CN104178005A - Single-component heavy-duty corrosion-resistant polyurea for buried pipeline and preparation method of polyurea - Google Patents
Single-component heavy-duty corrosion-resistant polyurea for buried pipeline and preparation method of polyurea Download PDFInfo
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Abstract
The invention discloses single-component heavy-duty corrosion-resistant polyurea for a buried pipeline. The polyurea is prepared from the following components in parts by weight: 25-70 parts of isocyanate, 50-80 parts of polyalcohol, 5-30 parts of hindered amine compound, 10-30 parts of solvent, 5-40 parts of filler, 0.5-2 parts of defoamer, 0.5-2 parts of catalyst, 1-3 parts of pigment, 5-15 parts of latent curing agent, 5-10 parts of water absorbent and 1-3 parts of retarder, wherein the isocyanate is aliphatic isocyanate and/or aromatic isocyanate. The hindered amine compound is added into the single-component heavy-duty corrosion-resistant polyurea, so that a urea group is introduced in the component to increase the polarity of the component, thereby increasing the attraction of a hard segment of the single-component heavy-duty corrosion-resistant polyurea. The single-component heavy-duty corrosion-resistant polyurea is more compact, and the oil resistance, the medium resistance and the microbial resistance of the single-component heavy-duty corrosion-resistant polyurea are improved. The single-component heavy corrosion-resistant polyurea disclosed by the invention can be used for repairing a heavy-duty corrosion-resistant coating for the buried pipeline.
Description
Technical field
The present invention relates to polyureas technology, relate in particular to heavy anticorrosion polyureas of single component and preparation method thereof for a kind of buried pipeline.
Background technology
Along with the development of national economy, buried pipeline, as important town and country Infrastructure, logistics channel, is being born important effect in social and economic activities.The advantage that buried pipeline is numerous is approved by masses day by day, yet the caused variety of problems of the leakage of buried pipeline is also paid attention to by popular day by day.The residing circumstance complication of buried pipeline is changeable, and corrosion condition is complicated, by its outer wall corrosion, causes that pipeline damage becomes the major cause of leakage.
The outer wall of buried pipeline is to be mainly subject to soil corrosion, comprises soil type, soil resistivity, soil moisture content (humidity), pH, sulfide content, redox potential, stray current and interfering current, microorganism, root system of plant etc.The corrosion of hence one can see that buried pipeline outer wall is very complicated.In the outer corrosion control > > of the buried or lower water metal piping system of NACE RP0169-1996 < <, stipulated the performance requriements of buried pipeline protective system: 1, effective electrical insulating property; 2, effective water preventing ability; 3, the method that is coated on pipeline can not have a negative impact to tube performance; 4, the deficiency of protection coating being coated on pipeline is few; 5, there is good sticking power with pipe surface; 6, can prevent that the defect that pipeline is filmed from developing in time; 7, can prevent that pin hole from developing in time; 8, the damage in the time of resisting handling storage and installation; 9, can effectively keep insulation resistance invariable in time; 10, peeling resistance; 11, anti-chemical mediator destroys; 12, mend wound easily; 13, physicals hold facility is strong; 14, nontoxic to environment; 15, can prevent that ground from storing and long-distance transportation process does not change and degrades.
Two-component spraying polyurea anti-corrosion coating has excellent physicals, antiseptic property and workability: quick solidifying, and be that coagulable is dry several seconds, and pipeline continuous spray does not trickle, the lower pipe time is short, and coating, without baking, is suitable for streamline high efficiency production; 100% solid content, non-volatility organism, meets environmental requirement; Coating is fine and close, and without seam, medium-resistance is outstanding, is applicable to use under strong corrosive environment; Physical strength is high, carrying, easy damaged not in hoisting process; Heavy anticorrosion carbamide paint, without primary coat, can be painted on sandblast to the steel substrate surface of Sa2.5 level; Use temperature wide ranges, can be in-50～150 ℃ life-time service; Dielectric strength is up to 25kV/mm; Good with galvanic protection matching capacity; Repaired mouth excellent property.At present two-component spraying polyurea materials has obtained large-scale application in the buried pipeline outer walls such as cast tube, cement pipe anticorrosion.
Polyurea anti-corrosion coating performance is superior, but has certain problem when construction.Spray polyurea coating is short because of the gel time of A component and B component, must use expensive spraying equipment ability spraying application.During to small area or little engineering construction, cost is expensive, is unfavorable for promoting, and engineering construction is limited, has hindered the development of polyurea materials.And after spray polyurea spraying, gel time is short, only there are short tens of seconds, curing speed is fast, at node, turning, duct sealing etc., locate construction time, be prone to coating thickness inhomogeneous, the phenomenons such as drain spray, are unfavorable for constructing in narrow, complex environment operating mode, have hindered the development and application of polyurea materials.
Two-component spraying polyureas has had application widely aspect anticorrosion buried pipeline outer wall is heavy, yet in transportation, in using, destroy to some extent unavoidably, lack, so the repairing of buried pipeline mostly occurs in broad field or underground, short of electricity, oil starvation, cannot accurate measurement, be unfavorable for repairing.For convenience of the repairing of buried pipeline outer wall corrosion protection coating, developing a kind of is very necessary without metering, the heavy anticorrosion carbamide paint of single component easily of constructing.The heavy anticorrosion carbamide paint component of single component is single, without accurate-metering, and can be by the technique that sprays or brush for the coating of buried pipeline outer wall or the repairing of coating after being uniformly mixed.
Summary of the invention
The small area that the object of the invention is, complex process short for the two-component spraying polyurea gel time, is not suitable for buried pipeline outer wall coating repair and bicomponent system cannot accurate-metering in severe environment, use the shortcomings such as limited, a kind of buried pipeline is proposed outer anticorrosion with the heavy anticorrosion polyureas of single component, it is when oil resistant, resistance to liquid medium, weathering resistance and ageing resistance are superior, consistent with its mechanical properties of the anticorrosion polyureas of pipeline outer wall, sticking power is excellent.
For achieving the above object, the application adopts following technical scheme:
The heavy anticorrosion polyureas of single component for buried pipeline, comprises each component that weight proportion is following: isocyanic ester 25-70 part, preferably 40-67 part; Polyvalent alcohol 50-80 part, preferably 65-72 part; Bulky amine compound 5-30 part, preferably 9-25 part; Solvent 10-30 part, preferably 10-20 part; Filler 5-40 part, preferably 15-30 part; Defoamer 0.5-2 part, preferably 1-2 part; Catalyzer 0.5-2 part, preferably 1-2 part; Pigment 1-3 part, preferably 2-3 part; Latent curing agent 5-15 part, preferably 5-9 part; Water-retaining agent 5-10 part, preferably 6-8 part; Retardant 1-3 part, preferably 2-3 part.Wherein, described isocyanic ester is aliphatic isocyanates and/or aromatic isocyanate.
Aliphatic isocyanates described in the present invention is one or more in isophorone diisocyanate (IPDI), 4,4 ' dicyclohexyl methane diisocyanate (HMDI) and hexamethylene diisocyanate (HDI).Be preferably HMDI and/or HDI.
Aromatic isocyanate described in the present invention is one or more in tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI) and PPDI (PPDI).Be preferably TDI and/or MDI.
Polyvalent alcohol described in the present invention is one or more in biopolyol, polyoxytrimethylene ethoxylated polyhydric alcohol and polytetrahydrofuran polyvalent alcohol.Preferred described biopolyol is Viscotrol C and derivative thereof, soybean oil polyvalent alcohol, plam oil polyvalent alcohol etc.Further preferred polyvalent alcohol is one or more in polyoxytrimethylene ether glycol, polyoxytrimethylene ether triol and polytetrahydrofuran diol; Described polyoxytrimethylene ether glycol, polyoxytrimethylene ether trivalent alcohol molecular weight are 1000,2000,3000, and described polytetrahydrofuran diol molecular weight is 650,1000,2000.
The compound of bulky amine described in the present invention is one or more in Desmophen NH1420, Desmophen NH1520, Desmophen NH1220, Unilink4200, Unilink4100, Clearlink1000, Clearlink3000, Jefflink555 and Jefflink754.
Solvent described in the present invention is one or more in ethyl acetate, butylacetate, acetone, toluene and dimethylbenzene, and solvent of the present invention need be processed dehydration with molecular sieve.Preferred described solvent is butylacetate and/or dimethylbenzene.
Filler described in the present invention is one or more in fine particle calcium carbonate, coarse whiting, talcum powder, calcium hydroxide, zinc phosphate and mica powder, and described filler is more than 800 orders.
Defoamer described in the present invention is one or more in BYK-066N, BYK-054 and BYK-5500.
Catalyzer described in the present invention is one or more in dibutyl tin laurate, dibutyltin diacetate, stannous octoate, isocaprylic acid lead, phenylmercury acetate.
Latent curing agent described in the present invention is one or more in imines class ALT-403, ALT-102.
A kind of for in calcium oxide or 4A molecular sieve of water-retaining agent described in the present invention.
Retardant described in the present invention is one or more in Benzoyl chloride, Tosyl chloride, citric acid.Preferred Benzoyl chloride.
One or more in the titanium dioxide of pigment optimization described in the present invention, iron oxide red, molybdenum red, indigo-blue indigo plant and carbon black.
Another object of the present invention is to provide the preparation method of above-mentioned buried pipeline with the heavy anticorrosion polyureas of single component, specifically comprise the steps:
A. when isocyanic ester is aliphatic isocyanates or aromatic isocyanate:
1. polyvalent alcohol, bulky amine compound, filler, pigment are added in container, open and stir, be heated to 110～120 ℃, vacuum hydro-extraction is removed raw water to water ratio and is less than 3/10000ths, and being cooled to liquid material temperature is 20-30 ℃, is preferably 25 ℃;
Stirring can make reaction raw materials thermally equivalent, is conducive to removing of moisture; Especially when polyvalent alcohol is while being multiple, stirring can also make multiple polyvalent alcohol mix;
2. solvent and isocyanic ester after molecular sieve dehydration being processed join in said vesse again, are warming up to 50 ℃, after stirring reaction 0.5-1 hour, be preferably 1 hour, after being slowly warming up to target temperature, continue reaction, sampling detects NCO% value and reaches after design load 98-102%, is cooled to 30 ℃; Wherein,
When isocyanic ester is aliphatic isocyanates, described target temperature is 110-120 ℃, continues reaction 7-8 hour;
When isocyanic ester is aromatic isocyanate, described target temperature is 80-90 ℃, continues reaction 2-3 hour;
3. in above-mentioned reaction system, add latent curing agent, defoamer, retardant, water-retaining agent and catalyzer, stir 0.5 hour, discharging sealing.
B. when isocyanic ester is aliphatic isocyanates and aromatic isocyanate:
The same A of method, but step is 2. for to join solvent and aliphatic isocyanates in container, be warming up to 50 ℃, after stirring reaction 0.5-1 hour, add again aromatic isocyanate, slowly be warming up to 80～90 ℃ of reaction 1.5-2.5 hour, sampling detects NCO% value and reaches after design load 98-102%, is cooled to 30 ℃.
Vacuum described in the inventive method adopts vacuum pump to realize, and vacuum tightness is-0.1～-0.08MPa; Described slow intensification is in 0.5-1 hour, by 50 ℃, rises to target temperature (80-90 ℃ or 110-120 ℃).Due to the rising along with temperature, reaction aggravation, is prone to implode, therefore need slowly to heat up, speed of response is little by little accelerated.Reaction finishes to be as the criterion to detect NCO, and NCO% value is similar to design load.NCO% design load of the present invention is to calculate theoretical nco value by formulating of recipe.
Single component polyurea protection coating provided by the invention adopts the curing mode film-forming of wet steam, be that NCO group in single component polyurea protection coating reacts with airborne steam and generates aminocompound, aminocompound again with remaining NCO radical reaction film-forming.
The present invention is incorporated into bulky amine compound in synthesizing of the heavy anticorrosion polyureas of single component.Adding of bulky amine compound makes to introduce urea groups in polyureas, increases the polarity of polyureas, promoted the soft or hard of material to be separated, and makes the performance after product film forming more superior.
Than prior art, buried pipeline provided by the invention has the following advantages with heavy anticorrosion polyureas of single component and preparation method thereof:
(1), the present invention is single-component system, includes latent curing agent, under air-proof condition, there is no steam in system, stable system is preserved.When Kaifeng is used, the latent curing agent in system preferentially reacts with airborne steam, generates amino chainextender, and amino chainextender weighs NCO radical reaction in anticorrosion polyureas, film-forming with single component again.Because gel time is long, surface drying time is 4-6 hour, and then has extended operable time, and application property is strong.The longer operating time can make form of construction work simple and convenient, can realize manual blade coating, brushing.Can in narrow, complicated operating mode, construct, especially in node, flex point or the construction of coating disappearance place.The heavy anticorrosion polyureas construction of single component of the present invention is simple, successful, for the repairing of buried pipeline anticorrosion coat, can reduce use cost, improves the working efficiency of complex working condition.
(2), the heavy anticorrosion polyureas of single component of the present invention is with aliphatic isocyanates, or the mixture of aliphatic isocyanates and aromatic isocyanate is main raw material, in single component, weigh in synthesizing of anticorrosion polyureas and add bulky amine compound, thereby in polyureas, introduce urea groups, increased the polarity of polyureas, the magnetism that has increased the hard section of material, makes material finer and close, has improved the oil-proofness of material, performance resistance to medium, resistance to microorganism.Buried pipeline of the present invention is used with the repairing that the heavy anticorrosion polyureas of single component can be used for buried pipeline anticorrosion coat.
(3), the present invention introduces urea groups in the heavy anticorrosion polyureas of single component, also increased the mechanics effect of polyurea materials, improves the sticking power with base material.Without primary coat in the situation that, the sticking power >=9MPa on steel substrate, sticking power is superior.The heavy anticorrosion polyureas film-forming back draft intensity >=18MPa of single component, elongation at break >=10%, tear strength >=60N/mm.
(4), preparation method of the present invention simply, easily goes, and can realize the heavy anticorrosion polyureas suitability for industrialized production of single component for buried pipeline.
Specific examples mode
Embodiment 1
The present embodiment discloses the heavy anticorrosion polyureas of single component for a kind of buried pipeline, comprises each component that weight proportion is following:
The preparation method of the heavy anticorrosion polyureas of single component for the buried pipeline that the present embodiment provides:
1. by above-mentioned weight part, Viscotrol C, Desmophen NH1420,800 order fine particle calcium carbonates, carbon black are joined in container, by liquid material stirring at low speed after 5 minutes, be heated to 110～120 ℃, open vacuum pump, vacuum tightness is-0.1～-0.08MPa, and vacuum hydro-extraction 2h removes a small amount of water containing in raw material, detect water ratio and reach below 3/10000ths, being cooled to liquid material temperature is 25 ℃ of left and right.
2. by weight N-BUTYL ACETATE, HDI are joined in said vesse, be warming up to 50 ℃, stirring reaction 1 hour, question response heat release finishes to be slowly warming up to 110～120 ℃ afterwards, keep reaction 8h, sampling, after detection NCO% value is qualified, is cooled to 30 ℃, add defoamer BYK-066N, catalyzer dibutyl tin laurate, latent curing agent ALT-403, sustained release dosage Benzoyl chloride and water-retaining agent 4A molecular sieve, stir after 0.5 hour discharging, sealing.
To the buried pipeline of above-mentioned preparation with the heavy anticorrosion polyureas of single component at 25 ℃, under humidity 65% environment, by the experimental technique GB/T16777-2008 of architectural waterproof material, carry out Mechanics Performance Testing, detected result is as shown in table 1.
The mechanical experimental results of table 1 embodiment 1
From table 1, buried pipeline prepared by the present embodiment has excellent oil-proofness and resistance to liquid medium performance with the heavy anticorrosion polyureas of single component; Mechanical property is good, reaches unanimity with the polyureas performance on pipeline, and compatible effect is good; Also there is longer gel time 3 hours, can realize manual blade coating, brushing.
Embodiment 2
The present embodiment discloses the heavy anticorrosion polyureas of single component for a kind of buried pipeline, comprises each component that weight proportion is following:
The preparation method of the heavy anticorrosion polyureas of single component for the buried pipeline that the present embodiment provides:
1. by above-mentioned weight part, polyoxytrimethylene ethoxylated polyhydric alcohol PPG-1000, Desmophen NH1420,800 order fine particle calcium carbonates, 800 order talcum powder, carbon black are joined in container, by liquid material stirring at low speed after 5 minutes, be heated to 110～120 ℃, open vacuum pump, vacuum tightness is-0.1～-0.08MPa, and vacuum hydro-extraction 2h removes a small amount of water containing in raw material, detect water ratio and reach below 3/10000ths, being cooled to liquid material temperature is 25 ℃ of left and right.
2. by weight N-BUTYL ACETATE, MDI are joined in said vesse, be warming up to 50 ℃, stirring reaction 1 hour, question response heat release finishes to be slowly warming up to 80～90 ℃ afterwards, keep reaction 2h, sampling, after detection NCO% value is qualified, is cooled to 30 ℃, add defoamer BYK-066N, catalyzer organo-bismuth, latent curing agent ALT-403, sustained release dosage phosphoric acid and water-retaining agent 4A molecular sieve, stir after 0.5 hour discharging, sealing.
To the buried pipeline of above-mentioned preparation with the heavy anticorrosion polyureas of single component at 25 ℃, under humidity 65% environment, by the experimental technique GB/T16777-2008 of architectural waterproof material, carry out Mechanics Performance Testing, detected result is as shown in table 1.
The mechanical experimental results of table 2 embodiment 2
From table 2, buried pipeline prepared by the present embodiment has excellent oil-proofness and resistance to liquid medium performance with the heavy anticorrosion polyureas of single component; Mechanical property is good, reaches unanimity with the polyureas performance on pipeline, and compatible effect is good; Also there is longer gel time 2.5 hours, can realize manual blade coating, brushing.
Embodiment 3
The present embodiment discloses the heavy anticorrosion polyureas of single component for a kind of buried pipeline, comprises each component that weight proportion is following:
The preparation method of the heavy anticorrosion polyureas of single component for the buried pipeline that the present embodiment provides:
1. by above-mentioned weight part, polyoxytrimethylene ethoxylated polyhydric alcohol PPG-1000, Desmophen NH1420,800 order talcum powder, carbon black are joined in container, by liquid material stirring at low speed after 5 minutes, be heated to 110～120 ℃, open vacuum pump, vacuum tightness is-0.1～-0.08MPa, and vacuum hydro-extraction 2h removes a small amount of water containing in raw material, detect water ratio and reach below 3/10000ths, being cooled to liquid material temperature is 25 ℃ of left and right.
2. by weight N-BUTYL ACETATE, HMDI are joined in container, be warming up to 50 ℃, stirring reaction 0.5 hour, after question response heat release finishes, add MDI, be slowly warming up to 80～90 ℃, keep reaction 2h, sampling, after detection NCO% value is qualified, is cooled to 30 ℃, add defoamer BYK-066N, the sub-tin of octoate catalyst, latent curing agent ALT-102, sustained release dosage Benzoyl chloride, water-retaining agent 4A molecular sieve, stir after 0.5 hour discharging, sealing.
To the buried pipeline of above-mentioned preparation with the heavy anticorrosion polyureas of single component at 25 ℃, under humidity 65% environment, by the experimental technique GB/T16777-2008 of architectural waterproof material, carry out Mechanics Performance Testing, detected result is as shown in table 2.
The mechanical experimental results of table 3 embodiment 3
From table 3, buried pipeline prepared by the present embodiment has excellent oil-proofness and resistance to liquid medium performance with the heavy anticorrosion polyureas of single component; Mechanical property is good, reaches unanimity with the polyureas performance on pipeline, and compatible effect is good; Also there is longer gel time 3h, can realize manual blade coating, brushing.
Claims (10)
1. for buried pipeline, single component weighs an anticorrosion polyureas, it is characterized in that each component that comprises that weight proportion is following:
Wherein, described isocyanic ester is aliphatic isocyanates and/or aromatic isocyanate.
2. for buried pipeline according to claim 1, single component weighs anticorrosion polyureas, it is characterized in that: described aliphatic isocyanates is one or more in isophorone diisocyanate, HMDI and hexamethylene diisocyanate.
3. the heavy anticorrosion polyureas of single component for buried pipeline according to claim 1, is characterized in that: described aromatic isocyanate is one or more in tolylene diisocyanate, diphenylmethanediisocyanate, PPDI.
4. the heavy anticorrosion polyureas of single component for buried pipeline according to claim 1, is characterized in that: described polyvalent alcohol is one or more in biopolyol, polyoxytrimethylene ethoxylated polyhydric alcohol and polytetrahydrofuran polyvalent alcohol.
5. the heavy anticorrosion polyureas of single component for buried pipeline according to claim 1, is characterized in that: described bulky amine compound is one or more in Desmophen NH1420, Desmophen NH1520, Desmophen NH1220, Unilink4200, Unilink4100, Clearlink1000, Clearlink3000, Jefflink555 and Jefflink754.
6. the heavy anticorrosion polyureas of single component for buried pipeline according to claim 1, is characterized in that: described solvent is one or more in ethyl acetate, butylacetate, acetone, toluene and dimethylbenzene.
7. the heavy anticorrosion polyureas of single component for buried pipeline according to claim 1, is characterized in that: described filler is one or more in fine particle calcium carbonate, coarse whiting, talcum powder, calcium hydroxide, zinc phosphate and mica powder, and described filler is more than 800 orders.
8. the heavy anticorrosion polyureas of single component for buried pipeline according to claim 1, is characterized in that: described catalyzer is one or more in dibutyl tin laurate, dibutyltin diacetate, stannous octoate, isocaprylic acid lead, phenylmercury acetate.
9. the heavy anticorrosion polyureas of single component for buried pipeline according to claim 1, is characterized in that: described defoamer is one or more in BYK-066N, BYK-054 and BYK-5500; Described latent curing agent is one or more in imines class ALT-403, ALT-102; Described water-retaining agent is a kind of in calcium oxide or 4A molecular sieve; Described retardant is one or more in Benzoyl chloride, Tosyl chloride, citric acid.
10. the preparation method of the heavy anticorrosion polyureas of single component for the buried pipeline described in any one claim in claim 1-9, is characterized in that, comprises the following steps:
A. when isocyanic ester is aliphatic isocyanates or aromatic isocyanate:
1. polyvalent alcohol, bulky amine compound, filler, pigment are added in container, open and stir, be heated to 110～120 ℃, vacuum hydro-extraction, removes moisture content to water ratio in raw material and is less than 3/10000ths, and being cooled to liquid material temperature is 20-30 ℃;
2. solvent and isocyanic ester are joined in container, be warming up to 50 ℃, after stirring reaction 0.5-1 hour, be slowly warming up to after target temperature and continue reaction, sampling detects NCO% value and reaches after design load 98-102%, is cooled to 30 ℃; Wherein,
When isocyanic ester is aliphatic isocyanates, described target temperature is 110-120 ℃, continues reaction 7-8 hour;
When isocyanic ester is aromatic isocyanate, described target temperature is 80-90 ℃, continues reaction 2-3 hour;
3. add latent curing agent, defoamer, retardant, water-retaining agent and catalyzer, stir discharging 0.5 hour;
B. when isocyanic ester is aliphatic isocyanates and aromatic isocyanate:
The same A of method, but step is 2. for to join solvent and aliphatic isocyanates in container, be warming up to 50 ℃, after stirring reaction 0.5-1 hour, add again aromatic isocyanate, slowly be warming up to 80～90 ℃ of reaction 1.5-2.5 hour, sampling detects NCO% value and reaches after design load 98-102%, is cooled to 30 ℃.
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