CN114836162A - Preparation method of modified polyurethane adhesive - Google Patents
Preparation method of modified polyurethane adhesive Download PDFInfo
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- CN114836162A CN114836162A CN202210332830.9A CN202210332830A CN114836162A CN 114836162 A CN114836162 A CN 114836162A CN 202210332830 A CN202210332830 A CN 202210332830A CN 114836162 A CN114836162 A CN 114836162A
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- Prior art keywords
- polyurethane adhesive
- modified polyurethane
- isophorone diisocyanate
- temperature
- prepolymer
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- 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.)
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 47
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 46
- 239000000853 adhesive Substances 0.000 title claims abstract description 41
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 30
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 23
- 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 abstract description 23
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 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 19
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920005862 polyol Polymers 0.000 claims abstract description 17
- 150000003077 polyols Chemical class 0.000 claims abstract description 17
- 229920000379 polypropylene carbonate Polymers 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 230000010355 oscillation Effects 0.000 claims abstract description 16
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 15
- 150000002009 diols Chemical class 0.000 claims abstract description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 15
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000012975 dibutyltin dilaurate Substances 0.000 claims abstract description 14
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 10
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 13
- -1 polypropylene carbonate Polymers 0.000 claims description 13
- 230000006837 decompression Effects 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 239000003517 fume Substances 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000000839 emulsion Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000005543 nano-size silicon particle Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000012940 solvent-free polyurethane adhesive Substances 0.000 description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- 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
- C09J175/06—Polyurethanes from polyesters
-
- 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
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
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- 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
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- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- 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
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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- 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
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6212—Polymers of alkenylalcohols; Acetals thereof; Oxyalkylation products thereof
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- 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
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- 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
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- C09J11/06—Non-macromolecular additives organic
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- 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
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- 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
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- Organic Chemistry (AREA)
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method of a modified polyurethane adhesive, belonging to the technical field of improved materials. The preparation method comprises the following steps: (1) preparing a reagent; (2) mixing isophorone diisocyanate, polycaprolactone diol and polyvinyl alcohol to obtain a mixed solution, cooling, then dropwise adding dimethylolpropionic acid and N-methyl pyrrolidone, and fully stirring to obtain a prepolymer; (3) and (3) adding the poly (propylene carbonate) polyol, 1, 4-butanediol, glycerol, methyl acrylate, dibutyltin dilaurate and ethyl orthosilicate into the prepolymer in the step (2), adding deionized water, performing ultrasonic oscillation, finally gradually dripping sodium persulfate, and keeping the temperature. Compared with the prior art, the preparation method avoids the use of hard particles, and the prepared modified polyurethane adhesive has strong comprehensive performance.
Description
Technical Field
The invention belongs to the technical field of improved materials, and particularly relates to an improved modified polyurethane adhesive.
Background
Polyurethane (PU) adhesives are adhesives which contain urethane groups (-NHCOO-) or isocyanate groups (-NCO) in the molecular chain. It has excellent performance and wide application. Because the carbamate and the isocyanate group have stronger polarity and higher reaction activity and can react with active hydrogen in materials, the polyurethane adhesive can provide stronger adhesive force for materials containing active hydrogen, such as wood, paper, leather, foam and the like.
For example, the prior art provides a preparation method of a solvent-free polyurethane adhesive, and the technical scheme is as follows:
the preparation method of the solvent-free polyurethane adhesive comprises the following steps:
step one, preparing polyurethane emulsion:
in a three-neck flask provided with a thermometer and a stirring rod, firstly self-made polyester diol is dehydrated in vacuum at 115 ℃ for 100min under the protection of N2, then the self-made polyester diol is cooled to 70 ℃, the rotating speed is adjusted to 200r/min, isophorone diisocyanate and dibutyltin dilaurate are slowly added, the using amount of the dibutyltin dilaurate is 0.01 percent of the mass of a reaction substance, the self-made polyester diol reacts for 2.5h at 90 ℃, the mass fraction of-NCO groups is measured by a di-N-butylamine method, when the mass fraction reaches a theoretical value of 9.59-9.69 percent, the self-made polyester diol is cooled to 78 ℃, metered dimethylol butyric acid and dibutyltin dilaurate are added, the using amount of the dibutyltin dilaurate is 0.01 percent of the mass of the reaction substance, the rotating speed is adjusted to 250r/min, and the self-made polyester diol reacts for 2.5h at 80 ℃; measuring the mass fraction of-NCO groups by a di-n-butylamine method, and finishing prepolymerization when the mass fraction reaches 5.55-5.65% of a theoretical value to obtain a prepolymer;
cooling the prepolymer to 38-42 ℃, adjusting the rotation speed to 300r/min, adding triethylamine, stirring for 3-6min, increasing the rotation speed to 2800r/min, adding deionized water and ethylenediamine, emulsifying and chain extending, stirring for 15min at 2800r/min, and stirring for 65min at 1000r/min to obtain a polyurethane emulsion with the solid content of 42-46%;
step two, preparation of modified nano silicon dioxide:
(1) adding 73.8mL of ethanol, 6mL of ethyl orthosilicate and 9.4mL of deionized water into a beaker, stirring for 20min, then dropwise adding 4.1mL of ammonia water, and stirring for 70min at room temperature of 200 r/min;
(2) slowly dripping 4.8mL of tetraethoxysilane, dripping 1.9mL of silane coupling agent KH-550, and continuously stirring for 60min at 200 r/min;
(3) centrifuging the product at 13000r/min for 5min, removing supernatant, and drying the lower precipitate in an oven at 80 ℃ for 5-6h to obtain white powdery modified nano silicon dioxide;
and step three, heating the polyurethane emulsion to 60-70 ℃, starting 150r/min and stirring at a constant speed, keeping stirring, slowly adding the modified nano-silica into the polyurethane emulsion, performing ultrasonic treatment for 20-30min, adding the defoaming agent, and continuously stirring at 150r/min for 10-15min to obtain the polyurethane adhesive.
It can be seen that the mechanical properties of the existing prepared polyurethane material are general, the use cost of the nano SiO2 molecules is high, and the silica particles are not better dispersed than micro droplets.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems in the prior art, the invention provides a preparation method of a modified polyurethane adhesive, and the prepared modified polyurethane adhesive has strong comprehensive performance.
2. Technical scheme
In order to solve the above problems, the present invention adopts the following technical solutions.
A method for preparing a modified polyurethane adhesive, comprising, but not limited to, the steps of:
(1) preparation of reagents:
preparing polyvinyl alcohol, isophorone diisocyanate, polycaprolactone diol, dimethylolpropionic acid, N-methyl pyrrolidone, polypropylene carbonate polyol, 1, 4-butanediol, glycerol, methyl acrylate, dibutyltin dilaurate, ethyl orthosilicate and sodium persulfate;
(2) first step reaction
Before use, the polyvinyl alcohol is subjected to reduced pressure dehydration until the moisture is completely lost;
mixing isophorone diisocyanate, polycaprolactone diol and polyvinyl alcohol to obtain a mixed solution, cooling, then dropwise adding dimethylolpropionic acid and N-methyl pyrrolidone, and fully stirring to obtain a prepolymer;
(3) second step reaction
And (3) adding the poly (propylene carbonate) polyol, 1, 4-butanediol, glycerol, methyl acrylate, dibutyltin dilaurate and ethyl orthosilicate into the prepolymer in the step (2), adding deionized water, performing ultrasonic oscillation, finally gradually dripping sodium persulfate, and keeping the temperature.
In the modified polyurethane adhesive, the reagent prepared in the step (1) is placed in a fume hood in a shady and cool place.
In the modified polyurethane adhesive, the pressure of the pressure reduction treatment in the step (2) is 300 bar;
the temperature of the decompression treatment in the step (2) is 60 ℃;
the time for the pressure reduction treatment in the step (2) is 2 hours.
In the modified polyurethane adhesive, the mass ratio of the isophorone diisocyanate, the polycaprolactone diol and the polyvinyl alcohol in the step (2) is 5: 7: 0.2;
the dropping amount of the dimethylolpropionic acid in the step (2) is 2 percent of the mass of the isophorone diisocyanate;
dispersing by using a high-speed disperser while mixing in the step (2), wherein the rotating speed of the dispersing is 3000r/min, and the time of the dispersing is 20 min;
the mixing temperature in the step (2) is 90 ℃;
the mixing pressure in the step (2) is 1.2 MPa.
In the modified polyurethane adhesive, the temperature after cooling in the step (2) is 70 ℃;
in the step (2), the mass ratio of the dimethylolpropionic acid to the N-methylpyrrolidone is 1: 5;
in the step (2), the mass ratio of the dimethylolpropionic acid to the isophorone diisocyanate is 1: 12.
in the modified polyurethane adhesive, the stirring speed in the step (2) is 2000 r/min;
keeping the temperature of the prepolymer obtained in the step (2) at 65 ℃ and keeping the prepolymer for no more than 24 hours.
In the modified polyurethane adhesive, in the step (3), the mass ratio of the polypropylene carbonate polyol, the 1, 4-butanediol, the glycerol, the methyl acrylate, the dibutyltin dilaurate to the ethyl orthosilicate is 2: 1: 1: 5: 1: 20;
in the step (3), the mass ratio of the polypropylene carbonate polyol to the isophorone diisocyanate is 1: 2.
in the modified polyurethane adhesive, the addition amount of deionized water in the step (3) is 30% of the mass of the polypropylene carbonate polyol.
In the modified polyurethane adhesive, the power of ultrasonic oscillation in the step (3) is 300W;
the ultrasonic oscillation time in the step (3) is 30 min;
the temperature of ultrasonic oscillation in the step (3) is 90 ℃;
and (4) applying pressure while carrying out ultrasonic oscillation in the step (3), wherein the pressure is 5 MPa.
In the modified polyurethane adhesive, the addition amount of sodium persulfate in the step (3) is 2% of the mass of isophorone diisocyanate;
the dropping time of the sodium persulfate in the step (3) is 2 h;
the temperature of the heat preservation in the step (3) is 65 ℃,
the heat preservation time in the step (3) is 6 hours.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
compared with the traditional test of adding nano silicon dioxide to strengthen the adhesive, the method adopts tetraethoxysilane to introduce the molecular chain of the adhesive, thereby improving the mechanical property after film forming. The tetraethoxysilane is easier to obtain, and the crosslinking degree of the system can be increased, for example, the silicon-oxygen bonds of the tetraethoxysilane are connected to the matrix of the polyurethane connected at intervals in the polymerized emulsion, and the connection or matching can be formed between the adjacent silicon-oxygen bonds. Meanwhile, the addition of the polyvinyl alcohol has a good promoting effect on the dispersion of the N-methyl pyrrolidone, and spherical liquid drop particles are promoted to be formed. In addition, dimethylolpropionic acid and methyl acrylate can generate intermolecular interaction with functional groups in the product, so that the comprehensive performance of the product is improved, the polyurethane material is used as a block polymer, the stability and the water resistance of the product can be improved by the content of-COOH, the crosslinking density of the polymer can be improved by the two substances, and more importantly, the dimethylolpropionic acid stably emulsifies the tetraethoxysilane, so that the tetraethoxysilane is fully contacted with the prepolymer.
Drawings
FIG. 1 is an FT-IR spectrum of the product of example 1 of the invention;
FIG. 2 is a scanning electron micrograph of the product of example 1 of the present invention.
Detailed Description
The invention is further described with reference to specific examples.
Example 1
The preparation method of the modified polyurethane adhesive of the embodiment includes, but is not limited to, the following steps:
(1) preparation of reagents:
preparing polyvinyl alcohol, isophorone diisocyanate, polycaprolactone diol, dimethylolpropionic acid, N-methyl pyrrolidone, polypropylene carbonate polyol, 1, 4-butanediol, glycerol, methyl acrylate, dibutyltin dilaurate, ethyl orthosilicate and sodium persulfate;
it should be reminded that the prepared reagent is placed in a fume hood in a cool and shady place, and a protective mask is recommended to be worn in the whole operation, so that toxic reagent poisoning is avoided.
In the production, the reagents are purchased from chemical reagents limited of the national drug group.
(2) First step reaction
Before use, the polyvinyl alcohol is subjected to reduced pressure dehydration until the moisture is completely lost;
mixing isophorone diisocyanate, polycaprolactone diol and polyvinyl alcohol to obtain a mixed solution, cooling, then dropwise adding dimethylolpropionic acid and N-methyl pyrrolidone, and fully stirring to obtain a prepolymer;
the specific parameter information is as follows:
the pressure of the decompression treatment in the step (2) is 300 bar;
the temperature of the decompression treatment in the step (2) is 60 ℃;
the time for the pressure reduction treatment in the step (2) is 2 hours.
In addition, regarding the dosage of each raw material, the mass ratio of the isophorone diisocyanate, the polycaprolactone diol and the polyvinyl alcohol in the step (2) is 5: 7: 0.2; in actual operation, the following proportional relationship can also be set, 5: 5: 0.2, 7: 5: 0.2, 5: 7: 0.5.
the dropping amount of the dimethylolpropionic acid in the step (2) is 2 percent of the mass of the isophorone diisocyanate; we also explored the addition of 1% and 3%, with a 2% content being more appropriate.
Dispersing by using a high-speed disperser while mixing in the step (2), wherein the rotating speed of the dispersing is 3000r/min, and the time of the dispersing is 20 min;
the mixing temperature in the step (2) is 90 ℃; in actual operation, 80 ℃ or 95 ℃ can be selected, but the temperature is not higher than 100 ℃;
the mixing pressure in the step (2) is 1.2MPa, and the range of 0.8MPa-1.6MPa can be selected during the specific operation.
In the modified polyurethane adhesive, the temperature after cooling in the step (2) is 70 ℃;
in the step (2), the mass ratio of the dimethylolpropionic acid to the N-methylpyrrolidone is 1: 5;
in the step (2), the mass ratio of the dimethylolpropionic acid to the isophorone diisocyanate is 1: 12.
the amounts of the above-mentioned substances have this critical influence on the preparation efficiency.
In the modified polyurethane adhesive, the stirring speed in the step (2) is 2000r/min, but not more than 3000r/min at most, and the reaction is not favorably carried out at an excessively high speed;
keeping the temperature of the prepolymer obtained in the step (2) at 65 ℃, keeping the prepolymer for no more than 24 hours, and selecting 18 hours for actual operation.
Again, care was taken to seal the prepolymer from light and to vent the reaction chamber.
(3) Second step reaction
And (3) adding the poly (propylene carbonate) polyol, 1, 4-butanediol, glycerol, methyl acrylate, dibutyltin dilaurate and ethyl orthosilicate into the prepolymer obtained in the step (2), adding deionized water, performing ultrasonic oscillation, finally gradually dripping sodium persulfate, and keeping the temperature. It is additionally suggested that the poly (propylene carbonate) polyol is purchased from Xingning chemical technology, Inc., Yixing City.
In the modified polyurethane adhesive, in the step (3), the mass ratio of the polypropylene carbonate polyol, the 1, 4-butanediol, the glycerol, the methyl acrylate, the dibutyltin dilaurate to the ethyl orthosilicate is 2: 1: 1: 5: 1: 20;
in the step (3), the mass ratio of the polypropylene carbonate polyol to the isophorone diisocyanate is 1: 2.
for the second reaction, the details of the reaction are as follows:
in the modified polyurethane adhesive, the addition amount of deionized water in the step (3) is 30% of the mass of the polypropylene carbonate polyol.
In the modified polyurethane adhesive, the power of ultrasonic oscillation in the step (3) is 300W;
the ultrasonic oscillation time in the step (3) is 30 min;
the temperature of ultrasonic oscillation in the step (3) is 90 ℃;
and (4) applying pressure while carrying out ultrasonic oscillation in the step (3), wherein the pressure is 5 MPa.
In the modified polyurethane adhesive, the addition amount of sodium persulfate in the step (3) is 2% of the mass of isophorone diisocyanate;
the dropping time of the sodium persulfate in the step (3) is 2 h;
the temperature of the heat preservation in the step (3) is 65 ℃,
the heat preservation time in the step (3) is 6 hours.
Comparative example 1
Basically, the same as example 1, except that:
and removing the polyvinyl alcohol.
Comparative example 2
Basically, the same as example 1, except that:
the dimethylolpropionic acid is removed.
Comparative example 3
Basically, the same as example 1, except that:
removing the N-methyl pyrrolidone.
Comparative example 4
Basically, the same as example 1, except that:
the methyl acrylate was removed.
Comparative example 5
Basically, the same as example 1, except that:
removing the ethyl orthosilicate.
Example 2
The samples prepared in example 1 were selected and tested for structural characterization and performance using laboratory instrumentation.
The infrared spectrum characteristic adopts the characteristic of a Fourier transform infrared spectrometer, and a sample to be tested is dried to be made into a film for testing, wherein the scanning wavelength range is 500 -1 -4000cm -1 。
As shown in FIG. 1, arrows indicate stretching vibration of-Si-O-bonds, indicating that tetraethoxysilane participates in the synthesis reaction process of the polyurethane material. Meanwhile, as shown in fig. 2, in combination with a scanning electron microscope test, it is found that N-methylpyrrolidone insoluble particles are dispersed in a sample solution, the N-methylpyrrolidone and the polyurethane material are physically blended to form an emulsion, and the N-methylpyrrolidone can effectively fill the void parts in the polyurethane material and may participate in the improvement of heat resistance.
Meanwhile, with reference to example 1 and comparative examples 1 to 5, preliminary tests were carried out in combination with the following tests:
5g of this was applied to a polytetrafluoroethylene plate and cured at 60 ℃ for 48h to give a coating film, after which the following results were obtained:
the tensile property is tested according to QB/T2415-1998, the sample after film forming is cut into a dumbbell shape, the temperature is 25 ℃, the relative humidity is 65% -85%, the tensile rate is 100mm/min, and the average value of 5 experiments is taken as the final result;
the cured polyurethane films were tested for T peel strength according to GB/T2791-1995, 5 samples per group and the average was calculated.
Example 1: peeling strength/6.7 N.mm -1 Tensile strength/32.9 MPa;
comparative example 1: peeling strength/5.8 N.mm -1 Tensile strength/30.4 MPa;
comparative example 2: peeling strength/5.1 N.mm -1 Tensile strength/27.6 MPa;
comparative example 3: peeling strength/5.6 N.mm -1 Tensile strength/29.2 MPa;
comparative example 4: peeling strength/6.2 N.mm -1 Tensile strength/32.0 MPa;
comparative example 5: peel strength/2.5 N.mm -1 Tensile strength/19.8 MPa.
While the invention has been described in further detail in connection with specific embodiments thereof, it will be understood that the invention is not limited thereto, and that various other modifications and substitutions may be made by those skilled in the art without departing from the spirit of the invention, which should be considered to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a modified polyurethane adhesive is characterized by comprising the following steps:
including, but not limited to, the following steps:
(1) preparation of reagents:
preparing polyvinyl alcohol, isophorone diisocyanate, polycaprolactone diol, dimethylolpropionic acid, N-methyl pyrrolidone, polypropylene carbonate polyol, 1, 4-butanediol, glycerol, methyl acrylate, dibutyltin dilaurate, ethyl orthosilicate and sodium persulfate;
(2) first step reaction
Before use, the polyvinyl alcohol is subjected to reduced pressure dehydration until the moisture is completely lost;
mixing isophorone diisocyanate, polycaprolactone diol and polyvinyl alcohol to obtain a mixed solution, cooling, then dropwise adding dimethylolpropionic acid and N-methyl pyrrolidone, and fully stirring to obtain a prepolymer;
(3) second step reaction
And (3) adding the poly (propylene carbonate) polyol, 1, 4-butanediol, glycerol, methyl acrylate, dibutyltin dilaurate and ethyl orthosilicate into the prepolymer in the step (2), adding deionized water, performing ultrasonic oscillation, finally gradually dripping sodium persulfate, and keeping the temperature.
2. The modified polyurethane adhesive of claim 1, wherein:
and (2) placing the reagent prepared in the step (1) in a fume hood in shade.
3. The modified polyurethane adhesive of claim 1, wherein:
the pressure of the decompression treatment in the step (2) is 300 bar;
the temperature of the decompression treatment in the step (2) is 60 ℃;
the time of the decompression treatment in the step (2) is 2 hours.
4. The modified polyurethane adhesive of claim 1, wherein:
in the step (2), the mass ratio of isophorone diisocyanate to polycaprolactone diol to polyvinyl alcohol is 5: 7: 0.2;
the dropping amount of the dimethylolpropionic acid in the step (2) is 2 percent of the mass of the isophorone diisocyanate;
dispersing by using a high-speed disperser while mixing in the step (2), wherein the rotating speed of the dispersing is 3000r/min, and the time of the dispersing is 20 min;
the mixing temperature in the step (2) is 90 ℃;
the mixing pressure in the step (2) is 1.2 MPa.
5. The modified polyurethane adhesive of claim 1, wherein:
the temperature after cooling in the step (2) is 70 ℃;
in the step (2), the mass ratio of the dimethylolpropionic acid to the N-methylpyrrolidone is 1: 5;
in the step (2), the mass ratio of the dimethylolpropionic acid to the isophorone diisocyanate is 1: 12.
6. the modified polyurethane adhesive of claim 1, wherein:
the stirring speed in the step (2) is 2000 r/min;
keeping the temperature of the prepolymer obtained in the step (2) at 65 ℃ and keeping the prepolymer for no more than 24 hours.
7. The modified polyurethane adhesive of claim 1, wherein:
in the step (3), the mass ratio of the polypropylene carbonate polyol to the 1, 4-butanediol to the glycerol to the methyl acrylate to the dibutyltin dilaurate to the ethyl orthosilicate is 2: 1: 1: 5: 1: 20;
in the step (3), the mass ratio of the polypropylene carbonate polyol to the isophorone diisocyanate is 1: 2.
8. the modified polyurethane adhesive of claim 1, wherein:
the adding amount of the deionized water in the step (3) is 30% of the mass of the polypropylene carbonate polyol.
9. The modified polyurethane adhesive of claim 1, wherein:
the power of ultrasonic oscillation in the step (3) is 300W;
the ultrasonic oscillation time in the step (3) is 30 min;
the temperature of ultrasonic oscillation in the step (3) is 90 ℃;
and (4) applying pressure while carrying out ultrasonic oscillation in the step (3), wherein the pressure is 5 MPa.
10. The modified polyurethane adhesive of claim 1, wherein:
in the step (3), the addition amount of the sodium persulfate is 2% of the mass of the isophorone diisocyanate;
the dropping time of the sodium persulfate in the step (3) is 2 h;
the temperature of the heat preservation in the step (3) is 65 ℃,
the heat preservation time in the step (3) is 6 hours.
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