CN103232579A - 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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- CN103232579A CN103232579A CN2013101176618A CN201310117661A CN103232579A CN 103232579 A CN103232579 A CN 103232579A CN 2013101176618 A CN2013101176618 A CN 2013101176618A CN 201310117661 A CN201310117661 A CN 201310117661A CN 103232579 A CN103232579 A CN 103232579A
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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
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Technical field
The invention belongs to technology field of membrane materials, be specifically related to the method that a kind of enzymolysis xylogen prepares transparent uv-absorbing mould material.
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Background technology
Along with continuous digestion and the environmental problem of oil, coal resources are 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 is to be only second to cellulosic natural polymer on the earth, and has inexpensive, degradable, characteristics such as pollution-free, so the research and development to the lignin-base material are all attached great importance in countries in the world.
The main means that xylogen obtains are to separate from the by product of chemical pulping with the biomass refining by the whole bag of tricks.In order to alleviate the petroleum-based energy crisis, utilize the concise technology of biomass to prepare ethanol energy product demand and increase severely, can produce a large amount of by products simultaneously, its composition mainly is xylogen.It is a kind of enzymolysis xylogen with high reaction activity and high and low molecular weights characteristics.At present, xylogen is less in the application aspect the macromolecular material as comonomer, and is main because the existence of phenolic hydroxyl group in the lignin structure has inhibition to free radical reaction.CN1693342A has proposed a kind ofly to carry out esterification with acyl chlorides p-sulfonic acid salt xylogen, phenolic hydroxyl group can be converted into vinyl, and then can carry out letex polymerization with other Acrylic Acid Monomer, and product application is in the timber sizing agent.Method by xylogen and matrix resin blend can obtain the uv-absorbing mould material, but this method can make the film devitrification, has limited its scope of application greatly.The present invention utilizes acyl chlorides that the phenolic hydroxyl group of enzymolysis xylogen is carried out selective esterification, and then does radical polymerization with Acrylic Acid Monomer, preparation lignin-base mould material.This mould material has the transparency preferably, and thermostability, absorption UV-light performance can be widely used in the uvioresistant paint field.
Ultraviolet ray not only has injury to human body and biology, also have for macromolecular material and to have bigger harm, under ultraviolet long-term irradiation, absorb the energy of UV-light as rubber, coating, synthon etc., cause the autoxidation reaction and cause degraded, accelerated deterioration, fade etc.In recent years, along with people are more deep to ultraviolet harm understanding, world many countries was all actively carried out the R and D of ultraviolet ray-resistant material.
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Summary of the invention
The technical problem that solves:The invention discloses the method that a kind of enzymolysis xylogen prepares transparent uv-absorbing mould material, adopt common radical polymerization mode to prepare the uv-absorbing mould material of high transparent, be the new direction of deep processing and utilization exploitation of biomass by product xylogen.
Technical scheme:A kind of enzymolysis xylogen prepares the method for ultraviolet absorption mould material, earlier xylogen is carried out graft modification and obtain the lignin-base macromonomer, lignin-base macromonomer, Acrylic Acid Monomer and radical polymerization being share initiator is that 100:300 ~ 1000:2 is dissolved in the organic solvent by mass ratio again, and logical nitrogen is removed oxygen, behind 50～100 ℃ of reaction 6～24h, polymkeric substance is precipitated in 30～60 ℃ of normal hexanes, filter then, obtain the ultraviolet absorption mould material after the drying.
The preparation method of described lignin-base macromonomer is: in the container of drying, add 2.0 ~ 8.0g LiCl and 98.0g N,N-DIMETHYLACETAMIDE, add dry enzymolysis xylogen 3.0g again, stir 1 ~ 3h at 20 ~ 70 ℃ and be dissolved to homogeneous phase solution; In above-mentioned homogeneous system, add catalyst of triethylamine 1.2g and hydroquinone of polymerization retarder 0.0450g, feed nitrogen protection simultaneously; Acrylate chloride or methacrylic chloride 2.4g are added above-mentioned solution, at 20 ~ 50 ℃ of reaction 3 ~ 12h; Reaction finishes, and reaction solution is poured in the 1000mL distilled water, stirs centrifugal collecting precipitation, repeatedly is washed to neutrality, and 50 ℃ are dried to constant weight, get the lignin-base macromonomer.
Described Acrylic Acid Monomer is butyl acrylate, butyl methacrylate or methyl methacrylate.
It is a kind of in azo-bis-isobutyl cyanide, the 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 for use, cheap biomass refining xylogen is that enzymolysis xylogen is raw material, prepare multi-purpose polymerisable lignin-base macromonomer, significant to the development and use that realize this huge renewable resources of xylogen.
2. among the present invention, the xylogen aromatic ring structure is really introduced in the polymer architecture, synthetic lignin-base mould material has hardness, thermostability, the absorption UV-light performance of high transparent, excellence, can be widely used in fields such as functional anti-ultraviolet paint.
Description of drawings
Fig. 1 is lignin-base macromonomer infrared spectrogram among the embodiment 2;
Fig. 2 is multipolymer among the embodiment 2
13C-NMR;
Fig. 3 is the ultraviolet-visible spectrogram of multipolymer and poly-n-butyl methacrylate among the embodiment 2;
Fig. 4 is the thermal multigraph of multipolymer and poly-n-butyl methacrylate among the embodiment 2.
Embodiment
Following examples further specify 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, modification and replacement to the inventive method, step or condition are done all belong to scope of the present invention.
If do not specialize the conventional means that used technique means is well known to those skilled in the art among the embodiment.
The enzymolysis xylogen that this method adopts makes by common process, be a kind of from wheat, maize straw process alkaline boiling, the enzymic hydrolysis process is extracted the natural macromolecular material obtain, not only can effectively utilize biomass resource but also alternative petrochemical materials, has important practical and is worth.
Embodiment 1
(1) in the 250mL of drying four-hole boiling flask, add 6.0g LiCl and 98.0g DMAc(N,N-DIMETHYLACETAMIDE), add dry enzymolysis xylogen (the pure company limited of Songyuan City hundred auspicious biological multielements) 3.0g again, 70 ℃ 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, feed nitrogen protection simultaneously; Acrylate chloride 2.4g is added above-mentioned solution, 50 ℃ of reaction 3h; Reaction finishes, and reaction solution is poured in the 1000mL distilled water, stirs centrifugal collecting precipitation, repeatedly is washed to neutrality, and 50 ℃ are dried to constant weight, get the lignin-base macromonomer.
(2) with lignin-base macromonomer 0.6g, butyl methacrylate 4g and AIBN(azo-bis-isobutyl cyanide) 92mg joins in the 30 mL dioxane, solvent transferred in the 100mL eggplant type reaction flask nitrogen bubble deoxygenation 10min.Get polymkeric substance after being warming up to 70 ℃ of reaction 10h then, the transformation efficiency of monomer is 90%, and polymkeric substance is precipitated in 30 ℃ normal hexane, and filtration, drying obtain multipolymer then, and this multipolymer is the ultraviolet absorption mould material.Molecular weight of copolymer Mw=267287, M
n(GPC)=47631 g/mol, PDI=5.62.Multipolymer is dissolved in the tetrahydrofuran (THF), pours in the mould of tetrafluoroethylene, be dried into transparent film for 50 ℃, hardness is B, can absorb 85% UV-light, can see through 80% visible light.
Embodiment 2
(1) in the 250mL of drying four-hole boiling flask, add 8.0g LiCl and 98.0g DMAc, add the dry enzymolysis xylogen 3.0g(Songyuan City pure company limited of hundred auspicious biological multielements again), 70 ℃ 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, feed nitrogen protection simultaneously; Acrylate chloride 2.4g is added above-mentioned solution, 50 ℃ of reaction 3h; Reaction finishes, and reaction solution is poured in the 1000mL distilled water, stirs centrifugal collecting precipitation, repeatedly is washed to neutrality, and 50 ℃ are dried to constant weight, get the lignin-base macromonomer.
(2) with lignin-base macromonomer 0.6g, butyl methacrylate 3g and AIBN(azo-bis-isobutyl cyanide) 72mg joins in the 30mL tetrahydrofuran (THF), solvent transferred in the 100mL eggplant type reaction flask nitrogen bubble deoxygenation 10 minutes.Get polymkeric substance after being warming up to 70 ℃ of reaction 10h then, the transformation efficiency of monomer is 92%, and polymkeric substance is precipitated in 50 ℃ normal hexane, and filtration, drying obtain multipolymer then, and this multipolymer is the ultraviolet absorption mould material.Molecular weight of copolymer Mw=85417, Mn (GPC)=34017 g/mol, PDI=2.51.Multipolymer is dissolved in the tetrahydrofuran (THF), pours in the mould of tetrafluoroethylene, be dried into transparent film for 50 ℃, hardness is H, can absorb 80% UV-light, can see through 82% visible light.
Embodiment 3
(1) in the 250mL of drying four-hole boiling flask, add 2.0g LiCl and 98.0g DMAc, add dry enzymolysis xylogen 3.0g again, 20 ℃ 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, feed nitrogen protection simultaneously; Acrylate chloride 2.4g is added above-mentioned solution, 40 ℃ of reaction 5h; Reaction finishes, and reaction solution is poured in the 1000mL distilled water, stirs centrifugal collecting precipitation, repeatedly is washed to neutrality, and 50 ℃ are dried to constant weight, get the lignin-base macromonomer.
(2) with lignin-base macromonomer 0.6g, butyl methacrylate 2.4g and AIBN(azo-bis-isobutyl cyanide) 60mg joins in the 30mL tetrahydrofuran (THF), solvent transferred in the 100mL eggplant type reaction flask nitrogen bubble deoxygenation 10 minutes.Get polymkeric substance after being warming up to 70 ℃ of reaction 10h then, the transformation efficiency of monomer is 88%, and polymkeric substance is precipitated in 40 ℃ normal hexane, and filtration, drying obtain multipolymer then, and this multipolymer is the ultraviolet absorption mould material.Molecular weight of copolymer Mw=77101, Mn (GPC)=32204 g/mol, PDI=2.39.Multipolymer is dissolved in the tetrahydrofuran (THF), pours in the mould of tetrafluoroethylene, be dried into transparent film for 50 ℃, hardness is 2H, can absorb 75% UV-light, can see through 70% visible light.
Embodiment 4
(1) in the 250mL of drying four-hole boiling flask, add 6.0g LiCl and 98.0g DMAc, add dry enzymolysis xylogen 3.0g again, 70 ℃ 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, feed nitrogen protection simultaneously; Acrylate chloride 2.4g is added above-mentioned solution, 20 ℃ of reaction 3h; Reaction finishes, and reaction solution is poured in the 1000mL distilled water, stirs centrifugal collecting precipitation, repeatedly is washed to neutrality, and 50 ℃ are dried to constant weight, get the lignin-base macromonomer.
(2) with lignin-base macromonomer 0.6g, butyl methacrylate 2.0g and AIBN(azo-bis-isobutyl cyanide) 52mg joins in the 30mL dioxane, solvent transferred in the 100mL eggplant type reaction flask nitrogen bubble deoxygenation 10 minutes.Get polymkeric substance after being warming up to 70 ℃ of reaction 10h then, the transformation efficiency of monomer is 92%, and polymkeric substance is precipitated in 30 ℃ normal hexane, and filtration, drying obtain multipolymer then, and this multipolymer is the ultraviolet absorption mould material.Molecular weight of copolymer Mw=46789, Mn (GPC)=29593 g/mol, PDI=1.58.Multipolymer is dissolved in the tetrahydrofuran (THF), pours in the mould of tetrafluoroethylene, be dried into transparent film for 50 ℃, hardness is H, can absorb 85% UV-light, can see through 90% visible light.
Embodiment 5
(1) in the 250mL of drying four-hole boiling flask, add 8.0g LiCl and 98.0g DMAc, add dry enzymolysis xylogen 3.0g again, 70 ℃ 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, feed nitrogen protection simultaneously; Acrylate chloride 2.4g is added above-mentioned solution, 50 ℃ of reaction 10h; Reaction finishes, and reaction solution is poured in the 1000mL distilled water, stirs centrifugal collecting precipitation, repeatedly is washed to neutrality, and 50 ℃ are dried to constant weight, get the lignin-base macromonomer.
(2) with lignin-base macromonomer 0.6g, butyl methacrylate 1.5g and AIBN(azo-bis-isobutyl cyanide) 42mg joins in the 30mL dioxane, solvent transferred in the 100mL eggplant type reaction flask nitrogen bubble deoxygenation 10 minutes.Get polymkeric substance after being warming up to 70 ℃ of reaction 10h then, the transformation efficiency of monomer is 92%, and polymkeric substance is precipitated in 30 ℃ normal hexane, and filtration, drying obtain multipolymer then, and this multipolymer is the ultraviolet absorption mould material.Molecular weight of copolymer Mw=12051, Mn (GPC)=4989 g/mol, PDI=2.42.Multipolymer is dissolved in the tetrahydrofuran (THF), pours in the mould of tetrafluoroethylene, 50 ℃ of oven dry, hardness is 4B, can absorb 78% UV-light, can see through 80% visible light.
Embodiment 6
(1) in the 250mL of drying four-hole boiling flask, add 6.0g LiCl and 98.0g DMAc, add dry enzymolysis xylogen 3.0g again, 70 ℃ 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, feed nitrogen protection simultaneously; Methacrylic chloride 3.6g is added above-mentioned solution, 30 ℃ of reaction 9h; Reaction finishes, and reaction solution is poured in the 1000mL distilled water, stirs centrifugal collecting precipitation, repeatedly is washed to neutrality, and 50 ℃ are dried to constant weight, get the lignin-base macromonomer.
(2) with lignin-base macromonomer 0.6g, butyl acrylate 3.0g and BPO(benzoyl peroxide) 72mg joins in the 30mL tetrahydrofuran (THF), solvent transferred in the 100mL eggplant type reaction flask nitrogen bubble deoxygenation 10 minutes.Get polymkeric substance after being warming up to 80 ℃ of reaction 24h then, the transformation efficiency of monomer is 94%, and polymkeric substance is precipitated in 40 ℃ of normal hexanes, and filtration, drying obtain multipolymer then, and this multipolymer is the ultraviolet absorption mould material.Molecular weight of copolymer Mw=77120, Mn (GPC)=33593 g/mol, PDI=2.30.Multipolymer is dissolved in the tetrahydrofuran (THF), pours in the mould of tetrafluoroethylene, be dried into transparent film for 50 ℃, hardness is 2B, can absorb 85% UV-light, can see through 82% visible light.
Embodiment 7
(1) in the 250mL of drying four-hole boiling flask, add 4.0g LiCl and 98.0g DMAc, add dry enzymolysis xylogen 3.0g again, 70 ℃ 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, feed nitrogen protection simultaneously; Methacrylic chloride 5.4g is added above-mentioned solution, 40 ℃ of reaction 8h; Reaction finishes, and reaction solution is poured in the 1000mL distilled water, stirs centrifugal collecting precipitation, repeatedly is washed to neutrality, and 50 ℃ are dried to constant weight, get the lignin-base macromonomer.
(2) with lignin-base macromonomer 0.6g, methyl methacrylate 2.0g and BPO(benzoyl peroxide) 72mg joins in the 30mL toluene, solvent transferred in the 100mL eggplant type reaction flask nitrogen bubble deoxygenation 10 minutes.Get polymkeric substance after being warming up to 90 ℃ of reaction 6h then, the transformation efficiency of monomer is 88%, and polymkeric substance is precipitated in 50 ℃ of normal hexanes, and filtration, drying obtain multipolymer then, and this multipolymer is the ultraviolet absorption mould material.Molecular weight of copolymer Mw=47120, Mn (GPC)=23593 g/mol, PDI=2.00.Multipolymer is dissolved in the tetrahydrofuran (THF), pours in the mould of tetrafluoroethylene, be dried into transparent film for 50 ℃, hardness is 2H, can absorb 70% UV-light, can see through 70% visible light.
Embodiment 8
(1) in the 250mL of drying four-hole boiling flask, add 8.0g LiCl and 98.0g DMAc, add dry enzymolysis xylogen 3.0g again, 70 ℃ 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, feed nitrogen protection simultaneously; Methacrylic chloride 5.4g is added above-mentioned solution, 50 ℃ of reaction 5h; Reaction finishes, and reaction solution is poured in the 1000mL distilled water, stirs centrifugal collecting precipitation, repeatedly is washed to neutrality, and 50 ℃ are dried to constant weight, get the lignin-base macromonomer.
(2) with lignin-base macromonomer 0.6g, butyl acrylate 2.0g and AIBN(azo-bis-isobutyl cyanide) 52mg joins in the 30mL tetrahydrofuran (THF), solvent transferred in the 100mL eggplant type reaction flask nitrogen bubble deoxygenation 10 minutes.Get polymkeric substance after being warming up to 60 ℃ of reaction 24h then, the transformation efficiency of monomer is 92%, and polymkeric substance is precipitated in 60 ℃ of normal hexanes, and filtration, drying obtain multipolymer then, and this multipolymer is the ultraviolet absorption mould material.Molecular weight of copolymer Mw=51120, Mn (GPC)=21593 g/mol, PDI=2.37.Multipolymer is dissolved in the tetrahydrofuran (THF), pours in the mould of tetrafluoroethylene, be dried into transparent film for 50 ℃, hardness is 2B, can absorb 80% UV-light, can see through 85% visible light.
Spectrum analysis:
Fig. 1 is infrared spectrogram before and after the acrylate chloride grafting enzymolysis xylogen, at 1731 cm
-1Ester carbonyl stretching vibration absorption peak and 1631 cm have appearred in the place
-1The C=C of place charateristic avsorption band shows that the lignin-base macromonomer is successfully synthetic;
Fig. 2 is multipolymer among the embodiment 2
13C-NMR, 58 ppm and 178 ppm are respectively ownership for the carbonyl of the methoxyl group of xylogen and butyl acrylate among the figure, show that the lignin-base mould material has prepared success;
Fig. 3 is the ultraviolet-visible spectrogram of multipolymer and poly-n-butyl methacrylate among the embodiment 2; As can be seen from the figure, relative poly-n-butyl methacrylate, the lignin-base mould material shows as excellent uv absorption property and the high transparency at ultraviolet region, can absorb the UV-light more than 80%, can see through 82% visible light;
Fig. 4 is the thermal multigraph of multipolymer and poly-n-butyl methacrylate among the embodiment 2; The result shows the thermally-stabilised poly-n-butyl methacrylate that is higher than of lignin-base mould material.
Claims (5)
1. an enzymolysis xylogen prepares the method for ultraviolet absorption mould material, it is characterized in that, earlier xylogen is carried out graft modification and obtain the lignin-base macromonomer, lignin-base macromonomer, Acrylic Acid Monomer and radical polymerization being share initiator is that 100:300 ~ 1000:2 is dissolved in the organic solvent by mass ratio again, and logical nitrogen is removed oxygen, behind 50～100 ℃ of reaction 6～24h, polymkeric substance is precipitated in 30～60 ℃ of normal hexanes, filter then, obtain the ultraviolet absorption mould material after the drying.
2. a kind of enzymolysis xylogen according to claim 1 prepares the method for transparent uv-absorbing mould material, the preparation method who it is characterized in that described lignin-base macromonomer is: in the container of drying, add 2.0 ~ 8.0g LiCl and 98.0g N,N-DIMETHYLACETAMIDE, add dry enzymolysis xylogen 3.0g again, stir 1 ~ 3h at 20 ~ 70 ℃ and be dissolved to homogeneous phase solution; In above-mentioned homogeneous system, add catalyst of triethylamine 1.2g and hydroquinone of polymerization retarder 0.0450g, feed nitrogen protection simultaneously; Acrylate chloride or methacrylic chloride 2.4g are added above-mentioned solution, at 20 ~ 50 ℃ of reaction 3 ~ 12h; Reaction finishes, and reaction solution is poured in the 1000mL distilled water, stirs centrifugal collecting precipitation, repeatedly is washed to neutrality, and 50 ℃ are dried to constant weight, get the lignin-base macromonomer.
3. a kind of enzymolysis xylogen according to claim 1 prepares the method for transparent uv-absorbing mould material, it is characterized in that described Acrylic Acid Monomer is butyl acrylate, butyl methacrylate or methyl methacrylate.
4. a kind of enzymolysis xylogen according to claim 1 prepares the method for transparent uv-absorbing mould material, it is characterized in that it is a kind of in azo-bis-isobutyl cyanide, the benzoyl peroxide that described radical polymerization share initiator.
5. a kind of enzymolysis xylogen according to claim 1 prepares the method for transparent uv-absorbing mould material, it is characterized in that described organic solvent is tetrahydrofuran (THF), dioxane or toluene.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107987621A (en) * | 2017-12-15 | 2018-05-04 | 安徽五岳松纳米技术有限公司 | A kind of aging resistant coating |
| CN114149581A (en) * | 2021-10-08 | 2022-03-08 | 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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2013
- 2013-04-07 CN CN201310117661.8A patent/CN103232579B/en not_active Expired - Fee Related
Patent 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107987621A (en) * | 2017-12-15 | 2018-05-04 | 安徽五岳松纳米技术有限公司 | A kind of aging resistant coating |
| CN114149581A (en) * | 2021-10-08 | 2022-03-08 | 南开大学 | Lignin-based hydrogen bond organic framework nano material and preparation method and application thereof |
| 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 |
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