CN108748517A - A kind of ceramics wood and manufacturing method based on oximes sealing end - Google Patents
A kind of ceramics wood and manufacturing method based on oximes sealing end Download PDFInfo
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- CN108748517A CN108748517A CN201810375198.XA CN201810375198A CN108748517A CN 108748517 A CN108748517 A CN 108748517A CN 201810375198 A CN201810375198 A CN 201810375198A CN 108748517 A CN108748517 A CN 108748517A
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- Prior art keywords
- timber
- oximes
- ceramics
- wood
- manufacturing
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
- B27K3/08—Impregnating by pressure, e.g. vacuum impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
- B27K3/50—Mixtures of different organic impregnating agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
- B27K5/001—Heating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/285—Nitrogen containing compounds
- C08G18/286—Oximes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
Abstract
The invention discloses a kind of ceramics wood and manufacturing method based on oximes sealing end.Ceramic wood includes timber, filled with the filler that reticular structure is combined and formed with lumber fibre with lumber fibre in the gap of timber, filler is prepared by polyisocyanates, aldoxime class sealer, polyester polyol, olefin polymerization catalysis, amino acid and water, manufacturing method is first to be closed to NCO, and NCO group concurrently biochemical reaction is unsealed after filler enters in timber.It is obtained using the ceramics wood of the present invention and by the manufacturing method ceramic wooden, anti-corrosion and waterproof, mothproof, dimensionally stable, service life are long as ceramics, performance is good, so that timber is not easy to deform, is mouldy, it is durable simultaneously, and the inner layer of ceramics wood is consistent with outer layer, and it is different with internal layer ceramics wood after will not being buffed off because of cladding material.
Description
Technical field
The present invention relates to ceramic wood and its manufacturing methods.Especially with to fixture, ornament materials, construction material, art
Ceramics wood on product.
Background technology
The application of timber is very extensive, such as furniture, ornament materials, construction material, the art work.For being used for a long time
Timber for, generally require and do anti-corrosion and waterproof processing, in carrying out above-mentioned processing procedure, generally use anti-corrosion waterproof material
Timber is handled, but current anti-corrosion waterproof material is only on the surface of timber, it is difficult to it enters in the gap of timber, this
Sample, once the anti-corrosion waterproof material of wood surface is destroyed, then the preservation of timber against decay, water resistance decline, and timber is susceptible to change
Shape, it is mouldy phenomena such as.The anticorrosive wood of market at present is handled using preservative, non-watertight, once preservative fails, is begun to
Burn into is mouldy, is not real anticorrosive wood.
Timber is a kind of natural organic, and there are many fibers in timber, and there are many gaps, thus
Hardness, antiseptic property, insect prevention performance, water resistance, dimensional stability of timber etc. can be caused not good enough, existing mode be
Wood surface coats a coating, once when coating is destroyed, performance of the coating on timber disappears immediately, and timber can equally be deposited
In drawbacks described above.
Invention content
The object of the present invention is to provide a kind of ceramics wood and manufacturing method based on oximes sealing end, utilize the ceramics of the present invention
Wood and the ceramics wood obtained by the manufacturing method, anti-corrosion and waterproof, mothproof, dimensionally stable, service life are long as ceramics,
Performance is good so that timber is not easy to deform, is mouldy, while durable, and the inner layer of ceramics wood is consistent with outer layer, will not be because of outer layer
Material is different with internal layer ceramics wood after being buffed off.
In order to achieve the above objectives, a kind of ceramics wood based on oximes sealing end, including timber, are filled in the gap of timber
Combined with lumber fibre and with lumber fibre formed reticular structure filler, filler by following weight percent raw material system
It is standby to form：
The manufacturing method that ceramics wood is blocked based on oximes is included the following steps：
(1) performed polymer is prepared, the polyester polyol of the polyisocyanates of 10%-15% and 8%-12% are reacted；
(2) the aldoxime class sealer of 10%-15% is added in performed polymer, with aldoxime class blocking agent NCO group shape
At enclosed type performed polymer, can split the carbon dioxide off in this step, alkene and primary amine；Primary amine is to freedom or free state NCO bases
Group is closed；
(3) be added in enclosed type performed polymer the olefin polymerization catalysis of 1%-2%, 16%-25% amino acid and
The water of 40%-50% forms maceration extract；
(3) by timber pickling in maceration extract, maceration extract entered wood under the pressure of 1-10MPa by 12-24 hours
In material；
(4) timber by dipping is taken out, is then placed in heating kettle, heating 10- is carried out to the timber by dipping
20 hours, heating temperature was 100-120 DEG C, during heating, is unsealed by the NCO group of aldoxime class blocking agent, together
When, the hydroxyl in amino acid is acted on by the closed enclosed type performed polymer of primary amine, is solved by the closed NCO group of primary amine
Envelope, while chemically reacting, after the completion of reaction, lumber fibre is formed in timber and constitutes the polymer of reticular structure and is made
Ceramic wood；The chemical reaction of generation mainly has：
Under the action of olefin polymerization catalysis addition polymerization occurs for alkene.
Further, olefin polymerization catalysis is chromium-based catalysts.
Further, the one or several kinds in polyisocyanates TDI, MDI, HDI, IPDI.
Further, polyester polyol is ethylene glycol, propylene glycol, diglycol, trimethylolpropane, pentaerythrite
In one kind.
In the present invention, based on the characteristic with hydroxyl, phenolic hydroxyl group and a large amount of water in timber, and in polyisocyanates
The activity of NCO group has unusual height, for this purpose, the present invention first closes NCO group, in the present invention, the closing of use
Agent is aldoxime class sealer, and current the study found that aldoxime class sealer can decomposite dioxy in blocked polyisocyanates
Change carbon, alkene and primary amine, the present invention exactly manufactures ceramics wood using this performance, and reason is：(1) generation of carbon dioxide can add
The flowing of fast enclosed type performed polymer, and the primary amine itself generated belongs to sealer, and its closed speed, to accelerate
Addition polymerization could occur under the effect of the catalyst under pressure for entire speed in a closed circuit, generated alkene needs,
Due to there is no pressure during preparing maceration extract, polyaddition reaction will not occur for alkene.In addition, in the present invention
Middle to use aldoxime class sealer, the temperature of deblocking is low, small to the damage of timber during deblocking.
After the completion of maceration extract preparation, allow maceration extract within the time of pressure and control completely into the gap to timber
Afterwards, NCO group is unsealed by heating, but due to more difficult by primary amine closed NCO group deblocking, mainly by
To the influence of electronic effect, therefore, the amino acid with-COOH is added, and the electronegativity of-COOH is more than the-CH3 in primary amine,
Therefore, the technical issues of being difficult to unseal because of primary amine closing NCO group is solved.During deblocking, NCO group and water, hydroxyl
Base, phenolic hydroxyl group carry out reaction and are formed by curing polymer, while addition polymerization occurs under the effect of the catalyst for alkene, increases wood
The loading of polymer in material, in the curing process, polymer, that is, filler and lumber fibre form reticular structure, in deblocking and
In solidification process, polyisocyanates fills timber gap primarily between a large amount of active hydrogen in isocyanate group and timber
Reaction be formed by chemical bond, such as the hydroxyl in cellulose, hemicellulose rope, the phenolic hydroxyl group in lignin, further includes institute in timber
The a large amount of water contained, they can react with isocyanates, this is that isocyanate group is formed with base material active hydrogen reaction
Chemical bonds；Secondly, the big polar group formation Hydrogenbond of isocyanate resin and the oxygen-containing, nitrogen of base material etc., isocyanate group
The asking for product of itself or isocyanate group and isocyanate group and timber can generate itself cross-linking reaction.In this way, not only by timber
In gap be filled up completely, and the inside and outside of timber is allowed to be consistent, allows timber anti-corrosion and waterproof, mothproof, size as ceramics
Stabilization, service life are long, and performance is good so that timber is not easy to deform, is mouldy, while durable.During heating, it unlocks and
Partially enclosed dose enter in wood-fibred, partially enclosed dose because the high reason of temperature is taken away by moisture, using heat stepwise
Purpose is that small molecule is allowed all to volatilize with moisture, achievees the purpose that environmental protection.
Specific implementation mode
The present invention will be described in further detail With reference to embodiment.
Ceramics wood based on oximes sealing end, including timber, in the gap of timber filled with combined with lumber fibre and with
Lumber fibre forms the filler of reticular structure, and filler is prepared by the raw material of following weight percent：
Wherein, the one or several kinds in polyisocyanates TDI, MDI, HDI, IPDI.Olefin polymerization catalysis is chromium
Base catalyst.Polyester polyol is one in ethylene glycol, propylene glycol, diglycol, trimethylolpropane, pentaerythrite
Kind.
Embodiment 1.
The manufacturing method that ceramics wood is blocked based on oximes is included the following steps：
(1) performed polymer is prepared, the polyester polyol of 15% polyisocyanates and 8% is reacted.
(2) 15% aldoxime class sealer is added in performed polymer, is formed and is closed with aldoxime class blocking agent NCO group
Type performed polymer can split the carbon dioxide off, alkene and primary amine in this step；Primary amine carries out freedom or free state NCO group
Closing.
(3) 1% olefin polymerization catalysis, 16% amino acid and 45% water are added in enclosed type performed polymer to be formed
Maceration extract.
(3) by timber pickling in maceration extract, maceration extract entered wood under the pressure of 1-10MPa by 12-24 hours
In material.
(4) timber by dipping is taken out, is then placed in heating kettle, heating 10- is carried out to the timber by dipping
20 hours, heating temperature was 100-120 DEG C, during heating, is unsealed by the NCO group of aldoxime class blocking agent, together
When, the hydroxyl in amino acid is acted on by the closed enclosed type performed polymer of primary amine, is solved by the closed NCO group of primary amine
Envelope, while chemically reacting, after the completion of reaction, lumber fibre is formed in timber and constitutes the polymer of reticular structure and is made
Ceramic wood；The chemical reaction of generation mainly has：
Addition polymerization occurs under the action of olefin polymerization catalysis for alkene, and the above percentage is weight percentage.
Embodiment 2.
The manufacturing method that ceramics wood is blocked based on oximes is included the following steps：
(1) performed polymer is prepared, the polyester polyol of 10% polyisocyanates and 12% is reacted.
(2) 10% aldoxime class sealer is added in performed polymer, is formed and is closed with aldoxime class blocking agent NCO group
Type performed polymer can split the carbon dioxide off, alkene and primary amine in this step；Primary amine carries out freedom or free state NCO group
Closing.
(3) 2% olefin polymerization catalysis, 25% amino acid and 41% water are added in enclosed type performed polymer to be formed
Maceration extract.
(3) by timber pickling in maceration extract, maceration extract entered wood under the pressure of 1-10MPa by 12-24 hours
In material.
(4) timber by dipping is taken out, is then placed in heating kettle, heating 10- is carried out to the timber by dipping
20 hours, heating temperature was 100-120 DEG C, during heating, is unsealed by the NCO group of aldoxime class blocking agent, together
When, the hydroxyl in amino acid is acted on by the closed enclosed type performed polymer of primary amine, is solved by the closed NCO group of primary amine
Envelope, while chemically reacting, after the completion of reaction, lumber fibre is formed in timber and constitutes the polymer of reticular structure and is made
Ceramic wood；The chemical reaction of generation mainly has：
Addition polymerization occurs under the action of olefin polymerization catalysis for alkene, and the above percentage is weight percentage.
Embodiment 3.
The manufacturing method that ceramics wood is blocked based on oximes is included the following steps：
(1) performed polymer is prepared, the polyester polyol of 11% polyisocyanates and 9% is reacted.
(2) 11% aldoxime class sealer is added in performed polymer, is formed and is closed with aldoxime class blocking agent NCO group
Type performed polymer can split the carbon dioxide off, alkene and primary amine in this step；Primary amine carries out freedom or free state NCO group
Closing.
(3) in enclosed type performed polymer be added 1.5% olefin polymerization catalysis, 17.5% amino acid and 50% water
Form maceration extract.
(3) by timber pickling in maceration extract, maceration extract entered wood under the pressure of 1-10MPa by 12-24 hours
In material.
(4) timber by dipping is taken out, is then placed in heating kettle, heating 10- is carried out to the timber by dipping
20 hours, heating temperature was 100-120 DEG C, during heating, is unsealed by the NCO group of aldoxime class blocking agent, together
When, the hydroxyl in amino acid is acted on by the closed enclosed type performed polymer of primary amine, is solved by the closed NCO group of primary amine
Envelope, while chemically reacting, after the completion of reaction, lumber fibre is formed in timber and constitutes the polymer of reticular structure and is made
Ceramic wood；The chemical reaction of generation mainly has：
Addition polymerization occurs under the action of olefin polymerization catalysis for alkene, and the above percentage is weight percentage.
In the present invention, based on the characteristic with hydroxyl, phenolic hydroxyl group and a large amount of water in timber, and in polyisocyanates
The activity of NCO group has unusual height, for this purpose, the present invention first closes NCO group, in the present invention, the closing of use
Agent is aldoxime class sealer, and current the study found that aldoxime class sealer can decomposite dioxy in blocked polyisocyanates
Change carbon, alkene and primary amine, the present invention exactly manufactures ceramics wood using this performance, and reason is：(1) generation of carbon dioxide can add
The flowing of fast enclosed type performed polymer, and the primary amine itself generated belongs to sealer, and its closed speed, to accelerate
Addition polymerization could occur under the effect of the catalyst under pressure for entire speed in a closed circuit, generated alkene needs,
Due to there is no pressure during preparing maceration extract, polyaddition reaction will not occur for alkene.In addition, in the present invention
Middle to use aldoxime class sealer, the temperature of deblocking is low, small to the damage of timber during deblocking.
After the completion of maceration extract preparation, allow maceration extract within the time of pressure and control completely into the gap to timber
Afterwards, NCO group is unsealed by heating, but due to more difficult by primary amine closed NCO group deblocking, mainly by
To the influence of electronic effect, therefore, the amino acid with-COOH is added, and the electronegativity of-COOH is more than the-CH3 in primary amine,
Therefore, the technical issues of being difficult to unseal because of primary amine closing NCO group is solved.During deblocking, NCO group and water, hydroxyl
Base, phenolic hydroxyl group carry out reaction and are formed by curing polymer, while addition polymerization occurs under the effect of the catalyst for alkene, increases wood
The loading of polymer in material, in the curing process, polymer, that is, filler and lumber fibre form reticular structure, in deblocking and
In solidification process, polyisocyanates fills timber gap primarily between a large amount of active hydrogen in isocyanate group and timber
Reaction be formed by chemical bond, such as the hydroxyl in cellulose, hemicellulose rope, the phenolic hydroxyl group in lignin, further includes institute in timber
The a large amount of water contained, they can react with isocyanates, this is that isocyanate group is formed with base material active hydrogen reaction
Chemical bonds；Secondly, the big polar group formation Hydrogenbond of isocyanate resin and the oxygen-containing, nitrogen of base material etc., isocyanate group
The asking for product of itself or isocyanate group and isocyanate group and timber can generate itself cross-linking reaction.In this way, not only by timber
In gap be filled up completely, and the inside and outside of timber is allowed to be consistent, allows timber anti-corrosion and waterproof, mothproof, size as ceramics
Stabilization, service life are long, and performance is good so that timber is not easy to deform, is mouldy, while durable.During heating, it unlocks and
Partially enclosed dose enter in wood-fibred, partially enclosed dose because the high reason of temperature is taken away by moisture, using heat stepwise
Purpose is that small molecule is allowed all to volatilize with moisture, achievees the purpose that environmental protection.
Claims (8)
1. a kind of ceramics wood based on oximes sealing end, including timber, it is characterised in that：It is filled in the gap of timber and timber
Fiber combine and with lumber fibre formed reticular structure filler, filler by following weight percent raw material prepare and
At：
2. the ceramics wood according to claim 1 based on oximes sealing end, it is characterised in that：Olefin polymerization catalysis is chromium base
Catalyst.
3. the ceramics wood according to claim 1 based on oximes sealing end, it is characterised in that：Polyisocyanates be TDI, MDI,
One or several kinds in HDI, IPDI.
4. the ceramics wood according to claim 1 based on oximes sealing end, it is characterised in that：Polyester polyol be ethylene glycol,
One kind in propylene glycol, diglycol, trimethylolpropane, pentaerythrite.
5. a kind of manufacturing method blocking ceramics wood based on oximes, it is characterised in that include the following steps：
(1) performed polymer is prepared, the polyester polyol of the polyisocyanates of 10%-15% and 8%-12% are reacted；
(2) the aldoxime class sealer of 10%-15% is added in performed polymer, is formed and is sealed with aldoxime class blocking agent NCO group
Closed form performed polymer can split the carbon dioxide off, alkene and primary amine in this step；Primary amine to freedom or free state NCO group into
Row closing；
(3) olefin polymerization catalysis of 1%-2%, the amino acid and 40%- of 16%-25% are added in enclosed type performed polymer
50% water forms maceration extract；
(3) by timber pickling in maceration extract, maceration extract was entered by 12-24 hours in timber under the pressure of 1-10MPa；
(4) timber by dipping is taken out, is then placed in heating kettle, it is small to carry out heating 10-20 to the timber by dipping
When, heating temperature is 100-120 DEG C, during heating, is unsealed by the NCO group of aldoxime class blocking agent, meanwhile, ammonia
Hydroxyl in base acid is acted on by the closed enclosed type performed polymer of primary amine, is unsealed by the closed NCO group of primary amine, simultaneously
It chemically reacts, after the completion of reaction, forms lumber fibre in timber and constitute the polymer of reticular structure and ceramics wood is made；
The chemical reaction of generation mainly has：
Addition polymerization occurs under the action of olefin polymerization catalysis for alkene, and the above percentage is weight percentage.
6. the manufacturing method according to claim 5 for blocking ceramics wood based on oximes, it is characterised in that：Olefinic polymerization catalysis
Agent is chromium-based catalysts.
7. the manufacturing method according to claim 5 for blocking ceramics wood based on oximes, it is characterised in that：Polyisocyanates is
One or several kinds in TDI, MDI, HDI, IPDI.
8. the manufacturing method according to claim 5 for blocking ceramics wood based on oximes, it is characterised in that：Polyester polyol is
One kind in ethylene glycol, propylene glycol, diglycol, trimethylolpropane, pentaerythrite.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810375198.XA CN108748517B (en) | 2018-04-24 | 2018-04-24 | Ceramic wood based on oxime end capping and manufacturing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810375198.XA CN108748517B (en) | 2018-04-24 | 2018-04-24 | Ceramic wood based on oxime end capping and manufacturing method thereof |
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| CN108748517A true CN108748517A (en) | 2018-11-06 |
| CN108748517B CN108748517B (en) | 2021-05-25 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1514763A (en) * | 2001-02-13 | 2004-07-21 | ��˹�ظ��о����� | Resin impregnated substrate, method of mfg. and system therefor |
| CN103586947A (en) * | 2013-11-11 | 2014-02-19 | 中南林业科技大学 | Method of in-situ self-assembly in solid wood to prepare polyurethane reinforced wood |
| CN103781605A (en) * | 2011-05-03 | 2014-05-07 | 科博尼Asa | Polymer impregnated bamboo |
| US9878464B1 (en) * | 2011-06-30 | 2018-01-30 | Apinee, Inc. | Preservation of cellulosic materials, compositions and methods thereof |
-
2018
- 2018-04-24 CN CN201810375198.XA patent/CN108748517B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1514763A (en) * | 2001-02-13 | 2004-07-21 | ��˹�ظ��о����� | Resin impregnated substrate, method of mfg. and system therefor |
| CN103781605A (en) * | 2011-05-03 | 2014-05-07 | 科博尼Asa | Polymer impregnated bamboo |
| US9878464B1 (en) * | 2011-06-30 | 2018-01-30 | Apinee, Inc. | Preservation of cellulosic materials, compositions and methods thereof |
| CN103586947A (en) * | 2013-11-11 | 2014-02-19 | 中南林业科技大学 | Method of in-situ self-assembly in solid wood to prepare polyurethane reinforced wood |
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| CN108748517B (en) | 2021-05-25 |
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