CN117903394A - Bio-based isocyanate crosslinking agent and preparation process thereof - Google Patents
Bio-based isocyanate crosslinking agent and preparation process thereof Download PDFInfo
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- CN117903394A CN117903394A CN202410316810.1A CN202410316810A CN117903394A CN 117903394 A CN117903394 A CN 117903394A CN 202410316810 A CN202410316810 A CN 202410316810A CN 117903394 A CN117903394 A CN 117903394A
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- 239000012948 isocyanate Substances 0.000 title claims abstract description 74
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 73
- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229920005862 polyol Polymers 0.000 claims abstract description 48
- 150000003077 polyols Chemical class 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- WQABCVAJNWAXTE-UHFFFAOYSA-N dimercaprol Chemical compound OCC(S)CS WQABCVAJNWAXTE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 15
- 239000008158 vegetable oil Substances 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 39
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 28
- -1 mercapto compound Chemical class 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000002981 blocking agent Substances 0.000 claims description 20
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 claims description 17
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 16
- 235000021388 linseed oil Nutrition 0.000 claims description 16
- 239000000944 linseed oil Substances 0.000 claims description 16
- 230000001804 emulsifying effect Effects 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 8
- 239000002383 tung oil Substances 0.000 claims description 8
- 239000004971 Cross linker Substances 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000009988 textile finishing Methods 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 239000013638 trimer Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- 239000004753 textile Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 3
- 239000003208 petroleum Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000012650 click reaction Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 14
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 10
- 238000002390 rotary evaporation Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 8
- 229960002887 deanol Drugs 0.000 description 8
- 239000012972 dimethylethanolamine Substances 0.000 description 8
- 239000004744 fabric Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 239000012267 brine Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 6
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229920000747 poly(lactic acid) Polymers 0.000 description 4
- 239000004626 polylactic acid Substances 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 3
- 229940035024 thioglycerol Drugs 0.000 description 3
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical compound CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 description 1
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of isocyanate, in particular to a bio-based isocyanate crosslinking agent and a preparation process thereof, comprising the following processes: the bio-based isocyanate and bio-based polyol are reacted, blocked and emulsified to obtain the bio-based isocyanate cross-linking agent, wherein the bio-based polyol is prepared from triallyl isocyanurate, 2, 3-dimercapto-1-propanol, vegetable oil and a photoinitiator. The bio-based isocyanate crosslinking agent takes renewable resources as main raw materials, so that the consumption of fossil resources and the influence on the environment in the process of petroleum material production and use can be reduced; the biological polyol is prepared by click reaction among triallyl isocyanurate, 2, 3-dimercapto-1-propanol and vegetable oil, so that the cross-linking agent with excellent mechanical property, water resistance and heat resistance is obtained, and when the cross-linking agent is used as a finishing agent, the wear resistance and the water resistance of textiles are improved, and the durability of the textiles is improved.
Description
Technical Field
The invention relates to the technical field of isocyanate, in particular to a bio-based isocyanate cross-linking agent and a preparation process thereof.
Background
It is known that a crosslinked polymer can be obtained by mixing a compound having an active hydrogen functional group with a polyisocyanate. Through this chemical mechanism, the isocyanate can be used as a crosslinker. The blocked isocyanate is a compound with one or more isocyanate (-NCO) end groups and the-NCO groups blocked by a blocking agent, has stable chemical property at normal temperature, can be deblocked at a certain temperature, regenerates the isocyanate groups, and has reactivity; can be widely used as a cross-linking agent in water-based paint. The common isocyanate crosslinking agent in the market is petroleum-based isocyanate, and is fossil material, which can bring about environmental change and pollution and enhance the greenhouse effect. Therefore, we propose a biobased isocyanate crosslinker and a process for its preparation.
Disclosure of Invention
The invention aims to provide a bio-based isocyanate cross-linking agent and a preparation process thereof, so as to solve the problems in the background art.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation process of a bio-based isocyanate crosslinking agent comprises the following steps:
Reacting biobased isocyanate with biobased polyol, sealing and emulsifying to obtain a biobased isocyanate crosslinking agent;
The bio-based polyol comprises the following components: triallyl isocyanurate, 2, 3-dimercapto-1-propanol, vegetable oil and photoinitiator.
Further, the bio-based polyol is prepared by the following process:
preparation of mercapto compound in step (1):
Dissolving triallyl isocyanurate in methylene dichloride, adding 2, 3-dimercapto-1-propanol and a photoinitiator under the condition of avoiding light, mixing, stirring at the temperature of 12-18 ℃, and irradiating for 20-25 min by an ultraviolet lamp; removing dichloromethane by rotary evaporation, and vacuum drying at 38-42 ℃ for 8h to obtain a sulfhydryl compound;
preparation of bio-based polyol in step (2):
Mixing vegetable oil, mercapto compound and photoinitiator in ethyl acetate in dark place, stirring at 22-27 deg.c and ultraviolet lamp to react for 24 hr; washing with deionized water and brine, drying with anhydrous magnesium sulfate, removing ethyl acetate by rotary evaporation, and drying in vacuum for 24 hours to obtain the bio-based polyol.
Further, the wavelength of the ultraviolet lamp is 365nm;
The photoinitiator is photoinitiator DMPA (2, 2-dimethoxy-2-phenylacetophenone);
the vegetable oil is one of linseed oil and tung oil.
Further, in the step (1), the mole ratio of triallyl isocyanurate to 2, 3-dimercapto-1-propanol is 1 (3.0-3.1);
The ratio of triallyl isocyanurate, photoinitiator and methylene chloride was 10g to 0.1g to 100mL.
In the step (2), the mass ratio of the vegetable oil to the sulfhydryl compound to the photoinitiator is 10 (28.2-67.1) to 0.4-0.8.
In the technical scheme, under the action of a photoinitiator, triallyl isocyanurate is used as a raw material, and carbon-carbon double bonds in the triallyl isocyanurate and mercapto groups in 2, 3-dimercapto-1-propanol are subjected to olefin-mercapto group clicking chemical reaction to prepare a compound containing triazine rings, mercapto groups and hydroxyl groups, and the compound is marked as a mercapto compound. Then, vegetable oil containing unsaturated bonds, such as linseed oil and tung oil, reacts with the sulfhydryl compound prepared in the previous step, and grafts the sulfhydryl compound on a vegetable oil molecular chain to obtain the bio-based polyol. The linseed oil and the tung oil are used as dry vegetable oil, are easy to dry and form a film, and can improve the mechanical property and the water resistance of the bio-based polyol; the sulfhydryl compound forms a branched chain on a vegetable oil molecular chain, and the introduction of a triazine ring increases the polarity, improves the interaction force of the molecular chain, increases the molecular winding, realizes the reinforcement and the toughening of the bio-based polyol, and effectively improves the mechanical property, the water resistance and the heat resistance of the prepared cross-linking agent.
Further, the biobased isocyanate is one of 1, 5-Pentanediisocyanate (PDI) or a trimer thereof.
Further, the bio-based isocyanate crosslinking agent is prepared by the following process:
mixing biobased isocyanate, biobased polyol and butanone, adding a catalyst, slowly heating to 80-90 ℃, and reacting for 120-150 min under heat preservation to obtain a prepolymer;
The temperature of the system is reduced to 60-70 ℃, a blocking agent is added, the reaction is continued for 180-200 min until the NCO content is less than 0.1%; adding organic base to regulate the pH value of the system to 7-8;
Adding deionized water accounting for 50-60% of the total mass of the system, emulsifying for 30-60 min at a rotating speed of 2000-3000 rpm, and carrying out suction filtration to obtain the bio-based isocyanate crosslinking agent.
Further, the catalyst is dibutyl tin dilaurate;
the end capping agent is one of 3, 5-dimethylpyrazole, methyl ethyl ketoxime, 2-methylimidazole, butanone oxime and epsilon-caprolactam;
the organic base is one of triethylamine, triethanolamine and dimethylethanolamine.
Further, the mass ratio of the bio-based isocyanate to the bio-based polyol to the blocking agent is 10 (19.6-33.0) to 6.2-7.5;
The ratio of the bio-based polyol to the butanone is 30g/100mL.
Furthermore, the bio-based isocyanate crosslinking agent is applied to the field of textile finishing.
Further, the process of the bio-based isocyanate crosslinking agent when applied to textile finishing is as follows:
Mixing a bio-based isocyanate crosslinking agent and water-based resin, adding deionized water, and adjusting the solid content to 50-75 g/L to obtain a finishing agent;
Soaking the fabric in finishing agent at 15-40 deg.c for 60-90 min in the bath ratio of 1 to 20; one-dip one-roll, the rolling residual rate is 60% -65%; drying at 110-130 deg.c and baking at 130-190 deg.c for 30-90 s.
In the technical scheme, the prepared bio-based polyol reacts with bio-based isocyanate 1, 5-pentanediisocyanate or a terpolymer thereof, and is blocked by a blocking agent, and after water is added for emulsification, a water-based bio-based isocyanate crosslinking agent is formed, so that the textile can be subjected to functional after-treatment, the finishing agent is prepared by mixing the water-based resin, the textile is immersed and rolled, and then the bio-based isocyanate crosslinking agent is deblocked by high-temperature treatment, so that the blocking agent in a molecular structure is removed, the crosslinking agent can react and crosslink with hydroxyl, carboxyl, amino and other active groups on the molecular chain of the water-based resin and on the surface of the textile, the adhesive force between the resin and the textile is improved, the wear resistance and the water resistance of the textile are improved, and the durability of the textile is improved.
Compared with the prior art, the invention has the following beneficial effects:
1. The preparation process of the bio-based isocyanate cross-linking agent, disclosed by the invention, prepares the bio-based isocyanate cross-linking agent by reacting, sealing and emulsifying the bio-based polyol and the bio-based isocyanate, takes renewable resources as main raw materials, and can reduce the consumption of fossil resources and the influence on the environment in the production and use processes of petroleum materials.
2. The preparation process of the bio-based isocyanate cross-linking agent is characterized in that the bio-based polyol containing triazine ring side chains and dry vegetable oil structures is prepared through the olefin-mercapto click chemical reaction among triallyl isocyanurate, 2, 3-dimercapto-1-propanol, linseed oil containing unsaturated bonds and tung oil, so that the bio-based polyol has good mechanical properties and waterproofness, the molecular chain interaction force is increased, the bio-based polyol is reinforced and toughened, and the cross-linking agent with more excellent mechanical properties, water resistance and heat resistance is obtained.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clearly and completely described, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following embodiments, the photoinitiator is the photoinitiator DMPA, derived from the merck group, germany;
1, 5-pentanediol diisocyanate, which is sourced from Sanjing Japan, has 99.8% of solid content, 0.004% of acid value and 54.5% of NCO content;
Flax oil: cas No. 463-40-1, 99% pure, from Hubei Jusheng technology Co., ltd;
Tung oil: cas number 8001-20-5, purity 99%, from Hubei Jusheng technology Co., ltd;
The polylactic acid dihydric alcohol is prepared by the following process: vacuum dehydrating L-lactide at 110deg.C for 30min, injecting 1, 4-butanediol and stannous octoate under nitrogen atmosphere, heating to 150deg.C, and reacting for 4 hr to obtain the final product; the mass ratio of the L-lactide to the 1, 4-butanediol to the stannous octoate is 10:1:0.03.
In the experimental project, the water-based resin is a fluorine-free waterproof agent NT-X028, and is derived from Nano-tex company in the United states;
The fabric is black polyester woven cloth, the texture is 80 multiplied by 80/inch, and the gram weight is 100g/m 2.
Example 1: a preparation process of a bio-based isocyanate crosslinking agent comprises the following steps:
preparation of mercapto compound in step (1):
10g of triallyl isocyanurate is dissolved in 100mL of dichloromethane, 2, 3-dimercapto-1-propanol and 0.1g of photoinitiator are added and mixed under the condition of avoiding light, and stirred at the temperature of 12 ℃ and irradiated by a 365nm ultraviolet lamp for 25min; removing dichloromethane by rotary evaporation, and vacuum drying at 38 ℃ for 8 hours to obtain a sulfhydryl compound; the mol ratio of triallyl isocyanurate to 2, 3-dimercapto-1-propanol is 1:3.0;
preparation of bio-based polyol in step (2):
Mixing linseed oil, a mercapto compound and a photoinitiator in ethyl acetate in a dark place, stirring at the temperature of 22 ℃, and carrying out ultraviolet lamp irradiation reaction for 24 hours; washing with deionized water and brine, drying with anhydrous magnesium sulfate, removing ethyl acetate by rotary evaporation, and vacuum drying for 24 hours to obtain bio-based polyol; the mass ratio of the linseed oil to the mercapto compound to the photoinitiator is 10:44.7:0.5;
preparing a bio-based isocyanate crosslinking agent in the step (3):
Mixing 30g of 1, 5-pentanediisocyanate, bio-based polyol and 100mL of butanone, adding a catalyst dibutyl tin dilaurate, slowly heating to 80 ℃, and carrying out heat preservation reaction for 150min to obtain a prepolymer;
the temperature of the system is reduced to 60 ℃,3, 5-dimethylpyrazole serving as a blocking agent is added, and the reaction is continued until the NCO content is less than 0.1%; adding dimethylethanolamine to regulate the pH value of the system to 7; the mass ratio of the 1, 5-pentanediisocyanate to the bio-based polyol to the blocking agent is 10:33.0:6.2;
Adding deionized water accounting for 60% of the total mass of the system, emulsifying for 60min at a rotating speed of 2000rpm, and carrying out suction filtration; adding deionized water, and mixing to obtain the bio-based isocyanate crosslinking agent with the solid content of 30%.
Example 2: a preparation process of a bio-based isocyanate crosslinking agent comprises the following steps:
preparation of mercapto compound in step (1):
10g of triallyl isocyanurate is dissolved in 100mL of dichloromethane, 2, 3-dimercapto-1-propanol and 0.1g of photoinitiator are added and mixed under the condition of avoiding light, and stirred at 15 ℃ and irradiated by a 365nm ultraviolet lamp for 22min; removing dichloromethane by rotary evaporation, and vacuum drying at 40 ℃ for 8 hours to obtain a sulfhydryl compound; the mol ratio of triallyl isocyanurate to 2, 3-dimercapto-1-propanol is 1:3.05;
preparation of bio-based polyol in step (2):
Mixing linseed oil, a mercapto compound and a photoinitiator in ethyl acetate in a dark place, stirring at the temperature of 24 ℃, and carrying out ultraviolet lamp irradiation reaction for 24 hours; washing with deionized water and brine, drying with anhydrous magnesium sulfate, removing ethyl acetate by rotary evaporation, and vacuum drying for 24 hours to obtain bio-based polyol; the mass ratio of the linseed oil to the mercapto compound to the photoinitiator is 10:67.1:0.8;
preparing a bio-based isocyanate crosslinking agent in the step (3):
Mixing 30g of 1, 5-pentanediisocyanate, bio-based polyol and 100mL of butanone, adding a catalyst dibutyl tin dilaurate, slowly heating to 85 ℃, and carrying out heat preservation reaction for 135min to obtain a prepolymer;
the temperature of the system is reduced to 65 ℃, 3, 5-dimethylpyrazole serving as a blocking agent is added, and the reaction is continued until the NCO content is less than 0.1%; adding dimethylethanolamine to regulate the pH value of the system to 7.5; the mass ratio of the 1, 5-pentanediisocyanate to the bio-based polyol to the blocking agent is 10:20.0:6.5;
Adding deionized water accounting for 55% of the total mass of the system, emulsifying for 45min at a rotating speed of 2500rpm, carrying out suction filtration, adding deionized water, and mixing to obtain the biobased isocyanate crosslinking agent with the solid content of 30%.
Example 3: a preparation process of a bio-based isocyanate crosslinking agent comprises the following steps:
preparation of mercapto compound in step (1):
10g of triallyl isocyanurate is dissolved in 100mL of dichloromethane, 2, 3-dimercapto-1-propanol and 0.1g of photoinitiator are added and mixed under the condition of avoiding light, and stirred at 18 ℃ and irradiated by a 365nm ultraviolet lamp for 20min; removing dichloromethane by rotary evaporation, and vacuum drying at 42 ℃ for 8 hours to obtain a sulfhydryl compound; the mol ratio of triallyl isocyanurate to 2, 3-dimercapto-1-propanol is 1:3.1;
preparation of bio-based polyol in step (2):
Mixing tung oil, a mercapto compound and a photoinitiator in ethyl acetate in a dark place, stirring at the temperature of 27 ℃, and carrying out ultraviolet lamp irradiation reaction for 24 hours; washing with deionized water and brine, drying with anhydrous magnesium sulfate, removing ethyl acetate by rotary evaporation, and vacuum drying for 24 hours to obtain bio-based polyol; the mass ratio of tung oil to mercapto compound to photoinitiator is 10:28.2:0.4;
preparing a bio-based isocyanate crosslinking agent in the step (3):
Mixing 30g of 1, 5-pentanediisocyanate, bio-based polyol and 100mL of butanone, adding a catalyst dibutyl tin dilaurate, slowly heating to 90 ℃, and carrying out heat preservation reaction for 120min to obtain a prepolymer;
the temperature of the system is reduced to 70 ℃,3, 5-dimethylpyrazole serving as a blocking agent is added, and the reaction is continued until the NCO content is less than 0.1%; adding dimethylethanolamine to regulate the pH value of the system to 8; the mass ratio of the 1, 5-pentanediisocyanate to the bio-based polyol to the blocking agent is 10:19.6:7.5;
Adding deionized water accounting for 50% of the total mass of the system, emulsifying for 30min at a rotating speed of 3000rpm, and carrying out suction filtration; adding deionized water, and mixing to obtain the bio-based isocyanate crosslinking agent with the solid content of 30%.
Comparative example 1: a preparation process of a bio-based isocyanate crosslinking agent comprises the following steps:
Preparation of bio-based polyol in step (1):
mixing linseed oil, thioglycerol and a photoinitiator in ethyl acetate in a dark place, stirring at the temperature of 22 ℃, and carrying out ultraviolet lamp irradiation reaction for 24 hours; washing with deionized water and brine, drying with anhydrous magnesium sulfate, removing ethyl acetate by rotary evaporation, and vacuum drying for 24 hours to obtain bio-based polyol; the mass ratio of the linseed oil to the thioglycerol to the photoinitiator is 10:11.7:0.3;
preparing a bio-based isocyanate crosslinking agent in the step (2):
Mixing 30g of 1, 5-pentanediisocyanate, bio-based polyol and 100mL of butanone, adding a catalyst dibutyl tin dilaurate, slowly heating to 80 ℃, and carrying out heat preservation reaction for 150min to obtain a prepolymer;
the temperature of the system is reduced to 60 ℃,3, 5-dimethylpyrazole serving as a blocking agent is added, and the reaction is continued until the NCO content is less than 0.1%; adding dimethylethanolamine to regulate the pH value of the system to 7; the mass ratio of the 1, 5-pentanediisocyanate to the bio-based polyol to the blocking agent is 10:5.6:6.5; adding deionized water accounting for 60% of the total mass of the system, emulsifying for 60min at a rotating speed of 2000rpm, and carrying out suction filtration; adding deionized water, and mixing to obtain the bio-based isocyanate crosslinking agent with the solid content of 30%.
Comparative example 2: a preparation process of a bio-based isocyanate crosslinking agent comprises the following steps:
Preparation of bio-based polyol in step (1):
Mixing linseed oil, 2-mercaptoethanol and a photoinitiator in ethyl acetate in a dark place, stirring at 22 ℃, and carrying out ultraviolet lamp irradiation reaction for 24 hours; washing with deionized water and brine, drying with anhydrous magnesium sulfate, removing ethyl acetate by rotary evaporation, and vacuum drying for 24 hours to obtain bio-based polyol; the mass ratio of the linseed oil to the 2-mercaptoethanol to the photoinitiator is 10:8.4:0.2;
preparing a bio-based isocyanate crosslinking agent in the step (2):
Mixing 30g of 1, 5-pentanediisocyanate, bio-based polyol and 100mL of butanone, adding a catalyst dibutyl tin dilaurate, slowly heating to 80 ℃, and carrying out heat preservation reaction for 150min to obtain a prepolymer;
The temperature of the system is reduced to 60 ℃,3, 5-dimethylpyrazole serving as a blocking agent is added, and the reaction is continued until the NCO content is less than 0.1%; adding dimethylethanolamine to regulate the pH value of the system to 7; the mass ratio of the 1, 5-pentanediisocyanate to the bio-based polyol to the blocking agent is 10:8.3:6.5; adding deionized water accounting for 60% of the total mass of the system, emulsifying for 60min at a rotating speed of 2000rpm, and carrying out suction filtration; adding deionized water, and mixing to obtain the bio-based isocyanate crosslinking agent with the solid content of 30%.
Comparative example 3: a preparation process of a bio-based isocyanate crosslinking agent comprises the following steps:
Mixing 30g of 1, 5-pentanediisocyanate, polylactic acid dihydric alcohol and 100mL of methylene dichloride, adding a catalyst dibutyl tin dilaurate, slowly heating to 80 ℃, and carrying out heat preservation reaction for 150min to obtain a prepolymer;
The temperature of the system is reduced to 60 ℃,3, 5-dimethylpyrazole serving as a blocking agent is added, and the reaction is continued until the NCO content is less than 0.1%; adding dimethylethanolamine to regulate the pH value of the system to 7; the mass ratio of the 1, 5-pentanediisocyanate to the polylactic acid dihydric alcohol to the blocking agent is 1.0:13.0:0.65; adding deionized water accounting for 60% of the total mass of the system, emulsifying for 60min at a rotating speed of 2000rpm, and carrying out suction filtration; adding deionized water, and mixing to obtain the bio-based isocyanate crosslinking agent with the solid content of 30%.
Comparative example 4: a preparation process of a bio-based isocyanate crosslinking agent comprises the following steps:
Mixing 30g of 1, 5-pentanediisocyanate, 3, 5-dimethylpyrazole and 100mL of dichloromethane, heating to 60 ℃ and reacting until the NCO content is less than 0.1%; adding dimethylethanolamine to regulate the pH value of the system to 7; the mass ratio of the 1, 5-pentanediol to the blocking agent is 10:11.8, deionized water accounting for 60 percent of the total mass of the system is added, emulsification is carried out for 60 minutes at the rotating speed of 2000rpm, suction filtration is carried out, deionized water is added, and the mixture is mixed, thus obtaining the isocyanate crosslinking agent with 30 percent of solid content.
Comparative example 5: NT-504F, which is derived from Nano-tex, USA, was taken as a crosslinking agent.
Experiment: mixing the cross-linking agents obtained in the examples 1-3 and the comparative examples 1-4 with water-based resin according to the mass ratio of 1:4, adding deionized water, adjusting the solid content to 50g/L, and adjusting the pH value to 4.5 to obtain a finishing agent; soaking the fabric in a finishing agent at 20 ℃ for 60min, wherein the bath ratio is 1:20; one-dip one-roll, the rolling surplus rate is 65%; drying at 130 ℃ and baking at 160 ℃ for 45s to prepare a sample, respectively detecting the performance of the sample and recording the detection result:
water repellency test: the test was performed on the water repellency properties of fabric samples using AATCC 22 as a reference standard;
washing fastness test: the wash fastness of the fabric samples was tested using AATCC 61 as a reference standard;
rubbing fastness test: taking AATCC 8 as a reference standard, carrying out an experiment on the rubbing fastness of a fabric sample;
Abrasion resistance experiment: the abrasion resistance of the fabric samples was tested using ASTM D4157 as a reference standard.
From the data in the above table, the following conclusions can be clearly drawn:
The crosslinking agents obtained in examples 1 to 3 were compared with the crosslinking agents obtained in comparative examples 1 to 4, and the results of the detection revealed,
The crosslinking agents obtained in examples 1-3 have more excellent water repellency, wash fastness, rubbing fastness and abrasion resistance experimental data than comparative examples, which fully demonstrates that the invention achieves improvements in abrasion resistance, water resistance and durability of textiles when the prepared biobased isocyanate crosslinking agents are used as finishing agents.
In comparison with example 1, the bio-based polyol of comparative example 1 was prepared from linseed oil, thioglycerol; the bio-based polyol in comparative example 2 was prepared from linseed oil, 2-mercaptoethanol; the bio-based isocyanate crosslinking agent in the comparative example 3 is prepared from 1, 5-pentanediisocyanate, polylactic acid dihydric alcohol and 3, 5-dimethylpyrazole; the isocyanate crosslinking agent in the comparative example 4 is prepared from 1, 5-pentanediisocyanate and 3, 5-dimethylpyrazole; the crosslinker in comparative example 5 was NT-504F. The experimental data of the water repellency, the washing fastness, the rubbing fastness and the wear resistance in the comparative experiment are reduced, and the process of the bio-based isocyanate crosslinking agent and the arrangement of the used components can promote the improvement of the wear resistance, the water resistance and the durability of the textile when the bio-based isocyanate crosslinking agent is used as a finishing agent.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1.A preparation process of a bio-based isocyanate crosslinking agent is characterized by comprising the following steps: the method comprises the following steps:
Reacting biobased isocyanate with biobased polyol, sealing and emulsifying to obtain a biobased isocyanate crosslinking agent;
the bio-based polyol comprises the following components: triallyl isocyanurate, 2, 3-dimercapto-1-propanol, vegetable oil and photoinitiator;
the bio-based polyol is prepared by the following process:
preparation of mercapto compound in step (1):
dissolving triallyl isocyanurate in dichloromethane, adding 2, 3-dimercapto-1-propanol under the condition of avoiding light, mixing with a photoinitiator, stirring at the temperature of 12-18 ℃, and irradiating for 20-25 min by an ultraviolet lamp to obtain a sulfhydryl compound;
preparation of bio-based polyol in step (2):
Mixing vegetable oil, mercapto compound and photoinitiator in ethyl acetate in dark place, stirring at 22-27 deg.c, and ultraviolet lamp irradiation to react for 24 hr to obtain the bio-based polyol.
2. The process for preparing a biobased isocyanate crosslinking agent according to claim 1, wherein: the vegetable oil is one of linseed oil and tung oil.
3. The process for preparing a biobased isocyanate crosslinking agent according to claim 1, wherein: in the step (1), the mole ratio of triallyl isocyanurate to 2, 3-dimercapto-1-propanol is 1 (3.0-3.1).
4. The process for preparing a biobased isocyanate crosslinking agent according to claim 1, wherein: in the step (2), the mass ratio of the vegetable oil to the sulfhydryl compound to the photoinitiator is 10 (28.2-67.1) to 0.4-0.8.
5. The process for preparing a biobased isocyanate crosslinking agent according to claim 1, wherein: the biobased isocyanate is one of 1, 5-pentanediisocyanate or trimer thereof.
6. The process for preparing a biobased isocyanate crosslinking agent according to claim 1, wherein: the bio-based isocyanate crosslinking agent is prepared by the following process:
mixing biobased isocyanate, biobased polyol and butanone, adding a catalyst, slowly heating to 80-90 ℃, and reacting for 120-150 min under heat preservation to obtain a prepolymer;
The temperature of the system is reduced to 60-70 ℃, a blocking agent is added, the reaction is continued for 180-200 min until the NCO content is less than 0.1%; adding organic base to regulate the pH value of the system to 7-8;
Adding deionized water accounting for 50-60% of the total mass of the system, emulsifying for 30-60 min at a rotating speed of 2000-3000 rpm, and carrying out suction filtration to obtain the bio-based isocyanate crosslinking agent.
7. The process for preparing a biobased isocyanate crosslinking agent according to claim 6, wherein: the mass ratio of the biobased isocyanate to the biobased polyol to the blocking agent is 10 (19.6-33.0) to 6.2-7.5.
8. A biobased isocyanate crosslinker prepared by a process according to any one of claims 1-7, characterized in that: the biobased isocyanate crosslinking agent is applied to the field of textile finishing.
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