CN103232579B - Method of preparing transparent ultraviolet absorption membrane material from enzymatic hydrolysis lignin - Google Patents
Method of preparing transparent ultraviolet absorption membrane material from enzymatic hydrolysis lignin Download PDFInfo
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Abstract
The invention relates to a method of preparing a transparent ultraviolet absorption membrane material from enzymatic hydrolysis lignin. The method comprises the following steps: subjecting lignin to graft modification so as to obtain a lignin-based macro-monomer; dissolving the lignin-based macro-monomer, an acrylic acid monomer and an initiator for free radical polymerization in an organic solvent, introducing nitrogen to remove oxygen and carrying out a reaction at a temperature of 50 to 100 DEG C for 6 to 24 h; and subjecting a polymer to precipitation in n-hexane with a temperature of 30 to 60 DEG C and carrying out filtering and drying so as to obtain the ultraviolet absorption membrane material. According to the invention, a lignin aromatic ring structure is genuinely introduced into a polymer structure, and the synthesized polymer lignin-based membrane material has the advantages of high transparency, excellent hardness, thermal stability and ultraviolet light absorption performance and can be widely applied in fields like functional uvioresistant paints.
Description
Technical field
The invention belongs to technology field of membrane materials, be specifically related to a kind of method that enzymolysis xylogen prepares transparent uv-absorbing mould material.
Background technology
Along with the continuous digestion of oil, coal resources and environmental problem outstanding day by day, whole world scientists all substitutes as petrochemical complex monomers such as ethene, vinylbenzene, vinyl acetate, acrylate and divinyl at the cheap biomass-based polymerisable monomer of research and development, thus preparation bio-based macromolecular material.Xylogen the earth is only second to cellulosic natural polymer, and have inexpensive, degradable, the feature such as pollution-free, and therefore the research and development to lignin-base material are all attached great importance in countries in the world.
Xylogen obtain Main Means be by various method chemically slurrying be separated with the by product of biorefinery.In order to alleviate petroleum-based energy crisis, utilizing biomass Scouring Technology to prepare ethanol energy product demand and increasing severely, a large amount of by products can be produced, its composition mainly xylogen simultaneously.It a kind ofly has higher reactive behavior and the enzymolysis xylogen of low molecular weights characteristics.At present, xylogen is less as the application of comonomer in macromolecular material, and the main existence because of phenolic hydroxyl group in lignin structure, has inhibition to free radical reaction.CN1693342A proposes one acyl chlorides p-sulfonic acid salt xylogen and carries out esterification, and phenolic hydroxyl group can be converted into vinyl, and then can carry out letex polymerization with other Acrylic Acid Monomer, product application is in based Wood Adhesives.Can obtain uv-absorbing mould material by xylogen and the blended method of matrix resin, but this method can make film devitrification, greatly limit its scope of application.The present invention utilizes acyl chlorides to carry out selective esterification to the phenolic hydroxyl group of enzymolysis xylogen, and then does radical polymerization with Acrylic Acid Monomer, prepares lignin-base mould material.This mould material has the good transparency, and thermostability, absorption UV-light performance, can be widely used in uvioresistant paint field.
Ultraviolet not only has injury to human body and biology, macromolecular material is also had there is larger harm, if rubber, coating, synthon etc. are under ultraviolet long-term irradiation, absorb the energy of UV-light, cause Auto-oxidation reaction and cause degraded, accelerated deterioration, fade.In recent years, along with people are more deep to ultraviolet harm understanding, world many countries all actively carried out the R and D of ultraviolet ray-resistant material.
Summary of the invention
the technical problem solved:the invention discloses a kind of method that enzymolysis xylogen prepares transparent uv-absorbing mould material, adopt general radical polymerization methods to prepare the uv-absorbing mould material of high transparent, the deep processing and utilization for biomass by-products xylogen develops new direction.
technical scheme:a kind of enzymolysis xylogen prepares the method for ultraviolet absorption mould material, first xylogen is carried out graft modification and obtain lignin-base macromonomer, again lignin-base macromonomer, Acrylic Acid Monomer and radical polymerization are share initiator in mass ratio for 100:300 ~ 1000:2 dissolves in organic solvent, and logical nitrogen removes oxygen, after 50 ~ 100 DEG C of reaction 6 ~ 24h, polymkeric substance is precipitated in 30 ~ 60 DEG C of normal hexanes, then filters, after drying, obtain ultraviolet absorption mould material.
The preparation method of described lignin-base macromonomer is: in the container of drying, adds 2.0 ~ 8.0g LiCl and 98.0g N,N-DIMETHYLACETAMIDE, then adds dry enzymolysis xylogen 3.0g, stirs 1 ~ 3h be dissolved to homogeneous phase solution at 20 ~ 70 DEG C; In above-mentioned homogeneous system, add catalyst of triethylamine 1.2g and hydroquinone of polymerization retarder 0.0450g, pass into nitrogen protection simultaneously; Acrylate chloride or methacrylic chloride 2.4g are added above-mentioned solution, at 20 ~ 50 DEG C of reaction 3 ~ 12h; Reaction terminates, and is poured into by reaction solution in 1000mL distilled water, and stir centrifugal collecting precipitation, be repeatedly washed to neutrality, 50 DEG C are dried to constant weight, obtain lignin-base macromonomer.
Described Acrylic Acid Monomer is butyl acrylate, butyl methacrylate or methyl methacrylate.
It is one in azo-bis-isobutyl cyanide, benzoyl peroxide that described radical polymerization share initiator.
Described organic solvent is tetrahydrofuran (THF), dioxane or toluene.
beneficial effect:
1. the present invention selects wide material sources, cheap biorefinery xylogen and enzymolysis xylogen are raw material, prepare multi-purpose polymerisable lignin-base macromonomer, significant to the exploitation realizing this huge renewable resources of xylogen.
2. in the present invention, really introduced in polymer architecture by xylogen aromatic ring structure, the lignin-base mould material of synthesis has high transparent, excellent hardness, thermostability, absorption UV-light performance, can be widely used in the fields such as functional anti-ultraviolet paint.
Accompanying drawing explanation
Fig. 1 is lignin-base macromonomer infrared spectrogram in embodiment 2;
Fig. 2 is multipolymer in embodiment 2
13c-NMR;
Fig. 3 is the ultraviolet-visible spectrogram of multipolymer and poly-n-butyl methacrylate in embodiment 2;
Fig. 4 is the thermal multigraph of multipolymer and poly-n-butyl methacrylate in embodiment 2.
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 amendment do the inventive method, step or condition and replacement, all belong to scope of the present invention.
If do not specialize, the conventional means that technique means used in embodiment is well known to those skilled in the art.
The enzymolysis xylogen that this method adopts is obtained by common process, be a kind of from wheat, maize straw through alkaline boiling, the natural macromolecular material that enzymic hydrolysis procedure extraction obtains, not only effectively can utilize biomass resource but also alternative petrochemical materials, had important practical and was worth.
embodiment 1
(1) in the 250mL four-hole boiling flask of drying, 6.0g LiCl and 98.0g DMAc(N,N-DIMETHYLACETAMIDE is added), then add dry enzymolysis xylogen (Songyuan Bairui Biological Polyalcohol Co., Ltd.) 3.0g, 70 DEG C of stirring and dissolving are to homogeneous phase solution; In above-mentioned homogeneous system, add catalyst of triethylamine 1.2g and hydroquinone of polymerization retarder 0.0450g, pass into nitrogen protection simultaneously; Acrylate chloride 2.4g is added above-mentioned solution, 50 DEG C of reaction 3h; Reaction terminates, and is poured into by reaction solution in 1000mL distilled water, and stir centrifugal collecting precipitation, be repeatedly washed to neutrality, 50 DEG C are dried to constant weight, obtain lignin-base macromonomer.
(2) by lignin-base macromonomer 0.6g, butyl methacrylate 4g and AIBN(azo-bis-isobutyl cyanide) 92mg joins in 30 mL dioxane, transferred to by solvent in 100mL eggplant type reaction flask, nitrogen bubble deoxygenation 10min.Then obtain polymkeric substance after being warming up to 70 DEG C of reaction 10h, the transformation efficiency of monomer is 90%, is precipitated by polymkeric substance in the normal hexane of 30 DEG C, and then filtration, drying obtain multipolymer, and this multipolymer is ultraviolet absorption mould material.Molecular weight of copolymer Mw=267287, M
n(GPC)=47631 g/mol, PDI=5.62.Be dissolved in by multipolymer in tetrahydrofuran (THF), pour in the mould of tetrafluoroethylene, 50 DEG C are dried into transparent film, and hardness is the UV-light of B, Absorbable rod 85%, can pass through the visible ray of 80%.
embodiment 2
(1) in the 250mL four-hole boiling flask of drying, add 8.0g LiCl and 98.0g DMAc, then add dry enzymolysis xylogen 3.0g(Songyuan Bairui Biological Polyalcohol Co., Ltd.), 70 DEG C of stirring and dissolving are to homogeneous phase solution; In above-mentioned homogeneous system, add catalyst of triethylamine 1.2g and hydroquinone of polymerization retarder 0.0450g, pass into nitrogen protection simultaneously; Acrylate chloride 2.4g is added above-mentioned solution, 50 DEG C of reaction 3h; Reaction terminates, and is poured into by reaction solution in 1000mL distilled water, and stir centrifugal collecting precipitation, be repeatedly washed to neutrality, 50 DEG C are dried to constant weight, obtain lignin-base macromonomer.
(2) by lignin-base macromonomer 0.6g, butyl methacrylate 3g and AIBN(azo-bis-isobutyl cyanide) 72mg joins in 30mL tetrahydrofuran (THF), transferred to by solvent in 100mL eggplant type reaction flask, nitrogen bubble deoxygenation 10 minutes.Then obtain polymkeric substance after being warming up to 70 DEG C of reaction 10h, the transformation efficiency of monomer is 92%, is precipitated by polymkeric substance in the normal hexane of 50 DEG C, and then filtration, drying obtain multipolymer, and this multipolymer is ultraviolet absorption mould material.Molecular weight of copolymer Mw=85417, Mn (GPC)=34017 g/mol, PDI=2.51.Be dissolved in by multipolymer in tetrahydrofuran (THF), pour in the mould of tetrafluoroethylene, 50 DEG C are dried into transparent film, and hardness is the UV-light of H, Absorbable rod 80%, can pass through the visible ray of 82%.
embodiment 3
(1) in the 250mL four-hole boiling flask of drying, add 2.0g LiCl and 98.0g DMAc, then add dry enzymolysis xylogen 3.0g, 20 DEG C are stirred 5h and are dissolved to homogeneous phase solution; In above-mentioned homogeneous system, add catalyst of triethylamine 1.2g and hydroquinone of polymerization retarder 0.0450g, pass into nitrogen protection simultaneously; Acrylate chloride 2.4g is added above-mentioned solution, 40 DEG C of reaction 5h; Reaction terminates, and is poured into by reaction solution in 1000mL distilled water, and stir centrifugal collecting precipitation, be repeatedly washed to neutrality, 50 DEG C are dried to constant weight, obtain lignin-base macromonomer.
(2) by lignin-base macromonomer 0.6g, butyl methacrylate 2.4g and AIBN(azo-bis-isobutyl cyanide) 60mg joins in 30mL tetrahydrofuran (THF), transferred to by solvent in 100mL eggplant type reaction flask, nitrogen bubble deoxygenation 10 minutes.Then obtain polymkeric substance after being warming up to 70 DEG C of reaction 10h, the transformation efficiency of monomer is 88%, is precipitated by polymkeric substance in the normal hexane of 40 DEG C, and then filtration, drying obtain multipolymer, and this multipolymer is ultraviolet absorption mould material.Molecular weight of copolymer Mw=77101, Mn (GPC)=32204 g/mol, PDI=2.39.Be dissolved in by multipolymer in tetrahydrofuran (THF), pour in the mould of tetrafluoroethylene, 50 DEG C are dried into transparent film, and hardness is the UV-light of 2H, Absorbable rod 75%, can pass through the visible ray of 70%.
embodiment 4
(1) in the 250mL four-hole boiling flask of drying, add 6.0g LiCl and 98.0g DMAc, then add dry enzymolysis xylogen 3.0g, 70 DEG C are stirred 2h and are dissolved to homogeneous phase solution; In above-mentioned homogeneous system, add catalyst of triethylamine 1.2g and hydroquinone of polymerization retarder 0.0450g, pass into nitrogen protection simultaneously; Acrylate chloride 2.4g is added above-mentioned solution, 20 DEG C of reaction 3h; Reaction terminates, and is poured into by reaction solution in 1000mL distilled water, and stir centrifugal collecting precipitation, be repeatedly washed to neutrality, 50 DEG C are dried to constant weight, obtain lignin-base macromonomer.
(2) by lignin-base macromonomer 0.6g, butyl methacrylate 2.0g and AIBN(azo-bis-isobutyl cyanide) 52mg joins in 30mL dioxane, transferred to by solvent in 100mL eggplant type reaction flask, nitrogen bubble deoxygenation 10 minutes.Then obtain polymkeric substance after being warming up to 70 DEG C of reaction 10h, the transformation efficiency of monomer is 92%, is precipitated by polymkeric substance in the normal hexane of 30 DEG C, and then filtration, drying obtain multipolymer, and this multipolymer is ultraviolet absorption mould material.Molecular weight of copolymer Mw=46789, Mn (GPC)=29593 g/mol, PDI=1.58.Be dissolved in by multipolymer in tetrahydrofuran (THF), pour in the mould of tetrafluoroethylene, 50 DEG C are dried into transparent film, and hardness is the UV-light of H, Absorbable rod 85%, can pass through the visible ray of 90%.
embodiment 5
(1) in the 250mL four-hole boiling flask of drying, add 8.0g LiCl and 98.0g DMAc, then add dry enzymolysis xylogen 3.0g, 70 DEG C are stirred 1h and are dissolved to homogeneous phase solution; In above-mentioned homogeneous system, add catalyst of triethylamine 1.2g and hydroquinone of polymerization retarder 0.0450g, pass into nitrogen protection simultaneously; Acrylate chloride 2.4g is added above-mentioned solution, 50 DEG C of reaction 10h; Reaction terminates, and is poured into by reaction solution in 1000mL distilled water, and stir centrifugal collecting precipitation, be repeatedly washed to neutrality, 50 DEG C are dried to constant weight, obtain lignin-base macromonomer.
(2) by lignin-base macromonomer 0.6g, butyl methacrylate 1.5g and AIBN(azo-bis-isobutyl cyanide) 42mg joins in 30mL dioxane, transferred to by solvent in 100mL eggplant type reaction flask, nitrogen bubble deoxygenation 10 minutes.Then obtain polymkeric substance after being warming up to 70 DEG C of reaction 10h, the transformation efficiency of monomer is 92%, is precipitated by polymkeric substance in the normal hexane of 30 DEG C, and then filtration, drying obtain multipolymer, and this multipolymer is ultraviolet absorption mould material.Molecular weight of copolymer Mw=12051, Mn (GPC)=4989 g/mol, PDI=2.42.Be dissolved in by multipolymer in tetrahydrofuran (THF), pour in the mould of tetrafluoroethylene, 50 DEG C of oven dry, hardness is the UV-light of 4B, Absorbable rod 78%, can pass through the visible ray of 80%.
embodiment 6
(1) in the 250mL four-hole boiling flask of drying, add 6.0g LiCl and 98.0g DMAc, then add dry enzymolysis xylogen 3.0g, 70 DEG C are stirred 2h and are dissolved to homogeneous phase solution; In above-mentioned homogeneous system, add catalyst of triethylamine 2.4g and hydroquinone of polymerization retarder 0.0450g, pass into nitrogen protection simultaneously; Methacrylic chloride 3.6g is added above-mentioned solution, 30 DEG C of reaction 9h; Reaction terminates, and is poured into by reaction solution in 1000mL distilled water, and stir centrifugal collecting precipitation, be repeatedly washed to neutrality, 50 DEG C are dried to constant weight, obtain lignin-base macromonomer.
(2) by lignin-base macromonomer 0.6g, butyl acrylate 3.0g and BPO(benzoyl peroxide) 72mg joins in 30mL tetrahydrofuran (THF), transferred to by solvent in 100mL eggplant type reaction flask, nitrogen bubble deoxygenation 10 minutes.Then obtain polymkeric substance after being warming up to 80 DEG C of reaction 24h, the transformation efficiency of monomer is 94%, is precipitated by polymkeric substance in 40 DEG C of normal hexanes, and then filtration, drying obtain multipolymer, and this multipolymer is ultraviolet absorption mould material.Molecular weight of copolymer Mw=77120, Mn (GPC)=33593 g/mol, PDI=2.30.Be dissolved in by multipolymer in tetrahydrofuran (THF), pour in the mould of tetrafluoroethylene, 50 DEG C are dried into transparent film, and hardness is the UV-light of 2B, Absorbable rod 85%, can pass through the visible ray of 82%.
embodiment 7
(1) in the 250mL four-hole boiling flask of drying, add 4.0g LiCl and 98.0g DMAc, then add dry enzymolysis xylogen 3.0g, 70 DEG C are stirred 3h and are dissolved to homogeneous phase solution; In above-mentioned homogeneous system, add catalyst of triethylamine 3.6g and hydroquinone of polymerization retarder 0.0450g, pass into nitrogen protection simultaneously; Methacrylic chloride 5.4g is added above-mentioned solution, 40 DEG C of reaction 8h; Reaction terminates, and is poured into by reaction solution in 1000mL distilled water, and stir centrifugal collecting precipitation, be repeatedly washed to neutrality, 50 DEG C are dried to constant weight, obtain lignin-base macromonomer.
(2) by lignin-base macromonomer 0.6g, methyl methacrylate 2.0g and BPO(benzoyl peroxide) 72mg joins in 30mL toluene, transferred to by solvent in 100mL eggplant type reaction flask, nitrogen bubble deoxygenation 10 minutes.Then obtain polymkeric substance after being warming up to 90 DEG C of reaction 6h, the transformation efficiency of monomer is 88%, is precipitated by polymkeric substance in 50 DEG C of normal hexanes, and then filtration, drying obtain multipolymer, and this multipolymer is ultraviolet absorption mould material.Molecular weight of copolymer Mw=47120, Mn (GPC)=23593 g/mol, PDI=2.00.Be dissolved in by multipolymer in tetrahydrofuran (THF), pour in the mould of tetrafluoroethylene, 50 DEG C are dried into transparent film, and hardness is the UV-light of 2H, Absorbable rod 70%, can pass through the visible ray of 70%.
embodiment 8
(1) in the 250mL four-hole boiling flask of drying, add 8.0g LiCl and 98.0g DMAc, then add dry enzymolysis xylogen 3.0g, 70 DEG C are stirred 2h and are dissolved to homogeneous phase solution; In above-mentioned homogeneous system, add catalyst of triethylamine 3.6g and hydroquinone of polymerization retarder 0.0450g, pass into nitrogen protection simultaneously; Methacrylic chloride 5.4g is added above-mentioned solution, 50 DEG C of reaction 5h; Reaction terminates, and is poured into by reaction solution in 1000mL distilled water, and stir centrifugal collecting precipitation, be repeatedly washed to neutrality, 50 DEG C are dried to constant weight, obtain lignin-base macromonomer.
(2) by lignin-base macromonomer 0.6g, butyl acrylate 2.0g and AIBN(azo-bis-isobutyl cyanide) 52mg joins in 30mL tetrahydrofuran (THF), transferred to by solvent in 100mL eggplant type reaction flask, nitrogen bubble deoxygenation 10 minutes.Then obtain polymkeric substance after being warming up to 60 DEG C of reaction 24h, the transformation efficiency of monomer is 92%, is precipitated by polymkeric substance in 60 DEG C of normal hexanes, and then filtration, drying obtain multipolymer, and this multipolymer is ultraviolet absorption mould material.Molecular weight of copolymer Mw=51120, Mn (GPC)=21593 g/mol, PDI=2.37.Be dissolved in by multipolymer in tetrahydrofuran (THF), pour in the mould of tetrafluoroethylene, 50 DEG C are dried into transparent film, and hardness is the UV-light of 2B, Absorbable rod 80%, can pass through the visible ray of 85%.
spectrum analysis:
Fig. 1 is infrared spectrogram before and after acrylate chloride grafting enzymolysis xylogen, at 1731 cm
-1there are ester carbonyl stretching vibration absorption peak and 1631 cm in place
-1place C=C charateristic avsorption band, shows that lignin-base macromonomer successfully synthesizes;
Fig. 2 is multipolymer in embodiment 2
13in C-NMR, figure, 58 ppm and 178 ppm are respectively and are attributed to the methoxyl group of xylogen and the carbonyl of butyl acrylate, show that lignin-base mould material is successfully prepared;
Fig. 3 is the ultraviolet-visible spectrogram of multipolymer and poly-n-butyl methacrylate in embodiment 2; As can be seen from the figure, relative poly-n-butyl methacrylate, lignin-base mould material shows as excellent uv absorption property and the high transparency at ultraviolet region, and the UV-light of Absorbable rod more than 80%, can pass through the visible ray of 82%;
Fig. 4 is the thermal multigraph of multipolymer and poly-n-butyl methacrylate in embodiment 2; Result shows the thermally-stabilised higher than poly-n-butyl methacrylate of lignin-base mould material.
Claims (1)
1. an enzymolysis xylogen prepares the method for transparent uv-absorbing mould material, it is characterized in that, in the 250mL four-hole boiling flask of drying, add 6.0g LiCl and 98.0g DMAc, add dry enzymolysis xylogen 3.0g again, 70 DEG C are stirred 2h and are dissolved to homogeneous phase solution; In above-mentioned homogeneous system, add catalyst of triethylamine 1.2g and hydroquinone of polymerization retarder 0.0450g, pass into nitrogen protection simultaneously; Acrylate chloride 2.4g is added above-mentioned solution, 20 DEG C of reaction 3h; Reaction terminates, and is poured into by reaction solution in 1000mL distilled water, and stir centrifugal collecting precipitation, be repeatedly washed to neutrality, 50 DEG C are dried to constant weight, obtain lignin-base macromonomer; (2) lignin-base macromonomer 0.6g, butyl methacrylate 2.0g and AIBN 52mg are joined in 30mL dioxane, solvent is transferred in 100mL eggplant type reaction flask, nitrogen bubble deoxygenation 10 minutes; Then obtain polymkeric substance after being warming up to 70 DEG C of reaction 10h, the transformation efficiency of monomer is 92%, is precipitated by polymkeric substance in the normal hexane of 30 DEG C, and then filtration, drying obtain multipolymer, and this multipolymer is ultraviolet absorption mould material; Molecular weight of copolymer Mw=46789, Mn (GPC)=29593 g/mol, PDI=1.58.
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| CN114149581B (en) * | 2021-10-08 | 2022-09-09 | 南开大学 | Lignin-based hydrogen bond organic framework nano material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1693342A (en) * | 2005-04-30 | 2005-11-09 | 江苏工业学院 | Process for preparing modified lignocellulose sulfonate graft copolymer |
| CN102604307A (en) * | 2012-03-08 | 2012-07-25 | 华东理工大学 | Novel polypropylene composite |
| CN102704269A (en) * | 2012-05-21 | 2012-10-03 | 江南大学 | Method for improving composite performance of laccase induced plant fiber grafted acrylic ester with resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1693342A (en) * | 2005-04-30 | 2005-11-09 | 江苏工业学院 | Process for preparing modified lignocellulose sulfonate graft copolymer |
| CN102604307A (en) * | 2012-03-08 | 2012-07-25 | 华东理工大学 | Novel polypropylene composite |
| CN102704269A (en) * | 2012-05-21 | 2012-10-03 | 江南大学 | Method for improving composite performance of laccase induced plant fiber grafted acrylic ester with resin |
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