CN105693985B - 一种水性荧光聚氨酯复合物的制备工艺 - Google Patents
一种水性荧光聚氨酯复合物的制备工艺 Download PDFInfo
- Publication number
- CN105693985B CN105693985B CN201610147307.3A CN201610147307A CN105693985B CN 105693985 B CN105693985 B CN 105693985B CN 201610147307 A CN201610147307 A CN 201610147307A CN 105693985 B CN105693985 B CN 105693985B
- Authority
- CN
- China
- Prior art keywords
- parts
- added
- necked flask
- heated
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 36
- 239000004814 polyurethane Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000203 mixture Substances 0.000 title claims abstract description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 34
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 21
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims abstract description 16
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012948 isocyanate Substances 0.000 claims abstract description 14
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 14
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 14
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 8
- 238000004448 titration Methods 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 7
- 230000018044 dehydration Effects 0.000 claims description 17
- 238000006297 dehydration reaction Methods 0.000 claims description 17
- 239000000839 emulsion Substances 0.000 claims description 13
- QQUZHNPGWNIYMK-UHFFFAOYSA-N 4-[1,2,2-tris(4-hydroxyphenyl)ethenyl]phenol Chemical group C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)=C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 QQUZHNPGWNIYMK-UHFFFAOYSA-N 0.000 claims description 7
- 150000002513 isocyanates Chemical class 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- 150000004672 propanoic acids Chemical class 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003643 water by type Substances 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 238000006862 quantum yield reaction Methods 0.000 abstract description 9
- 239000007787 solid Substances 0.000 abstract description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004945 emulsification Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000008367 deionised water Substances 0.000 abstract description 2
- 229910021641 deionized water Inorganic materials 0.000 abstract description 2
- -1 react Chemical compound 0.000 abstract description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 abstract 1
- 239000012975 dibutyltin dilaurate Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 239000006210 lotion Substances 0.000 description 4
- 150000002171 ethylene diamines Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 102100034112 Alkyldihydroxyacetonephosphate synthase, peroxisomal Human genes 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 101000799143 Homo sapiens Alkyldihydroxyacetonephosphate synthase, peroxisomal Proteins 0.000 description 1
- 244000207740 Lemna minor Species 0.000 description 1
- 235000006439 Lemna minor Nutrition 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 235000001855 Portulaca oleracea Nutrition 0.000 description 1
- 241000425573 Talanes Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000000848 angular dependent Auger electron spectroscopy Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical class [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
-
- 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
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- 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
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1425—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1433—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
Abstract
本发明公开了一种水性荧光聚氨酯复合物的制备工艺，包括以下步骤：将各组分脱水备用；脱水后的聚丙二醇2000和二羟甲基丙酸加入三口烧瓶中，氮气保护下加热，滴入甲苯二异氰酸酯和丙酮，再加入二月桂酸二丁基锡，反应，反应过程中用二正丁胺反滴定；降温至40‑50℃，加入三乙胺，反应；降至室温，加入去离子水和乙二胺，乳化，减压蒸馏，即得。本发明制得的水性荧光聚氨酯复合物固含量高，储存稳定性长，荧光量子产率高，荧光性能优越。
Description
技术领域
本发明涉及高分子荧光材料，尤其是涉及一种水性荧光聚氨酯复合物的制备工艺。
背景技术
荧光材料分无机荧光材料和有机荧光材料，荧光材料具有光吸收能力强，转换效率高，发射谱带分布区域宽，荧光寿命长等特点。水性聚氨酯具有硬度高、附着力强、耐腐蚀、耐溶剂好、挥发性有机化合物(VOC)含量低等特点，而且使用方便。水性荧光聚氨酯的制备可以使水性聚氨酯中嵌入荧光材料以达到荧光效果，使得水性聚氨酯的使用更加广泛，如路面、城市街道上的井盖、灯柱等。
《水性聚氨酯荧光材料的制备及其荧光性能》(解芝茜、王继印、陶灿、杨明娣、黄毅萍、许戈文；《功能高分子学报》；2014、04期)公开了通过不同方式制备出的水性聚氨酯荧光材料来研究荧光性能的强弱，通过将4-胺基-4’-(N,N-二苯基氨基)-1，2-二苯乙烯(ADAS)溶解于N,N-二甲基甲酰胺(DMF)中后分别以混合和接枝的方式引入水性聚氨酯，制备了不同软段和扩链剂的水性聚氨酯荧光材料(FWPU)；其中混合法制备的FWPU其荧光强度最大可以增加76倍，接枝法制备的FWPU最大可增加47倍。制得的水性聚氨酯荧光材料应用广泛，加上两种方法制备的水性聚氨酯荧光材料荧光强度不同，荧光量子产率分别是0.8,0.9，因此加强水性聚氨酯荧光材料的发展有着长远意义。
公开号为CN104177585A的中国专利申请，公开了一种荧光性聚氨酯乳液的制备方法，首先制备出聚氨酯的预聚体，用成盐剂反应形成聚氨酯离散体，然后进行乳化，同时加入小分子荧光材料制得荧光性聚氨酯乳液，制得的荧光性聚氨酯乳液的固含量和粘度较高，荧光量子产率是0.9，适用于印染、涂料、皮革、塑料等行业，但是荧光强度不足。
发明内容
本发明提供一种水性荧光聚氨酯复合物的制备工艺，制备的水性聚氨酯复合物具有固含量高，储存稳定性长，荧光量子产率高，荧光性能优越等特点。
一种水性荧光聚氨酯复合物的制备工艺，包括以下步骤：
(1)以重量份计，分别将30-70份聚丙二醇2000和2-7份二羟甲基丙酸加热至100-140℃，在真空度≤0.1MPa的条件下，脱水处理2-3h；丙酮、三乙胺采用4A分子筛脱水，备用；
(2)将脱水后的聚丙二醇2000和二羟甲基丙酸加入三口烧瓶中，氮气保护下加热至70-90℃，滴入10-15份甲苯二异氰酸酯和10-30份丙酮，再加入0.01-0.03份二月桂酸二丁基锡，反应2-4h，反应过程中用二正丁胺反滴定至游离的异氰酸酯量浓度为3-5％；
(3)将三口烧瓶中温度降至40-50℃，加入2-7份三乙胺中和，反应0.5-1h；
(4)将三口烧瓶中温度降至室温，在高速搅拌下加入100-400份去离子水和1-5份乙二胺，乳化，减压蒸馏，得到水性聚氨酯乳液。
优选地，上述步骤(2)中，反应2-4h后再加入10-30份1，1，2，2-四(4-羟苯基)乙烯，保持温度不变，二次反应2-4h，二正丁胺反滴定过程在二次反应中进行，使得游离的异氰酸酯浓度为1.8-2.5％。
优选地，上述1，1，2，2-四(4-羟苯基)乙烯加入之前需加热至50-70℃脱水2-3h。
优选地，上述步骤(3)中中和度为100％-120％。
优选地，上述步骤(4)中乳化时间为0.5-1h。
有益效果:本发明以甲苯二异氰酸脂和聚丙二醇2000、二羟甲基丙酸混合反应，形成长链，反应充分后，两端都是异氰酸酯根，然后再加入1.1.2.2-四(4-羟苯基)乙烯形成预聚物，再加入三乙胺形成亲水基团，最后加入去离子水和乙二胺的混合物，高速搅拌形成水性荧光聚氨酯；制得的水性荧光聚氨酯乳液能够有效的将荧光材料与水性聚氨酯复合，增强水性聚氨酯的荧光性，增大水性聚氨酯的使用范围，粒径小，固含量高，在30.6-41.3％之间，储存稳定性长，达到6个月，荧光量子产率高，在0.9-0.93之间，荧光性能优越。
具体实施方式
实施例1：
一种水性荧光聚氨酯复合物的制备工艺，包括以下步骤：
(1)以重量份计，分别将30份聚丙二醇2000和2份二羟甲基丙酸加热到100℃，真空度≤0.1MPa的条件下，脱水处理2h；丙酮、三乙胺采用4A分子筛脱水，备用；
(2)将脱水后的聚丙二醇2000和二羟甲基丙酸加入三口烧瓶中，通入氮气保护并且加热到70℃，缓慢滴入10份甲苯二异氰酸酯和10份丙酮，再加入0.01份二月桂酸二丁基锡，保持反应2h；反应过程中用二正丁胺反滴定，使得游离的异氰酸酯浓度为3-5％；
(3)将三口烧瓶中温度降至40℃，加入2份三乙胺中和，中和度为100％，反应0.5h；
(4)将三口烧瓶中温度降至室温，在高速搅拌下加入100份去离子水和1份乙二胺，乳化0.5h，减压蒸馏去除丙酮，得到水性聚氨酯乳液。
本实施例制得的水性荧光聚氨酯乳液的荧光量子产率为0.90，固含量为30.6％，呈微黄色乳液，机械离心后换算能够储存6个月。
实施例2：
一种水性荧光聚氨酯复合物的制备工艺，包括以下步骤：
(1)以重量份计，分别将40份聚丙二醇2000和4份二羟甲基丙酸加热到120℃，真空度≤0.1MPa的条件下，脱水处理2.5h；将20份1.1.2.2-四(4-羟苯基)乙烯加热到50℃，脱水处理2.5h；丙酮、三乙胺采用4A分子筛脱水，备用；
(2)将脱水后的聚丙二醇2000和二羟甲基丙酸加入三口烧瓶中，通入氮气保护并且加热到75℃，缓慢滴入15份甲苯二异氰酸酯和20份丙酮，再加入0.02份二月桂酸二丁基锡，保持反应3h；再加入20份1，1，2，2-四(4-羟苯基)乙烯，保持温度不变，二次反应2h，二次反应过程中用二正丁胺反滴定，使得游离的异氰酸酯浓度为1.8-2.5％；
(3)将三口烧瓶中温度降至45℃，加入3份三乙胺中和，中和度为110％，反应0.7h；
(4)将三口烧瓶中温度降至室温，在高速搅拌下加入150份去离子水和2份乙二胺，乳化0.7h，减压蒸馏去除丙酮，得到水性聚氨酯乳液。
本实施例制得的水性荧光聚氨酯乳液的荧光量子产率为0.92，固含量为41％，呈微黄色乳液，机械离心后换算能够储存6个月。
实施例3：
一种水性荧光聚氨酯复合物的制备工艺，包括以下步骤：
(1)以重量份计，分别将60份聚丙二醇2000和7份二羟甲基丙酸加热到140℃，真空度≤0.1MPa的条件下，脱水处理3h；将30份1.1.2.2-四(4-羟苯基)乙烯加热到70℃，脱水处理3h；丙酮、三乙胺采用4A分子筛脱水，备用；
(2)将脱水后的聚丙二醇2000和二羟甲基丙酸加入三口烧瓶中，通入氮气保护并且加热到90℃，缓慢滴入15份甲苯二异氰酸酯和20份丙酮，再加入0.03份二月桂酸二丁基锡，保持反应4h；再加入30份1，1，2，2-四(4-羟苯基)乙烯，保持温度不变，二次反应2h，二次反应过程中用二正丁胺反滴定，使得游离的异氰酸酯浓度为1.8-2.5％；
(3)将三口烧瓶中温度降至50℃，加入3份三乙胺中和，中和度为105％，反应0.5h；
(4)将三口烧瓶中温度降至室温，在高速搅拌下加入400份去离子水和5份乙二胺，乳化1h，减压蒸馏去除丙酮，得到水性聚氨酯乳液。
本实施例制得的水性荧光聚氨酯乳液的荧光量子产率为0.91，固含量为37.7％，呈微黄色乳液，机械离心后换算能够储存6个月。
实施例4：
一种水性荧光聚氨酯复合物的制备工艺，包括以下步骤：
(1)以重量份计，分别将70份聚丙二醇2000和5份二羟甲基丙酸加热到110℃，真空度≤0.1MPa的条件下，脱水处理2h；将10份1.1.2.2-四(4-羟苯基)乙烯加热到70℃，脱水处理2h；丙酮、三乙胺采用4A分子筛脱水，备用；
(2)将脱水后的聚丙二醇2000和二羟甲基丙酸加入三口烧瓶中，通入氮气保护并且加热到75℃，缓慢滴入13份甲苯二异氰酸酯和30份丙酮，再加入0.01份二月桂酸二丁基锡，保持反应3h；再加入10份1，1，2，2-四(4-羟苯基)乙烯，保持温度不变，二次反应2h，二次反应过程中用二正丁胺反滴定，使得游离的异氰酸酯浓度为1.8-2.5％；
(3)将三口烧瓶中温度降至50℃，加入7份三乙胺中和，中和度为120％，反应1h；
(4)将三口烧瓶中温度降至室温，在高速搅拌下加入300份去离子水和4份乙二胺，乳化0.5h，减压蒸馏去除丙酮，得到水性聚氨酯乳液。
本实施例制得的水性荧光聚氨酯乳液的荧光量子产率为0.93，固含量为41.3％，呈微黄色乳液，机械离心后换算能够储存6个月。
Claims (1)
1.一种水性荧光聚氨酯复合物的制备工艺，其特征在于：包括以下步骤：
（1）以重量份计，分别将30-70份聚丙二醇2000和2-7份二羟甲基丙酸加热至100-140℃，在真空度≤0.1MPa的条件下，脱水处理2-3h；丙酮、三乙胺采用4A分子筛脱水，备用；
（2）将脱水后的聚丙二醇2000和二羟甲基丙酸加入三口烧瓶中，氮气保护下加热至70-90℃，滴入10-15份甲苯二异氰酸酯和10-30份丙酮，再加入0.01-0.03份二月桂酸二丁基锡，反应2-4h，反应2-4h后再加入10-30份1，1，2，2-四（4-羟苯基）乙烯，保持温度不变，二次反应2-4h，二正丁胺反滴定过程在二次反应中进行，使得游离的异氰酸酯浓度为1.8-2.5%；所述1，1，2，2-四（4-羟苯基）乙烯加入之前需加热至50-70℃脱水2-3h；
（3）将三口烧瓶中温度降至40-50℃，加入2-7份三乙胺中和，反应0.5-1h，中和度为100%-120%；
（4）将三口烧瓶中温度降至室温，在高速搅拌下加入100-400份去离子水和1-5份乙二胺，乳化0.5-1h，减压蒸馏，得到水性聚氨酯乳液。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610147307.3A CN105693985B (zh) | 2016-03-16 | 2016-03-16 | 一种水性荧光聚氨酯复合物的制备工艺 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610147307.3A CN105693985B (zh) | 2016-03-16 | 2016-03-16 | 一种水性荧光聚氨酯复合物的制备工艺 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105693985A CN105693985A (zh) | 2016-06-22 |
| CN105693985B true CN105693985B (zh) | 2019-01-18 |
Family
ID=56221718
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610147307.3A Active CN105693985B (zh) | 2016-03-16 | 2016-03-16 | 一种水性荧光聚氨酯复合物的制备工艺 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105693985B (zh) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106833345A (zh) * | 2016-12-13 | 2017-06-13 | 苏州赛斯德工程设备有限公司 | 一种防腐疏水阀 |
| CN109575230B (zh) * | 2018-12-06 | 2021-01-22 | 黑龙江大学 | 一种多功能聚氨酯衍生物的制备方法和应用 |
| CN109400836B (zh) * | 2018-12-06 | 2021-01-22 | 黑龙江大学 | 含有三芳胺结构及四苯乙烯基团的聚氨酯衍生物的制备方法和应用 |
| CN109912773B (zh) * | 2019-03-29 | 2021-10-26 | 中国科学院宁波材料技术与工程研究所 | 一种形状记忆聚氨酯及其制备方法 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172829A (zh) * | 2013-03-21 | 2013-06-26 | 中国科学技术大学 | 基于二异氰酸酯中发色团的荧光型水性聚氨酯乳液的制法 |
| CN103254396A (zh) * | 2013-06-05 | 2013-08-21 | 中国科学技术大学 | 一种基于二元醇中发色团的荧光型水性聚氨酯及其制备方法 |
-
2016
- 2016-03-16 CN CN201610147307.3A patent/CN105693985B/zh active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172829A (zh) * | 2013-03-21 | 2013-06-26 | 中国科学技术大学 | 基于二异氰酸酯中发色团的荧光型水性聚氨酯乳液的制法 |
| CN103254396A (zh) * | 2013-06-05 | 2013-08-21 | 中国科学技术大学 | 一种基于二元醇中发色团的荧光型水性聚氨酯及其制备方法 |
Non-Patent Citations (1)
| Title |
|---|
| "水性聚氨酯荧光材料的制备及其荧光性能";解芝茜等;《功能高分子学报》;20141231;第27卷(第4期);第426-431页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105693985A (zh) | 2016-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105693985B (zh) | 一种水性荧光聚氨酯复合物的制备工艺 | |
| CN100569887C (zh) | 一种鞋用水性聚氨酯粘合剂制备方法 | |
| CN1052020C (zh) | 不用氟氯烃的生产多孔聚氨酯模塑件的方法 | |
| CN1304452C (zh) | 乙烯基酯脲 | |
| CN101203488B (zh) | 异氰酸酯的制造方法、由该方法得到的异氰酸酯及其用途 | |
| CN1204117C (zh) | 制备广相容性、储存稳定、流变性活化的脲氨基甲酸酯溶液的方法 | |
| US7176271B2 (en) | Method for the production of highly functional, highly branched polyureas | |
| WO2002098944A1 (fr) | Polymere de polyurethane | |
| CN111171364A (zh) | 一种力响应聚合物泡沫颗粒及其制备方法 | |
| CN101056908A (zh) | 聚氨酯 | |
| CN1939950A (zh) | 一种木质素改性水性聚氨酯的制备方法 | |
| CN111253610A (zh) | 一种动态聚合物泡沫复合材料 | |
| CN109988281A (zh) | 一种含有二硫键的疏水性能和力学性能双重自修复无溶剂聚氨酯的制备方法 | |
| IL192815A (en) | Curing agents for epoxy-functional compounds | |
| CN1153184A (zh) | 用于制备聚氨酯的氨基丙基双(氨基乙基)醚组合物 | |
| CN108003313A (zh) | 一种嵌段型聚碳化二亚胺水性交联剂及其制备方法 | |
| CN106753180A (zh) | 粗tdi的处理方法 | |
| KR101859813B1 (ko) | 이중 경화가 가능한 저온가교형 블록이소시아네이트 및 이를 포함하는 조성물 | |
| CN102050936B (zh) | 单组份水性聚氨酯涂饰剂的合成工艺 | |
| JP6254173B2 (ja) | アニオン性イソシアネート化合物および乳化剤としてのその使用 | |
| CN1090052C (zh) | 用n,n－二烷基脲降低表面张力 | |
| CN106893064A (zh) | 一种超支化聚胺酯/蒙脱土改性聚氨酯浆料及其制备方法 | |
| JP2018506601A (ja) | 化学発泡剤及び熱膨張性の熱可塑性組成物 | |
| CN113631632A (zh) | 基于二羟基内酰胺的聚合物、其组合物及其应用 | |
| CN108373533B (zh) | 一种自乳化水性环氧固化剂的制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201022 Address after: 215500 No.13, Caotang Road, Changshu, Suzhou, Jiangsu Province Patentee after: Changshu intellectual property operation center Co.,Ltd. Address before: Meng Xi Road 212003 Zhenjiang city of Jiangsu province Jingkou District No. 2 Patentee before: JIANGSU University OF SCIENCE AND TECHNOLOGY Effective date of registration: 20201022 Address after: 215500 second floor, building 1, kinetic energy industrial park, 50 Shanghu Avenue, Shanghu Town, Changshu City, Suzhou City, Jiangsu Province Patentee after: JIANGSU GREAT CREATIVITY NEW MATERIALS Co.,Ltd. Address before: 215500 No.13, Caotang Road, Changshu, Suzhou, Jiangsu Province Patentee before: Changshu intellectual property operation center Co.,Ltd. |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20211029 Address after: 276022 Fuzhuang street, Luozhuang District, Linyi City, Shandong Province, 50 meters northwest of the intersection of Tongda South Road and Sande Road Patentee after: Shandong huamantian cultural and Creative Industry Co.,Ltd. Address before: 215500 second floor, building 1, kinetic energy industrial park, 50 Shanghu Avenue, Shanghu Town, Changshu City, Suzhou City, Jiangsu Province Patentee before: JIANGSU GREAT CREATIVITY NEW MATERIALS CO.,LTD. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211210 Address after: 276022 west of the intersection of Yice road and Shuichang Road, Fuzhuang street, Luozhuang, Linyi City, Shandong Province Patentee after: Shandong huamantian Decoration Co.,Ltd. Address before: 276022 Fuzhuang street, Luozhuang District, Linyi City, Shandong Province, 50 meters northwest of the intersection of Tongda South Road and Sande Road Patentee before: Shandong huamantian cultural and Creative Industry Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230713 Address after: 276022 Fuzhuang street, Luozhuang District, Linyi City, Shandong Province, 50 meters northwest of the intersection of Tongda South Road and Sande Road Patentee after: Shandong huamantian cultural and Creative Industry Co.,Ltd. Address before: 276022 west of the intersection of Yice road and Shuichang Road, Fuzhuang street, Luozhuang, Linyi City, Shandong Province Patentee before: Shandong huamantian Decoration Co.,Ltd. |
|
| TR01 | Transfer of patent right |