CN103224606A - Polyurethane node material for submarine oil-gas pipeline interface wet type thermal insulation, and preparation method thereof - Google Patents
Polyurethane node material for submarine oil-gas pipeline interface wet type thermal insulation, and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a polyurethane node material for submarine oil-gas pipeline interface wet type thermal insulation. The polyurethane node material is prepared from a component A and a component B, wherein the component A comprises polyether polyol, a chain extender and a catalyst, the component B is trimerization modified isocyanate or a derivative thereof, a NCO mass content is 10-30% in the component B, and a mass ratio of the component A to the component B is 0.25-6:1. According to the present invention, the used catalyst does not contain mercury, and characteristics of environmental protection, long liquidity, and rapid curing at a late stage are provided; a production cycle is short, a mold temperature is low, and the material is suitable for marine on-site casting operations; and the product contains a trimer structure, and good high temperature resistance stability is provided.
Description
Technical field
The present invention relates to a kind of sea-bottom oil-gas pipeline interface wet type insulation urethane gusset material and preparation method thereof.
Background technology
In ocean energy resources especially oil, gas extraction, for preventing the sea down gas hydrate that cause of low temperature and the formation blocking pipe of oil wax, the generation that causes the accident, pipe-line must adopt the pipeline with certain thickness heat preservation protective layer to carry, and the protection of this type of pipe main body, insulation and preservative coat are to finish by specific equipment is prefabricated in factory, and the quality of its protective layer and insulation antiseptic layer is reliable.Therefore, in the on-the-spot process of deployment in ocean, the protection of interface then is the key that ensures the submerged pipeline safe operation with filling.
The filling of early stage seabed utilidor interface, main bitumastic+the sandstone that adopts mixes pouring technology, shaping needs to be heated to more than 200 ℃ in the process, can easily cause preservative coat burn or burning like this, and construction environment smog is big, produce obnoxious flavour, contaminate environment, seawater and marine organisms are also constituted a threat to, and opening-supplementing material intensity is low by (1.5～5MPa), influence the integral heat insulation effect of pipeline, be difficult to guarantee the safe operation of submerged pipeline, ban use of in local marine site at present.
At present, external widespread use be urethane joint technology, but this joint technology (the especially preparation of joint material) has only the external several companies of minority to grasp.Domestic interfacing about pipeline mainly concentrates on the corrosion-resistant thermal insulation structure design of pipe joint, as 200520103653.9,200520026468.4.Less about the on-the-spot interface of submerged pipeline with the disclosed patent of the preparation of non-polyurathamc gusset material, patent 201210258634.8 has been announced a kind of full water open-cell rigid polyurethane foams of submerged pipeline joint, the urethane foam thermal conductivity is lower, high insulating effect, but rate of closed hole does not reach 100%, cause material water-intake rate height, ultimate compression strength is low, is not suitable for the security application of deep-sea wet type utilidor interface.
Summary of the invention
The purpose of this invention is to provide a kind of sea-bottom oil-gas pipeline interface wet type insulation urethane gusset material and preparation method thereof.
The urethane gusset material is used in a kind of sea-bottom oil-gas pipeline interface wet type insulation provided by the present invention, and it is made by component A and B component;
Described component A is made up of polyether glycol, chainextender and catalyzer;
Described B component is a trimerization modified isocyanate or derivatives thereof, and in the described B component, the quality percentage composition of NCO is 10～30%;
The mass ratio of described component A and described B component is 0.25～6:1.
In the above-mentioned urethane gusset material, the quality percentage composition of NCO can be 19.55%～23.09%, 19.55%, 21.72%, 22.55% or 23.09 in the described B component;
The mass ratio of described component A and described B component specifically can be 1.17:1,1.19:1,1.2:1 or 1.28:1.
In the above-mentioned urethane gusset material, among the described component A, the mass ratio of described polyether glycol, described chainextender and described catalyzer can be 12～70:2～20:0.001～4, specifically can be 459.83～462.88:68.6～81.48:2.85,462.88:81.48:2.85,462.43:79.56:2.85,462.73:76.61:2.85 or 459.83:68.6:2.85.
In the above-mentioned urethane gusset material, described polyether glycol is made up of polyether glycol I and polyether glycol I I,
The hydroxyl value of described polyether glycol I can be 28～250mgKOH/g, and as 150～190mgKOH/g, the hydroxyl value of described polyether glycol I I is 14～400mgKOH/g, as 50～60mgKOH/g;
The mass ratio of described polyether glycol I and described polyether glycol I I can be 1～15:20～55, specifically can be 47.66:415.22,47.21:415.22,45.51:415.22 or 44.61:415.22.
In the above-mentioned urethane gusset material, described polyether glycol I can be plam oil polyvalent alcohol, soybean oil base polyol, castor oil-base polyvalent alcohol, hydroxy-terminated polybutadienes polyvalent alcohol and is that initiator, ethylene oxide/propylene oxide are one or more in the polyether glycol of polymerization single polymerization monomer with the little branch alcohol of 3 functionality or hydramine or 4 functionality small molecular alcohols;
Described polyether glycol I I can be one or more in PTMG, polypropylene glycol, polyoxyethylene glycol and their copolyether.
In the above-mentioned urethane gusset material, described chainextender can be 1,4-butyleneglycol, ethylene glycol, propylene glycol, glycol ether, glycerol, TriMethylolPropane(TMP), 1,4-cyclohexanediol, Hydrogenated Bisphenol A, 1,6-hexylene glycol, diethanolamine, trolamine, methyldiethanolamine, diethyl toluene diamine or 3,5-diformazan sulfenyl tolylene diamine.
In the above-mentioned urethane gusset material, described catalyzer is that organic amine catalyzer or its salt are (as triethylene diamine (TEDA), 1,8-diazabicyclo (5,4,0) undecylene-7 or its organic salt (as phenolate, 2-ethylhexoate or formate) or organo-metallic class catalyzer (as organotin, organo-bismuth, organic zinc, acetylacetonate nickel or methyl ethyl diketone zirconium) are as the catalyzer CT-2X of Aladdin reagent company production.
In the above-mentioned urethane gusset material, described B component specifically can be trimerization modified aliphatic isocyanic ester, trimerization modified aromatic family's isocyanic ester and derivative thereof; Described trimerization modified aliphatic isocyanic ester is made up of aliphatics isocyanide ester and aliphatic poly isocyanide ester tripolymer, the trimerical quality percentage composition of described aliphatic poly isocyanide ester is 5～40%, specifically can be 11.79%～37.86%, 11.79%, 15.77%, 21.85% or 37.86%.；
Described trimerization modified aromatic family isocyanide ester is made up of aromatic series isocyanide ester and fragrant adoption isocyanide ester tripolymer, and the trimerical quality percentage composition of described fragrant adoption isocyanide ester is 5～40%.
The present invention also further provides the preparation method of above-mentioned urethane gusset material, comprises the steps: described polyether glycol is carried out vacuum-drying; In described mixture after drying, add described chainextender and described catalyzer then, obtain described component A;
Described B component is added among the described component A, after mixing, is poured in the ferrule mold of pipe joint, solidify after the demoulding promptly gets described urethane gusset material.
Among the above-mentioned preparation method, described vacuum drying temperature can be 80～120 ℃, and the time can be 1～4 hour, as at 95 ℃ of following vacuum-drying 2.5h;
When adding described B component in described component A, the temperature of described component A and described B component all can be 10～60 ℃, as 30 ℃;
In the step of described cast, the temperature of the ferrule mold of described pipe joint can be 40～150 ℃, as 80 ℃.
The present invention has following beneficial effect:
1, catalyst system therefor does not have mercury, environmental protection, and flow periods is long, the later stage quick solidifying.
2, with short production cycle, die temperature is low, is applicable to marine cast-in-site operation.
3, goods contain the tripolymer structure, have heat-resistant stable preferably.
Embodiment
Following embodiment is used for further specifying preparation of the present invention and application specific details, does not constitute the restriction to spirit and scope of the invention.
Employed experimental technique is ordinary method if no special instructions among the following embodiment.
Used material, reagent etc. if no special instructions, all can obtain from commercial channels among the following embodiment.
Used raw material is as follows among the following embodiment:
Polypropylene glycol (PPG), hydroxyl value 50～60mgKOH/g, Shandong blue star east major company;
PTMG (PTMEG), hydroxyl value 35～400mgKOH/g, German BASF AG;
1,4-butyleneglycol (BDO), glycol ether (DEG), Shanghai Ling Feng chemistry company limited;
Catalyzer CT-2X, Aladdin reagent company;
4,4'-MDI, Hensel steps Shanghai urethane company limited.
NCO-B is trimerization modification MDI, and the technical indicator of used modification MDI is shown in the table 1 among the following embodiment, and wherein, B0 is the ester modified MDI of ammonia, and NCO content is 24.69%, does not contain tripolymer.
The technical indicator of table 1 modification MDI
Product performance among the following embodiment are carried out in accordance with the following methods:
Hardness test: according to testing standard ASTM D2240-04, thickness of sample 6mm(or be lower than the stackable of 6mm to 6mm), width width between centers limit is 12mm at least, 23 ± 2 ℃ of temperature.During test, it is parallel with table top that sclerometer pressing pin angle keeps, and pressing is pressed certain speed decline, after pressing stops in 1s reading.If sclerometer is equipped with maximum reading telltale, then read down full-scale reading, get the 6mm of being separated by at least and get five points and test respectively, get arithmetical av or intermediate value.
The tensile strength test: according to testing standard ASTM D638, sample is a dumbbell shape, and thickness is 3.2 ± 0.4mm, and it is 25.00 ± 0.25mm that graticule is measured length, 23 ± 2 ℃ of temperature, humidity 50 ± 5%.During test, be the scope startup drawing machine of 100 ± 50mm/min with speed, the record load draws-stretches curve, ruptures in the designated area up to sample.Each goods is got five sample tests at least, gets arithmetical av or intermediate value.
Thermogravimetric analysis (TGA): adopt N2 atmosphere, flow is 1mL/min, temperature range 40 ℃～800, and temperature rise rate is 10 ℃/min.
The thermo-oxidative ageing test: adopted 120 ℃/60 days, the thermal ageing under the aerobic conditions, the velocity of variation situation of mechanical property (hardness of material, tensile strength, elongation at break) is investigated in contrast.
Umber among the following embodiment is parts by weight.
Embodiment 1,
In the reactor that has vacuum and heating unit, with PPG(415.22 part) and PTMEG (47.66 parts) mixes and in 95 ℃ of following vacuum-drying 2.5h, slowly cool after 50 ℃, just dried BDO(81.48 part) and catalyzer CT-2X(2.85 part) add, after mixing stirring 15min, vacuum outgas gets the A component.
Control A, B temperature of charge are 30 ℃, in above-mentioned A component, add 455.63 parts of NCO-B1, stir fast after the degassing, pour into the mould temperature and be in 80 ℃ the mould, promptly get submerged pipeline of the present invention scene interface with containing the non-polyurathamc gusset material of isocyanurate ring.
Embodiment 2,
In the reactor that has vacuum and heating unit, with PPG(415.22 part), PTMEG (47.21 parts) mixes and in 95 ℃ of following vacuum-drying 2.5h, slowly cool after 60 ℃, just dried BDO(79.56 part) and catalyzer CT-2X(2.85 part) add, after mixing stirring 15min, vacuum outgas gets the A component.
Control A, B temperature of charge are 30 ℃, in above-mentioned A component, add 458 parts of NCO-B2, stir fast after the degassing, pour into the mould temperature and be in 80 ℃ the mould, promptly get submerged pipeline of the present invention scene interface with containing the non-polyurathamc gusset material of isocyanurate ring.
Embodiment 3,
In the reactor that has vacuum and heating unit, with PPG(415.22 part), PTMEG (46.51 parts) mixes and in 95 ℃ of following vacuum-drying 2.5h, slowly cool after 50 ℃, just dried BDO(76.61 part) and catalyzer CT-2X(2.85 part) add, after mixing stirring 15min, vacuum outgas gets the A component.
Control A, B temperature of charge are 30 ℃, in above-mentioned A component, add 461.65 parts of NCO-B3, stir fast after the degassing, pour into the mould temperature and be in 80 ℃ the mould, promptly get submerged pipeline of the present invention scene interface with containing the non-polyurathamc gusset material of isocyanurate ring.
Embodiment 4,
In the reactor that has vacuum and heating unit, with PPG(415.22 part), PTMEG (44.61 parts) mixes and in 95 ℃ of following vacuum-drying 2.5h, slowly cool after 50～60 ℃, just dried BDO(68.6 part) and catalyzer CT-2X(2.85 part) add, after mixing stirring 15min, vacuum outgas gets the A component.
Control A, B temperature of charge are 30 ℃, in above-mentioned A component, add 471.57 parts of NCO-B4, stir fast after the degassing, pour into the mould temperature and be in 80 ℃ the mould, promptly get submerged pipeline of the present invention scene interface with containing the non-polyurathamc gusset material of isocyanurate ring.
Comparative Examples 1,
In the reactor that has vacuum and heating unit, with PPG(415.22 part), PTMEG (48.98 parts) mixes and in 95 ℃ of following vacuum-drying 2.5h, slowly cool after 50～60 ℃, just dried BDO(87.02 part) and catalyzer CT-2X(2.85 part) add, after mixing stirring 15min, vacuum outgas gets the A component.
Control A, B temperature of charge are 30 ℃, add 448.78 parts of ester modified isocyanic ester of B0 ammonia in above-mentioned A component, after the degassing that stirs fast, pour into the mould temperature and are in 80 ℃ the mould, promptly get submerged pipeline of the present invention scene interface with non-polyurathamc gusset material.
Performance characteristics by the prepared gusset material of Comparative Examples 1 and embodiment 1 to 4 is as shown in table 2.
The performance of table 2 gusset material
Performance variation rate behind the heat oxygen aging resistance of table 3 gusset material
Can learn by the data in the table 2, the tensile strength height of gusset material provided by the invention, thermotolerance is better, can serve the interface construction of ocean utilidor, and its comprehensive mechanical property performance is better than prior art.
As shown in table 3 by velocity of variation behind the high temperature resistant aging resistance of the prepared gusset material of Comparative Examples 1 and embodiment 1 to 4, can learn that by the data in the table 3 along with the increase of tripolymer content in the gusset material, the heat-proof aging of material stability obviously improves.
Above-mentioned described technology is protected as a technical scheme of finishing, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.But every for breaking away from patented technology scheme content of the present invention, according to any simple modification, equivalent variations or the remodeling that technical spirit of the present invention is done above said content, still belong to the protection domain of technical solution of the present invention.
Claims (9)
1. the urethane gusset material is used in a sea-bottom oil-gas pipeline interface wet type insulation, and it is characterized in that: described urethane gusset material is made by component A and B component;
Described component A is made up of polyether glycol, chainextender and catalyzer;
Described B component is a trimerization modified isocyanate or derivatives thereof, and in the described B component, the quality percentage composition of NCO is 10～30%;
The mass ratio of described component A and described B component is 0.25～6:1.
2. urethane gusset material according to claim 1 is characterized in that: among the described component A, the mass ratio of described polyether glycol, described chainextender and described catalyzer is 12～70:2～20:0.001～4.
3. urethane gusset material according to claim 2 is characterized in that: described polyether glycol is made up of polyether glycol I and polyether glycol I I,
The hydroxyl value of described polyether glycol I is 28～250mgKOH/g, and the hydroxyl value of described polyether glycol I I is 14～400mgKOH/g;
The mass ratio of described polyether glycol I and described polyether glycol I I is 1～15:20～55.
4. urethane gusset material according to claim 3 is characterized in that: described polyether glycol I is plam oil polyvalent alcohol, soybean oil base polyol, castor oil-base polyvalent alcohol, hydroxy-terminated polybutadienes polyvalent alcohol and is that initiator, ethylene oxide/propylene oxide are one or more in the polyether glycol of polymerization single polymerization monomer with the little branch alcohol of 3 functionality or hydramine or 4 functionality small molecular alcohols;
Described polyether glycol I I is one or more in PTMG, polypropylene glycol, polyoxyethylene glycol and their copolyether.
5. according to each described urethane gusset material among the claim 1-4, it is characterized in that: described chainextender is 1,4-butyleneglycol, ethylene glycol, propylene glycol, glycol ether, glycerol, TriMethylolPropane(TMP), 1,4-cyclohexanediol, Hydrogenated Bisphenol A, 1,6-hexylene glycol, diethanolamine, trolamine, methyldiethanolamine, diethyl toluene diamine or 3,5-diformazan sulfenyl tolylene diamine.
6. according to each described urethane gusset material among the claim 1-5, it is characterized in that: described catalyzer is organic amine catalyzer or its salt, 1,8-diazabicyclo (5,4,0) undecylene-7 or its organic salt or organo-metallic class catalyzer.
7. according to each described urethane gusset material among the claim 1-6, it is characterized in that: described B component is trimerization modified aliphatic isocyanic ester, trimerization modified aromatic family isocyanic ester or derivatives thereof.
Described trimerization modified aliphatic isocyanic ester is made up of aliphatics isocyanide ester and aliphatic poly isocyanide ester tripolymer, and the trimerical quality percentage composition of described aliphatic poly isocyanide ester is 5～40%;
Described trimerization modified aromatic family isocyanide ester is made up of aromatic series isocyanide ester and fragrant adoption isocyanide ester tripolymer, and the trimerical quality percentage composition of described fragrant adoption isocyanide ester is 5～40%.
8. the preparation method of each described urethane gusset material among the claim 1-7 comprises the steps: described polyether glycol is carried out vacuum-drying; In described mixture after drying, add described chainextender and described catalyzer then, obtain described component A;
Described B component is added among the described component A, after mixing, is poured in the ferrule mold of pipe joint, solidify after the demoulding promptly gets described urethane gusset material.
9. preparation method according to claim 8 is characterized in that: described vacuum drying temperature is 80～120 ℃, and the time is 1～4 hour;
When adding described B component in described component A, the temperature of described component A and described B component is 10～60 ℃;
In the step of described cast, the temperature of the ferrule mold of described pipe joint is 40～150 ℃.
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Co-patentee after: CNOOC research institute limited liability company Patentee after: China Offshore Oil Group Co., Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Co-patentee before: CNOOC Research Institute Patentee before: China National Offshore Oil Corporation |