foaming
Agent, 5~20wt% char forming catalysts, 0.5~2wt% curing accelerators, 2~10 wt% color stuffings and 0.1~2wt% levelling agents, and
And the content sum of above-mentioned each component is 100%.
Wherein, the silicon P Modification epoxy resin base-material is the epoxy resin base-material by silicon P Modification；Preferably, it is described
Epoxy resin base-material is bisphenol A epoxide resin, phenolic aldehyde-epoxy resin, polyglycol type epoxy resins or cycloaliphatic epoxy resin.
The epoxy curing agent of the siliceous nitrogen has following molecular structural formula：
Wherein, n=1~2500, R is the substituent containing organic amine；Preferably amido, fatty amido or anilino- etc..
Preferably, the epoxy curing agent of the siliceous nitrogen is polydimethylsiloxane, the hexichol amido two that amido is blocked
The polydimethylsiloxane of methyl-monosilane, dimethyl dibutyl amino silane or amido end-blocking.
Furthermore it is preferred that the carbon forming agent is organic polyhydroxy compound；
Preferably, the foaming agent is melamine or dicyandiamide；
Preferably, the char forming catalyst is ammonium phosphate, urea phosphate, APP, APP potassium, APP magnesium
Or combination more than one or both of melamine phosphate；
Preferably, the curing accelerator is imidazoles or imdazole derivatives；
Preferably, the color stuffing is precipitated calcium carbonate, barium sulfate, silica flour, talcum powder, wollastonite, iron oxide, oxidation
Combination more than one or both of aluminium, titanium dioxide or zinc oxide；
Preferably, the levelling agent is polyacrylate and its copolymer, Pioloform, polyvinyl acetal or acetate fiber material
Combination more than one or both of material.
It is highly preferred that the carbon forming agent be starch, glucose, cellulose, hemicellulose, lignin or pentaerythrite and its
One or both of derivative.
It is highly preferred that the curing accelerator is imidazoles, 2-methylimidazole or 3- methylimidazoles.The effect of curing accelerator
It is added in the epoxy curing agent of siliceous nitrogen to promote epoxy resin cure.
Present invention also offers a kind of preparation method of the preferred silicon P Modification epoxy resin base-material, specific steps are such as
Under：
S1. according to 500mL：50~80g：5~20 g ratio, adds epoxy resin base-material, dichloro organic in toluene
Silane and/or chlorine end-blocking dimethyl silicone polymer, 3~5h of back flow reaction；
S2. the hydrogen chloride produced in reacting is absorbed with triethylamine, after product is washed with water, evaporation of solvent, and product is done
Dry 1~3h；
S3. dried product is again with after the toluene dissolving of equivalent, according to the ratio that 10g is added in every 500mL toluene,
Add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 3~5h of back flow reaction；
S4. after product is washed with water, evaporation of solvent, product dries 1~3h；
S5. dried product is ground to 100~200 mesh, and silicon P Modification epoxy resin base-material is made.
Wherein, epoxy resin base-material described in step S1 is bisphenol A epoxide resin, phenolic aldehyde-epoxy resin, polyethylene glycol type ring
Oxygen tree fat or cycloaliphatic epoxy resin.
As a kind of embodiment, it is highly preferred that the preparation method of the silicon P Modification epoxy resin base-material is：Every
50~80g epoxy resin base-material, 5~20g dichloros organosilan and/or chlorine end-blocking polydimethylsiloxanes are put into 500mL toluene
Alkane, gas outlet alkali liquor absorption hydrogen chloride, using 3~5h of back flow reaction, the hydrogen chloride produced in reaction is absorbed with triethylamine, production
After thing is washed with water, solvent is removed in rotary evaporator, product dries 1~3h；Dried product uses 500mL first again
After benzene dissolving, 10g DOPO are added（9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide）, 3~5h of back flow reaction, production
After thing is washed with water, solvent is removed in rotary evaporator, product dries 1~3h, is ground to 100~200 mesh, and silicon phosphorus is made
Modified epoxy base-material.
Preferably, the preparation method of the chlorine end-blocking dimethyl silicone polymer is as follows：
S11. according to 100mL：10g：1g ratio, adds the poly- dimethoxysilane and two of dihydroxy end-blocking in toluene
Chlorodimethylsilane, 3~5h of back flow reaction；
S12. the hydrogen chloride alkali liquor absorption produced in reacting, after product is washed with water, evaporation of solvent is dried to obtain
Chlorine blocks dimethyl silicone polymer.
As a kind of embodiment, it is highly preferred that the chlorine blocks the preparation method of dimethyl silicone polymer：Every
Be put into 500mL toluene 50~100g dihydroxy end-blocking poly- dimethoxysilane, 5~10g dichlorodimethylsilane, using return
Stream 3~5h of reaction, the hydrogen chloride alkali liquor absorption produced in reaction after product is washed with water, is removed in rotary evaporator
Solvent, is dried to obtain chlorine end-blocking dimethyl silicone polymer.
In addition, present invention also offers the preparation method of the epoxy powder coating of above-mentioned silicon nitrogen phosphorus cooperative flame retardant, step
It is rapid as follows：
S1. chlorine end-blocking dimethyl silicone polymer is prepared, method is as described above；
S2. silicon P Modification epoxy resin base-material is prepared, method is as described above；
S3. according to mass ratio, silicon P Modification epoxy resin base-material and levelling agent are mixed at 110 DEG C, premixing is made
Material；
S4. according to mass ratio, by the epoxy curing agent of premix and siliceous nitrogen, curing accelerator, carbon forming agent, into
After Pd/carbon catalyst, foaming agent, color stuffing mixing, ball mill is put into, 12~24h of ball milling obtains the powder of 100~200 mesh after screening
Last coating.
The epoxy powder coating that the present invention also provides above-mentioned silicon nitrogen phosphorus cooperative flame retardant is improving steel pipe fire resistance side
The application in face.Preferably, it is to be sprayed on steel tube surface as surface coating（It is preferred that coating thickness is 2.5~3cm）, to improve it
Fire resistance, further, other combination properties of steel pipe（Such as weatherability, corrosion resistance）Also it is increased dramatically.Specifically
The method of application is to use electrostatic coating method, by powder paint to the steel tube surface for being preheated to 130 DEG C.
The present invention is explored and studied by a large amount of, and epoxy resin base-material is first carried out into organic-silicon-modified, P Modification successively, obtained
To silicon P Modification epoxy resin base-material, then again with the epoxy curing agent of siliceous nitrogen, carbon forming agent, foaming agent, be catalyzed into charcoal
12~24h of ball milling after agent, curing accelerator, color stuffing and levelling agent are mixed, it is screened to obtain 100~200 mesh powders
Coating.Raw materials used and proportioning is obtained by a large amount of explorative experiments and checking, has reached that silicon nitrogen phosphorus Synergistic is fire-retardant
Purpose, oxygen index (OI) is higher than 33 after the modified epoxy solidification prepared（General oxygen index (OI) ＞ 27 just belongs to category nonflammable material,
And oxygen index (OI) is higher shows that fire resistance is better）, the epoxy powder coating prepared is sprayed on preheating steel, in height
Fire resistance period under the conditions of 800~1000 DEG C of temperature is longer than 2h.
The invention has the advantages that：
Epoxy resin base-material is carried out organic-silicon-modified, P Modification by the present invention successively first, obtains silicon P Modification asphalt mixtures modified by epoxy resin
Aliphatic radical material, then solidified with the epoxy curing agent of siliceous nitrogen, to improve the anti-flammability of epoxy resin.Modified epoxy
Oxygen index (OI) is above 33 after solidification, and the fire resistance period under the conditions of 800~1000 DEG C of high temperature is longer than 2h, ethoxyline resin antiflaming performance
Obtain the lifting of matter.
The present invention is added containing higher on the basis of silicon, nitrogen, phosphor coordinate antiflaming system is obtained in coating system
Nitrogen, phosphorus than foaming agent and char forming catalyst, its advantage embody it is as follows：In heated or combustion process, phosphorus promotes burnt
Charcoal is formed, and silicon increases the heat endurance of these carbon-coatings, and nitrogen can discharge the gas formation Foam Expansion structure of non-flammable, suppress
The formation of flammable volatile matter and the entrance of extraneous oxygen, further improve matrix fire resistance.
The epoxy powder coating of the present invention is with low cost, and the adhesion with metal surface is high, heat-resist, in steel
Surface spraying is into 2.5~3cm coating, and the fire resistance period under the conditions of 800~1000 DEG C of high temperature is longer than 2h.
Embodiment
The present invention is further illustrated below in conjunction with specific embodiment, but embodiment does not do any type of to the present invention
Limit.Unless stated otherwise, the reagent of the invention used, method and apparatus is the art conventional reagent, methods and apparatus.
Unless stated otherwise, agents useful for same and material of the present invention are purchased in market.
Embodiment 1
1st, chlorine end-blocking dimethyl silicone polymer is prepared
Under nitrogen protection, 500mL toluene, poly- the two of 50g dihydroxy end-blocking are added in the there-necked flask equipped with condenser pipe
Methoxy silane, 5g dichlorodimethylsilane, gas outlet alkali liquor absorption hydrogen chloride, 3~5h of back flow reaction.Product is washed with water
Solvent is removed in rotary evaporator again afterwards, chlorine end-blocking dimethyl silicone polymer is dried to obtain.
2nd, silicon P Modification epoxy resin base-material is prepared
Under nitrogen protection, 500mL toluene, 50g epoxy resin base-materials BE188 are added in the there-necked flask equipped with condenser pipe
（Epoxide equivalent 182-192g/mol）, 10g chlorine end-blocking dimethyl silicone polymer, gas outlet alkali liquor absorption hydrogen chloride, using return
Stream 3~5h of reaction, the hydrogen chloride produced in reaction is absorbed with triethylamine, after product is washed with water, and is removed in rotary evaporator
Solvent is removed, product dries 1~3h, again with after the dissolving of 500mL toluene, add 10g DOPO（Miscellaneous-the 10- of 9,10- dihydro-9-oxies
Phospho hetero phenanthrene -10- oxides）, 3~5h of back flow reaction after product is washed with water, removes solvent, product in rotary evaporator
1~3h is dried, 100~200 mesh are ground to, silicon P Modification epoxy resin base-material is made.
3rd, silicon P Modification epoxy resin base-material solidifies
Under the conditions of 130 DEG C, the poly- diformazan that organic silicon-phosphorus modified epoxy base-material obtained above is blocked with amido
Base silane（Molecular weight 600）Solidification crosslinking.Its limited oxygen index is tested to obtain according to GB/T2406.1-2008 methods（LOI）It is
36.3。
4th, fire retarding epoxide resin powder paint is prepared
（1）Prepare 100kg epoxy powder coatings：1.5kg CDS-55-1 cellaburates and 44kg silicon phosphorus are changed
Property epoxy resin base-material mixed at 110 DEG C after be made premix, then with 3kg curing agent amine groups block polydimethylsiloxane
（Molecular weight 600）, 0.5kg curing accelerators 2-methylimidazole, 15kg carbon forming agents pentaerythrite, 15kg char forming catalyst tricresyl phosphates
Poly cyanamid, 15kg foaming agents dicyandiamide, 6kg color stuffing precipitated calcium carbonates are put into the powder that 200 mesh are obtained after ball mill 12h, screening
Last coating.
（2）Gained powdery paints will be prepared and carry out cell combustion method measure with reference to GB/T 15442.4-1995, as a result shown
Show, mass loss is 3.4g, char volume is 6.5cm3。
5th, fire retarding epoxide resin powder paint obtained above is sprayed onto using electrostatic coating method using spray gun and be preheated to
On 130 DEG C of steel pipe, thickness is 3cm.
Embodiment 2
1st, chlorine end-blocking dimethyl silicone polymer, method be the same as Example 1 are prepared.
2nd, silicon P Modification epoxy resin base-material is prepared
Under nitrogen protection, 500mL toluene, 50g epoxy resin base-materials BE188 are added in the there-necked flask equipped with condenser pipe
（Epoxide equivalent 182-192g/mol）, 5g chlorine end-blocking dimethyl silicone polymer, 5g dichlorodimethylsilane, gas outlet is inhaled with alkali lye
Hydrogen chloride is received, using 3~5h of back flow reaction, the hydrogen chloride produced in reaction is absorbed with triethylamine, after product is washed with water, in rotation
Solvent is removed in rotatable evaporator, product dries 1~3h, again with after the dissolving of 500mL toluene, add 10g DOPO（9,10- bis-
Hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxides）, 3~5h of back flow reaction, after product is washed with water, in rotary evaporator
Solvent is removed, product dries 1~3h, is ground to 100~200 mesh, and silicon P Modification epoxy resin base-material is made.
3rd, silicon P Modification epoxy resin base-material solidifies
Under the conditions of 130 DEG C, by organic silicon-phosphorus modified epoxy base-material obtained above hexichol amido dimethyl-silicon
Alkane solidification crosslinking.Its limited oxygen index is tested to obtain according to GB/T2406.1-2008 methods（LOI）It is 35.1.
4th, fire retarding epoxide resin powder paint is prepared
（1）Prepare 100kg epoxy powder coatings：1.5kg CDS-55-1 cellaburates and 44kg silicon phosphorus are changed
Property epoxy resin base-material mixed at 110 DEG C after be made premix, then with 3kg hexichol amido dimethylsilanes, 0.5kg solidification
Accelerator 2-methylimidazole, 15kg carbon forming agents lignin, 15kg char forming catalysts ammonium phosphate, 15kg foaming agents melamine, 3kg
Color stuffing talcum powder, 3kg color stuffing titanium dioxide, which are put into after ball mill 12h, screening, obtains 200 mesh powder coating.
（2）Gained powdery paints will be prepared and carry out cell combustion method measure with reference to GB/T 15442.4-1995, as a result shown
Show, mass loss is 3.2 g, and char volume is 5.4cm3。
5th, fire retarding epoxide resin powder paint obtained above is sprayed onto using electrostatic coating method using spray gun and be preheated to
On 150 DEG C of steel pipe, thickness is 2.5cm.
Embodiment 3
1st, chlorine end-blocking dimethyl silicone polymer, method be the same as Example 1 are prepared.
2nd, silicon P Modification epoxy resin base-material is prepared
Under nitrogen protection, 500mL toluene, 80g epoxy resin base-materials are added in the there-necked flask equipped with condenser pipe
DER331（Epoxide equivalent 182-192g/mol）, 10g dichlorodimethylsilane, gas outlet alkali liquor absorption hydrogen chloride, using return
Stream 3~5h of reaction, the hydrogen chloride produced in reaction is absorbed with triethylamine, after product is washed with water, and is removed in rotary evaporator
Solvent is removed, product dries 1~3h, again with after the dissolving of 500mL toluene, add 10g DOPO（Miscellaneous-the 10- of 9,10- dihydro-9-oxies
Phospho hetero phenanthrene -10- oxides）, 3~5h of back flow reaction, product removes solvent in rotary evaporator again after being washed with water, product is done
Dry 1~3h, is ground to 100~200 mesh, and silicon P Modification epoxy resin base-material is made.
3rd, silicon P Modification epoxy resin base-material solidifies
Under the conditions of 130 DEG C, by organic silicon-phosphorus modified epoxy base-material obtained above dimethyl dibutyl amino silicon
Alkane solidification crosslinking.Its limited oxygen index is tested to obtain according to GB/T2406.1-2008 methods（LOI）It is 33.8.
4th, fire retarding epoxide resin powder paint is prepared
（1）Prepare 100kg epoxy powder coatings：1.5kg CDS-55-1 cellaburates and 44kg silicon phosphorus are changed
Property epoxy resin base-material mixed at 110 DEG C after be made premix, then with 3kg curing agent dimethyl dibutyl amino silane,
0.5kg curing accelerators 2-methylimidazole, 15kg carbon forming agents lignin, 15kg char forming catalysts ammonium phosphate, 15kg foaming agents three
Poly cyanamid, 3kg color stuffings talcum powder, 3kg color stuffing titanium dioxide, which are put into after ball mill 12h, screening, obtains the painting of 200 mesh powders
Material.
（2）Gained powdery paints will be prepared and carry out cell combustion method measure with reference to GB/T 15442.4-1995, as a result shown
Show, mass loss is 2.9 g, and char volume is 4.8cm3。
5th, fire retarding epoxide resin powder paint obtained above is sprayed onto using electrostatic coating method using spray gun and be preheating to
On 130 DEG C of steel pipe, thickness is 3cm.
Embodiment 4
1st, chlorine end-blocking dimethyl silicone polymer and silicon P Modification epoxy resin base-material, method be the same as Example 1 are prepared.
2nd, silicon P Modification epoxy resin base-material solidifies
Under the conditions of 130 DEG C, the poly- diformazan that organic silicon-phosphorus modified epoxy base-material obtained above is blocked with amido
Base silane（Molecular weight 600）Solidification crosslinking.Its limited oxygen index is tested to obtain according to GB/T2406.1-2008 methods（LOI）It is
35.5。
3rd, fire retarding epoxide resin powder paint is prepared
（1）Prepare 100kg epoxy powder coatings：By 1kg butyl acrylates and 50kg silicon P Modification epoxy resin-matrixes
Premix, then the polydimethylsiloxane blocked with 4kg curing agent amine groups is made in material after being mixed at 90 DEG C（Molecular weight 600）,
0.5kg curing accelerators 2-methylimidazole, 15kg carbon forming agents pentaerythrite, 15kg char forming catalysts melamine phosphate, 15kg
Foaming agent dicyandiamide, 6kg color stuffing iron oxide, which are put into after ball mill 12h, screening, obtains 200 mesh powder coating.
（2）Gained powdery paints will be prepared and carry out cell combustion method measure with reference to GB/T 15442.4-1995, as a result shown
Show, mass loss is 2.8g, char volume is 6.2cm3。
4th, fire retarding epoxide resin powder paint obtained above is sprayed onto using electrostatic coating method using spray gun and be preheated to
On 130 DEG C of steel pipe, thickness is 3cm.
Comparative example
1st, silicon P Modification epoxy resin base-material is prepared according to the method for embodiment 1.
2nd, it is grouped
First group is that silicon P Modification epoxy resin base-material coordinates different curing agent；
Second group is curing agent that epoxy resin BE188 coordinates siliceous nitrogen；
3rd group is the curing agent also without siliceous nitrogen both without silicon P Modification epoxy resin base-material.
It is specific as shown in table 1.
3rd, according to each group of table 1 epoxy resin base-material and curing agent combination, solidified according to the method for embodiment 1,
Limited oxygen index LOI is tested according to GB/T2406.1-2008 methods after solidification crosslinking, as a result as shown in table 1.
Table 1
Claims (6)
1. a kind of method for the fire resistance for improving the epoxy resin suitable for steel pipe, it is characterised in that first successively to epoxy
Resin carries out silicon, P Modification and obtains silicon P Modification epoxy resin base-material, then solidified with the epoxy curing agent of siliceous nitrogen；
The epoxy curing agent of the siliceous nitrogen has following molecular structural formula：
Wherein, n=1~2500, R is the substituent containing organic amine；
The preparation method of the silicon P Modification epoxy resin base-material is as follows：
S1. according to toluene：Epoxy resin base-material：Dichloro organosilan and/or chlorine end-blocking dimethyl silicone polymer=500mL：50~
80g：5~20g ratio, adds epoxy resin base-material, dichloro organosilan and/or chlorine end-blocking polydimethylsiloxanes in toluene
Alkane, 3~5h of back flow reaction；
S2. the hydrogen chloride produced in reacting is absorbed with triethylamine, after product is washed with water, evaporation of solvent, and product drying 1~
3h；
S3. dried product, according to the ratio that 10g is added in every 500mL toluene, is added again with after the toluene dissolving of equivalent
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 3~5h of back flow reaction；
S4. after product is washed with water, evaporation of solvent, product dries 1~3h；
S5. dried product is ground to 100~200 mesh, and silicon P Modification epoxy resin base-material is made；
Wherein, epoxy resin base-material described in step S1 is bisphenol A epoxide resin, phenolic aldehyde-epoxy resin, polyglycol type epoxy tree
Fat or cycloaliphatic epoxy resin.
2. according to the method described in claim 1, it is characterised in that the preparation method of the chlorine end-blocking dimethyl silicone polymer is such as
Under：
S11. according to 100mL：10g：1g ratio, adds the poly- dimethoxysilane and dichloro two of dihydroxy end-blocking in toluene
Methyl-monosilane, 3~5h of back flow reaction；
S12. the hydrogen chloride alkali liquor absorption produced in reacting, after product is washed with water, evaporation of solvent is dried to obtain chlorine envelope
Hold dimethyl silicone polymer.
3. the epoxy powder coating of a kind of silicon nitrogen phosphorus cooperative flame retardant suitable for steel pipe, it is characterised in that by following component
Composition：30~80wt% silicon P Modification epoxy resin base-material, the epoxy curing agent of the siliceous nitrogen of 2~10wt%, 5~15wt% into
Charcoal agent, 5~20wt% foaming agents, 5~20wt% char forming catalysts, 0.5~2wt% curing accelerators, 2~10 wt% color stuffings and
0.1~2wt% levelling agents；
The carbon forming agent is organic polyhydroxy compound；
The foaming agent is melamine or dicyandiamide；
The char forming catalyst is ammonium phosphate, urea phosphate, APP, APP potassium, APP magnesium or phosphoric acid trimerization
Combination more than one or both of cyanamide；
The curing accelerator is imidazoles or imdazole derivatives；
The color stuffing is precipitated calcium carbonate, barium sulfate, silica flour, talcum powder, wollastonite, iron oxide, aluminum oxide, titanium dioxide
Or combination more than one or both of zinc oxide；
The levelling agent be polyacrylate and its one kind in copolymer, Pioloform, polyvinyl acetal or cellulose acetate material or
Two or more combinations；
The epoxy curing agent of the siliceous nitrogen is as described in the appended claim 1；
The preparation method of the silicon P Modification epoxy resin base-material is as described in the appended claim 1.
4. being applied to the epoxy powder coating of the silicon nitrogen phosphorus cooperative flame retardant of steel pipe according to claim 3, its feature exists
In the carbon forming agent is one kind in starch, glucose, cellulose, hemicellulose, lignin or pentaerythrite and its derivative
Or two or more combinations；The curing accelerator is imidazoles, 2-methylimidazole or 3- methylimidazoles.
5. it is applied to the epoxy powder coating of the silicon nitrogen phosphorus cooperative flame retardant of steel pipe, its feature according to claim 3 or 4
It is, is prepared by the method comprised the following steps：
S1. chlorine end-blocking dimethyl silicone polymer is prepared, method is as claimed in claim 2；
S2. silicon P Modification epoxy resin base-material is prepared, method is as claimed in claim 1；
S3. according to mass ratio, silicon P Modification epoxy resin base-material and levelling agent are mixed at 110 DEG C, premix is made；
S4. according to mass ratio, by premix and the epoxy curing agent of siliceous nitrogen, curing accelerator, carbon forming agent, urge into charcoal
After agent, foaming agent, color stuffing mixing, 12~24h of ball milling obtains 100~200 mesh powder coating after screening.
6. the epoxy powder coating of the silicon nitrogen phosphorus cooperative flame retardant described in claim 3 or 4 suitable for steel pipe is improving steel pipe
Application in terms of fire resistance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110760244A (en) * | 2019-11-20 | 2020-02-07 | 应急管理部四川消防研究所 | Epoxy steel structure fireproof coating |
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| CN106008919B (en) * | 2016-06-12 | 2018-02-09 | 福州大学 | A kind of silane hydrophobically modified phosphorus-containing flame-retardant epoxy resin and preparation method thereof |
| CN106189566B (en) * | 2016-07-25 | 2018-09-07 | 太原理工大学 | A kind of expandable flame retardant coating and preparation method thereof for engineering plastic surface |
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| CN107057517B (en) * | 2016-12-22 | 2019-11-05 | 广东一通科技股份有限公司 | A kind of silicon nitrogen phosphorus cooperative flame retardant aqueous epoxy resins and preparation method thereof of silsesquioxane crosslinking |
| CN107474223B (en) * | 2017-08-19 | 2019-07-09 | 福建师范大学泉港石化研究院 | A kind of siliceous nitrogen benzimidazole type epoxy curing agent and preparation method thereof |
| CN109096471B (en) * | 2018-07-27 | 2020-11-27 | 武汉工程大学 | P-N-Si synergistic flame-retardant epoxy resin curing agent and preparation method thereof |
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| CN114032011B (en) * | 2021-12-17 | 2022-05-17 | 佛山市蓝林新材料科技有限公司 | High-brightness electroplating effect imitating powder coating and preparation method thereof |
| CN116928492B (en) * | 2023-07-06 | 2024-01-30 | 辽宁华益管业有限责任公司 | Coating composite steel pipe for coal mine |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101698700A (en) * | 2009-11-03 | 2010-04-28 | 厦门大学 | Silicon, nitrogen and phosphor coordinate antiflaming epoxide resin |
| CN101712749A (en) * | 2009-11-19 | 2010-05-26 | 中国科学院广州化学研究所 | Silicon nitride hybridization type epoxy resin curing agent and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101044204A (en) * | 2004-11-26 | 2007-09-26 | 株式会社Lg化学 | Non-halogen flame retardant epoxy resin composition, and prepreg and copper-clad laminate using the same |
-
2014
- 2014-11-05 CN CN201410616991.6A patent/CN104448237B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101698700A (en) * | 2009-11-03 | 2010-04-28 | 厦门大学 | Silicon, nitrogen and phosphor coordinate antiflaming epoxide resin |
| CN101712749A (en) * | 2009-11-19 | 2010-05-26 | 中国科学院广州化学研究所 | Silicon nitride hybridization type epoxy resin curing agent and preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110760244A (en) * | 2019-11-20 | 2020-02-07 | 应急管理部四川消防研究所 | Epoxy steel structure fireproof coating |
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