CN104628982A - Preparation method of alkali lignin-based waterborne polyurethane - Google Patents
Preparation method of alkali lignin-based waterborne polyurethane Download PDFInfo
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Abstract
The invention relates to a preparation method of alkali lignin-based waterborne polyurethane. The preparation method comprises the following step of adding alkali lignin in a process of synthesizing a waterborne polyurethane emulsion by adopting a prepolymer dispersion method by taking diisocyanate, polyether polyol, alkali lignin, a chain extender, a neutralizer and the like as raw materials so as to further prepare a series of alkali lignin-based waterborne polyurethane with different alkali lignin contents. According to the method provided by the invention, alkali lignin is introduced into a waterborne polyurethane system and is one of the ideal methods for reducing the use level of polyhydric alcohols, improving the performance of the waterborne polyurethane material and endowing the product with biodegradability.
Description
Technical field
The invention belongs to natural macromolecular material field, also belong to environmental friendliness ecomaterial field, relate to a kind of preparation method of alkali lignin base water polyurethane.
Technical background
Xylogen (lignin) is called for short lignin, is to be only second to the abundant natural aromatic polymer of Mierocrystalline cellulose second in vegitabilia, and industrial lignin derives from black liquid, thus has inexpensive, renewable, advantages of environment protection.The diversity of the complicacy of lignin structure, the diversity in source and leaching process causes the difficulty of exploitation and industrialized obstruction, thus researches and develops xylogen macromolecular material and is faced with huge opportunities and challenges.At present, along with the develop rapidly of society, petroleum resources are increasingly exhausted, and the various high polymer monomer from oil is restricted, and had a strong impact on the raw material sources of polyurethane industrial, and the moment affects the development of polyurethane industrial.Therefore huge, the reproducible environmentally friendly biological raw material of output more and more obtains attention and the favor of people.Alkali lignin is exactly a kind of abundance, cheap renewable plant resources, so the abundant reasonableness of alkali lignin utilizes, the energy face alleviation current mankind and ecocrisis are all of great practical significance and strategic importance.
And aqueous polyurethane makes formed film often have higher surface energy due to the introducing of main chain or pendant hydrophilic group, although make urethane can be dispersed in aqueous phase by the method for salify, just because the existence of these groups makes the poor-performings such as Water-resistance of Waterborne Polyurethane, solvent resistance, chemical-resistant and physical strength.For overcoming above-mentioned shortcoming, adopt different methods to carry out to aqueous polyurethane the focus that study on the modification has become aqueous polyurethane research in recent years, domestic and international many researchers have carried out a large amount of deeply comprehensively research.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide a kind of preparation method of alkali lignin base water polyurethane, the physical strength of products therefrom is higher, and preparation technology is simple and with low cost.
To achieve these goals, the technical solution used in the present invention is as follows:
A preparation method for alkali lignin base water polyurethane, comprises the following steps:
Step one: the refining alkali lignin of preparation;
Step 2: vulcabond, polyether glycol and refining alkali lignin are joined in there-necked flask, stirring reaction 1 ~ 5h at 60 ~ 90 DEG C, then 50 ~ 70 DEG C are cooled to, add DMPA hydrophilic chain extender and acetone again, reaction 1 ~ 4h, be cooled to 20 ~ 50 DEG C of dischargings, obtain Waterborne Polyurethane Prepolymer;
Step 3: by gained Waterborne Polyurethane Prepolymer neutralizing agent and after, add water and carry out emulsify at a high speed, namely underpressure distillation obtains aqueous polyurethane emulsion after sloughing solvent.
The preparation method of described refining alkali lignin is: the NaOH solution of the aqueous solution mass concentration 5% ~ 10% of raw alkaline lignin is regulated pH to 13 ~ 14, alkali lignin is fully dissolved, cross and filter insolubles, then at 60 DEG C, pH to 2 ~ 3 are regulated with the hydrochloric acid of mass concentration 12%, filter, repeatedly be precipitated to neutrality with distilled water wash, vacuum-drying and get final product.
In described step 2, the mol ratio of polyether glycol and vulcabond is 1:(2 ~ 4), the add-on of refining alkali lignin is 0.5% ~ 3.0% of refining alkali lignin and polyether glycol quality sum, the add-on of DMPA hydrophilic chain extender is 2.0% ~ 5.0% of vulcabond, polyether glycol and refining alkali lignin total mass, and the add-on of acetone is 10 ~ 80mL.
In described step 2, refining alkali lignin is to mix with vulcabond and polyether glycol after acetone solution again, and the amount of dissolving acetone used is 20mL.
In described step 2, add catalyzer before stirring reaction, the add-on of catalyzer is 0.05% ~ 0.2% of vulcabond, polyether glycol and refining alkali lignin total mass.
Described catalyzer is dibutyl tin laurate (being abbreviated as DBTDL).
Described vulcabond is isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI) or ditan-4,4 ‵-vulcabond (MDI).
Described polyether glycol is polypropylene glycol (PPG), PTMG (PTMG) or polyoxyethylene glycol (PEG), and number-average molecular weight is 2000.
Described neutralizing agent is triethylamine, sodium hydroxide or potassium hydroxide, and the mol ratio of add-on and DMPA is 1:1.
Compared with prior art, the present invention by adding alkali lignin in the building-up process of aqueous polyurethane emulsion, and the mechanical property of the mould material formed after the solidification of its emulsion significantly improves.Xylogen in the present invention is alkali lignin, is the byproduct of paper industry, with low cost, abundance.Aqueous polyurethane is a kind of ep-type material, industrial waste xylogen is combined the material both obtaining improved performance by the present invention with environment-friendly water-based polyurethane, and improve the using value of xylogen, simultaneously its low production cost and there is feature that is biodegradable, environmental protection, and present invention process is simple, has higher technology content.The physical strength of the alkali lignin modified aqueous polyurethane that this invention obtains is significantly improved, and can be used as the material such as film, coating.
Accompanying drawing explanation
Fig. 1 is for IPDI, the synthetic route chart of alkali lignin base water polyurethane.
Embodiment
Below in conjunction with embodiment, the present invention is described in further details.
Embodiment one
A preparation method for alkali lignin base water polyurethane, the synthetic route chart of product as shown in Figure 1, comprises the following steps:
Step one: the aqueous solution of the raw alkaline lignin NaOH solution of mass concentration 6% is regulated pH to 13 ~ 14, alkali lignin is fully dissolved.Cross and filter insolubles, then lower about pH to 2 with the hydrochloric acid of mass concentration 12% in 60 DEG C, filter, be repeatedly precipitated to neutrality with distilled water wash, namely vacuum-drying obtain refining alkali lignin.
Step 2: by 17.2g isophorone diisocyanate (IPDI), 50.0g polypropylene glycol (PPG2000), 0.26g refines alkali lignin (with acetone solution) and 0.05g dibutyl tin laurate joins in there-necked flask, stirring reaction 3h at 85 DEG C, then 65 DEG C are cooled to, add the acetone of 2.46g DMPA and 30mL again, reaction 3h, be cooled to 40 DEG C of dischargings, obtain Waterborne Polyurethane Prepolymer.
Step 3: performed polymer step 2 obtained is with after neutralizing with the DMPA mol ratio triethylamine (TEA) that is 1:1, and add water and carry out emulsify at a high speed, namely underpressure distillation obtains modified aqueous polyurethane emulsion after sloughing solvent.
Performance verification: emulsion be evenly poured on polyfluortetraethylene plate, at room temperature place for some time, then put into baking oven, at 60 DEG C after dry 48h, strikes out the test piece of standard dumbbell.Adopt XWW-20B electronic universal tester, measure tensile strength and the elongation at break of glued membrane by GB/T1040-92.Result shows: its tensile strength is increased to 36.3MPa by 27.6MPa, and elongation at break is increased to 457.2% by 456.4%, and physical strength significantly improves.
Embodiment two
A preparation method for alkali lignin base water polyurethane, comprises the following steps:
Step one: the aqueous solution of the raw alkaline lignin NaOH solution of mass concentration 6% is regulated pH to 13 ~ 14, alkali lignin is fully dissolved.Cross and filter insolubles, then lower about pH to 2 with the hydrochloric acid of mass concentration 12% in 60 DEG C, filter, be repeatedly precipitated to neutrality with distilled water wash, namely vacuum-drying obtain refining alkali lignin.
Step 2: by 12.5g tolylene diisocyanate (TDI), 45.0g PTMG (PTMG2000), 0.25g refines alkali lignin (with acetone solution) and 0.05g dibutyl tin laurate joins in there-necked flask, stirring reaction 4h at 85 DEG C, then 60 DEG C are cooled to, add the acetone of 1.74g DMPA and 40mL again, reaction 2h, be cooled to 35 DEG C of dischargings, obtain Waterborne Polyurethane Prepolymer.
Step 3: performed polymer step 2 obtained joins in the middle of the NaOH aqueous solution, high shear agitation, in carrying out and emulsification, namely underpressure distillation obtains modified aqueous polyurethane emulsion after sloughing solvent.Wherein NaOH and DMPA mol ratio is 1:1.
Performance verification: emulsion be evenly poured on polyfluortetraethylene plate, at room temperature place for some time, then put into baking oven, at 60 DEG C after dry 48h, strikes out the test piece of standard dumbbell.Adopt XWW-20B electronic universal tester, measure tensile strength and the elongation at break of glued membrane by GB/T1040-92.Result shows: its tensile strength is increased to 12.7MPa by 11.2MPa, and elongation at break change is little, and physical strength slightly improves.
Embodiment three
A preparation method for alkali lignin base water polyurethane, comprises the following steps:
Step one: the aqueous solution of the raw alkaline lignin NaOH solution of mass concentration 6% is regulated pH to 13 ~ 14, alkali lignin is fully dissolved.Cross and filter insolubles, then lower about pH to 2 with the hydrochloric acid of mass concentration 12% in 60 DEG C, filter, be repeatedly precipitated to neutrality with distilled water wash, namely vacuum-drying obtain refining alkali lignin.
Step 2: by 13.75g ditan-4,4 ‵-vulcabond (MDI), 47.6g polyoxyethylene glycol (PEG2000), 0.28g refine alkali lignin (with acetone solution) and 0.05g dibutyl tin laurate joins in there-necked flask, stirring reaction 5h at 85 DEG C, then be cooled to 65 DEG C, then add the acetone of 2.24g DMPA and 35mL, reaction 1.5h, be cooled to 30 DEG C of dischargings, obtain Waterborne Polyurethane Prepolymer.
Step 3: performed polymer step 2 obtained joins in the middle of the KOH aqueous solution, high shear agitation, in carrying out and emulsification, namely underpressure distillation obtains modified aqueous polyurethane emulsion after sloughing solvent.Wherein KOH and DMPA mol ratio is 1:1.
Performance verification: emulsion be evenly poured on polyfluortetraethylene plate, at room temperature place for some time, then put into baking oven, at 60 DEG C after dry 48h, strikes out the test piece of standard dumbbell.Adopt XWW-20B electronic universal tester, measure tensile strength and the elongation at break of glued membrane by GB/T1040-92.Result shows: its tensile strength is increased to 38.6MPa by 30.8MPa, and elongation at break is increased to 443.5% by 433.6%, and physical strength significantly improves.
Claims (9)
1. a preparation method for alkali lignin base water polyurethane, is characterized in that, comprises the following steps:
Step one: the refining alkali lignin of preparation;
Step 2: vulcabond, polyether glycol and refining alkali lignin are joined in there-necked flask, stirring reaction 1 ~ 5h at 60 ~ 90 DEG C, then 50 ~ 70 DEG C are cooled to, add DMPA hydrophilic chain extender and acetone again, reaction 1 ~ 4h, be cooled to 20 ~ 50 DEG C of dischargings, obtain Waterborne Polyurethane Prepolymer;
Step 3: by gained Waterborne Polyurethane Prepolymer neutralizing agent and after, add water and carry out emulsify at a high speed, namely underpressure distillation obtains aqueous polyurethane emulsion after sloughing solvent.
2. the preparation method of a kind of alkali lignin base water polyurethane according to claim 1, it is characterized in that: the preparation method of described refining alkali lignin is: the NaOH solution of the aqueous solution mass concentration 5% ~ 10% of raw alkaline lignin is regulated pH to 13 ~ 14, alkali lignin is fully dissolved, cross and filter insolubles, then at 60 DEG C, pH to 2 ~ 3 are regulated with the hydrochloric acid of mass concentration 12%, filter, be repeatedly precipitated to neutrality with distilled water wash, vacuum-drying and get final product.
3. the preparation method of a kind of alkali lignin base water polyurethane according to claim 1, it is characterized in that: in described step 2, the mol ratio of polyether glycol and vulcabond is 1:(2 ~ 4), the add-on of refining alkali lignin is 0.5% ~ 3.0% of refining alkali lignin and polyether glycol quality sum, the add-on of DMPA hydrophilic chain extender is 2.0% ~ 5.0% of vulcabond, polyether glycol and refining alkali lignin total mass, and the add-on of acetone is 10 ~ 80mL.
4. the preparation method of a kind of alkali lignin base water polyurethane according to claim 1, it is characterized in that: in described step 2, refining alkali lignin is to mix with vulcabond and polyether glycol after acetone solution again, and the amount of dissolving acetone used is 20mL.
5. the preparation method of a kind of alkali lignin base water polyurethane according to claim 1, it is characterized in that: in described step 2, add catalyzer before stirring reaction, the add-on of catalyzer is 0.05% ~ 0.2% of vulcabond, polyether glycol and refining alkali lignin total mass.
6. the preparation method of a kind of alkali lignin base water polyurethane according to claim 5, is characterized in that: described catalyzer is dibutyl tin laurate (being abbreviated as DBTDL).
7. the preparation method of a kind of alkali lignin base water polyurethane according to claim 1, it is characterized in that: described vulcabond is isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI) or ditan-4,4 ‵-vulcabond (MDI).
8. the preparation method of a kind of alkali lignin base water polyurethane according to claim 1, it is characterized in that: described polyether glycol is polypropylene glycol (PPG), PTMG (PTMG) or polyoxyethylene glycol (PEG), and number-average molecular weight is 2000.
9. the preparation method of a kind of alkali lignin base water polyurethane according to claim 1, is characterized in that: described neutralizing agent is triethylamine, sodium hydroxide or potassium hydroxide, the mol ratio of add-on and DMPA is 1:1.
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Cited By (16)
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| CN106590510A (en) * | 2016-12-23 | 2017-04-26 | 安庆市德诚化工有限公司 | Waterborne polyurethane adhesive used for preventing paper packaging box from degumming and preparation method for waterborne polyurethane adhesive |
| CN106634794A (en) * | 2016-12-23 | 2017-05-10 | 安庆市德诚化工有限公司 | Waterborne polyurethane adhesive for paper packing box and preparation method of waterborne polyurethane adhesive |
| CN106753176A (en) * | 2016-12-23 | 2017-05-31 | 安庆市德诚化工有限公司 | A kind of aqueous polyurethane cardboard adhesive of Antimicrobial preservative excellent performance and preparation method thereof |
| CN107384291A (en) * | 2016-12-23 | 2017-11-24 | 安庆市德诚化工有限公司 | One kind can quick-setting aqueous polyurethane cardboard adhesive and preparation method thereof |
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| CN112063154A (en) * | 2020-08-26 | 2020-12-11 | 东莞市雄林新材料科技股份有限公司 | Microporous repairable TPU (thermoplastic polyurethane) film material and preparation method thereof |
| CN112226159A (en) * | 2020-10-09 | 2021-01-15 | 东北林业大学 | Paint for preventing wood aging and preparation method and application thereof |
| CN112920365A (en) * | 2021-01-28 | 2021-06-08 | 合肥国轩高科动力能源有限公司 | Preparation method of novel anionic-nonionic aqueous polyurethane polymer electrolyte |
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| CN113201112B (en) * | 2021-04-06 | 2022-06-14 | 华南理工大学 | Waterborne polyurethane with lignin as chain extender and preparation method and application thereof |
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| CN116239752A (en) * | 2023-03-24 | 2023-06-09 | 浙江梅盛新材料有限公司 | Preparation method of bio-based aqueous polyurethane, textile and leather |
| CN116239752B (en) * | 2023-03-24 | 2024-04-30 | 浙江梅盛新材料有限公司 | Preparation method of bio-based aqueous polyurethane, textile and leather |
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