CN113444482A - 一种高粘结强度耐水的水性聚氨酯粘合剂的制备方法 - Google Patents
一种高粘结强度耐水的水性聚氨酯粘合剂的制备方法 Download PDFInfo
- Publication number
- CN113444482A CN113444482A CN202110574140.XA CN202110574140A CN113444482A CN 113444482 A CN113444482 A CN 113444482A CN 202110574140 A CN202110574140 A CN 202110574140A CN 113444482 A CN113444482 A CN 113444482A
- Authority
- CN
- China
- Prior art keywords
- stirring
- dispersion
- reaction
- preparation
- polyurethane
- 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.)
- Pending
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 38
- 239000004814 polyurethane Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000000853 adhesive Substances 0.000 title claims abstract description 34
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 35
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical class O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 239000006185 dispersion Substances 0.000 claims abstract description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 230000007062 hydrolysis Effects 0.000 claims abstract description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 13
- 239000003112 inhibitor Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims abstract description 12
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims abstract description 12
- 150000002009 diols Chemical class 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 12
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 235000019441 ethanol Nutrition 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 10
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- 238000004945 emulsification Methods 0.000 claims abstract description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 229920003009 polyurethane dispersion Polymers 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004014 plasticizer Substances 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 2
- 230000003712 anti-aging effect Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000003995 emulsifying agent Substances 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 5
- 239000000945 filler Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 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
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- 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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 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
- C08G18/6625—Compounds of groups C08G18/42, 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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C08G2170/00—Compositions for adhesives
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
本发明公开了一种高粘结强度耐水的水性聚氨酯粘合剂的制备方法，涉及粘合剂技术领域，包括以下步骤：将硅烷偶联剂KH550和钛酸四丁酯分散到无水乙醇中，得分散液；将乙醇水溶液和水解抑制剂滴加到分散液中，升温搅拌反应，抽滤洗涤干燥，得改性TiO2；将聚四氢呋喃二醇、聚己二酸乙二醇酯、二异氰酸酯、二羟甲基丙酸、催化剂混合，升温反应；加入乙二胺，升温反应，得聚氨酯预聚体，降温，加入改性TiO2，搅拌反应；加入三乙胺中和；降至室温，加入去离子水乳化分散，减压蒸馏，即得聚氨酯分散体；再加入其它助剂，乳化分散，即得。本发明采用一步法合成KH550改性TiO2纳米粒子并作为填料，有效改善材料的耐水性和机械强度，制备的聚氨酯粘合剂综合性能好。
Description
技术领域
本发明涉及粘合剂技术领域，尤其涉及一种高粘结强度耐水的水性聚氨酯粘合剂的制备方法。
背景技术
水性聚氨酯具有安全环保、不易燃烧、优异的弹性、柔韧性、附着力等优点，常被用来代替溶剂型聚氨酯材料应用于涂料、粘合剂、弹性体、印刷油墨等领域。然而，现有的水性聚氨酯粘合剂性能不佳，主要表现为耐水性不佳，且粘结性也有待进一步提高。因此，需要改善水性聚氨酯材料的综合性能以扩大其应用范围。
发明内容
基于背景技术存在的技术问题，本发明提出了一种高粘结强度耐水的水性聚氨酯粘合剂的制备方法，采用一步法合成KH550改性TiO2纳米粒子并作为填料，有效改善材料的耐水性和机械强度，制备的聚氨酯粘合剂综合性能好。
本发明提出的一种高粘结强度耐水的水性聚氨酯粘合剂的制备方法，包括以下步骤：
S1、改性TiO2的制备：将硅烷偶联剂KH550和钛酸四丁酯分散到无水乙醇中，得到分散液；将乙醇水溶液和水解抑制剂滴加到分散液中，升温至50-60℃搅拌反应，抽滤，洗涤，干燥，即得改性TiO2；
S2、聚氨酯预聚体制备：将聚四氢呋喃二醇、聚己二酸乙二醇酯、二异氰酸酯、二羟甲基丙酸、催化剂加入到反应容器中，升温至70-75℃，搅拌反应；然后加入乙二胺，并加入丙酮降低体系黏度，升温至75-80℃搅拌反应，即得聚氨酯预聚体；
S3、聚氨酯分散体制备：将S2的反应体系降温至30-40℃，加入改性TiO2，搅拌反应；最后加入三乙胺中和；降至室温，加入去离子水乳化分散，减压蒸馏除去丙酮，即得聚氨酯分散体；
S4、粘合剂制备：向聚氨酯分散体加入其它助剂，乳化分散，即得。
优选地，S1中，分散液中的KH550、钛酸四丁酯、无水乙醇的体积比为1-2：10：15-20；乙醇水溶液的体积分数为95％，乙醇水溶液和分散液的体积比为1：1-1.5。
优选地，S1中，水解抑制剂是由盐酸和醋酸按照1-1.5：1-1.5的体积比组成的。
优选地，S1中，升温至50-60℃，搅拌反应4-6h。
优选地，S2中，二异氰酸酯是由六亚甲基二异氰酸酯和异佛尔酮二异氰酸酯按照2-3：2-3的重量比组成的。
优选地，S2中，将聚四氢呋喃二醇、聚己二酸乙二醇酯、二异氰酸酯、二羟甲基丙酸、催化剂加入到反应容器中，升温至70-75℃，搅拌反应2-3h；然后加入乙二胺，并加入丙酮降低体系黏度，升温至75-80℃搅拌反应2-3h，即得聚氨酯预聚体。
优选地，S3中，加入改性TiO2，搅拌反应60-90min。
优选地，聚四氢呋喃二醇、聚己二酸乙二醇酯、二异氰酸酯、二羟甲基丙酸、催化剂、乙二胺、改性TiO2的重量比为40-50：50-60：20-35：3-6：0.1-0.2：2-5：3-10。
优选地，乳化分散的搅拌转速为3000-4000r/min。
优选地，S4中，其它助剂包括增塑剂、乳化剂、防老剂、阻燃剂中的一种或多种。
有益效果：本发明的水性聚氨酯粘合剂通过合理选择原料组成，并优化各原料用量，以聚四氢呋喃二醇、聚己二酸乙二醇酯、二异氰酸酯、二羟甲基丙酸、乙二胺、改性TiO2为主要原料，制得的水性聚氨酯性能优异；采用一步法合成KH550改性的TiO2纳米粒子并将其用作聚氨酯填料，KH550和TiO2配合能够有效改善材料的耐水性和机械强度，且相较于现有技术中先制备TiO2纳米粒子再利用KH550共混改性，本发明的改性TiO2纳米粒子用作水性聚氨酯填料，其剥离强度提高了7.5％以上、剪切强度提高了6.4％以上，这可能是由于采用一步法合成的改性TiO2纳米粒子的团聚有所改善，从而提高其在高分子聚合物的分散性；所制备的聚氨酯粘合剂综合性能好，具有良好的粘接性和耐水性，对塑料、金属、木材、玻璃等多种基材具有良好的粘结性能。
具体实施方式
下面，通过具体实施例对本发明的技术方案进行详细说明。
实施例1
本发明提出的一种高粘结强度耐水的水性聚氨酯粘合剂的制备方法，包括以下步骤：
S1、改性TiO2的制备：将1体积的硅烷偶联剂KH550和10体积的钛酸四丁酯分散到15体积的无水乙醇中，得到分散液；将1体积的95vt％乙醇水溶液和0.04体积的水解抑制剂滴加到1体积的分散液中，升温至50℃，搅拌反应4h，抽滤，洗涤，干燥，即得改性TiO2；其中，水解抑制剂是由盐酸和醋酸按照1：1的体积比组成的；
S2、聚氨酯预聚体制备：S2中，将40重量份的聚四氢呋喃二醇、60重量份的聚己二酸乙二醇酯、10重量份的六亚甲基二异氰酸酯、10重量份的异佛尔酮二异氰酸酯、3重量份的二羟甲基丙酸、0.1重量份的催化剂加入到反应容器中，升温至70℃，搅拌反应2h；然后加入2重量份的乙二胺，并加入丙酮降低体系黏度，升温至75℃搅拌反应2h，即得聚氨酯预聚体；
S3、聚氨酯分散体制备：将S2的反应体系降温至30℃，加入3重量份的改性TiO2，搅拌反应60min；最后加入三乙胺中和；降至室温，加入去离子水3000r/min搅拌转速下乳化分散，减压蒸馏除去丙酮，即得聚氨酯分散体；
S4、粘合剂制备：向聚氨酯分散体加入增塑剂，在3000r/min乳化分散，即得。
实施例2
本发明提出的一种高粘结强度耐水的水性聚氨酯粘合剂的制备方法，包括以下步骤：
S1、改性TiO2的制备：将1.4体积的硅烷偶联剂KH550和10体积的钛酸四丁酯分散到17体积的无水乙醇中，得到分散液；将1体积的95vt％乙醇水溶液和0.04体积的水解抑制剂滴加到1.2体积的分散液中，升温至55℃，搅拌反应4.5h，抽滤，洗涤，干燥，即得改性TiO2；其中，水解抑制剂是由盐酸和醋酸按照1：1.5的体积比组成的；
S2、聚氨酯预聚体制备：S2中，将45重量份的聚四氢呋喃二醇、55重量份的聚己二酸乙二醇酯、10重量份的六亚甲基二异氰酸酯、15重量份的异佛尔酮二异氰酸酯、4重量份的二羟甲基丙酸、0.15重量份的催化剂加入到反应容器中，升温至70℃，搅拌反应2.5h；然后加入3重量份的乙二胺，并加入丙酮降低体系黏度，升温至75℃搅拌反应2.5h，即得聚氨酯预聚体；
S3、聚氨酯分散体制备：将S2的反应体系降温至35℃，加入5重量份的改性TiO2，搅拌反应70min；最后加入三乙胺中和；降至室温，加入去离子水3500r/min搅拌转速下乳化分散，减压蒸馏除去丙酮，即得聚氨酯分散体；
S4、粘合剂制备：向聚氨酯分散体加入增塑剂，在3500r/min乳化分散，即得。
实施例3
本发明提出的一种高粘结强度耐水的水性聚氨酯粘合剂的制备方法，包括以下步骤：
S1、改性TiO2的制备：将1.7体积的硅烷偶联剂KH550和10体积的钛酸四丁酯分散到18体积的无水乙醇中，得到分散液；将1体积的95vt％乙醇水溶液和0.05体积的水解抑制剂滴加到1.3体积的分散液中，升温至55℃，搅拌反应5h，抽滤，洗涤，干燥，即得改性TiO2；其中，水解抑制剂是由盐酸和醋酸按照1.5：1的体积比组成的；
S2、聚氨酯预聚体制备：S2中，将47重量份的聚四氢呋喃二醇、53重量份的聚己二酸乙二醇酯、15重量份的六亚甲基二异氰酸酯、15重量份的异佛尔酮二异氰酸酯、5重量份的二羟甲基丙酸、0.15重量份的催化剂加入到反应容器中，升温至75℃，搅拌反应2.5h；然后加入4重量份的乙二胺，并加入丙酮降低体系黏度，升温至80℃搅拌反应2.5h，即得聚氨酯预聚体；
S3、聚氨酯分散体制备：将S2的反应体系降温至40℃，加入7重量份的改性TiO2，搅拌反应80min；最后加入三乙胺中和；降至室温，加入去离子水3000-4000r/min搅拌转速下乳化分散，减压蒸馏除去丙酮，即得聚氨酯分散体；
S4、粘合剂制备：向聚氨酯分散体加入增塑剂，在3500r/min乳化分散，即得。
实施例4
本发明提出的一种高粘结强度耐水的水性聚氨酯粘合剂的制备方法，包括以下步骤：
S1、改性TiO2的制备：将2体积的硅烷偶联剂KH550和10体积的钛酸四丁酯分散到20体积的无水乙醇中，得到分散液；将1体积的95vt％乙醇水溶液和0.05体积的水解抑制剂滴加到1.5体积的分散液中，升温至60℃，搅拌反应6h，抽滤，洗涤，干燥，即得改性TiO2；其中，水解抑制剂是由盐酸和醋酸按照1.2：1.3的体积比组成的；
S2、聚氨酯预聚体制备：S2中，将50重量份的聚四氢呋喃二醇、50重量份的聚己二酸乙二醇酯、15重量份的六亚甲基二异氰酸酯、20重量份的异佛尔酮二异氰酸酯、6重量份的二羟甲基丙酸、0.2重量份的催化剂加入到反应容器中，升温至75℃，搅拌反应3h；然后加入5重量份的乙二胺，并加入丙酮降低体系黏度，升温至80℃搅拌反应3h，即得聚氨酯预聚体；
S3、聚氨酯分散体制备：将S2的反应体系降温至40℃，加入10重量份的改性TiO2，搅拌反应90min；最后加入三乙胺中和；降至室温，加入去离子水3000-4000r/min搅拌转速下乳化分散，减压蒸馏除去丙酮，即得聚氨酯分散体；
S4、粘合剂制备：向聚氨酯分散体加入增塑剂，在4000r/min乳化分散，即得。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种高粘结强度耐水的水性聚氨酯粘合剂的制备方法，其特征在于，包括以下步骤：
S1、改性TiO2的制备：将硅烷偶联剂KH550和钛酸四丁酯分散到无水乙醇中，得到分散液；将乙醇水溶液和水解抑制剂滴加到分散液中，升温至50-60℃搅拌反应，抽滤，洗涤，干燥，即得改性TiO2；
S2、聚氨酯预聚体制备：将聚四氢呋喃二醇、聚己二酸乙二醇酯、二异氰酸酯、二羟甲基丙酸、催化剂加入到反应容器中，升温至70-75℃，搅拌反应；然后加入乙二胺，并加入丙酮降低体系黏度，升温至75-80℃搅拌反应，即得聚氨酯预聚体；
S3、聚氨酯分散体制备：将S2的反应体系降温至30-40℃，加入改性TiO2，搅拌反应；最后加入三乙胺中和；降至室温，加入去离子水乳化分散，减压蒸馏除去丙酮，即得聚氨酯分散体；
S4、粘合剂制备：向聚氨酯分散体加入其它助剂，乳化分散，即得。
2.根据权利要求1所述的高粘结强度耐水的水性聚氨酯粘合剂的制备方法，其特征在于，S1中，分散液中的KH550、钛酸四丁酯、无水乙醇的体积比为1-2：10：15-20；乙醇水溶液的体积分数为95％，乙醇水溶液和分散液的体积比为1：1-1.5。
3.根据权利要求1或2所述的高粘结强度耐水的水性聚氨酯粘合剂的制备方法，其特征在于，S1中，水解抑制剂是由盐酸和醋酸按照1-1.5：1-1.5的体积比组成的。
4.根据权利要求1-3任一项所述的高粘结强度耐水的水性聚氨酯粘合剂的制备方法，其特征在于，S1中，升温至50-60℃，搅拌反应4-6h。
5.根据权利要求1-4任一项所述的高粘结强度耐水的水性聚氨酯粘合剂的制备方法，其特征在于，S2中，二异氰酸酯是由六亚甲基二异氰酸酯和异佛尔酮二异氰酸酯按照2-3：2-3的重量比组成的。
6.根据权利要求1-5任一项所述的高粘结强度耐水的水性聚氨酯粘合剂的制备方法，其特征在于，S2中，将聚四氢呋喃二醇、聚己二酸乙二醇酯、二异氰酸酯、二羟甲基丙酸、催化剂加入到反应容器中，升温至70-75℃，搅拌反应2-3h；然后加入乙二胺，并加入丙酮降低体系黏度，升温至75-80℃搅拌反应2-3h，即得聚氨酯预聚体。
7.根据权利要求1-6任一项所述的高粘结强度耐水的水性聚氨酯粘合剂的制备方法，其特征在于，S3中，加入改性TiO2，搅拌反应60-90min。
8.根据权利要求1-7任一项所述的高粘结强度耐水的水性聚氨酯粘合剂的制备方法，其特征在于，聚四氢呋喃二醇、聚己二酸乙二醇酯、二异氰酸酯、二羟甲基丙酸、催化剂、乙二胺、改性TiO2的重量比为40-50：50-60：20-35：3-6：0.1-0.2：2-5：3-10。
9.根据权利要求1-8任一项所述的高粘结强度耐水的水性聚氨酯粘合剂的制备方法，其特征在于，乳化分散的搅拌转速为3000-4000r/min。
10.根据权利要求1-9任一项所述的高粘结强度耐水的水性聚氨酯粘合剂的制备方法，其特征在于，S4中，其它助剂包括增塑剂、乳化剂、防老剂、阻燃剂中的一种或多种。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110574140.XA CN113444482A (zh) | 2021-05-25 | 2021-05-25 | 一种高粘结强度耐水的水性聚氨酯粘合剂的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110574140.XA CN113444482A (zh) | 2021-05-25 | 2021-05-25 | 一种高粘结强度耐水的水性聚氨酯粘合剂的制备方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113444482A true CN113444482A (zh) | 2021-09-28 |
Family
ID=77810196
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110574140.XA Pending CN113444482A (zh) | 2021-05-25 | 2021-05-25 | 一种高粘结强度耐水的水性聚氨酯粘合剂的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113444482A (zh) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921379A (zh) * | 2010-04-16 | 2010-12-22 | 江苏大学 | 一种水性聚氨酯/纳米二氧化钛杂化材料的制备方法 |
| CN103031103A (zh) * | 2012-12-27 | 2013-04-10 | 广东达美新材料有限公司 | 一种保护膜用纳米改性水性聚氨酯压敏胶及其制备方法 |
| CN104276599A (zh) * | 2014-09-18 | 2015-01-14 | 安徽工程大学 | 改性纳米二氧化钛及其制备方法 |
| CN108192322A (zh) * | 2017-12-04 | 2018-06-22 | 张芸 | 一种疏水亲油型聚氨酯海绵的制备方法 |
-
2021
- 2021-05-25 CN CN202110574140.XA patent/CN113444482A/zh active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921379A (zh) * | 2010-04-16 | 2010-12-22 | 江苏大学 | 一种水性聚氨酯/纳米二氧化钛杂化材料的制备方法 |
| CN103031103A (zh) * | 2012-12-27 | 2013-04-10 | 广东达美新材料有限公司 | 一种保护膜用纳米改性水性聚氨酯压敏胶及其制备方法 |
| CN104276599A (zh) * | 2014-09-18 | 2015-01-14 | 安徽工程大学 | 改性纳米二氧化钛及其制备方法 |
| CN108192322A (zh) * | 2017-12-04 | 2018-06-22 | 张芸 | 一种疏水亲油型聚氨酯海绵的制备方法 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109796631B (zh) | 改性无机纳米粒子、复合水性聚氨酯树脂及其用途 | |
| CN101945906B (zh) | 含有聚氨酯和乙烯基聚合物的水性涂料组合物 | |
| US5034475A (en) | Graft polymers, containing polyvinyl acetal groups, on polyurethane grafting substrates, processes for the preparation thereof, and the use thereof | |
| JPH11512772A (ja) | 水分散性ブロックトイソシアネート | |
| CN106590394B (zh) | 一种连续法制备水性聚氨酯光学涂料的工艺 | |
| CN111040426A (zh) | 一种纳米氧化锌改性水性聚氨酯乳液及其制备方法 | |
| KR20080036226A (ko) | 아미노기 말단의 점성 증가제, 이 점성 증가제의 결과생성물 및 그 이용 | |
| CN111793352B (zh) | 水性聚氨酯粉体粘合剂、弹性材料及其制备方法 | |
| JPH10176006A (ja) | 非イオン水性ポリウレタン分散液及びその製造方法 | |
| EP1153051B1 (en) | Process for the preparation of anionic aqueous polymer dispersions containing no volatile tertiary amine, obtained dispersion and coating resulting from said dispersion | |
| JP2896995B2 (ja) | 印刷インキ用バインダ−および印刷インキ | |
| CN113444482A (zh) | 一种高粘结强度耐水的水性聚氨酯粘合剂的制备方法 | |
| JP5473224B2 (ja) | 複合シート貼り合わせのためのポリウレタン分散体 | |
| KR100722820B1 (ko) | 폴리올레핀용 수성 수지 조성물 및 이의 제조방법 | |
| CN111925643B (zh) | 一种高水氧阻隔性水性聚氨酯、其制备方法及双组分聚氨酯胶 | |
| EP0062598B1 (en) | Storage flowable polypropylene ether urethane composition | |
| CN115160528B (zh) | 一种生物基水性聚氨酯液体车衣的制备方法和应用 | |
| JPS6337809B2 (zh) | ||
| CN115820191A (zh) | 一种用于动力电池高弹性粘接的双组份聚氨酯结构胶 | |
| WO2016158135A1 (ja) | １液型水性接着剤組成物 | |
| CN112795361B (zh) | 一种高耐热可热变弯曲的红木粘结剂的制备方法 | |
| JPH0885716A (ja) | 自己乳化型ポリイソシアネート混合物、並びにこれを用いた水系塗料組成物および水性接着剤組成物 | |
| CN110643029B (zh) | 水溶性聚碳酸酯二醇及其制备方法和在柔感涂料中的应用 | |
| JP2002212534A (ja) | 一液湿気硬化型ウレタン接着剤組成物 | |
| JP3493529B2 (ja) | 水分散性ポリウレタンの製造方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210928 |
|
| RJ01 | Rejection of invention patent application after publication |