WO2022141717A1 - 含缓释胶囊的二次膨胀型高聚物注浆材料及其制备方法 - Google Patents
含缓释胶囊的二次膨胀型高聚物注浆材料及其制备方法 Download PDFInfo
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- capsule
- sustained
- polyurethane
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- copolymer
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- 239000002775 capsule Substances 0.000 title claims abstract description 133
- 239000000463 material Substances 0.000 title claims abstract description 133
- 238000013268 sustained release Methods 0.000 title claims abstract description 70
- 239000012730 sustained-release form Substances 0.000 title claims abstract description 70
- 229920000642 polymer Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims description 21
- 239000004814 polyurethane Substances 0.000 claims abstract description 72
- 229920002635 polyurethane Polymers 0.000 claims abstract description 72
- 239000002245 particle Substances 0.000 claims abstract description 49
- 229920001577 copolymer Polymers 0.000 claims abstract description 25
- 239000002105 nanoparticle Substances 0.000 claims abstract description 16
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 10
- 229920000570 polyether Polymers 0.000 claims abstract description 10
- 229920005862 polyol Polymers 0.000 claims abstract description 10
- 150000003077 polyols Chemical class 0.000 claims abstract description 10
- 239000012948 isocyanate Substances 0.000 claims abstract description 7
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 48
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 25
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229920001228 polyisocyanate Polymers 0.000 claims description 5
- 239000005056 polyisocyanate Substances 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims 2
- 238000000643 oven drying Methods 0.000 claims 2
- 238000000967 suction filtration Methods 0.000 claims 2
- UABGZMHKAQKPDG-UHFFFAOYSA-N 2,3-dichloro-2-methylpropanenitrile Chemical group ClCC(Cl)(C)C#N UABGZMHKAQKPDG-UHFFFAOYSA-N 0.000 claims 1
- 229920000265 Polyparaphenylene Polymers 0.000 claims 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- -1 polyphenylene Polymers 0.000 claims 1
- 239000002861 polymer material Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 201000010099 disease Diseases 0.000 description 5
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- 229920006389 polyphenyl polymer Polymers 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Definitions
- the invention relates to the technical field of polyurethane grouting materials, in particular to a secondary expansion type high polymer grouting material containing slow-release capsules and a preparation method thereof.
- the polymer grouting material is a two-component polyurethane material, including polyurethane white material and polyurethane black material, which is an existing commercial product.
- White materials include polyether polyols, additives, etc., and black materials are isocyanates. It is injected into the diseased area by drilling, and the mixture of black and white materials quickly reacts chemically, and expands to form a foam-like solid with a certain strength, fills the voids, and makes the loose medium around the disease tend to be dense, thereby improving the structural integrity of the restoration. .
- the technology has the following characteristics: small damage to the restoration (minor damage), fast construction speed, high safety, good durability, high expansion, and good waterproof performance. At present, it has been widely used in the rapid maintenance of basic projects in the fields of highways, bridges, tunnels, airports, houses, dams and so on.
- the polyurethane white material contains the sustained-release capsule B with the polyurethane white material doped particles as the capsule core and the St-BA copolymer as the capsule wall.
- the described sustained-release capsule A with the polyurethane black material doped particles as the capsule core and the St-BA copolymer as the capsule wall is prepared by the following method:
- the doped particles A are prepared by solution polymerization with styrene (St), butyl acrylate (BA), initiator azobisisobutyronitrile (AIBN) and organic solvent, and the isocyanate-doped particles are used as capsule cores, Sustained-release capsule A with St-BA copolymer as capsule wall.
- the described sustained-release capsule B with the polyurethane white material doped particles as the capsule core and the St-BA copolymer as the capsule wall is prepared by the following method:
- the polyurethane black material isocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate and polyphenyl polymethyl polyisocyanate; the polyol is polyether diol and/or polyether ternary alcohol.
- the preparation method of the secondary expansion type polymer grouting material containing sustained-release capsules of the present invention comprises the following steps:
- the double-expandable polymer grouting material containing sustained-release capsules prepared by the invention has higher compressive strength and flexural strength because it contains a large amount of inorganic nanoparticles.
- the butyl acrylate was mixed evenly, the addition amount of the initiator azobisisobutyronitrile was 1.5% of the molar amount of styrene, the reaction temperature was 70 °C, and the reaction time was 5 h; the reaction mixture was filtered while hot, and dried in a vacuum oven at 60 °C , to obtain sustained-release capsule A.
- Ethylene and butyl acrylate were mixed evenly, the amount of initiator azobisisobutyronitrile added was 2% of the molar amount of styrene, the reaction temperature was 80°C, and the reaction time was 6h; the reaction mixture was filtered while hot, and vacuumed at 60°C oven-dried to obtain sustained-release capsule B.
- the sustained-release capsule A was added to the polyurethane black material according to 50% of the mass fraction of the black material, and mixed uniformly.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
一种含缓释胶囊的二次膨胀型高聚物注浆材料,包括聚氨酯白料和聚氨酯黑料,其特征在于所述聚氨酯黑料中含有以聚氨酯黑料掺杂颗粒为囊芯、以St-BA共聚物为囊壁的缓释胶囊A;所述聚氨酯白料中含有以聚氨酯白料掺杂颗粒为囊芯、以St-BA共聚物为囊壁的缓释胶囊B。所述材料在高聚物材料形成固结体后,缓释胶囊A和B中含有的黑料异氰酸酯、白料聚醚多元醇等,可通过St-BA共聚物囊壁缓慢释放,并产生二次膨胀,体积可达到原固结体体积的0.5~3倍,很好地解决了传统材料收缩问题,以及修复后的病害再扩大而无法根治的问题,克服了注浆效果不佳,病害复发的问题。并且,纳米粒子可提高注浆材料的力学性能,因此在建筑行业具有广泛的应用价值和市场前景。
Description
本发明涉及聚氨酯注浆材料技术领域,具体涉及一种含缓释胶囊的二次膨胀型高聚物注浆材料及其制备方法。
高聚物注浆技术是20世纪60年代发展起来的基础工程设施快速维修技术,在道路、机场跑道等基础设施快速维修中已得到很好应用。高聚物注浆是按照一定的配比,通过专用的注浆设备,向地基中注入双组份的高聚物材料,材料混合后快速发生反应并形成泡沫状固体,在注浆压力和材料反应体积膨胀的作用下,不断填充周围土体中的空隙和压实土体,并将路基中的积水沿裂缝挤出,从而达到排除积水、填充脱空、加固地基的目的。
高聚物注浆材料是双组分聚氨酯材料,包括聚氨酯白料和聚氨酯黑料,是一种现有的商售产品。白料包括聚醚多元醇、添加剂等,黑料则为异氰酸酯。由钻孔注入到病害处,黑白料混合即快速发生化学反应,并膨胀形成一定强度的泡沫状固体,填满空隙孔洞,并使病害周围松散介质趋于密集,从而提高修复体的结构整体性。该技术有以下特点:对修复体破坏小(微损),施工速度快、安全性高、耐久性好、膨胀性高、防水性能好。目前已推广应用于公路、桥梁、隧道、机场、房屋、水坝等领域的基础工程快速维修。
但现有的高聚物注浆技术在应用中存在如下问题:注浆后虽解决了空隙、孔洞、松散等病害,但随着时间推移,病害有可能继续发展,再次出现的空隙、脱空等问题,而高聚物材料无法再膨胀填充这些病害,导致维修失败。此外,现有的高聚物灌浆材料在抗收缩效果仍需要进一步改进。根据Q/320282NS012-2009检测标准常规的产品固化后体积收缩率高达5-10%。上述问题若得不到解决,将使高聚物注浆技术的应用受到了极大的限制。
发明内容
本发明的目的在于克服上述现有高聚物注浆材料存在的缺陷,提出了一种含缓释胶囊的二次膨胀型高聚物注浆材料及其制备方法。可实现注浆材料的二次膨胀,提高了材料的抗收缩效果,使高聚物注浆技术的应用更加广泛。
本发明提出的含缓释胶囊的二次膨胀型高聚物注浆材料,包括聚氨酯白料(高聚白物料)和聚氨酯黑料(高聚物黑料),其特征是:
所述聚氨酯黑料中含有以聚氨酯黑料掺杂颗粒为囊芯、以St-BA共聚物为囊壁的缓释胶囊A。
所述聚氨酯白料中含有以聚氨酯白料掺杂颗粒为囊芯、以St-BA共聚物为囊壁的缓释胶囊B。
所述聚氨酯黑料的成分为异氰酸酯,所述聚氨酯白料为多元醇、催化剂和匀泡剂混合物。
所述以聚氨酯黑料掺杂颗粒为囊芯、以St-BA共聚物为囊壁的缓释胶囊A,由以下方法制得:
步骤1.将聚氨酯黑料与多孔纳米粒子混合,通过浸渍法制成掺杂颗粒A。
步骤2.将掺杂颗粒A与苯乙烯(St)、丙烯酸丁酯(BA)、引发剂偶氮二异丁腈(AIBN)和有机溶剂通过溶液聚合法制成以异氰酸酯掺杂颗粒为囊芯,以St-BA共聚物为囊壁的缓释胶囊A。
所述以聚氨酯白料掺杂颗粒为囊芯、以St-BA共聚物为囊壁的缓释胶囊B,由以下方法制得:
步骤1.将聚氨酯白料与多孔纳米粒子混合,通过浸渍法制成掺杂颗粒B。
步骤2.将掺杂颗粒B与苯乙烯(St)、丙烯酸丁酯(BA)、引发剂偶氮二异丁腈(AIBN)和有机溶剂通过溶液聚合法制成以聚氨酯白料掺杂颗粒为囊芯,以St-BA共聚物为囊壁的缓释胶囊B。
所述的多孔纳米粒子为多孔纳米二氧化硅、多孔纳米二氧化钛、ZSM-5、HZSM-5中的一种。
所述的聚氨酯黑料异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、多苯基多甲基多异氰酸酯的一种或几种;所述多元醇为聚醚二元醇和/或聚醚三元醇。
所述苯乙烯与丙烯酸丁酯摩尔比为2:1~5:1,引发剂偶氮二异丁腈添加量为苯乙烯摩尔量的1~2%,所述有机溶剂为二氯甲烷、氯仿、异丁醇中的一种。
进一步的,所述聚氨酯黑料中含有质量百分比10%~50%的以聚氨酯黑料掺杂颗粒为囊芯、以St-BA共聚物为囊壁的缓释胶囊A;所述聚氨酯黑白中含有质量百分比10%~50%的以聚氨酯白料掺杂颗粒为囊芯、以St-BA共聚物为囊壁的缓释胶囊B。
本发明含缓释胶囊的二次膨胀型高聚物注浆材料的制备方法,其步骤如下:
制备缓释胶囊A:将多孔纳米粒子通过超声搅拌分散在聚氨酯黑料中,时间不少于1h。搅拌结束后静置24h,再通过10000r/min~12000r/min离心机离心获得有机/无机掺杂颗粒A;通过溶液聚合法,将掺杂颗粒A与苯乙烯、丙烯酸丁酯、引发剂偶氮二异丁腈以及有机溶剂混合均匀,反应温度60~80℃、反应时间4~6h;将反应后的混合液趁热抽滤,60℃真空箱干燥,得到缓释胶囊A。
制备缓释胶囊B:将多孔纳米粒子通过超声搅拌分散在聚氨酯白料中,时间不少于 1h。搅拌结束后静置24h,再通过10000r/min~12000r/min离心机离心获得有机/无机掺杂颗粒B;通过溶液聚合法,将掺杂颗粒B与苯乙烯、丙烯酸丁酯、引发剂偶氮二异丁腈以及有机溶剂混合均匀,反应温度60~80℃、反应时间4~6h;将反应后的混合液趁热抽滤,60℃真空箱干燥,得到缓释胶囊B。
将缓释胶囊A按设定的比例加入到聚氨酯黑料中,搅拌均匀。将缓释胶囊B按设定的比例加入到聚氨酯黑料中,搅拌均匀。
本发明含缓释胶囊的二次膨胀型高聚物注浆材料,使用时,将添加缓释胶囊A的黑料与添加缓释胶囊B的白料按照体积比1:1进行混合,反应后即可得到含缓释胶囊的二次膨胀型高聚物注浆料。
与传统高聚物注浆材料相比,本发明具有以下几个明显的优点:
(1)力学强度高。本发明制备的含缓释胶囊的二次膨胀型高聚物注浆材料因含有大量的无机纳米粒子,相比于传统高聚物注浆材料具有更高的抗压强度和抗折强度。
(2)不收缩且可以产生二次膨胀。本发明制备的含缓释胶囊的二次膨胀型高聚物注浆材料,在高聚物材料形成固结体后,缓释胶囊A和B中含有的黑料异氰酸酯、白料聚醚多元醇等,可通过St-BA共聚物囊壁缓慢释放,并产生二次膨胀后体积可达到原固结体体积的0.5~3倍。很好解决了传统材料收缩问题,以及修复后的病害再扩大而无法根治的问题。
(3)缓释胶囊中黑白料释放速度可通过苯乙烯与丙烯酸丁酯的摩尔比自由调节,释放周期从1个月到3年不等,满足不同工况需要。摩尔比越大,囊壁越致密,释放速度越慢;摩尔比越小,囊壁越疏松,释放速度越快。
实施例1
(1)缓释胶囊A的制备
将50g多孔纳米二氧化硅通过超声搅拌分散在100ml聚氨酯黑料甲苯二异氰酸酯中,时间不少于1h。搅拌结束后静置24h,再通过12000r/min离心机离心获得有机/无机掺杂颗粒A(纳米颗粒);通过溶液聚合法,以二氯甲烷作溶剂,将纳米颗粒A与摩尔比为2:1的苯乙烯、丙烯酸丁酯混合均匀,引发剂偶氮二异丁腈添加量为苯乙烯摩尔量的1%,反应温度60℃、反应时间4h;将反应后的混合液趁热抽滤,60℃真空箱干燥,得到缓释胶囊A。
(2)缓释胶囊B的制备
将50g多孔纳米二氧化硅通过超声搅拌分散在100ml高聚物白料组合聚醚多元醇及添加剂中,时间不少于1h。搅拌结束后静置24h,再通过12000r/min离心机离心获得有机/无机掺杂颗 粒B(纳米颗粒);通过溶液聚合法,以二氯甲烷作溶剂,将纳米颗粒B与摩尔比2:1的苯乙烯、丙烯酸丁酯混合均匀反应,引发剂偶氮二异丁腈添加量为苯乙烯摩尔量的1%,反应温度60℃、反应时间4~6h;将反应后的混合液趁热抽滤,60℃真空箱干燥,得到缓释胶囊B。
(3)含有以聚氨酯黑料掺杂颗粒为囊芯、以St-BA共聚物为囊壁的缓释胶囊B的聚氨酯黑料(改性后的黑料)的制备
按黑料质量分数的10%将缓释胶囊A添加到聚氨酯黑料中,混合均匀。
(4)含有以聚氨酯白料掺杂颗粒为囊芯、以St-BA共聚物为囊壁的缓释胶囊B的聚氨酯白料(改性后的白料)的制备
按白料质量分数的10%将缓释胶囊B添加到聚氨酯白料中,混合均匀。
使用时,按照体积比1:1称取改性后的黑料和改性后的白料,用玻璃棒搅拌均匀,制得含缓释胶囊的二次膨胀型高聚物注浆材料。
经测试:固结体抗压强度21.3MPa,胶囊缓释周期大于6个月,二次膨胀后体积可达到原固结体体积的1.5倍。
实施例2
(1)缓释胶囊A的制备
将50g多孔纳米二氧化钛通过超声搅拌分散在100ml高聚物黑料多苯基多甲基多异氰酸酯中,时间不少于1h。搅拌结束后静置24h,再通过10000r/min离心机离心获得有机/无机掺杂颗粒A;通过溶液聚合法,以氯仿作溶剂,将掺杂颗粒A与摩尔比为3:1的苯乙烯、丙烯酸丁酯混合均匀,引发剂偶氮二异丁腈添加量为苯乙烯摩尔量的1.5%,反应温度70℃、反应时间5h;将反应后的混合液趁热抽滤,60℃真空箱干燥,得到缓释胶囊A。
(2)缓释胶囊B的制备
将50g多孔纳米二氧化硅通过超声搅拌分散在100ml高聚物白料组合聚醚多元醇及添加剂中,时间不少于1h。搅拌结束后静置24h,再通过10000r/min离心机离心获得有机/无机掺杂颗粒B;通过溶液聚合法,以氯仿作溶剂,将掺杂颗粒B与摩尔比为3:1的苯乙烯、丙烯酸丁酯混合均匀,引发剂偶氮二异丁腈添加量为苯乙烯摩尔量的1.5%,反应温度70℃、反应时间5h;将反应后的混合液趁热抽滤,60℃真空箱干燥,得到缓释胶囊B。
(3)含有以聚氨酯黑料掺杂颗粒为囊芯、以St-BA共聚物为囊壁的缓释胶囊B的聚氨酯黑料(改性后的黑料)的制备
按黑料质量分数的30%将缓释胶囊A添加到聚氨酯黑料中,混合均匀。
(4)含有以聚氨酯白料掺杂颗粒为囊芯、以St-BA共聚物为囊壁的缓释胶囊B的聚氨酯白料(改性后的白料)的制备
按白料质量分数的30%将缓释胶囊B添加到聚氨酯白料中,混合均匀。
经测试:固结体抗压强度24.7MPa,胶囊缓释周期大于18个月,二次膨胀后体积可达到原固结体体积的2.1倍。
实施例3
(1)缓释胶囊A的制备
将50g分子筛ZSM-5通过超声搅拌分散在100ml高聚物黑料多苯基多甲基多异氰酸酯中,时间不少于1h。搅拌结束后静置24h,再通过11000r/min离心机离心获得有机/无机掺杂颗粒A;通过溶液聚合法,以异丁醇作溶剂,将掺杂颗粒A与摩尔比为5:1的苯乙烯、丙烯酸丁酯混合均匀,引发剂偶氮二异丁腈添加量为苯乙烯摩尔量的2%,反应温度80℃、反应时间6h;将反应后的混合液趁热抽滤,60℃真空箱干燥,得到缓释胶囊A。
(2)缓释胶囊B的制备
将50g多孔纳米二氧化硅通过超声搅拌分散在100ml高聚物白料组合聚醚多元醇及添加剂中,时间不少于1h。搅拌结束后静置24h,再通过10000r/min离心机离心获得有机/无机掺杂颗粒B;通过溶液聚合法,以异丁醇作溶剂,将掺杂颗粒B与摩尔比为5:1的苯乙烯、丙烯酸丁酯混合均匀,引发剂偶氮二异丁腈添加量为苯乙烯摩尔量的2%,反应温度80℃、反应时间6h;将反应后的混合液趁热抽滤,60℃真空箱干燥,得到缓释胶囊B。
(3)含有以聚氨酯黑料掺杂颗粒为囊芯、以St-BA共聚物为囊壁的缓释胶囊B的聚氨酯黑料(改性后的黑料)的制备
按黑料质量分数的50%将缓释胶囊A添加到聚氨酯黑料中,混合均匀。
(4)含有以聚氨酯白料掺杂颗粒为囊芯、以St-BA共聚物为囊壁的缓释胶囊B的聚氨酯白料(改性后的白料)的制备
按白料质量分数的50%将缓释胶囊B添加到聚氨酯白料中,混合均匀。
使用时,按照体积比1:1称取改性后的黑料和改性后的的白料,用玻璃棒搅拌均匀,制得含缓释胶囊的二次膨胀型高聚物注浆材料。
经测试:固结体抗压强度35.7MPa,胶囊缓释时间大于36个月,二次膨胀后体积可达到原固结体体积的3.10倍。
Claims (7)
- 一种含缓释胶囊的二次膨胀型高聚物注浆材料,包括聚氨酯白料和聚氨酯黑料,其特征是:所述聚氨酯黑料中含有以聚氨酯黑料掺杂颗粒为囊芯、以St-BA共聚物为囊壁的缓释胶囊A;所述聚氨酯白料中含有以聚氨酯白料掺杂颗粒为囊芯、以St-BA共聚物为囊壁的缓释胶囊B。
- 根据权利要求1所述的含缓释胶囊的二次膨胀型高聚物注浆材料,其特征是:所述聚氨酯黑料的成分为异氰酸酯,所述聚氨酯白料为多元醇、催化剂和匀泡剂混合物。
- 根据权利要求1所述的含缓释胶囊的二次膨胀型高聚物注浆材料,其特征是:所述以聚氨酯黑料掺杂颗粒为囊芯、以St-BA共聚物为囊壁的缓释胶囊A,由以下方法制得:步骤1.将聚氨酯黑料与多孔纳米粒子混合,通过浸渍法制成掺杂颗粒A;步骤2.将掺杂颗粒A与苯乙烯、丙烯酸丁酯、引发剂偶氮二异丁腈和有机溶剂通过溶液聚合法制成以异氰酸酯掺杂颗粒为囊芯,以St-BA共聚物为囊壁的缓释胶囊A;所述以聚氨酯白料掺杂颗粒为囊芯、以St-BA共聚物为囊壁的缓释胶囊B,由以下方法制得:步骤a.将聚氨酯白料与多孔纳米粒子混合,通过浸渍法制成掺杂颗粒B;步骤b.将掺杂颗粒B与苯乙烯、丙烯酸丁酯、引发剂偶氮二异丁腈和有机溶剂通过溶液聚合法制成以聚氨酯白料掺杂颗粒为囊芯,以St-BA共聚物为囊壁的缓释胶囊B。
- 根据权利要求3所述的含缓释胶囊的二次膨胀型高聚物注浆材料,其特征是:所述的多孔纳米粒子为多孔纳米二氧化硅、多孔纳米二氧化钛、ZSM-5、HZSM-5中的一种;所述苯乙烯与丙烯酸丁酯摩尔比为2:1~5:1,偶氮二异丁腈添加量为苯乙烯摩尔量的1~2%,所述有机溶剂为二氯甲烷、氯仿、异丁醇中的一种。
- 根据权利要求2所述的含缓释胶囊的二次膨胀型高聚物注浆材料,其特征是:所述的聚氨酯黑料异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、多苯基多甲基多异氰酸酯的一种或几种;所述多元醇为聚醚二元醇和/或聚醚三元醇。
- 根据权利要求1所述的含缓释胶囊的二次膨胀型高聚物注浆材料,其特征是:所述聚氨酯黑料中含有质量百分比10%~50%的以聚氨酯黑料掺杂颗粒为囊芯、以St-BA共聚物为囊壁的缓释胶囊A;所述聚氨酯白料中含有质量百分比10%~50%的以聚氨酯白料掺杂颗粒为囊芯、以St-BA共聚物为囊壁的缓释胶囊B。
- 一种权利要求1-6所述的含缓释胶囊的二次膨胀型高聚物注浆材料的制备方法,其步骤如下:制备缓释胶囊A:将多孔纳米粒子通过超声搅拌分散在聚氨酯黑料中,时间不少于1h;搅拌结束后静置24h,再通过10000r/min~12000r/min离心机离心获得有机/无机掺杂颗粒A;通过溶液聚合法,将掺杂颗粒A与苯乙烯、丙烯酸丁酯、偶氮二异丁腈以及有机溶剂混合均匀,反应温度60~80℃、反应时间4~6h;将反应后的混合液趁热抽滤,60℃真空箱干燥,得到缓释胶囊A;制备缓释胶囊B:将多孔纳米粒子通过超声搅拌分散在聚氨酯白料中,时间不少于1h;搅拌结束后静置24h,再通过10000r/min~12000r/min离心机离心获得有机/无机掺杂颗粒B;通过溶液聚合法,将掺杂颗粒B与苯乙烯、丙烯酸丁酯、偶氮二异丁腈以及有机溶剂混合均匀,反应温度60~80℃、反应时间4~6h;将反应后的混合液趁热抽滤,60℃真空箱干燥,得到缓释胶囊B;将缓释胶囊A按设定的比例加入到聚氨酯黑料中,搅拌均匀;将缓释胶囊B按设定的比例加入到聚氨酯黑料中,搅拌均匀。
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