CN102618032A - Full-biology-base composite material - Google Patents
Full-biology-base composite material Download PDFInfo
- Publication number
- CN102618032A CN102618032A CN2012100762769A CN201210076276A CN102618032A CN 102618032 A CN102618032 A CN 102618032A CN 2012100762769 A CN2012100762769 A CN 2012100762769A CN 201210076276 A CN201210076276 A CN 201210076276A CN 102618032 A CN102618032 A CN 102618032A
- Authority
- CN
- China
- Prior art keywords
- composite material
- full
- benzoxazine
- biology
- full bio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses a prepared composite material, which relates to a full-biology-base composite material, in particular to a full-biology-base composite material, which is prepared by compounding benzoxazine copolymerized resin serving as a substrate and biological and inorganic fillers. On the aspect of development of natural renewable resources, the composite material is prepared by adopting a die pressing method; and the resin of the substrate is prepared with solvent-free and solvent methods. The researching process is as follows: a full-biology-base benzoxazine monomer with high performance is synthesized by undergoing a Mannich reaction on pure natural raw materials including furfuryl amine, guaiacol and paraformaldehyde or formaldehyde. A monomer copolymer is taken as a substrate, and the full-biology-base composite material is compounded by adding a filler. As proved by a result, the composite material has the advantages of superior impact resistance, high hoisting strength, high thermal resistance and flame retardance.
Description
Technical field
The present invention relates to one type of full bio-based composite material, is base material with full bio-based benzoxazine copolymer resins.Specifically, be through non-petroleum base route synthesized polymer material,, form through two kinds and above resin copolymerization again as the synthetic benzoxazine colophony of raw material by natural reproducible resource.Its meaning is the development and utilization to natural reproducible resource, belongs to the environment-friendly material research category.
Background technology
Matrix material is to pass through physics or chemical process by two or more different substances material, forms the material with new capability.Various materials make up for each other's deficiencies and learn from each other on performance, produce synergistic effect, make the over-all properties of matrix material be superior to former composition material and satisfy various requirement.The employed base material of full bio-based composite material of the present invention is full bio-based benzoxazine colophony.
Benzoxazine colophony is the one type of novel hot setting resin that on the basis of traditional resol, grows up; It is one type of heterogeneous ring compound that contains benzene ring structure, can be synthetic through the Mannich condensation reaction by phenol, formaldehyde and primary amine under solution or fusion (solvent-free) state.Under heat effect, benzoxazine generation ring-opening polymerization generates nitrogenous and is similar to the reticulated structure of resol.The Polybenzoxazine resin that is generated is compared with other thermosetting resins (like epoxy resin, resol, bimaleimide resin etc.), and many performances are more good, are more suitable for preparing various composite material parts as resin base material.Its melt viscosity is lower, is convenient to forming process; Do not have small molecules during polymerization and emit, can guarantee that the goods porosity is low; Almost do not have volumetric shrinkage during ring-opening polymerization, can guarantee the goods precision.The Polybenzoxazine resin has high Tg and good thermostability, flame retardant resistance, mechanical property and electric property, especially, when synthetic Polybenzoxazine resin, can carry out molecular designing very flexibly.
At present, the research of full bio-based composite material report is not found as yet.Research about using the synthetic benzoxazine colophony of renewable resources is also fewer; People such as Cal ò at first utilized cardanol, ammoniacal liquor and formaldehyde to synthesize a kind of novel polyphenyl Bing oxazine resin in 2007, and had prepared a kind of new bio based composites with tossa is compound.(Emanue?calo，Alfonso?Maffezzoli，Giuseppe?Mwle，Francesca?Martina，Selma?E.Mazzetto，Amtonella?Tarziac?and?Cristina?Stifani.Green?Chemistry，2007，9，754-759)。Liu etc. have reported that chaff amine and phenol and dihydroxyphenyl propane preparation contain the benzoxazine colophony of furan structure, and utilize itself and maleimide to obtain the backbone chain type benzoxazine colophony through Diels-Aleder.(referring to 1.Journal of polymer science:part A:polymer chemistry, vol.43,5267-5282 (2005); 2.Journal of polymer science:part A:polymer chemistry, vol.46,6509-6517 (2008).2009, contrivers such as the surplus ancient cooking vessel sound of Beijing University of Chemical Technology were in patent " based on the benzoxazine colophony of renewable resources and its composition and method of making the same " (one Chinese patent application number: 201010178513.3) at first disclosed with the phenol and the amine that come from renewable resources and synthesize benzoxazine colophony.But above these reports are not proper full bio-based materials, all belong to half bio-based category.And some patents (one Chinese patent application number: 201010178513.3) compsn in the report is a mechanical blending, but not copolymerization.The full bio-based composite material base material that the present invention proposes is two kinds and above full bio-based benzoxazine copolymer resins.
Formula 1, the natural origin primary amine of part
Formula 2, the natural origin phenolic cpd of part
The copolymer resins monomer of the full bio-based composite material of the present invention is all synthetic through organism-based raw material.Raw material bio-based primary amine compounds is quite a lot.For example; Chaff amine is a kind of fine chemical material commonly used (Fig. 1) that uses plant materials such as corn cob, cotton seed hulls and bagasse to produce; Contain the more plant material of pentosan behind acidolysis and cyclodehydration generation furfural; Through ammonification, the synthetic chaff amine that can obtain higher yields of chemical reactions such as catalytic hydrogenation.Fat primary amine (carbon chain lengths 8-22) is a kind of in addition " green " raw material (Fig. 1) of synthetic benzoxazine.With the animal, plant fatty acid is raw material, and the production technology route that makes repeated hydrogenation primary amine by fatty behind the fatty nitrile through ammoniation process is quite ripe.At present, most of aliphatic amide surfactant product derives from the natural fats and oils raw material.The perhaps amino diamine (carbon chain lengths 2-18) of end group, as by 1 of bio-based Succinic Acid preparation, 4-tetramethylenediamine, existing at present large scale of production.So far do not find tetramethylenediamine and armeen are used for the research report of synthetic benzoxazine.Occurring in nature aldehydes matter raw material is also very abundant.For example, cashew nut shell oil is a kind of forestry byproducts, abounds with in areas such as India, Vietnam, Brazil and China Hainan, and YO at present is about 2,000,000 tons.It has been used to replace phenol to make epoxy hardener, liquid or pulverous heat-reactive phenolic resin.The staple of cashew nut shell oil is cardanol aldehydes matters such as (Fig. 2).Tyrosine is a kind of aromatic series polare Aminosaeren of phenolic hydroxy group, can extract in the hydrolyzed solution by materials such as useless silk, caseins, also can produce the bacterium fermentation and gets through tyrosine., can be used as the phenol surrogate and use (Fig. 2) with amido protecting or after removing through simple chemical treatment.In addition, can also from the forestry byproducts creosote, extract methyl catechol (Fig. 2), prepare hypotoxic Phloroglucinol (Fig. 2) by forestry chemicals tanpic acid.Xylogen also is a kind of potential phenol surrogate.Its aboundresources, all regenerate with 50,000,000,000 tons speed every year.Pulp and paper industry is annual to produce a large amount of xylogen sub products, but the overwhelming majority enter rivers or concentrate after burn, seldom be utilized effectively.Contain a large amount of aromatic nucleus, phenolic hydroxyl group isoreactivity group in the complicated molecule structure of xylogen, the methyl catechol structure therein in the highest flight.The synthetic required formaldehyde raw material of benzoxazine can make through oxide treatment methyl alcohol, and methyl alcohol can be obtained by fermenting crops straws.It is quite ripe that biochemical process prepares methyl alcohol and the existing scale operation of formaldehyde and production technique.Above-mentioned organism-based raw material does not only conflict with the grain industry, and cheap, wide material sources, is the optional good resource that is used for synthetic full biological poly benzoxazine colophony.
Less and insufficient shortcoming is respectively arranged in order to overcome Polybenzoxazine resin kind in performance; Can significantly adjust the molecular structure of full biological poly benzoxazine colophony and can widen resin property through two kinds and above benzoxazine monomer copolymerization, be a method reliable and with low cost that solves complete this key issue of biological poly benzoxazine colophony Molecular Structure Design limited flexibility.And also have no report so far, also do not find technological invention or the bibliographical information of the full bio-based benzoxazine of any use copolymer resins as the polymer base material of matrix material about full bio-based benzoxazine copolymer resins.
Summary of the invention
Its base material benzoxazine copolymer resins of full bio-based composite material of the present invention is directly to use the synthetic natural biological based raw material that perhaps uses of natural full organism-based raw material to remake to raw material synthetic through further processing.
Polymer base material in the full bio-based composite material that the present invention proposes is formed by two kinds and above benzoxazine monomer copolymerization; The phenols that is used for synthetic benzoxazine colophony base material comprises cardanol, methyl catechol, Eugenol, pyrogallol, Phloroglucinol, xylogen, chitosan for coming from bio-based phenol and verivate thereof; Amine is unary primary amine, the binary primary amine that comes from bio-based, comprises chaff amine, 1, the aliphatic amides (carbochain 8-22) such as diamine (carbochain 2-18), stearylamine and laurylamine that end groups such as 4-tetramethylenediamine are amino.
The used packing material of full bio-based composite material that the present invention proposes is vegetable fibre or particle and inorganic substance, and they all are not petroleum products.
The full bio-based composite material that the present invention proposes, the used monomer of base material benzoxazine copolymerization is full bio-based benzoxazine, and its method is to form copolymer resins through common ring-opening polymerization effect, but not mechanical blending.To obtain better performance and can enlarge the resin range of application well.
Embodiment
Embodiment 1
1. monomer 1 is synthetic: and chaff amine (4.40L, 50mol), Paraformaldehyde 96 (3.00kg, 100mol); Stirring at room to solid dissolves, and the adding methyl catechol (6.21kg, 50mol); Stirring is warming up to 70 ℃, reacts 1 hour, obtains the white-yellowish solid crude product; Through anhydrous alcohol solution and recrystallization purifying, vacuum-drying removes to desolvate and obtains white solid product (productive rate 92%), proves desired benzoxazine product through detecting.
2. monomer 2 is synthetic: (4.40L, 50mol) ((6.21kg 50mol) makes white solid product (productive rate 91%) as stated above to add methyl catechol again for 2.90kg, 25mol) the synthetic two chaff amido valeric acids of reaction under acidic conditions with levulinic acid earlier with chaff amine.Product is characterized, and the result proves desired benzoxazine product.
3. Composite Preparation and performance characterization: (mol ratio) copolymerization in 1: 1 in proportion of above-mentioned two kinds of monomers takes by weighing chaff amine-methyl catechol type benzoxazine monomer (0.58kg) and mixes with difurfuryl valeric acid-methyl catechol type benzoxazine monomer (1.39kg).The flax fiber that adds mass ratio and be 3%-5% adopts compression molding temperature programming curing process: 180 1h, 2001h, 220 2h as strengthening the fiberfill fibers material.Obtain dark-brown copolymer resins based composites batten.Residual rate is 57.7% during 800 ℃ in this copolymer resins matrix material, and thermotolerance is better.Batten is carried out each performance test, and the result is tensile modulus 4.05GPa, tensile strength 49MPa, tension set 1.58%; Modulus in flexure 3.65GPa, flexural strength 131MPa; Shock strength 3.29KJ/m
2265 ℃ of second-order transition temperatures; Under 800 ℃ of heating and the nitrogen protection condition, decompose back sample carbon residue rate 55%.
Embodiment 2
1. monomer 1 is synthetic: (13.48kg 50mol) adds 201 anhydrous alcohol solutions to stearylamine, stirs 30 minutes, and (100mol), temperature is controlled at below 10 ℃ formalin for 37wt%, 7.50L, stirs 20 minutes.Triphenol is more created in adding, and (6.21kg 25mol), stirred 25 minutes, was warming up to 70 ℃, reacted 6 hours, obtained yellow dope, and through anhydrous alcohol solution and recrystallization purifying, the product that vacuum-drying obtains is a faint yellow solid.Productive rate 88%.Product is carried out various signs, and the result proves desired benzoxazine product.
2. monomer 2 is synthetic: with chaff amine (4.40Ll; 50mol) (2.90kg 25mol) reacts synthetic two chaff amido valeric acids under acidic conditions, add cardanol (15.08kg again with levulinic acid earlier; 50mol) make dark red brown liquid product, productive rate 91% as stated above.Product is characterized, and the result proves desired benzoxazine product.
3. Composite Preparation and performance characterization: (mass ratio) copolymerization in 1: 1 in proportion of above-mentioned two kinds of monomers; Take by weighing chaff amine methyl catechol type benzoxazine monomer (0.58g) and be dissolved in the 20L acetone, be mixed with uniform solution with difurfuryl valeric acid-methyl catechol type benzoxazine monomer (0.58kg).Remove acetone, vacuum-drying.Adding mass ratio is flax fiber (1.7-2.9g) strongthener of 0.3%-0.5%, adopts compression molding temperature programming curing process: 180 1h, 2001h, 220 2h.Obtain dark-brown copolymer resins based composites batten.Batten is carried out each performance test, and the result is tensile modulus 4.15GPa, tensile strength 51MPa, tension set 1.92%; Modulus in flexure 3.73GPa, flexural strength 139MPa; Shock strength 3.41KJ/m
2258 ℃ of second-order transition temperatures; Under 800 ℃ of heating and the nitrogen protection condition, decompose back sample carbon residue rate 50%.
Embodiment 3
Said according to embodiment 1; Only 1. the phenol of monomer in synthetic change into Phloroglucinol (2.10kg, the product that 16.7mol) obtains are pale brown look solid (productive rate 90%), again with same procedure and 2. monomer prepare matrix material; Sample is carried out each performance test; The result is tensile modulus 3.25GPa, tensile strength 43MPa, tension set 1.61%; Modulus in flexure 3.23GPa, flexural strength 128MPa; Shock strength 3.27KJ/m
2255 ℃ of second-order transition temperatures; Under 800 ℃ of heating and the nitrogen protection condition, decompose back sample carbon residue rate 52%.
Embodiment 4
Said according to embodiment 1; Only 1. the phenol of monomer in synthetic change into cardanol (15.08kg, the product that 50mol) obtains are brown liquid (productive rate 93%), again with same procedure and 2. monomer prepare matrix material; Sample is carried out each performance test; The result is tensile modulus 3.85GPa, tensile strength 55MPa, tension set 2.11%; Modulus in flexure 4.13GPa, flexural strength 132MPa; Shock strength 3.97KJ/m
2270 ℃ of second-order transition temperatures; Under 800 ℃ of heating and the nitrogen protection condition, decompose back sample carbon residue rate 51%.
Embodiment 5
Said according to embodiment 2, the amine during only 1. monomer synthesizes changes 1 into, 4-tetramethylenediamine (2.20kg; 25mol), obtain white solid product (productive rate 87%), prepare matrix material with same procedure and 2. monomer again; Sample is carried out each performance test; The result is tensile modulus 3.88GPa, tensile strength 53MPa, tension set 1.96%; Modulus in flexure 3.83GPa, flexural strength 130MPa; Shock strength 3.74KJ/m
2263 ℃ of second-order transition temperatures; Under 800 ℃ of heating and the nitrogen protection condition, decompose back sample carbon residue rate 49%.
Claims (4)
1. one type of full bio-based composite material; It is characterized in that used polymer base material is to be formed by two kinds and the copolymerization of above full bio-based benzoxazine colophony, and syntheticly should handle gained by biomass through extraction, hydrolysis or chemically modified etc. with full bio-based monomer is raw materials used.
2. full bio-based composite material according to claim 1; It is characterized in that used filler is that natural fiber, bombax cotton, flax fiber, vegetalitas straw powder mince, renewable materials such as fruit thing duricrust crushed material or chaff shell, and inorganic materials such as spun glass, lime carbonate.
3. according to the said full bio-based composite material of claim 2; It is characterized by the raw material that is used for synthetic benzoxazine is that carbon numbers such as chaff amine, stearylamine and laurylamine are 8～22 aliphatic amide; 1, the two or more material in diamines such as 4-tetramethylenediamine (carbochain 2～18) and the materials such as cardanol, tyrosine, methyl catechol, Eugenol, Phloroglucinol, pyrogallol, chitosan or xylogen.
4. full bio-based composite material according to claim 2, it is characterized by at least a in the used comonomer is that amine and the aldehydes matter of enumerating in levulinic acid and the claim 3 reacts the monomer with bi-benzoxazine structure that synthesizes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100762769A CN102618032A (en) | 2012-03-15 | 2012-03-15 | Full-biology-base composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100762769A CN102618032A (en) | 2012-03-15 | 2012-03-15 | Full-biology-base composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102618032A true CN102618032A (en) | 2012-08-01 |
Family
ID=46558258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100762769A Pending CN102618032A (en) | 2012-03-15 | 2012-03-15 | Full-biology-base composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102618032A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275243A (en) * | 2013-05-17 | 2013-09-04 | 合肥工业大学 | Benzoxazine prepared by taking biomass chitosan as amine source and preparation method of benzoxazine |
| TWI563037B (en) * | 2015-10-27 | 2016-12-21 | Sungo Green Science And Technology Inc | A bio-composite substrate simulating metal |
| CN106397421A (en) * | 2016-09-20 | 2017-02-15 | 重庆工商大学 | Preparation method of full-bio-based benzoxazine |
| CN107747230A (en) * | 2017-10-27 | 2018-03-02 | 浙江理工大学 | A kind of preparation method of Xin types benzoxazine composite |
| CN108070040A (en) * | 2017-12-14 | 2018-05-25 | 江苏大学 | A kind of chitosan-based benzoxazine colophony and preparation method thereof |
| CN108589298A (en) * | 2018-04-16 | 2018-09-28 | 华东理工大学 | A kind of full bio-based composite material and preparation method thereof based on biology base benzoxazine and plant fiber |
| CN109134799A (en) * | 2018-08-28 | 2019-01-04 | 广西师范学院 | Tannin type benzoxazine and preparation method thereof |
| CN111100120A (en) * | 2019-11-04 | 2020-05-05 | 江苏大学 | Bio-based bis-benzoxazine monomer and preparation method thereof |
| CN114573879A (en) * | 2022-04-01 | 2022-06-03 | 扬州超峰汽车内饰件有限公司 | Bio-based fiber composite material resin and preparation method thereof |
| CN117004180A (en) * | 2023-09-27 | 2023-11-07 | 常州宏巨电子科技有限公司 | Main chain type benzoxazine foam material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1923874A (en) * | 2005-09-03 | 2007-03-07 | 三星Sdi株式会社 | Polybenzoxazine-based compound, electrolyte membrane including the same, and fuel cell employing the electrolyte membrane |
| CN101550235A (en) * | 2009-06-02 | 2009-10-07 | 北京化工大学 | Benzoxazine colophony based on renewable resources, its composition and preparing method thereof |
-
2012
- 2012-03-15 CN CN2012100762769A patent/CN102618032A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1923874A (en) * | 2005-09-03 | 2007-03-07 | 三星Sdi株式会社 | Polybenzoxazine-based compound, electrolyte membrane including the same, and fuel cell employing the electrolyte membrane |
| CN101550235A (en) * | 2009-06-02 | 2009-10-07 | 北京化工大学 | Benzoxazine colophony based on renewable resources, its composition and preparing method thereof |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275243B (en) * | 2013-05-17 | 2015-07-22 | 合肥工业大学 | Benzoxazine prepared by taking biomass chitosan as amine source and preparation method of benzoxazine |
| CN103275243A (en) * | 2013-05-17 | 2013-09-04 | 合肥工业大学 | Benzoxazine prepared by taking biomass chitosan as amine source and preparation method of benzoxazine |
| TWI563037B (en) * | 2015-10-27 | 2016-12-21 | Sungo Green Science And Technology Inc | A bio-composite substrate simulating metal |
| CN106397421A (en) * | 2016-09-20 | 2017-02-15 | 重庆工商大学 | Preparation method of full-bio-based benzoxazine |
| CN107747230A (en) * | 2017-10-27 | 2018-03-02 | 浙江理工大学 | A kind of preparation method of Xin types benzoxazine composite |
| CN107747230B (en) * | 2017-10-27 | 2020-09-08 | 浙江理工大学 | Preparation method of benzoxazine composite material |
| CN108070040A (en) * | 2017-12-14 | 2018-05-25 | 江苏大学 | A kind of chitosan-based benzoxazine colophony and preparation method thereof |
| CN108589298A (en) * | 2018-04-16 | 2018-09-28 | 华东理工大学 | A kind of full bio-based composite material and preparation method thereof based on biology base benzoxazine and plant fiber |
| CN108589298B (en) * | 2018-04-16 | 2020-11-20 | 华东理工大学 | Full-bio-based composite material based on bio-based benzoxazine and plant fiber and preparation method thereof |
| CN109134799B (en) * | 2018-08-28 | 2021-02-02 | 南宁师范大学 | Tannin type benzoxazine and preparation method thereof |
| CN109134799A (en) * | 2018-08-28 | 2019-01-04 | 广西师范学院 | Tannin type benzoxazine and preparation method thereof |
| CN111100120A (en) * | 2019-11-04 | 2020-05-05 | 江苏大学 | Bio-based bis-benzoxazine monomer and preparation method thereof |
| CN111100120B (en) * | 2019-11-04 | 2022-08-23 | 江苏大学 | Bio-based bis-benzoxazine monomer and preparation method thereof |
| CN114573879A (en) * | 2022-04-01 | 2022-06-03 | 扬州超峰汽车内饰件有限公司 | Bio-based fiber composite material resin and preparation method thereof |
| CN117004180A (en) * | 2023-09-27 | 2023-11-07 | 常州宏巨电子科技有限公司 | Main chain type benzoxazine foam material and preparation method and application thereof |
| CN117004180B (en) * | 2023-09-27 | 2023-12-26 | 常州宏巨电子科技有限公司 | Main chain type benzoxazine foam material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102618032A (en) | Full-biology-base composite material | |
| Yin et al. | PREPARATION AND PROPERTIES OF LIGNIN-EPOXY RESIN COMPOSITE. | |
| Sathish et al. | Studies on mechanical and thermal properties of cellulosic fiber fillers reinforced epoxy composites | |
| Thirukumaran et al. | New benzoxazines from renewable resources for green composite applications | |
| Sini et al. | Thermal behaviour of bis-benzoxazines derived from renewable feed stock'vanillin' | |
| CN100528926C (en) | Enzymatic hydrolysis lignin epoxy resin material formula and its preparation method | |
| Ping et al. | Wood adhesives from agricultural by-products: Lignins and tannins for the elaboration of particleboards | |
| CN101792581A (en) | Composite material and preparation method thereof | |
| Wang et al. | Mechanical and Thermal Properties of Polyurethane Films from Peroxy-acid Wheat Straw Lignin. | |
| CN103160116A (en) | Modified plastics and preparation method thereof | |
| CN106589882A (en) | Polycarbonate and polyketone alloy and preparation method thereof | |
| CN101899155A (en) | Benzoxazine resin based on furfuryl amine, composition and preparation method thereof | |
| CN108026227A (en) | Method for producing purified lignin, resin composition, and molded article | |
| CN111848977A (en) | Modified lignin, preparation method and application thereof in toughening flame-retardant composite material | |
| CN102378786A (en) | Environmentally friendly electronic device housings | |
| CN111019365B (en) | Method for preparing biological asphalt from lignocellulose biomass hydrothermal carbon | |
| CN104530639A (en) | Lignin-modified phenolic molding plastic and preparation method thereof | |
| CN106432697A (en) | Preparation method of degradable polyglycolic acid | |
| CN101709113A (en) | Preparation of macromolecular compatible additive, namely urea-formaldehyde modified lignin and application of macromolecular compatible additive | |
| CN106380887A (en) | Preparation method of lignin-base phenolic aldehyde molding compound | |
| Li et al. | Preparation and characterization of novolak phenol formaldehyde resin from liquefied brown‐rotted wood | |
| CN103232605A (en) | Hydrogenated phenolic pyrolysis lignin and preparation method thereof | |
| JP6645440B2 (en) | Lignin resin composition, cured product and molded product | |
| Enjoji et al. | Wood‐derived phenol novolaks and their wood/epoxy biocomposites | |
| CN101555311B (en) | Lignin composite polyester material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120801 |