CN103214648A - Wet type polyurethane joint material for thermal insulation for seabed oil and gas pipeline interface and preparation method of wet type polyurethane joint material - Google Patents
Wet type polyurethane joint material for thermal insulation for seabed oil and gas pipeline interface and preparation method of wet type polyurethane joint material Download PDFInfo
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- CN103214648A CN103214648A CN2013101597481A CN201310159748A CN103214648A CN 103214648 A CN103214648 A CN 103214648A CN 2013101597481 A CN2013101597481 A CN 2013101597481A CN 201310159748 A CN201310159748 A CN 201310159748A CN 103214648 A CN103214648 A CN 103214648A
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- polyurethane
- polyether polyol
- polyol
- node material
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- 239000000463 material Substances 0.000 title claims abstract description 53
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 43
- 239000004814 polyurethane Substances 0.000 title claims abstract description 42
- 238000009413 insulation Methods 0.000 title abstract description 6
- 238000002360 preparation method Methods 0.000 title description 9
- 229920005862 polyol Polymers 0.000 claims abstract description 45
- 150000003077 polyols Chemical class 0.000 claims abstract description 45
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 28
- 229920000570 polyether Polymers 0.000 claims abstract description 28
- -1 polysiloxane Polymers 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000012948 isocyanate Substances 0.000 claims abstract description 15
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 12
- 239000004970 Chain extender Substances 0.000 claims abstract description 9
- 239000003921 oil Substances 0.000 claims abstract description 7
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 229920001451 polypropylene glycol Polymers 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 2
- IAXFZZHBFXRZMT-UHFFFAOYSA-N 2-[3-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=CC(OCCO)=C1 IAXFZZHBFXRZMT-UHFFFAOYSA-N 0.000 claims description 2
- WTPYFJNYAMXZJG-UHFFFAOYSA-N 2-[4-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=C(OCCO)C=C1 WTPYFJNYAMXZJG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 2
- 235000019482 Palm oil Nutrition 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- MRUXVMBOICABIU-UHFFFAOYSA-N [3,5-bis(methylsulfanyl)phenyl]methanediamine Chemical compound CSC1=CC(SC)=CC(C(N)N)=C1 MRUXVMBOICABIU-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011363 dried mixture Substances 0.000 claims description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 239000002540 palm oil Substances 0.000 claims description 2
- 229920001228 polyisocyanate Chemical group 0.000 claims description 2
- 239000005056 polyisocyanate Chemical group 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 235000019198 oils Nutrition 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 3
- 239000013535 sea water Substances 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 238000005266 casting Methods 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract 1
- 150000005846 sugar alcohols Polymers 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 9
- 238000007872 degassing Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000011417 postcuring Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000009849 vacuum degassing Methods 0.000 description 2
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- PGYPOBZJRVSMDS-UHFFFAOYSA-N loperamide hydrochloride Chemical class Cl.C=1C=CC=CC=1C(C=1C=CC=CC=1)(C(=O)N(C)C)CCN(CC1)CCC1(O)C1=CC=C(Cl)C=C1 PGYPOBZJRVSMDS-UHFFFAOYSA-N 0.000 description 1
- 239000013521 mastic Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a wet type polyurethane joint material for thermal insulation for a seabed oil and gas pipeline interface. The polyurethane joint material comprises a component A and a component B, wherein the component A comprises polyether polyol, polysiloxane polyhydric alcohol, a chain extender and a catalyst; the component B is modified isocyanate or a derivate of the modified isocyanate; the component B comprises 10 to 30% of NCO (Isocyanate Group) based on mass percent; and the mass ratio of the component A to the component B is 0.25 to 4:1. The wet type polyurethane joint material has the beneficial effects as shown in follows: 1, the adopted catalyst is mercury-free, environment-friendly, long in flowing period and fast to cure in later period; 2, the production cycle is short, a die is at low temperature, and the offshore in-situ casting work can be conveniently carried out; and 3, a product is a silicon-containing material and has relatively low water absorption and is resistant to seawater corrosion.
Description
Technical Field
The invention relates to a polyurethane node material for wet-type heat preservation of a submarine oil and gas pipeline interface and a preparation method thereof.
Background
In the exploitation of marine energy, especially petroleum and natural gas, in order to prevent the pipeline from being blocked by the formation of natural gas hydrate and petroleum wax caused by low temperature under sea, and the accident is caused, the oil and gas transmission pipeline must adopt a pipeline with a certain thickness of heat preservation protective layer for transmission, and the protection, heat preservation and corrosion prevention layer of the pipeline main body is prefabricated by special equipment in a factory, and the quality of the protective layer and the heat preservation and corrosion prevention layer is reliable. Therefore, in the ocean field laying process, the protection and filling of the interface are the key points for ensuring the safe operation of the submarine pipeline.
The filling of the early submarine heat-insulating pipeline interface mainly adopts a mixed pouring process of asphalt mastic and sand stone, the temperature is required to be heated to more than 200 ℃ in the processing and forming process, thus the corrosion-resistant layer is easy to burn or burn, the smoke of the construction environment is large, harmful gas is generated, the environment is polluted, the sea water and marine organisms are threatened, the strength of the joint repairing material is low (1.5-5 MPa), the overall heat-insulating effect of the pipeline is influenced, the safe operation of the submarine pipeline is difficult to ensure, and the use in local sea areas is forbidden at present.
Currently, polyurethane joint technology is widely used abroad, but the joint technology (especially the preparation of joint materials) is mastered by only a few foreign companies. The domestic pipeline joint technology mainly focuses on the anti-corrosion and thermal insulation structure design of pipeline joints, such as 200520103653.9 and 200520026468.4. The patent disclosed about the preparation of the non-foaming polyurethane node material for the submarine pipeline field interface is less, and the patent 201210258634.8 discloses a full-water open-cell rigid polyurethane foam for a submarine pipeline joint, wherein the polyurethane foam has a lower heat conductivity coefficient and a good heat insulation effect, but the closed cell rate is less than 100%, so that the material has high water absorption rate and low compressive strength, and is not suitable for the protection application of a deep-sea wet-type heat insulation pipeline interface.
Disclosure of Invention
The invention aims to provide a polyurethane node material for wet-type heat preservation of a submarine oil and gas pipeline interface and a preparation method thereof.
The invention provides a polyurethane node material for wet-type heat preservation of a submarine oil and gas pipeline interface, which is prepared from a component A and a component B;
the component A consists of polyether polyol, polysiloxane polyol, a chain extender and a catalyst;
the component B is modified isocyanate or a derivative thereof, and in the component B, the mass percentage of NCO is 10-30%;
the mass ratio of the component A to the component B is 0.25-4: 1.
in the polyurethane node material, the mass percentage of NCO in the component B can be 19%;
the mass ratio of the component A to the component B can be specifically 0.77-0.85: 1. 0.77: 1. 0.78: 1 or 0.85: 1.
in the polyurethane node material, in the component a, the mass ratio of the polyether polyol, the polysiloxane polyol, the chain extender and the catalyst may be 30-130: 2-30: 5-30: 0.001 to 4, specifically 280 to 332.5: 17.5-52.5: 79.03-116.91: 2.85, such as 297.5: 52.5: 85.17: 2.85, 332.5: 17.5: 83.17: 2.85, 280: 70: 82.77: 2.85, 332.5: 17.5: 116.91: 2.85 or 315: 35: 79: 2.85.
in the polyurethane node material, the polyether polyol consists of polyether polyol I and polyether polyol II,
the hydroxyl value of the polyether polyol I is 8-100 mgKOH/g, such as 50-60 mgKOH/g, and the hydroxyl value of the polyether polyol II is 100-200 mgKOH/g, such as 160-175 mgKOH/g;
the mass ratio of the polyether polyol I to the polyether polyol II is 20-80: 20 to 55, specifically 20 to 42: 20-24.5, 35.5: 21. 42: 24.5, 1: 1 or 38.5: 24.5.
in the polyurethane node material, the polyether polyol I can be one or more of polytetrahydrofuran ether glycol (PTMEG), polypropylene glycol (PPG), polyethylene glycol (PEG) and copolyether thereof;
the polyether polyol II can be one or more of palm oil polyol, soybean oil polyol, castor oil polyol, hydroxyl-terminated polybutadiene polyol and polyether polyol which takes 3-functionality small molecular alcohol or alcohol amine or 4-functionality small molecular alcohol as an initiator and takes ethylene oxide/propylene oxide as a polymerization monomer.
In the polyurethane node material, the hydroxyl value of the polysiloxane polyol is 45-100 mgKOH/g, such as 40-50 mgKOH/g;
the structural formula of the polysiloxane polyol is shown in a formula I,
formula I
Wherein n = 1-100; r1～6The alkanes are straight-chain or branched alkanes with 1-4 carbon atoms, and are the same or different; r7、 8Is hydroxyl, amino, epoxy or unsaturated double bond, and is the same or different.
In the polyurethane node material, the chain extender may be 1, 4-Butanediol (BDO), ethylene glycol, propylene glycol, diethylene glycol, glycerol, trimethylolpropane, 1, 4-cyclohexanediol, hydrogenated bisphenol a, 1, 6-hexanediol, diethanolamine, triethanolamine, methyldiethanolamine, diethyltoluenediamine, 3, 5-dimethylthiotoluenediamine, 3 '-dichloro-4, 4' -diaminodiphenylmethane or a derivative thereof, hydroquinone bis (2-hydroxyethyl) ether or a derivative thereof, resorcinol bis (2-hydroxyethyl) ether or a derivative thereof.
In the above-mentioned polyurethane node material, the catalyst may be an organic amine catalyst or a salt thereof (e.g., triethylene diamine (TEDA) and an organic salt thereof, bis (dimethylaminoethyl) ether and an organic salt thereof), 1, 8-diazabicyclo (5, 4, 0) undecene-7 or an organic salt thereof (e.g., phenolate, 2-ethylhexanoate or formate), or an organic metal catalyst (e.g., organotin, organobismuth, organozinc, nickel acetylacetonate or zirconium acetylacetonate), such as the catalyst CT-2X of the company adadin reagent.
In the polyurethane node material, the component B can be aliphatic isocyanate, alicyclic isocyanate, aromatic isocyanate, polyisocyanate or isocyanate prepolymer, such as Suprasec series produced by Hensmei polyurethane Co., Ltd, wherein NCO% is 19% by mass;
the aromatic isocyanate can be diphenylmethane diisocyanate or other liquefied modified MDI, and the structure of the aromatic isocyanate contains modified structures such as uretonimine, biuret, allophanate, isocyanurate, carbodiimide, urethane and the like.
The invention further provides a preparation method of the polyurethane node material, which comprises the following steps: vacuum drying the mixture of polyether polyol and polysiloxane polyol; then adding the chain extender and the catalyst into the dried mixture to obtain the component A;
and adding the component B into the component A, uniformly mixing, pouring into a sleeve mold of a pipeline interface, curing, and demolding to obtain the polyurethane node material.
In the preparation method, the temperature of the vacuum drying can be 80-120 ℃, and the time can be 1-4 hours, for example, the vacuum drying is carried out for 2.5 hours at 95 ℃;
when the component B is added into the component A, the temperature of both the component A and the component B can be 10-60 ℃, such as 30 ℃;
in the step of pouring, the temperature of the sleeve mould of the pipeline interface can be 40-150 ℃, and specifically can be 70 ℃ or 80 ℃.
The invention has the following beneficial effects:
1. the catalyst has no mercury, is environment-friendly, has long flowing period and quick later-period curing.
2. The production period is short, the temperature of the die is low, and the method is suitable for offshore site pouring operation.
3. The product is a silicon-containing material, has low water absorption and seawater corrosion resistance.
Detailed Description
The following examples are presented to further illustrate details of the preparation and use of the present invention and are not to be construed as limiting the spirit and scope of the invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The raw materials used in the following examples are as follows:
hydroxyl-terminated polysiloxane DS-3 with a hydroxyl value of 40-50 mgKOH/g, Rhodia, France;
polypropylene glycol (PPG-1) with a hydroxyl value of 50-60 mgKOH/g, Shandong Lanxingdao company;
polyether glycol GE-2 with a hydroxyl value of 160-175 mgKOH/g, and is used for Shanghai high-bridge petrochemical industry;
1, 4-Butanediol (BDO), diethylene glycol (DEG), Shanghai Lingmeng Chemicals, Inc.;
catalyst CT-2X, Aladdin reagent, Inc.;
NCO-B, modified MDI, Superasec, NCO% 19%; hensmeiurethane, Inc.
The product properties in the following examples were carried out according to the following methods:
and (3) hardness testing: according to the test standard ASTM D2240-04, the samples have a thickness of 6mm (or less than 6mm can be superimposed to 6 mm), a width of at least 12mm from the center to the edge, and a temperature of 23. + -. 2 ℃. During testing, the needle pressing angle of the hardness tester is kept parallel to the table top, the needle pressing descends at a certain speed, and the reading is carried out within 1s after the needle pressing is stopped. If the hardness meter is fitted with a maximum reading indicator, the maximum reading is read, five points are taken at least 6mm apart and tested separately, taking the arithmetic mean or median.
And (3) testing tensile strength: according to the test standard ASTM D638, the samples were dumbbell-shaped, 3.2. + -. 0.4mm in thickness, 25.00. + -. 0.25mm in length measured on a scale, at a temperature of 23. + -. 2 ℃ and a humidity of 50. + -. 5%. During the test, the tensile force is applied at a speed of 100. + -.50 mm/min, and the load tensile-elongation curve is recorded until the specimen breaks in the specified area. At least five samples were tested per article, taking the arithmetic mean or median.
Water absorption test: temperature as measured by ASTM D570-98: 90 plus or minus 2 ℃; humidity 50 +/-5%. The thickness of the prepared sample is 3.2mm, the length is 76.2mm, the width is 25.4mm, and the soaking time in water is 24 h.
The parts in the following examples are parts by weight unless otherwise specified.
Examples 1,
In a reaction kettle with a vacuum and heating device, uniformly mixing DS-3 (52.5 parts), PPG-1 (192.5 parts) and GE-2 (105 parts), drying in vacuum at 95 ℃ for 2.5h, slowly cooling to 60 ℃, adding dried BDO (85.17 parts) and a catalyst CT-2X (2.85 parts), mixing and stirring for 15min, and degassing in vacuum to obtain a component A.
Controlling the temperature of the component A at 30 ℃, adding 564.83 parts of NCO-B, quickly stirring uniformly, degassing, and pouring into a mold with the mold temperature of 70 ℃ to obtain the non-foamed polyurethane node material for the submarine pipeline field interface.
The gel time of the non-foamed polyurethane node material prepared in the embodiment is 5min, and the demolding time is 18 min.
Through testing, the node material prepared in the embodiment has an initial tensile strength of 3.22MPa and a hardness (shore a) of 70 during demolding, and has a tensile strength of 18.22MPa after post-curing, an elongation at break of 492.05%, a 100% stress at definite elongation of 67.7MPa, a hardness (shore a) of 89, and a water absorption of 1.25.
Examples 2,
In a reaction kettle with a vacuum and heating device, DS-3 (17.5 parts), PPG-1 (210.0 parts) and GE-2(122.5 parts) are uniformly mixed and dried in vacuum at 95 ℃ for 2.5h, after being slowly cooled to 50 ℃, dried BDO (83.70 parts) and a catalyst CT-2X (2.85 parts) are added, mixed and stirred for 15min, and then the component A is obtained by vacuum degassing.
Controlling the temperature of the component A at 30 ℃, adding 566.30 parts of NCO-B, quickly stirring uniformly, degassing, and pouring into a mold with the mold temperature of 70 ℃ to obtain the non-foamed polyurethane node material for the submarine pipeline field interface.
The gel time of the non-foamed polyurethane node material prepared in the embodiment is 4min, and the demolding time is 16 min.
Through testing, the node material prepared in the embodiment has the initial strength of 4.13MPa, the hardness (shore a) of 78, the tensile strength after post curing of 14.46MPa, the elongation at break of 406.33%, the 100% stress at definite elongation of 4.85MPa, the hardness (shore a) of 83 and the water absorption of 1.16.
Examples 3,
In a reaction kettle with a vacuum and heating device, uniformly mixing DS-3 (70 parts), PPG-1 (140 parts) and GE-2(140 parts), drying in vacuum at 95 ℃ for 2.5h, slowly cooling to 50 ℃, adding dried BDO (82.77 parts) and a catalyst CT-2X (2.85 parts), mixing and stirring for 15min, and degassing in vacuum to obtain a component A.
Controlling the temperature of the component A to be 30 ℃, adding 567.23 parts of NCO-B, quickly stirring, uniformly degassing, and pouring into a mold with the mold temperature of 70 ℃ to obtain the non-foamed polyurethane node material for the submarine pipeline field interface.
The gel time of the non-foamed polyurethane node material prepared in the embodiment is 6min, and the demolding time is 20 min.
The node material when demolded had an initial strength of 3.89MPa, a hardness (Shore A) of 75, a tensile strength after post-curing of 16.30MPa, an elongation at break of 293.4%, a 100% stress at elongation of 7.55MPa, a hardness (Shore A) of 89, and a water absorption of 1.38.
Examples 4,
In a reaction kettle with a vacuum and heating device, DS-3 (17.5 parts), PPG-1 (210.0 parts) and GE-2(122.5 parts) are uniformly mixed and dried in vacuum at 95 ℃ for 2.5h, the mixture is slowly cooled to 50 ℃, dried DEG (116.91 parts) and a catalyst CT-2X (2.85 parts) are added, and after mixing and stirring for 15min, the component A is obtained by vacuum degassing.
Controlling the temperature of the component A at 30 ℃, adding 554.09 parts of NCO-B, quickly stirring uniformly, degassing, and pouring into a mold with the mold temperature of 70 ℃ to obtain the non-foamed polyurethane node material for the submarine pipeline field interface.
The gel time of the non-foamed polyurethane node material prepared in the embodiment is 5min, and the demolding time is 18 min.
The node material has the initial strength of 3.52MPa, the hardness (Shore A) of 75, the tensile strength of 16.84MPa after post curing, the elongation at break of 303.8%, the 100% stress at definite elongation of 6.39MPa, the hardness (Shore A) of 86 and the water absorption of 1.04.
Examples 5,
In a reaction kettle with a vacuum and heating device, uniformly mixing DS-3 (35 parts), PPG-1 (192.5 parts) and GE-2(122.5 parts), drying in vacuum at 95 ℃ for 2.5h, slowly cooling to 60 ℃, adding dried DEG (79.03 parts) and a catalyst CT-2X (2.85 parts), mixing and stirring for 15min, and degassing in vacuum to obtain a component A.
Controlling the temperature of the component A at 30 ℃, adding 553.97 parts of NCO-B, quickly stirring uniformly, degassing, and pouring into a mold with the mold temperature of 80 ℃ to obtain the non-foamed polyurethane node material for the road field interface.
The gel time of the non-foamed polyurethane node material prepared in the embodiment is 4min, and the demolding time is 15 min.
The node material has the initial strength of 4.3MPa, the hardness (Shore A) of 81, the tensile strength of 17.35MPa after post curing, the elongation at break of 486.07%, the 100% stress at definite elongation of 65.3MPa, the hardness (Shore A) of 88 and the water absorption of 1.21.
The embodiment shows that the node material prepared by the invention has the advantages of rapid curing and demolding, high initial demolding strength, capability of serving for the field interface construction of the marine heat-insulating pipeline and better comprehensive mechanical property than the prior art.
The above-described technology is to be protected as a complete solution, and any person skilled in the art may, using the teachings disclosed above, make changes or modifications to equivalent embodiments with equivalent variations. However, any simple modification, equivalent change or modification made to the above-mentioned contents according to the technical essence of the present invention, which is not departing from the technical contents of the present invention, still belongs to the protection scope of the technical solution of the present invention.
Claims (10)
1. The utility model provides a submarine oil gas pipeline interface wet-type polyurethane node material for heat preservation which characterized in that: the polyurethane node material is prepared from a component A and a component B;
the component A consists of polyether polyol, polysiloxane polyol, a chain extender and a catalyst;
the component B is modified isocyanate or a derivative thereof, and in the component B, the mass percentage of NCO is 10-30%;
the mass ratio of the component A to the component B is 0.25-4: 1.
2. the polyurethane node material of claim 1, wherein: in the component A, the mass ratio of the polyether polyol, the polysiloxane polyol, the chain extender and the catalyst is 30-130: 2-30: 5-30: 0.001 to 4.
3. The polyurethane node material of claim 2, wherein: the polyether polyol consists of polyether polyol I and polyether polyol II,
the hydroxyl value of the polyether polyol I is 8-100 mgKOH/g, and the hydroxyl value of the polyether polyol II is 100-200 mgKOH/g;
the mass ratio of the polyether polyol I to the polyether polyol II is 20-80: 20 to 55.
4. The polyurethane node material of claim 3, wherein: the polyether polyol I is one or more of polytetrahydrofuran ether glycol, polypropylene glycol, polyethylene glycol and copolyether thereof;
the polyether polyol II is one or more of palm oil polyol, soybean oil polyol, castor oil polyol, hydroxyl-terminated polybutadiene polyol and polyether polyol which takes 3-functionality micromolecule alcohol or alcohol amine or 4-functionality micromolecule alcohol as an initiator and takes ethylene oxide/propylene oxide as a polymerization monomer.
5. The polyurethane node material of any one of claims 1-4, wherein: the hydroxyl value of the polysiloxane polyol is 45-100 mgKOH/g;
the structural formula of the polysiloxane polyol is shown in a formula I,
formula I
Wherein,n=1～100；R1～6the alkanes are straight-chain or branched alkanes with 1-4 carbon atoms, and are the same or different; r7、 8Is hydroxyl, amino, epoxy or unsaturated double bond, and is the same or different.
6. The polyurethane node material of any one of claims 1-5, wherein: the chain extender is 1, 4-butanediol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, trimethylolpropane, 1, 4-cyclohexanediol, hydrogenated bisphenol A, 1, 6-hexanediol, diethanolamine, triethanolamine, methyldiethanolamine, diethyltoluenediamine, 3, 5-dimethylthiotoluenediamine, 3 '-dichloro-4, 4' -diaminodiphenylmethane or a derivative thereof, hydroquinone bis (2-hydroxyethyl) ether or a derivative thereof, resorcinol bis (2-hydroxyethyl) ether or a derivative thereof.
7. The polyurethane node material of any one of claims 1-6, wherein: the catalyst is organic amine catalyst or salt thereof, 1, 8-diazabicyclo (5, 4, 0) undecene-7 or organic salt or organic metal catalyst.
8. The polyurethane node material of any one of claims 1-7, wherein: the component B is aliphatic isocyanate, alicyclic isocyanate, aromatic isocyanate, polyisocyanate or isocyanate prepolymer;
the aromatic isocyanate is diphenylmethane diisocyanate.
9. A method of making the polyurethane node material of any one of claims 1-8, comprising the steps of: vacuum drying the mixture of polyether polyol and polysiloxane polyol; then adding the chain extender and the catalyst into the dried mixture to obtain the component A;
and adding the component B into the component A, uniformly mixing, pouring into a sleeve mold of a pipeline interface, curing, and demolding to obtain the polyurethane node material.
10. The method of claim 9, wherein: the temperature of the vacuum drying is 80-120 ℃, and the time is 1-4 hours;
when the component B is added into the component A, the temperature of both the component A and the component B is 10-60 ℃;
in the step of pouring, the temperature of a sleeve mould of the pipeline connector is 40-150 ℃.
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| US10208178B2 (en) | 2013-10-30 | 2019-02-19 | Dow Global Technologies Llc | Syntactic polyurethane elastomers having distinct morphology for use in subsea pipeline insulation |
| US10301481B2 (en) | 2013-10-30 | 2019-05-28 | Dow Global Technologies Llc | Syntactic polyurethane elastomers based on low unsaturation polyols for use in subsea pipeline insulation |
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| WO2015065772A1 (en) * | 2013-10-30 | 2015-05-07 | Dow Global Technologies Llc | Syntactic polyurethane elastomer based on soft segment prepolymer and non-mercury catalyst for use in subsea pipeline insulation |
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