CN103497300A - Preparation method for cellulose acetate modified lignin polyurethane film - Google Patents
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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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
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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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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- C08J2375/08—Polyurethanes from polyethers
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- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/08—Cellulose derivatives
- C08J2401/10—Esters of organic acids
- C08J2401/12—Cellulose acetate
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
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Abstract
A preparation method for a cellulose acetate modified lignin polyurethane film comprises the steps: mixing of cellulose acetate, lignin and a polyol; formation of the cellulose acetate modified lignin polyurethane film; removing of a solvent from the cellulose acetate modified lignin polyurethane film; and slaking of the cellulose acetate modified lignin polyurethane film. According to the preparation method, cellulose acetate fiber is taken as an auxiliary material for adding, and is fully uniformly mixed with lignin and the polyol in the solvent, so that through blending modification, the cellulose acetate modified lignin polyurethane film is enhanced in mechanical properties and improved in hydrophilic performance, and thus the lignin polyurethane film is substantially expanded in application scope, and the cellulose acetate modified lignin polyurethane film has certain meaning on practical application of lignin polyurethane films.
Description
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Technical field
The invention belongs to the xylogen Application Areas, be specifically related to the preparation method that a kind of cellulose acetate strengthens the lignin polyurethane film.
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Background technology
Along with scientific and technical development, the application of polymeric film in national economy is more and more extensive, also more and more higher to the requirement of thin-film material use properties.Polyurethane film has high tensile, high-tensile strength, water-proof breathable properties, obdurability and ageing-resistant performance, and there is excellent biology and blood compatibility and chemical proofing, simultaneously because its goods are easy to use, the reasons such as functional diversities, make polyurethane film obtain development rapidly, and be widely used in a plurality of fields such as health care, high-grade weaving face fabric, industry, deeply be subject to user's welcome and favor.
At present, the exhaustion day by day of fossil resource is one of difficult problem of generally facing of the whole world, and the renewable biomass resource has just caused and pays close attention to widely, and substituting fossil resource development chemical industry with biomass resource is the only way which must be passed of human kind sustainable development.Xylogen is that vegitabilia is only second to cellulosic the abundantest a kind of larger molecular organics matter, and it is the aromatic polymer of the complexity that is aggregating in a certain way by phenylpropyl alcohol alkyl structure unit.Prove after deliberation; xylogen with a large amount of alcoholic extract hydroxyl groups and phenolic hydroxyl group can replace polyvalent alcohol and isocyanic ester generation nucleophilic addition for the preparation of polyurethane material; so not only can reduce the dependency to petroleum products; improve the added value of xylogen; and for polyurethane industrial has reduced cost, to the development of polyurethane industrial and extenuate energy dilemma and all be of great practical significance and strategic importance.
But the partial properties of traditional lignin polyurethane film does not reach the performance of conventional polyurethanes film, limited the scope of its industrial applications, therefore improving its performance has important meaning for the range of application that enlarges the lignin polyurethane film.
In the present invention, prepare cellulose acetate modified lignin resin polyurethane film by the method for blend, its mechanical property improves, and also increased the wetting ability of lignin polyurethane film, thereby enlarge the range of application of lignin polyurethane film, for the practical application of lignin polyurethane, certain meaning is arranged.
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Summary of the invention
the technical problem solved:the object of the invention is to provide a kind of preparation method of cellulose acetate modified lignin resin polyurethane film.It is raw material that such polyurethane film be take cellulose acetate and xylogen, the proportioning of cellulose acetate and xylogen and polyvalent alcohol by the analysis to its mechanical property, thermal characteristics and hydrophilicity and then while finding the optimum performance of film.
technical scheme:the preparation method of cellulose acetate modified lignin resin polyurethane film, step is:
(1) mixing of cellulose acetate, xylogen and polyvalent alcohol: take the cellulose acetate of 5 ~ 40 mass parts, the xylogen of 5 ~ 40 mass parts is dissolved in organic solvent, and adds the polyvalent alcohol of 15 ~ 75 mass parts, at 50 ~ 60 ℃, stirs 0.5 ~ 2h, and it is fully mixed;
(2) formation of cellulose acetate modified lignin resin polyurethane film: the isocyanic ester of 40 ~ 70 mass parts is added in the liquid mixture of step (1) gained and stir, after 60 ~ 80 ℃ of lower confined reaction 1 ~ 1.5 h, pour in the tetrafluoroethylene mould, mould is inserted on a horizontal stand to standing 12 ~ 24 h;
(3) slaking of cellulose acetate modified lignin resin polyurethane film: the film of step (2) gained is put into to baking oven at 80 ~ 100 ℃ of lower slaking 1 ~ 3 h;
(4) the dispelling of solvent in cellulose acetate modified lignin resin polyurethane film: the film of step (3) gained is put under the water room temperature and soaked 24 ~ 36 h;
(5) the further slaking of cellulose acetate modified lignin resin polyurethane film: the film of step (4) gained is put into to baking oven obtain the finished product after 100 ~ 200 ℃ of lower slaking 1 ~ 3 h.
The ethanoyl quality percentage composition of described cellulose acetate is 30 ~ 40%, and corresponding hydroxyl quality percentage composition is 4.0 ~ 9.0%.
Described organic solvent is by acetone and the DMF organic solvent that 2:3 mixes by volume.
Described polyol component is one or more the mixture in the polyvalent alcohol that in molecule, hydroxy radical content is 2 ~ 3, relative molecular mass is 600 ~ 2000.
Described isocyanic ester is tolylene diisocyanate (TDI), diphenylmethanediisocyanate (comprising PAPI and MDI), hexamethylene diisocyanate (HDI) or isophorone diisocyanate (PPDI).
The molecular weight of described xylogen is 1000 ~ 20000; Described xylogen is vitriol xylogen, alkali lignin, sulfonated lignin, high-boiling alcohol lignin, enzymolysis xylogen, thermo-cracking xylogen, acetic acid lignin, Peracetic Acid xylogen or peroxy acid xylogen.
Principle of the present invention is: utilize cellulose acetate can well be dissolved in mixed solvent and fully mix with xylogen and isocyanic ester, and the acetoxy group on cellulose acetate and residual hydroxyl can with urethane on the isocyanic acid ester bond form hydrogen bond, thereby improve its mechanical property, and the introducing of acetoxy group, thereby the wetting ability that has increased again lignin polyurethane finally obtains the quality homogeneous, good mechanical property and there is the film of good hydrophilicity.
beneficial effect:
(1) the present invention improves mechanical property and the hydrophilicity of lignin polyurethane film by the method for direct interpolation cellulose acetate blend, with respect to by the wooden method of usually improving lignin polyurethane film mechanical property of chemical modification, having reduced the pollution to environment, and the extra consumption of having avoided modification to bring, conscientiously reduce raw materials cost, reduce the dependence to petroleum resources, saved the energy.
(2) the present invention utilizes the mixed solvent of acetone and DMF preparation, can well dissolved lignin, itself and other reaction raw materials is well mixed, make the film smooth texture homogeneous of preparing, and acetone can volatilize very soon after film forming, can greatly reduce static solidifying the time used, more efficient as solvent than simple use DMF or tetrahydrofuran (THF).
(4) the cellulose acetate modified lignin resin polyurethane film that prepared by the present invention is compared normal wood quality polyurethane film than the tensile strength of traditional lignin polyurethane film and has been promoted approximately 30% left and right, Young's modulus is brought up to 2 ~ 3 times, thereby has improved the mechanical property of lignin polyurethane film.
(5) the cellulose acetate modified lignin resin polyurethane film that prepared by the present invention is compared normal wood quality polyurethane film with the average contact angle of ultrapure water and has been reduced 23% left and right, comparing the conventional polyurethanes film has better wetting ability, has enlarged the range of application of lignin polyurethane film.
The accompanying drawing explanation
Fig. 1 is for without the lignin polyurethane film of cellulose acetate and be added with the surface of fracture that cellulose acetate content is respectively 20% and 40% cellulose acetate wood composite quality polyurethane film and amplify the scanning electron microscope (SEM) photograph of 200 times, as can be seen from Figure, increase along with cellulose acetate content, the distribution (circle spot) of cellulose acetate in film becomes large, is separated more and more obvious.
The DSC figure that Fig. 2 is cellulose acetate modified lignin resin polyurethane film.Known in figure, along with the increase of cellulose acetate content, the Tg of polyurethane film increases gradually, and when cellulose acetate content reaches 20%, it is maximum that Tg reaches.Major cause is that the increase of cellulose acetate content causes the increase of the hydrogen bond that forms between cellulose acetate and urethane and the increase of cellulose acetate particle, the mobility variation that causes the polyurethane flexible section, thereby cause the Tg of film to increase, but the increase of cellulose acetate particle can cause again the link between urethane soft or hard section to weaken, thereby, when cellulose acetate content surpasses 20%, Tg reduces gradually.
Fig. 3 is that cellulose acetate content is on the tensile stress-strain performance of polyurethane film and the impact of Young's modulus.As we can see from the figure, tensile strength and Young's modulus increase along with the increase of cellulose acetate content, when cellulose acetate content reaches 20%, it is maximum that tensile strength reaches, result conforms to the impact of cellulose acetate content on the Tg of film, and elongation rate of tensile failure is to reduce along with the increase of cellulose acetate content.
The impact that Fig. 4 is cellulose acetate content contact angle when polyurethane film is contacted to 3s with ultrapure water.Along with the increase of cellulose acetate content, the contact angle of lignin polyurethane film and ultrapure water contact angle reduces, and the hydrophilicity of polyurethane film increases.When cellulose acetate content is increased to 40%, polyurethane film has reduced by 23% with the contact angle of ultrapure water than the lignin polyurethane film that does not add cellulose acetate.
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Embodiment
Following examples further illustrate content of the present invention, but should not be construed as limitation of the present invention.Without departing from the spirit and substance of the case in the present invention, the modification that the inventive method, step or condition are done and replacement, all belong to scope of the present invention.
If do not specialize, the conventional means that in embodiment, technique means used is well known to those skilled in the art.
the starting material source:
Enzymolysis xylogen is provided by Shandong company of Long Li company, and its number-average molecular weight is 1200 ~ 2200 g/mol, the about 4.1mmol/g of total hydroxy radical content.
Cellulose acetate is bought from Aladdin reagent company limited.
Tolylene diisocyanate (TDI) is bought from West Asia reagent, is chemical pure;
Cetomacrogol 1000 (PEG1000) is bought from Chemical Reagent Co., Ltd., Sinopharm Group, is chemical pure;
Acetone is bought from Nanjing Chemistry Reagent Co., Ltd., is analytical pure;
Dimethyl formamide (DMF) is bought from sky, Tianjin next scientific and technological development company limited, is analytical pure.
detection method:
1, scanning electron microscope analysis adopts on the S3400N-1 of HIT type scanning electronic microscope and observes the sample breakage face, and electron accelerating voltage is 25 KV.
2, DSC measures the Diamond DSC type differential scanning calorimeter that adopts U.S. Perkin Elmer company.Amount of samples: 2～5 mg; Intensification scope :-60 ℃～150 ℃; Temperature rise rate: 20 ℃/min; Carrier gas kind: nitrogen; Carrier gas flux: 20 mL/min.For avoiding or reducing as far as possible the impact of sample thermal history on the DSC data, this experiment is when carrying out the analysis of DSC heat, and the data that obtain while with second, taking turns temperature programming are as the criterion.
3, the test of tensile property is used and is newly thought carefully CMT-4304 type electronic universal material testing machine, under room temperature (25 ℃) and normal atmosphere conditions, is tested.Tensile property is pressed the mensuration of GBT 528-2009 vulcanized rubber or thermoplastic elastomer tensile stress-strain performance, testing sample is the dumb-bell shape style, and total length is 100 mm, and crevice length is 25 mm, narrow parallel width is 5 mm, and trial speed is 200 mm/min.Tensile strength and elongation at break data are all the mean value at least three parallel sample.
4, the DSA100 type contact angle instrument of the German Kruss of contact angle test employing company is measured, the surfacing of film, and be fitted in the veneer surface.
embodiment 1
Take in the mixed solvent that 4 g enzymolysis xylogens are dissolved in 40 mL acetone and 60 mL DMF, and add 16 g PEG1000 to stir 0.5 h at 60 ℃, it is fully mixed.The TDI of 6.53 g is added, stir, pour the tetrafluoroethylene mould into after 75 ℃ of lower confined reaction 1 h in, mould is inserted on a horizontal stand to standing 24 h, after the film of gained is put into to baking oven dry 3 h under 80 ℃, soak 24 h under room temperature in water, finally put into 120 ℃ of further slakings of 3h of baking oven, take out diaphragm (LPU), put into vacuum drying oven, in order to its various performances are further tested.
embodiment 2
Take 4 g enzymolysis xylogens and 1 g cellulose acetate is dissolved in the mixed solvent of 40 mL acetone and 60 mL DMF, and add 15 g PEG1000 to stir 0.5 h at 60 ℃, it is fully mixed.The TDI of 6.59 g is added, stir, pour the tetrafluoroethylene mould into after 75 ℃ of lower confined reaction 1 h in, mould is inserted on a horizontal stand to standing 24 h, after the film of gained is put into to baking oven dry 3 h under 80 ℃, soak 24 h under room temperature in water, finally put into 120 ℃ of further slakings of 3h of baking oven, take out diaphragm (LPU-CA1), put into vacuum drying oven, in order to its various performances are further tested.
embodiment 3
Take 4 g enzymolysis xylogens and 2 g cellulose acetate are dissolved in the mixed solvent of 40 mL acetone and 60 mL DMF, and add 14 g PEG1000 to stir 0.5 h at 60 ℃, it is fully mixed.The TDI of 6.64 g is added, stir, pour the tetrafluoroethylene mould into after 75 ℃ of lower confined reaction 1 h in, mould is inserted on a horizontal stand to standing 24 h, after the film of gained is put into to baking oven dry 3 h under 80 ℃, soak 24 h under room temperature in water, finally put into 120 ℃ of further slakings of 3h of baking oven, take out diaphragm (LPU-CA2), put into vacuum drying oven, in order to its various performances are further tested.
embodiment 4
Take 4 g enzymolysis xylogens and 3 g cellulose acetate are dissolved in the mixed solvent of 40 mL acetone and 60 mL DMF, and add 13 g PEG1000 to stir 0.5 h at 60 ℃, it is fully mixed.The TDI of 6.69 g is added, stir, pour the tetrafluoroethylene mould into after 75 ℃ of lower confined reaction 1 h in, mould is inserted on a horizontal stand to standing 24 h, after the film of gained is put into to baking oven dry 3 h under 80 ℃, soak 24 h under room temperature in water, finally put into 120 ℃ of further slakings of 3h of baking oven, take out diaphragm (LPU-CA3), put into vacuum drying oven, in order to its various performances are further tested.
embodiment 5
Take 4 g enzymolysis xylogens and 4 g cellulose acetate are dissolved in the mixed solvent of 40 mL acetone and 60 mL DMF, and add 12 g PEG1000 to stir 0.5 h at 60 ℃, it is fully mixed.The TDI of 6.75 g is added, stir, pour the tetrafluoroethylene mould into after 75 ℃ of lower confined reaction 1 h in, mould is inserted on a horizontal stand to standing 24 h, after the film of gained is put into to baking oven dry 3 h under 80 ℃, soak 24 h under room temperature in water, finally put into 120 ℃ of further slakings of 3h of baking oven, take out diaphragm (LPU-CA4), put into vacuum drying oven, in order to its various performances are further tested.
The test data of embodiment 1-5 as table 1 successively as shown in:
Table 1
| Sample | Enzymolysis xylogen content/% a | Cellulose acetate content/% a | Isocyanate index | Elongation rate of tensile failure/% | Tensile strength/MPa | Glass transition temperature/℃ | Contact angle/° |
| |
30 | 0 | 1.55 | 252.98 | 5.88 | -24.66 | 89.86 |
| LPU-CA1 | 30 | 10 | 1.55 | 213.51 | 6.69 | -17.77 | 86.91 |
| LPU- |
30 | 20 | 1.55 | 158.38 | 7.61 | ?14.23 | 82.14 |
| LPU- |
30 | 30 | 1.55 | 139.92 | 7.47 | ?15.64 | 75.31 |
| LPU-CA4 | 30 | 40 | 1.55 | 109.71 | 6.93 | ?15.55 | 69.27 |
A: with respect to the quality percentage composition of PEG1000.
Claims (6)
1. the preparation method of cellulose acetate modified lignin resin polyurethane film is characterized in that step is:
(1) mixing of xylogen and polyvalent alcohol: the xylogen that takes 5 ~ 40 mass parts is dissolved in organic solvent, and adds the polyvalent alcohol of 15 ~ 75 mass parts, at 50 ~ 60 ℃, stirs 0.5 ~ 1h, and it is fully mixed;
(2) formation of cellulose acetate modified lignin resin polyurethane film: the isocyanic ester of 40 ~ 70 mass parts is added in the liquid mixture of step (1) gained and stir, after 50 ~ 75 ℃ of lower confined reaction 1 ~ 1.5 h, pour in the tetrafluoroethylene mould, mould is placed on a horizontal stand to standing 12 ~ 24 h;
(3) slaking of cellulose acetate modified lignin resin polyurethane film: the film of step (2) gained is put into to baking oven at 80 ~ 100 ℃ of lower slaking 1 ~ 3 h;
(4) the dispelling of solvent in cellulose acetate modified lignin resin polyurethane film: the film of step (3) gained is put under the water room temperature and soaked 24 ~ 36 h;
(5) the further slaking of cellulose acetate modified lignin resin polyurethane film: the film of step (4) gained is put into to baking oven obtain the finished product after 100 ~ 200 ℃ of lower slaking 1 ~ 3 h.
2. the preparation method of cellulose acetate modified lignin resin polyurethane film according to claim 1, is characterized in that described organic solvent is by acetone and the DMF organic solvent that 2:3 mixes by volume.
3. the preparation method of cellulose acetate modified lignin resin polyurethane film according to claim 1, is characterized in that described polyol component is one or more the mixture in the polyvalent alcohol that in molecule, hydroxy radical content is 2 ~ 3, relative molecular mass is 600 ~ 2000.
4. the preparation method of cellulose acetate modified lignin resin polyurethane film according to claim 1, is characterized in that described isocyanic ester is tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate or isophorone diisocyanate.
5. the preparation method of cellulose acetate modified lignin resin polyurethane film according to claim 1, the molecular weight that it is characterized in that described xylogen is 1000 ~ 20000; Described xylogen is vitriol xylogen, alkali lignin, sulfonated lignin, high-boiling alcohol lignin, enzymolysis xylogen, thermo-cracking xylogen, acetic acid lignin, Peracetic Acid xylogen or peroxy acid xylogen.
6. the preparation method of cellulose acetate modified lignin resin polyurethane film according to claim 1, is characterized in that the ethanoyl quality percentage composition of described cellulose acetate is 30% ~ 40%, and corresponding hydroxyl quality percentage composition is 4.0% ~ 9.0%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105330810A (en) * | 2015-11-27 | 2016-02-17 | 南京林业大学 | Preparation method of attapulgite modified lignin type polyurethane material |
| CN105601985A (en) * | 2016-03-27 | 2016-05-25 | 华南理工大学 | Lignin melamine-based surface hydrophobic foam and preparation method thereof |
| CN114409921A (en) * | 2022-02-22 | 2022-04-29 | 华南农业大学 | Modified lignin polyol and preparation method of polyurethane hot melt adhesive thereof |
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| CN101928373A (en) * | 2010-08-27 | 2010-12-29 | 华南理工大学 | Plant fiber component-based polyalcohol and preparation method thereof |
| CN103183801A (en) * | 2013-03-20 | 2013-07-03 | 中国林业科学研究院林产化学工业研究所 | Method for preparing polyurethane film by CIMV wheat straw lignin |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928373A (en) * | 2010-08-27 | 2010-12-29 | 华南理工大学 | Plant fiber component-based polyalcohol and preparation method thereof |
| CN103183801A (en) * | 2013-03-20 | 2013-07-03 | 中国林业科学研究院林产化学工业研究所 | Method for preparing polyurethane film by CIMV wheat straw lignin |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105330810A (en) * | 2015-11-27 | 2016-02-17 | 南京林业大学 | Preparation method of attapulgite modified lignin type polyurethane material |
| CN105330810B (en) * | 2015-11-27 | 2018-10-26 | 南京林业大学 | A kind of preparation method of attapulgite modified lignin type polyurethane material |
| CN105601985A (en) * | 2016-03-27 | 2016-05-25 | 华南理工大学 | Lignin melamine-based surface hydrophobic foam and preparation method thereof |
| CN105601985B (en) * | 2016-03-27 | 2019-06-18 | 华南理工大学 | A kind of lignin melamine primary surface hydrophobic foam and preparation method thereof |
| CN114409921A (en) * | 2022-02-22 | 2022-04-29 | 华南农业大学 | Modified lignin polyol and preparation method of polyurethane hot melt adhesive thereof |
| CN114409921B (en) * | 2022-02-22 | 2022-11-18 | 华南农业大学 | Modified lignin polyol and preparation method of polyurethane hot melt adhesive thereof |
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