CN114686153A - Sucrose-based non-isocyanate polyurethane adhesive and preparation method thereof - Google Patents
Sucrose-based non-isocyanate polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN114686153A CN114686153A CN202210435495.5A CN202210435495A CN114686153A CN 114686153 A CN114686153 A CN 114686153A CN 202210435495 A CN202210435495 A CN 202210435495A CN 114686153 A CN114686153 A CN 114686153A
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- 239000000853 adhesive Substances 0.000 title claims abstract description 64
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 64
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 title claims abstract description 57
- 229930006000 Sucrose Natural products 0.000 title claims abstract description 57
- 239000005720 sucrose Substances 0.000 title claims abstract description 51
- 239000012948 isocyanate Substances 0.000 title claims abstract description 42
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 41
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 40
- 239000004814 polyurethane Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 229960004793 sucrose Drugs 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims 2
- 230000035484 reaction time Effects 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- 150000004985 diamines Chemical class 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 21
- 239000002028 Biomass Substances 0.000 description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002023 wood Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 241000208140 Acer Species 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- 240000000111 Saccharum officinarum Species 0.000 description 3
- 235000007201 Saccharum officinarum Nutrition 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229960001124 trientine Drugs 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 235000016068 Berberis vulgaris Nutrition 0.000 description 2
- 241000335053 Beta vulgaris Species 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 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 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 235000010319 Acer grandidentatum Nutrition 0.000 description 1
- 235000010328 Acer nigrum Nutrition 0.000 description 1
- 235000002629 Acer saccharinum Nutrition 0.000 description 1
- 235000010157 Acer saccharum subsp saccharum Nutrition 0.000 description 1
- 241000219310 Beta vulgaris subsp. vulgaris Species 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 235000021536 Sugar beet Nutrition 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 238000007098 aminolysis reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 150000002016 disaccharides Chemical class 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- -1 formaldehyde, isocyanate Chemical class 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000012069 sugar maple Nutrition 0.000 description 1
- 235000019605 sweet taste sensations Nutrition 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance 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
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
- C08G71/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention belongs to the technical field of adhesive preparation, and particularly relates to a sucrose-based non-isocyanate polyurethane adhesive and a preparation method thereof; the sucrose-based non-isocyanate polyurethane adhesive is prepared by using sucrose as a raw material and reacting with dimethyl carbonate and diamine, and is used for producing shaving boards by mixing a crosslinking curing agent.
Description
Technical Field
The invention belongs to the technical field of adhesive preparation, and particularly relates to a sucrose-based non-isocyanate polyurethane adhesive and a preparation method thereof.
Background
Since the middle of the last century, the formaldehyde-free adhesives (i.e., urea-formaldehyde resin adhesives, melamine-formaldehyde resin adhesives, phenol-formaldehyde resin adhesives) using formaldehyde as a raw material have been the main types of adhesives used in the wood industry, especially in the artificial board industry, but they inevitably have a problem of formaldehyde release. In recent decades, with the improvement of the living standard of people and the awareness of environmental protection, the research of preparing artificial boards by non-formaldehyde adhesives or non-toxic adhesives has become a hotspot. Among them, biomass adhesives prepared from natural renewable raw materials have become an important research direction.
There are many biomass materials, one of which is sucrose. Sucrose is a disaccharide obtained by condensation dehydration of a hemiacetal hydroxyl group of a molecule of glucose and a hemiacetal hydroxyl group of a molecule of fructose, and is almost universally present in leaves, flowers, stems, seeds and fruits of the plant kingdom. The content of the sugar cane, the beet and the maple juice is particularly rich, and the sugar cane, the beet and the maple juice are simple and easily obtained biological resources. Because of its sweet taste, sugar is the main ingredient of sugar, and is used as an important food and sweet seasoning. Of course, sucrose, a readily available biomass material, has also been used to develop biomass-based adhesives. Researches report that sucrose is used for replacing part of formaldehyde to synthesize the sucrose resorcinol resin adhesive, but the bonding performance of the resin is not ideal. It has also been reported that sucrose and citric acid or phosphoric acid (salt) are used to prepare wood adhesive through esterification condensation reaction, but the adhesive needs high temperature curing, the production energy consumption is high, and high temperature can also damage the wood base material of the artificial board.
In recent years, the preparation of non-isocyanate polyurethane resin (NIPU) from biomass materials has become a new research favorite in the chemical industry, and has made certain progress in the application of products such as foam materials, coatings and the like. The non-isocyanate polyurethane is a compound with a carbamate structure, which is prepared by using no isocyanate as a raw material. Unlike conventional polyurethanes, which are polymerized from isocyanate monomers, such as diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI), and the like, and polyols, the most common synthetic process for NIPU is by reacting cyclic carbonates with polyamines. The harm to the environment and the human health caused by the use of the toxic substance isocyanate is effectively avoided. In addition, isocyanates are expensive, sensitive to moisture in the environment of use, and have high requirements for storage and transport equipment, whereas NIPU does not have this problem and can reduce storage and transport costs relatively.
Patent document CN201010617980.1 discloses a sucrose-melamine-formaldehyde copolycondensation resin wood adhesive and a preparation method thereof, wherein the adhesive is mainly prepared by copolycondensation of sucrose, melamine and formaldehyde and can be used for the production process of various artificial boards. The problem of formaldehyde release inevitably exists, and certain influence is exerted on human bodies and the environment.
Patent document CN201611068113.0 discloses a cationic waterborne polyurethane resin, a preparation method thereof and a waterborne polyurethane adhesive, which is obtained by reacting poly (carbonate-ether) diol with diisocyanate to obtain a first product, reacting the first product with a hydrophilic chain extender under the action of a catalyst to obtain a second product, reacting the second product, sucrose and butanediol, and adding acid to neutralize. The preparation method is complex in process and increases the production cost.
The document, "synthesis and modification of environment-friendly sucrose urea adhesive" (guixue, master paper, 2014.) studies the synthesis and modification of environment-friendly sucrose urea adhesive, wherein a technical scheme that sucrose and urea are subjected to polycondensation reaction under the catalysis of phosphoric acid and sodium hydroxide respectively to synthesize the adhesive is disclosed, and the performance of the adhesive is correspondingly tested. The adhesive synthesized by sucrose and urea has different performances from adhesives prepared by non-isocyanate polyurethane, the problem to be solved is to solve the problem of formaldehyde pollution, but the prepared adhesive has unsatisfactory strength and performance.
The document "a novel environment-friendly non-isocyanate polyurethane acrylate adhesive preparation process" (Dongyang, Qiao, Masheng, Sun Lin, modern chemical engineering, 2019.) discloses a novel environment-friendly non-isocyanate polyurethane acrylate adhesive preparation process, wherein a non-isocyanate polyurethane (NIPU) monomer is prepared by aminolysis ring-opening reaction of Ethylenediamine (EDA) on Propylene Carbonate (PC), and the synthesized NIPUA monomer, Butyl Acrylate (BA), Acrylic Acid (AA) and other acrylic compounds are subjected to polyaddition reaction under the action of Benzoyl Peroxide (BPO) and N, N-Dimethylaniline (DMP) to prepare the novel non-isocyanate polyurethane acrylate adhesive. The method does not meet the relevant requirements of the current green technology in terms of process and raw materials.
Disclosure of Invention
The invention provides a sucrose-based non-isocyanate polyurethane adhesive and a preparation method thereof to solve the problems.
The method is realized by the following technical scheme:
1. a sucrose-based non-isocyanate polyurethane adhesive is prepared from the following raw materials: 15-40g of distilled water, 20-40g of dimethyl carbonate, 35-50g of cane sugar, 20-50g of amine and a catalyst.
Further, the amine is any one of ethylenediamine, hexamethylenediamine, diethylenetriamine and triethylenetetramine.
Further, the catalyst is any one of sodium carbonate, potassium carbonate and ammonium bicarbonate.
2. The preparation method of the sucrose-based non-isocyanate polyurethane adhesive specifically comprises the following steps:
under the water bath environment of 70 ℃, adding dimethyl carbonate and distilled water into a three-neck round-bottom flask provided with a stirring rod, a thermometer and a condenser, starting a stirrer, adding sucrose and a catalyst, heating to 70-100 ℃, preserving heat, stirring for reaction for 2-2.5h, adding amine into the flask, continuing preserving heat for reaction for 2-2.5h, cooling and discharging to obtain the sucrose-based non-isocyanate polyurethane adhesive.
3. The sucrose-based non-isocyanate polyurethane adhesive is applied to the manufacture of shaving boards, and has the following performance indexes: the internal bonding strength is more than 0.8MPa, and the expansion rate of the water absorption thickness after 2 hours of cold water soaking is as follows: less than or equal to 12 percent.
In conclusion, the beneficial effects of the invention are as follows: the sucrose-based non-isocyanate polyurethane adhesive is prepared by taking sucrose as a raw material and successfully reacting with dimethyl carbonate and diamine, and is used for producing shaving boards by mixing a crosslinking curing agent.
Compared with the traditional polyurethane, the NIPU has different structures and performances, namely the beta-position carbon atom of the structural unit carbamate contains hydroxyl, and the hydroxyl and carbonyl in a carbamate bond can form an intramolecular hydrogen bond six-membered ring stable structure. The weak bond structure characteristic in the traditional polyurethane is compensated, so that the NIPU has excellent chemical resistance, hydrolysis resistance, permeability resistance and the like. This also allows the application range of NIPU in the adhesive field to be expanded. The adhesive prepared by the invention is suitable for production of shaving boards all the time, and has good adhesive joint strength and water resistance.
The invention has the following advantages:
1. the material source is wide. Sucrose is a biomass material that is almost ubiquitous in leaves, flowers, stems, seeds and fruits of the plant kingdom, and is particularly abundant in sugarcane, sugar beet and maple juice.
2. The preparation is simple. The reaction is only carried out under the conditions of normal pressure and water bath heating, and compared with the existing common preparation method of non-isocyanate polyurethane which needs high-temperature pressurization catalysis, the synthesis reaction condition of the invention is milder, the equipment requirement cost is lower, and the energy consumption is less.
3. Is green and environment-friendly. The main raw material of the adhesive is renewable biomass material, and the adhesive conforms to the large circle of sustainable development. Harmful substances such as formaldehyde, isocyanate and the like are not used in the synthesis, the product is green and environment-friendly, and the method conforms to the advocation and policy development of the concept of current green technology intellectual property protection.
4. As a biomass adhesive, the adhesive meets the requirements of green ecological civilized construction and the growing environmental awareness and consumption of people, is favorable for reducing the dependence degree of the wood industry on synthetic resin based on petrochemical resources, provides a green environment-friendly adhesive for the production of shaving boards, and has important significance for the development of the wood industry and the coping with the petrochemical crisis problem.
Detailed Description
The following is a detailed description of the embodiments of the present invention, but the present invention is not limited to these embodiments, and any modifications or substitutions in the basic spirit of the embodiments are included in the scope of the present invention as claimed in the claims.
Example 1
1. A sucrose-based non-isocyanate polyurethane adhesive is prepared from the following raw materials: 35g of distilled water, 30g of dimethyl carbonate, 45g of cane sugar, 35g of ethylenediamine and 0.4g of sodium carbonate.
2. The preparation method of the sucrose-based non-isocyanate polyurethane adhesive specifically comprises the following steps:
under the water bath environment of 70 ℃, adding dimethyl carbonate and distilled water into a three-neck round-bottom flask provided with a stirring rod, a thermometer and a condenser pipe, starting a stirrer, adding cane sugar and sodium carbonate, heating to 85 ℃, preserving heat, stirring for reaction for 2 hours, adding 35g of ethylenediamine into the flask, continuing preserving heat for reaction for 2 hours, cooling and discharging to obtain the sucrose-based non-isocyanate polyurethane adhesive.
Example 2
1. A sucrose-based non-isocyanate polyurethane adhesive is prepared from the following raw materials: 15g of distilled water, 20g of dimethyl carbonate, 35g of cane sugar, 20g of diethylenetriamine and 0.3g of potassium carbonate.
2. The preparation method of the sucrose-based non-isocyanate polyurethane adhesive specifically comprises the following steps:
under the water bath environment of 70 ℃, adding dimethyl carbonate and distilled water into a three-neck round-bottom flask provided with a stirring rod, a thermometer and a condenser, starting a stirrer, adding sucrose and potassium carbonate, heating to 70 ℃, preserving heat, stirring for reaction for 2 hours, adding diethylenetriamine into the flask, continuing preserving heat for reaction for 2 hours, cooling and discharging to obtain the sucrose-based non-isocyanate polyurethane adhesive.
Example 3
1. A sucrose-based non-isocyanate polyurethane adhesive is prepared from the following raw materials: 40g of distilled water, 40g of dimethyl carbonate, 50g of cane sugar, 50g of triethylene tetramine and 0.5g of ammonium bicarbonate.
2. The preparation method of the sucrose-based non-isocyanate polyurethane adhesive specifically comprises the following steps:
under the water bath environment of 70 ℃, adding dimethyl carbonate and distilled water into a three-neck round-bottom flask provided with a stirring rod, a thermometer and a condenser pipe, starting a stirrer, adding sucrose and ammonium bicarbonate, heating to 100 ℃, preserving heat, stirring for reaction for 2.5 hours, adding triethylenetetramine into the flask, continuing preserving heat for reaction for 2.5 hours, cooling and discharging to obtain the sucrose-based non-isocyanate polyurethane adhesive.
Examples of the experiments
In the experiment, sucrose, dimethyl carbonate and hexamethylene diamine are used as raw materials, three groups of sucrose-based non-isocyanate polyurethane adhesives are prepared under different material proportions to prepare a shaving board in a laboratory, the corresponding performances of the shaving board are measured, and the specific results are shown in table 1:
TABLE 1 sucrose-based NIPU resin preparation protocol and properties of particle boards made therefrom
Claims (7)
1. The sucrose-based non-isocyanate polyurethane adhesive is characterized by comprising the following raw materials: 15-40g of distilled water, 20-40g of dimethyl carbonate, 35-50g of cane sugar, 20-50g of amine and 0.3-1.0g of catalyst.
2. The sucrose-based, non-isocyanate polyurethane adhesive of claim 1, wherein the amine is any one of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine.
3. The sucrose-based, non-isocyanate polyurethane adhesive of claim 1, wherein the catalyst is any one of sodium carbonate, potassium carbonate, and ammonium bicarbonate.
4. The method of claim 1, wherein the method comprises the steps of:
under the water bath environment, adding dimethyl carbonate and distilled water into a flask, adding sucrose and a catalyst while stirring, heating for reaction, adding amine for continuous heat preservation reaction, and cooling to obtain the sucrose-based non-isocyanate polyurethane adhesive.
5. The method for preparing the sucrose-based non-isocyanate polyurethane adhesive according to claim 4, wherein the temperature-rising reaction is a constant temperature reaction after the temperature is raised to 70-100 ℃, and the reaction time is 2-2.5 h.
6. The method for preparing the sucrose-based non-isocyanate polyurethane adhesive according to claim 4, wherein the reaction is carried out under the condition of heat preservation, the temperature is 70-100 ℃, and the reaction time is 2-2.5 h.
7. The method of preparing the sucrose-based non-isocyanate polyurethane adhesive of claim 4, wherein the method of preparation is specifically:
under the environment of 70 ℃ water bath, adding dimethyl carbonate and distilled water into a three-neck round-bottom flask provided with a stirring rod, a thermometer and a condenser, starting a stirrer, adding sucrose and a catalyst, heating to 70-100 ℃, keeping the temperature, stirring for reaction for 2-2.5 hours, adding amine into the flask, continuing to keep the temperature for reaction for 2-2.5 hours, cooling and discharging to obtain the sucrose-based non-isocyanate polyurethane adhesive.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115093546A (en) * | 2022-08-03 | 2022-09-23 | 山西省建筑科学研究院有限公司 | Diamine epoxy curing agent and preparation method thereof, polyurethane anticorrosive paint containing diamine epoxy curing agent and preparation method thereof |
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| CN102558542A (en) * | 2011-12-09 | 2012-07-11 | 东南大学 | Method for preparing sucrose polyether carbonate polyol |
| CN104497953A (en) * | 2014-12-02 | 2015-04-08 | 佛山铭乾科技有限公司 | Process for producing waterborne polyurethane adhesive for shoes according to a prepolymer dispersion method |
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| CN102558542A (en) * | 2011-12-09 | 2012-07-11 | 东南大学 | Method for preparing sucrose polyether carbonate polyol |
| CN104497953A (en) * | 2014-12-02 | 2015-04-08 | 佛山铭乾科技有限公司 | Process for producing waterborne polyurethane adhesive for shoes according to a prepolymer dispersion method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115093546A (en) * | 2022-08-03 | 2022-09-23 | 山西省建筑科学研究院有限公司 | Diamine epoxy curing agent and preparation method thereof, polyurethane anticorrosive paint containing diamine epoxy curing agent and preparation method thereof |
| CN115093546B (en) * | 2022-08-03 | 2023-09-01 | 山西省建筑科学研究院集团有限公司 | Diamine epoxy curing agent and preparation method thereof, polyurethane anticorrosive paint containing diamine epoxy curing agent and preparation method thereof |
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