CN1084525A - The batching of the lignocellulose of modification, its preparation method and preparation structured material - Google Patents
The batching of the lignocellulose of modification, its preparation method and preparation structured material Download PDFInfo
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- CN1084525A CN1084525A CN92111598.9A CN92111598A CN1084525A CN 1084525 A CN1084525 A CN 1084525A CN 92111598 A CN92111598 A CN 92111598A CN 1084525 A CN1084525 A CN 1084525A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
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Abstract
Material of the present invention be characterised in that to the position, oh group place of raw material wood cellulose materials-the O-key in conjunction with following group:
Wherein: R, R
1-low alkyl group (1-9C) or R
1The low-grade alkenyl (1-5C) that the low alkyl group (1-9C) that-halogen or phenyl replace, low-grade alkenyl (1-9C), phenyl replace, its content is 21.0～58.4% (weight).
Method is included in the organic solvent medium, at high temperature, uses the mixture acidylate ligno-cellulosic materials by acid anhydrides and carboxylic acid or two kinds of acid anhydrides.
Batching contains ligno-cellulosic materials and the plant or the inorganic sources filler of tackiness agent-modification, and its proportioning is 10～90: 90～10.
Description
The present invention relates to produce macromolecule product, relate to the batching of ligno-cellulosic materials, its preparation method and the preparation structured material of modification more specifically by plant-origin material.
Consume gradually at present and the expansion of polymer production causes seeking new raw material source because of oil, coal, gas resource.The most promisingly be to use the annual plant-sourced that upgrades, as the timber of needle and broad-leaved kind, cotton short fiber, agricultural waste (reed, standing grain are not plump, sunflower shell, corn stalk, bagasse, shive).
The main component of ligno-cellulosic materials is a biological polymer: xylogen, Mierocrystalline cellulose and hemicellulose, their polymer form complicated supramolecular structure and have a large amount of hydrogen bond features, and the oh group of ligno-cellulosic materials is participated when it forms.Because this, natural ligno-cellulosic materials does not have the feature of synthetic linear polymer: solvability and thermoplasticity.
The known method that has various to the ligno-cellulosic materials chemical modification, it is based on the hydrogen atom of substituted hydroxy group and guaranteed the solvability and the thermoplasticity of gained material.
When the ligno-cellulosic materials modification, modification can be whole to it, also can some composition that enter its composition be carried out.
The xyloid method of known chemical modification is that its part is converted into wooden thermoplastic polymer (US.A, 4026847), comprises timber under 95 ℃, soaks into the aqueous solution that contains methyl alcohol, cresols, formaldehyde, ammonia-material, and they form prepolymer in timber.The material that will soak into is heated to 160 ℃, generates multipolymer between natural lignin and prepolymer.
The wooden thermoplastic polymer of gained is in 100 kilograms per centimeter
2Under pressure and the 160 ℃ of temperature, press process 30 minutes and form material of construction.Constitute xyloid most Mierocrystalline cellulose and hemicellulose (reaching 70%(weight)) do not carry out modification and in wooden thermoplastic polymer as not compliant inert filler.
Because the polymkeric substance of gained has portion of hot plasticity and lacks deliquescent characteristics, has limited its processing and possibility of its application.By ecological view, the material of construction that is obtained by this wooden thermoplastic polymer has actual harm to the mankind, because in use can separate out toxic substance cresols and formaldehyde.
Aforesaid method is sub-economic, because processing is all wooden, and modification only is to be no more than 30%(weight) and determine the thermoplastic xylogen of gained material.
Known ligno-cellulosic materials with timber is modified as fibrous method (" research in wood chemistry field ".In the paper a collection of selected materials of for the first time young scholar's report, (P и г а in 1975, Β e к e р e М. Р., М и ц а н e Л. and В. " п р и м e н e н и e М о g и ф и р о в а н н ы х п о с р eg с т в а и а ц e т и л и р о в а н и я g р e в e с н ы х в о л о к о н в и
г о т о в л e н и и п л и т с ц e л ь ю п о в ы ш e н и я и х г и g р о ф о ó н о с т и и г и g р о с т о и к о с т и ")).Method is to carry out esterification in organic solvent.The wood fibre degree of acetylation is about 19%(weight), proved the esterification of the oh group that is positioned at the wood fibre upper layer.Because the material degree of esterification is low, be in high temperature (T=220-240 ℃) processing, the wood fibre board of gained is harmless to the mankind on ecology.
The gained material is limited to its low thermoplasticity, solvability and binding property, and its range of application is narrower.Aforesaid method can not be used for industry, because must handle whole ligno-cellulosic materials things, has caused poor efficiency.
Based on the present invention, the task of proposition is to make the ligno-cellulosic materials of modification, and it has high thermoplasticity, the solvability in all kinds of SOLVENTS and to the binding property of the material of various character.The preparation method of research modification ligno-cellulosic materials, approach is by selecting corresponding modified condition, to guarantee that the gained material has desired characteristic and can make them carry out modification by simple process within the required range, also study the batching that has high physical mechanical index and ecological harmless structured material in order to prepare.
The solution of task is the ligno-cellulosic materials of suggestion modification, it is characterized in that to the position, oh group place of initial wood mass cellulose materials-the O-key in conjunction with following group:
Wherein R-has the low alkyl group of 1-7 carbon atom (1-7C);
R
1-low alkyl group (1-9C), the low alkyl group (1-9C) that halogen replaces, the low alkyl group (1-5C) that phenyl replaces, low-grade alkenyl (1-9C), the low-grade alkenyl (1-5C) that phenyl replaces, its content is 21.0～58.4%(weight).
Described material is the product of whole moiety modifications of ligno-cellulosic materials, has high thermoplasticity (softening temperature is in 70～200 ℃ of scopes), at various organic solvents (acetone, methylethylketone, chloroform, methylene dichloride, and they and benzene or methanol mixture) in solubleness reach 98%, and various materials are had good binding property.This character is by the carboxyl groups that has high molecular weight carboxylic in material (its introducing amount is 21～58.4%(weight)) and the xylogen acyl derivative caused, they have played inner polymeric plasticizer.
According to invention, bonded carboxyl groups amount is lower than the 21%(weight of material) time, then have the acidylate of low degree, and character and protolignin cellulose materials similar in fact.The upper limit of carboxyl groups content is decided by the maximum possible of the substituted oh group of energy.
In modifying process, in the ligno-cellulosic materials bonded carboxyl groups amount increase and correspondingly the infrared spectra that reduces by products therefrom of oh group confirmed.When the carboxyl groups amount increases, at the scope (3500-3200cm of oh group vibration
-1) in the intensity of absorption spectrum reduce, and at c h bond (2920-2880cm
-1) and C=O key (1740cm
-1) the intensity of absorption spectrum in the oscillating region obviously increases.
Requirement in the ligno-cellulosic materials of modification
Group content is a 5.3-31.3%(weight) and
The content of group is 10.0-38.8%(weight).
Such ratio has been guaranteed to adjust its softening temperature and deliquescent possibility in desired scope.
The softening temperature that reduces the modification ligno-cellulosic materials can make with its be base serve as that preparation structured material and the processing treatment temperature of preliminary batching reduce to be directed at and reduce energy waste and simplify its preparation technology.
Solubleness according to the ligno-cellulosic materials of modification of the present invention plays a big part in the use of gained thermoplastic material, it in structured material and when cellulose ester is separated out as binding agent.
According to the present invention, task is to solve like this, and the method for the ligno-cellulosic materials of suggestion preparation modification is that ligno-cellulosic materials is passed through the modification with the acidylate mixture process, and this mixture contains general formula (RCO)
2The acid anhydrides of O, the wherein low alkyl group of R-1～7 carbon atom, an and composition, it is selected from R
1The carboxylic acid of COOH general formula and (R
1CO)
2The acid anhydrides of O general formula, wherein R
1The low-grade alkenyl (1-5C) that the low alkyl group (1-5C) that-low alkyl group (1-9C), phenyl replace, low-grade alkenyl (1-9C), phenyl replace, the mol ratio of above-mentioned acid anhydrides and mentioned component is 1: 0.5-3, in the trifluoroacetic acid medium, at high temperature handle, at this moment guarantee to position, raw material wood cellulose materials oh group place-the O-key in conjunction with following group:
The feature of present method is that technology is simple, does not need to anticipate ligno-cellulosic materials with chemical reagent.Modification is to use various different materials and the acidylate mixture that obtains forms and a step realizes.Present method can solve the xyloid problem of utilizing because of having used whole modification ligno-cellulosic materials.Method can and be implemented in existing equipment by the technology of closure.Present method can prepare the modification ligno-cellulosic materials with the characteristic that requires and guarantee that its performance can adjust in given range.
The inventive method can be used and be selected from following ligno-cellulosic materials: the timber of broad-leaved and needle kind, cotton short fiber, agricultural waste (reed, standing grain are not plump, sunflower shell, corn stalk, bagasse, shive).
In esterification, acid anhydrides (RCO)
2O and carboxylic acid (R
1COOH) with 1: the mol ratio of 0.5-3, enter the acid anhydrides shift reaction and form mixed acid anhydride, it also participates in the esterification of ligno-cellulosic materials (Л Ц М) oh group:
Two kinds of acid anhydrides (RCO) are arranged in the acidylate mixture as stated above
2O and (R
1CO)
2O participates in esterification.1: the 0.5-3 mol ratio is by the amount decision of the above-mentioned carboxyl groups of introducing ligno-cellulosic materials.Further increase carboxylic acid or acid anhydrides (R
1CO)
2The amount of O has detrimentally affect to the character that is used as the trifluoroacetic acid of solvent and catalyzer in this flow process.The feature of trifluoroacetic acid (Т Ф y К) is that cellulosic supramolecular structure is had specific effect, and is than mineral acid such as sulfuric acid, hydrochloric acid, hydrolytic reagent that phosphoric acid is softer.This acidylate mixture and Т Ф y К cooperate and at high temperature implement modification, can make ligno-cellulosic materials its morphological structure of destruction dark modifying process with make the minimum while of high-molecular biologic polymkeric substance depolymerization and deposit.
In order to implement modification procedure in the best way; preferably to 1 part of (weight) ligno-cellulosic materials; use the acidylate mixture of 2-24 part (weight), 1 part of (weight) ligno-cellulosic materials is used the Т Ф y К of 3-30 part (weight), and reaction is to carry out under 30～120 ℃ of temperature.
Can be with different methods by separating the purpose product in the reaction mixture.
When adding precipitation agent, the ligno-cellulosic materials of modification just precipitates, filter then, by in the acidylate mixture with its separation.
Products therefrom can tetrafluoroethylene or make by stainless steel with on compress evaporating solvent and lower boiling acid simultaneously under the condition that is precipitated as thin slice and is reducing pressure by the rapping plate that narrow slit is arranged.Stay acid on the thin slice under 50～70 ℃ of temperature, with containing 30-50%(weight) the deionized water flush away of the aqueous solution of alcohol (methyl alcohol, ethanol).Like this, can prepare the modification ligno-cellulosic materials of various forms (powdery, sheet), described form depends on separation condition and later application.
Task also is to solve like this, and according to the present invention, the batching of suggestion structured material is to contain as the modification ligno-cellulosic materials of the present invention of tackiness agent and the filler of plant or inorganic sources, and its weight ratio is 10～90: 90～10.
Batching of the present invention makes can produce harmless structured material on new, the ecology, and can not separate out deleterious and deleterious material in preparation process and use.
This structured material has different density (700～2200kg/m
3) and high physics-mechanical index, guaranteed that this material has wide application.
10%(weight) binder content is minimum limit, and this moment, structured material had necessary strength.Increase binder content and reach 90%(weight) intensity and the density that then can regulate the resulting structures material according to the character of filler.
As adhesive material, inorganic or plant-sourced filler there are high material bounding force, guaranteed low water-imbibition value, expansion index and the high breakdown point when bending of structured material.
Preferably, the plant-sourced filler that batching contains is selected from: the timber of needle or broad-leaved kind, agricultural waste, its consumption are 10～50%(weight).Increasing amount of binder in this case and be higher than 50%(weight) Shi Buhui increases the physics-mechanical properties of material greatly, but increases its density simultaneously.
That this structured material can be used for preparing wood particle and wood fibre board.Containing weight up to 90%() composition of tackiness agent and plant-sourced filler can be used for preparing xyloid compacting plastics and lignin plastics.
Best is that the inorganic sources filler that batching contains is selected from: the clay that marble, granite, sintering are crossed, sand, glass, glass fibre.
When using mineral filler, increase amount of binder and cause increasing the physics-mechanical index of structured material and reduce its density.
There is the batching of mineral filler to can be used for preparing protection slab and decorative sheet, sanitation and other goods.For improving the character of resulting structures material, can in batching, introduce additive: pigment, packing composition (fiber, fabric), the additive of raising photostabilization and weather proofing, resistivity against fire.
Structured material is that method by hot pressing on existing installation or shaping is by described batching preparation.
Implement method preferably of the present invention.
In the circular flat bottom flask of agitator and reflux cooler is housed; add 10 gram ligno-cellulosic materials (Л Ц М); use the sawdust of timber to make ligno-cellulosic materials, add the acidylate mixture that 110 gram trifluoroacetic acids and 380 grams are made up of 20.4 gram (0.2 mole) diacetyl oxides and 17.6 gram (0.2 mole) oleic acid afterwards.Modifying process is to carry out under 70 ℃ of temperature and under constantly stirring, reaching necessary amount up to the carboxyl groups of introducing, and this amount is measured in advance by sampling method.After reaction finishes, by the ligno-cellulosic materials of the prepared modification of separation in the reaction mixture, add the 250ml deionized water on a small quantity by pressing under vigorous stirring, later filtering-depositing is reducing under the pressure in the sour also drying of 60 ℃ of flush awaies.
The purpose product amount of gained is 16 grams (weightening finish 60%(weight)).The ligno-cellulosic materials of gained modification contains 14.5%(weight) CH
3CO-group (ethanoyl), 24.0%(weight) C
3H
7CO-group (butyryl radicals), its solubleness in acetone is 68%, beginning remollescent temperature (T
p) be 160 ℃.
Gained modification lignocellulose is used to prepare the batching that contains the plant-sourced filler.
Preparation of batch and implement by following mode by the structured material of this batching preparation.
With 9 grams (15%(weight)) prepared modification Л Ц М is dissolved in 100 milliliters of acetone.With the suspension of gained and 51 grams (85%(weight)) wood substance grain of wood-curing waste mixes.Dry gained batching is till removing solvent fully under 60 ℃ of temperature, is placed in the pressing mold under 30～50 ℃ of initial softening temperatures that surpasses tackiness agent to carry out hot pressing.Hot pressing is 1mm thickness during 0.5 minute, then resulting product is cooled to 100～120 ℃ of temperature.Press currently known methods and measure the physics-mechanical index of gained sample.
This structures of samples material has following characteristic:
Density, kg/m
3820
Transverse modulus of rupture, MPa 35.0
Suction, % 14.2
Expand, % 4.0
According to described method, by containing 18 grams (30%(weight)) above-mentioned tackiness agent and prepare structured material as the batching of the sunflower shell of filler.It has following physics-mechanical index:
Density, kg/m
3980
Transverse modulus of rupture, MPa 32.5
Suction, % 6.8
Expand, % 2.0
When using the inorganic sources filler, preparation of batch and processing are implemented by following method.
Get modification ligno-cellulosic materials 18 gram (30%(weight) of above-mentioned batching) with 41.4 grams (60%(weight)) in exploitation and saw marble the waste material and 0.6 of gained restrain (1%(weight)) pigment mixes mutually.
The gained batching is carried out hot pressing under the temperature that is higher than 30～50 ℃ of the initial softening temperatures of tackiness agent, be pressed into 1mm thickness 0.5 fen clock time.Resulting product is cooled to 100-120 ℃ of temperature.
Resulting product has following physics-mechanical index:
Density, kg/m
31900
Transverse modulus of rupture, MPa 47.4
Suction, % 0.2
Expand, % 0
Table 1 has been listed by the present invention below, the mixture of acidylate shown in the use, modified condition and other embodiment of the modification ligno-cellulosic materials that makes and the characteristic of purpose product.
Table 1
| Sequence number | The used acidylate mixture of 1 gram lignocellulose is formed | Ratio (ROC) 2O/R 1The COOH moles/mole | |||
| Acid anhydrides | Acid (acid anhydrides) | ||||
| （RCO) 2O | m,g | R 1COOH | m,g | ||
| 1 | 2 | 3 | 4 | 5 | 6 |
| 1 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 | (CH 3CO) 2O (CH 3CO) 2O (CH 3CO) 2O (CH 3CO) 2O (CH 3CO) 2O (CH 3CO) 2O (CH 3CO) 2O (CH 3CO) 2O (CH 3CO) 2O (CH 3CO) 2O (C 2H 5CO) 2O (C 2H 5CO) 2O (C 3H 7CO) 2O (C 3H 7CO) 2O (C 4H 9CO) 2O (C 4H 9CO) 2O (C 7H 15CO) 2O (C 7H 15CO) 2O (C 7H 15CO) 2O (CH 3CO) 2O (CH 3CO) 2O (CH 3CO) 2O | 1,53 2,04 2,04 2,04 2,04 2,04 2,04 2,04 2,04 3,06 2,06 3,25 2,37 3,95 5,58 5,58 6,75 6,75 8,10 1,53 1,53 2,04 | C
2H
5COOH C
4H
9COOH C
7H
15COOH C
9H
19COOH CH
2COOH CH
3CHCI-CH
2COOH CI(CH
2)
5COOH C
5H
5(CH
2)
2COOH CH
3-CH=CH-CH
2COOH C
5H
5-CH=CHCOOH CH
3COOH C
3H
7COOH C
4H
9COOH CI-C
7H
14COOH C
4H
9COOH
   |
0,56 4,08 2,88 3,44 11,15 2,45 3,29 6,00 2,00 4,44 1,20 2,20 1,53 4,46 1,53 5,16 1,50 2,55 5,16 3,39 2,31 4,28 | 1:0.5 1:2 1:1 1:1 1:3 1:1 1:1 1:2 1:1 1:1 1:1 1:1 1:1 1:1 1:0.5 1:1 1:1 1:1 1:1 1:1 1:1 1:1 |
Table 2 has been listed by the present invention below, the ligno-cellulosic materials of filler shown in the use and modification, press temperature, and the embodiment of the structured material that is made by batching and the physics-mechanical index of resulting structures material.
*-and to produce and the work in-process waste material, granularity is less than 0.5mm
1～5% pigment of the total composition amount of *-contain.
Industrial application
Modification ligno-cellulosic materials of the present invention can be used as the preparation plastics, interim corrosion-resistant coating, and the raw material of cellulose ester also can be as tackiness agent in the preparation structured material.Found the application of chemical treatment plant-sourced aspect according to method of the present invention.Use the structured material of described material to can be used for the product industry (material that is used for floor, wall and ceiling mask, rectangular goods, precoated plate) of preparation building, be used to prepare the wooden pressed material of finishing material, part and furniture industry goods, hygiene product.
Claims (11)
1, the ligno-cellulosic materials of modification, it is characterized in that to the position, oh group place of raw material wood cellulose materials-the O-key in conjunction with following group:
Wherein R-has the low alkyl group of 1-7 carbon atom; R
1-low alkyl group (1-9C), the low alkyl group (1-9C) that halogen replaces, the low alkyl group (1-5C) that phenyl replaces, low-grade alkenyl (1-9C), the low-grade alkenyl (1-5C) that phenyl replaces, its content accounts for 21.0～58.4% (weight).
2, according to the material of claim 1, it is characterized in that wherein
The content of group is 5.3-31.3%(weight), and
Content be 10.0-38.8%(weight).
3,, it is characterized in that its softening temperature is in 70-200 ℃ of scope according to the material of claim 1.
4,, it is characterized in that its solubleness is 5～98% in organic solvent according to the material of claim 1.
5, according to the preparation method of the modification ligno-cellulosic materials of claim 1, the modification that it is characterized in that ligno-cellulosic materials is by carrying out with the acidylate mixture process, and this mixture contains general formula (RCO)
2The acid anhydrides of O, wherein R-has the low alkyl group of 1-7 carbon atom, and a composition, and it is selected from general formula is R
1The carboxylic acid of COOH and general formula (R
1CO)
2The acid anhydrides of O, wherein R
1The low-grade alkenyl (1-5C) that the low alkyl group (1-5C) that the low alkyl group (1-9C) that-low alkyl group (1-9C), halogen replace, phenyl replace, low-grade alkenyl (1-9C), phenyl replace, the mol ratio of described acid anhydrides and above-mentioned composition is 1: 0.5-3, processing is at high temperature to carry out in the trifluoroacetic acid medium, at this moment guarantee to the raw material wood cellulose materials position, oh group place-O-in conjunction with following group:
Then separate the purpose product.
6, according to the method for claim 5, the consumption that it is characterized in that the acidylate mixture is that the ligno-cellulosic materials of per 1 part of weight is got 2-24 part weight.
7, according to the method for claim 5, the consumption that it is characterized in that trifluoroacetic acid is that the ligno-cellulosic materials of per 1 part of weight is got 3-30 part weight.
8,, it is characterized in that ligno-cellulosic materials is to carry out esterification under 30～120 ℃ of temperature according to the method for claim 5.
9, the batching of preparation structured material, it is characterized in that containing as tackiness agent by the modification ligno-cellulosic materials of claim 1 and the filler of plant-sourced or inorganic sources, its weight ratio is 10～90: 90～10.
10, according to the batching of claim 9, it is characterized in that it contains to be selected from following plant-sourced filler: timber, the wastes of crops of needle or broad-leaved kind, its consumption are 10～50%(weight).
11,, it is characterized in that it contains to be selected from following inorganic sources filler: the clay that marble, granite, sintering are crossed, sand, glass, glass fibre according to the batching of claim 9.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/RU1992/000028 WO1993006153A1 (en) | 1991-09-19 | 1992-02-18 | Modified lignocellulose material, method of obtaining it and composition for obtaining composite material |
| AU13454/92A AU1345492A (en) | 1991-09-19 | 1992-02-18 | Modified lignocellulose material, method of obtaining it and composition for obtaining composite material |
| CN92111598.9A CN1084525A (en) | 1991-09-19 | 1992-09-19 | The batching of the lignocellulose of modification, its preparation method and preparation structured material |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SU5004606 | 1991-09-19 | ||
| CN92111598.9A CN1084525A (en) | 1991-09-19 | 1992-09-19 | The batching of the lignocellulose of modification, its preparation method and preparation structured material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1084525A true CN1084525A (en) | 1994-03-30 |
Family
ID=36790921
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92111598.9A Pending CN1084525A (en) | 1991-09-19 | 1992-09-19 | The batching of the lignocellulose of modification, its preparation method and preparation structured material |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN1084525A (en) |
| AU (1) | AU1345492A (en) |
| WO (1) | WO1993006153A1 (en) |
Cited By (7)
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|---|---|---|---|---|
| CN102050952A (en) * | 2010-11-11 | 2011-05-11 | 华南理工大学 | Homogeneous method for preparing wood fiber derivative under room temperature |
| CN102206917A (en) * | 2011-03-29 | 2011-10-05 | 中国林业科学研究院林产化学工业研究所 | Method for manufacturing methyl malei-eleostearate anhydride modified wood fiber |
| CN103992589A (en) * | 2014-04-30 | 2014-08-20 | 山东霞光实业有限公司 | Wood-plastic building template produced by utilizing recovered waste material and preparation method thereof |
| WO2015003398A1 (en) * | 2013-07-11 | 2015-01-15 | 南通醋酸纤维有限公司 | Direct synthesis process for cellulose ester soluble in acetone and the product thereof |
| CN106117566A (en) * | 2016-06-25 | 2016-11-16 | 芜湖三刀材料科技有限公司 | A kind of preparation method of modified wood powder |
| CN110506061A (en) * | 2017-03-29 | 2019-11-26 | 伊士曼化工公司 | The cellulose esters that regioselectivity replaces |
| CN111117274A (en) * | 2019-11-28 | 2020-05-08 | 贾瑞红 | Fiber board capable of adsorbing smoke for automobile object covering curtain and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU391924A1 (en) * | 1972-06-26 | 1973-07-27 | WATERWATER RESISTANT MATERIAL | |
| SU406738A1 (en) * | 1972-07-18 | 1973-11-21 | Авторы изобретени | WATERWATER RESISTANT MATERIAL |
| DE3023914A1 (en) * | 1980-06-26 | 1982-02-04 | Hoechst Ag, 6000 Frankfurt | METHOD FOR PRODUCING CURABLE BINDERS |
| SU977163A1 (en) * | 1980-07-04 | 1982-11-30 | Латвийская Ордена Трудового Красного Знамени Сельскохозяйственная Академия | Method of chemical modification of wood |
| SU1096105A1 (en) * | 1983-02-08 | 1984-06-07 | Институт механики металлополимерных систем АН БССР | Method of modifying wood |
| JPS59209103A (en) * | 1983-05-12 | 1984-11-27 | 大建工業株式会社 | Method of improving woody material |
| JPS63183910A (en) * | 1987-01-26 | 1988-07-29 | Okura Ind Co Ltd | Production of plastic-like woody molded article |
-
1992
- 1992-02-18 WO PCT/RU1992/000028 patent/WO1993006153A1/en unknown
- 1992-02-18 AU AU13454/92A patent/AU1345492A/en not_active Abandoned
- 1992-09-19 CN CN92111598.9A patent/CN1084525A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050952A (en) * | 2010-11-11 | 2011-05-11 | 华南理工大学 | Homogeneous method for preparing wood fiber derivative under room temperature |
| CN102050952B (en) * | 2010-11-11 | 2012-12-05 | 华南理工大学 | Homogeneous method for preparing wood fiber derivative under room temperature |
| CN102206917A (en) * | 2011-03-29 | 2011-10-05 | 中国林业科学研究院林产化学工业研究所 | Method for manufacturing methyl malei-eleostearate anhydride modified wood fiber |
| CN102206917B (en) * | 2011-03-29 | 2012-06-27 | 中国林业科学研究院林产化学工业研究所 | Method for manufacturing methyl malei-eleostearate anhydride modified wood fiber |
| WO2015003398A1 (en) * | 2013-07-11 | 2015-01-15 | 南通醋酸纤维有限公司 | Direct synthesis process for cellulose ester soluble in acetone and the product thereof |
| CN103992589A (en) * | 2014-04-30 | 2014-08-20 | 山东霞光实业有限公司 | Wood-plastic building template produced by utilizing recovered waste material and preparation method thereof |
| CN103992589B (en) * | 2014-04-30 | 2015-07-29 | 山东霞光实业有限公司 | A kind of wood plastic building mould utilizing recovery waste material to produce and preparation method thereof |
| CN106117566A (en) * | 2016-06-25 | 2016-11-16 | 芜湖三刀材料科技有限公司 | A kind of preparation method of modified wood powder |
| CN110506061A (en) * | 2017-03-29 | 2019-11-26 | 伊士曼化工公司 | The cellulose esters that regioselectivity replaces |
| CN110506061B (en) * | 2017-03-29 | 2022-10-21 | 伊士曼化工公司 | Regioselectively substituted cellulose esters |
| CN111117274A (en) * | 2019-11-28 | 2020-05-08 | 贾瑞红 | Fiber board capable of adsorbing smoke for automobile object covering curtain and preparation method thereof |
| CN111117274B (en) * | 2019-11-28 | 2021-12-17 | 淮北市荣恋科技有限公司 | Fiber board capable of adsorbing smoke for automobile object covering curtain and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| AU1345492A (en) | 1993-04-27 |
| WO1993006153A1 (en) | 1993-04-01 |
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