CN108582355B - Colored ceramic wood and manufacturing method thereof - Google Patents

Colored ceramic wood and manufacturing method thereof Download PDF

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Publication number
CN108582355B
CN108582355B CN201810375455.XA CN201810375455A CN108582355B CN 108582355 B CN108582355 B CN 108582355B CN 201810375455 A CN201810375455 A CN 201810375455A CN 108582355 B CN108582355 B CN 108582355B
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Prior art keywords
wood
solvent
acetic acid
ceramic
initiator
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CN108582355A (en
Inventor
谢煌
黄玉真
王荣克
杨海景
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Zhongjiya (Shandong) New Materials Co.,Ltd.
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GUANGZHOU JINGDIAN POLYMER MATERIALS PRODUCT CO Ltd
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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
    • B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
    • B27K5/02—Staining or dyeing wood; Bleaching wood
    • 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
    • B27K3/086—Impregnating by pressure, e.g. vacuum impregnation using supercritical or high pressure fluids
    • 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
    • B27K5/0085—Thermal treatments, i.e. involving chemical modification of wood at temperatures well over 100°C
    • 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
    • B27K2240/00—Purpose of the treatment
    • B27K2240/20—Removing fungi, molds or insects

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)

Abstract

A colored ceramic wood and a manufacturing method thereof, the manufacturing method comprises the following steps: adding acetic acid; allowing acetic acid to enter the wood; putting wood into a stainless steel closed storage, introducing ethylene and oxygen, and allowing the ethylene and the oxygen to enter the wood under the action of pressure to generate vinyl acetate in the wood; putting wood into a mixed solution of a reactive dye, a solvent with a chain transfer constant less than 5 and an initiator; taking out the wood, and generating a high molecular weight polymer at the normal temperature, wherein the high molecular weight polymer and wood fibers form a net structure to prepare the ceramic wood. By utilizing the technical scheme of the invention, the ceramic wood has good corrosion resistance, water resistance and moth resistance, stable size, long service life and good performance, so that the wood is not easy to deform and mildew, and is durable, and the inner layer and the outer layer of the ceramic wood are consistent, and are not different from the inner layer of the ceramic wood after the outer layer of the ceramic wood is polished. And the wood has color, and simultaneously, the structure of the wood is changed.

Description

Colored ceramic wood and manufacturing method thereof
Technical Field
The invention relates to ceramic wood, in particular to ceramic wood used for furniture, decorative materials, building materials and artworks.
Background
The application of the wood is very wide, such as furniture, decorative materials, building materials, artworks and the like. For wood used for a long time, anticorrosion and waterproof treatment is generally needed, and in the above treatment process, anticorrosion and waterproof materials are usually adopted to treat the wood, but the existing anticorrosion and waterproof materials are only on the surface of the wood and are difficult to enter into the gaps of the wood, so that once the anticorrosion and waterproof materials on the surface of the wood are damaged, the anticorrosion and waterproof properties of the wood are reduced, and the wood is easy to deform, mildew and the like. The existing anticorrosive wood on the market is treated by the preservative, is not waterproof, starts to corrode and mildew once the preservative fails, and is not a real anticorrosive wood.
In addition, the logs have their own colors, and users have requirements on the use of the colors during the use, so that the use of the logs is limited.
Disclosure of Invention
The invention aims to provide a colored ceramic wood and a manufacturing method thereof. And can be made into ceramic wood with different colors according to the requirement, and the added reactive dye can react with the wood.
In order to achieve the purpose, the manufacturing method of the colored ceramic wood comprises the following steps:
(1) preparing a storage, and adding acetic acid into the storage;
(2) putting the wood into a storage with acetic acid, sealing the storage for 10-24 hours at normal temperature, and allowing the acetic acid to enter the wood;
(3) taking out the wood after the step (2) is finished, putting the wood into a stainless steel closed storage, controlling the pressure in the stainless steel closed storage to be 0.5-1MPa, controlling the temperature in the stainless steel closed storage to be 140-180 ℃, then introducing ethylene and oxygen into the stainless steel closed storage, and introducing the ethylene and the oxygen into the wood under the action of the pressure to generate vinyl acetate in the wood;
(4) putting the wood in the step (3) into a mixed solution of a reactive dye, a solvent with a chain transfer constant less than 5 and an initiator, and soaking the wood for 8-10 hours in an environment with the pressure of 2-4MPa and the temperature of 30-50 ℃;
(5) taking out the wood, generating a high molecular weight polymer at normal temperature, forming a net structure by the high molecular weight polymer and wood fibers, reacting molecules of the reactive dye with hydroxyl in the wood and amino in protein fibers, generating covalent bonds between active groups in the reactive material and the fibers during dyeing, generating dye-fibers, and dyeing the wood.
The modified ceramic wood is characterized in that gaps of wood are filled with high molecular weight polymers to form a net structure with wood fibers, and reactive dyes and the fibers generate covalent bonds during dyeing to generate dye-fibers.
Further, the weight percentages of acetic acid, ethylene, oxygen, solvent and initiator are as follows:
20 to 30 percent of acetic acid
16 to 25 percent of ethylene
7 to 12 percent of oxygen
35 to 50 percent of solvent
0.1 to 0.5 percent of initiator.
Further, the solvent is one of chloroform, dichloromethane, methyl acetate and vinyl acetate.
Further, the initiator is benzoyl peroxide.
The material is a naturally-growing organic material and consists of high molecular substances and low molecular substances. The main substances forming the wood cell wall are three high polymers, wherein the three high polymers are cellulose, hemicellulose and lignin respectively and account for 97-99% of the weight of the wood.
Cellulose is a linear natural high molecular compound formed by connecting a plurality of D-grape pond groups through l, 4-beta-glucoside bonds, plays a role of a skeleton in the wood cell wall, generally accounts for more than 40% of the wood components, and accounts for about 50% of the wood cells. Its chemical properties and supramolecular structure have important influence on wood properties and processability.
The hemicellulose is a substance tightly connected with cellulose in the wood cell wall, plays a role of bonding, mainly consists of five neutral monosaccharides such as hexose, mannose, galactose, pentose and an arable leveler, and has a molecular chain far shorter than that of the cellulose and a certain branching degree.
Lignin is an aromatic compound consisting of phenylpropane units, the last high polymer deposited in the cell wall during cell formation, which interpenetrates cellulose and serves to strengthen the cell wall.
Based on the structure, the wood has a plurality of gaps.
The invention has the beneficial effects that:
(1) according to the manufacturing method, in the wood, the high molecular weight polymer and the wood fiber form a net structure, the high molecular weight polymer fills gaps in the wood, the original internal structure of the wood is changed, the wood is good in waterproof, mildew-proof, anticorrosion and mothproof performances, and the ceramic wood is good in size stability because no gap exists in the ceramic wood. Because the high molecular weight polymer is filled in the wood instead of the surface layer, the inner layer and the outer layer of the ceramic wood are consistent, and the ceramic wood is not different from the inner layer of the ceramic wood after the outer layer of the ceramic wood is polished. For the above reasons, the ceramic wood of the present invention is durable and has a long life.
(2) In the ceramic wood manufacturing process, firstly, acetic acid enters the wood, and a vinyl acetate monomer is formed in the wood, the reason for adopting the mode is that the acetic acid is easier to enter the wood than the vinyl acetate, the technical problem of incomplete filling of wood gaps is avoided, in addition, because the vinyl acetate easily generates polymerization reaction, and before the vinyl acetate does not enter the wood, the vinyl acetate needs to be controlled to generate polymerization reaction, therefore, the acetic acid with stable performance is adopted as one of the raw materials, and the vinyl acetate is formed in the wood.
(3) In order to reduce the chance of vinyl acetate polymerization during the formation of vinyl acetate in the wood, the reservoir was closed with stainless steel.
(4) After vinyl acetate is formed in the wood, a solvent and initiator are added in order to form a high molecular weight polymer. In addition to three fractions of chain initiation, chain extension and chain termination, vinyl acetate polymerization reactions in which chain transfer should be minimized, such as to form high molecular weight polymers, are also known to occur due to RCH2CHOCOCH3The growing active chain is easily transferred to the solvent, to the monomer and to the polymer macromolecule already formed. For transfer to the solvent, see the following equation:
Mn+HA→MnH+A
if A is.Inactive, non-reactive with the monomer, or having a very low reaction rate if A.Is active and is susceptible to the reaction of monomers to re-initiate polymerization, and therefore, it is important to control the chain transfer reaction solvent, including the amount and type of solvent used, and the amount of solvent used is [ AB]/[M]Ratio determination according to the formula
Figure 767250DEST_PATH_IMAGE003
It can be seen that the degree of polymerization is determined primarily by the Cs of the solvent, but also by the amount of solvent used, whereas in the present invention it is desired to obtain a material with a higher degree of polymerization, and therefore the initiator and amount used in the present invention. DP of the above formula is the degree of polymerization, DP0The average polymerization degree of the polymer in the absence of a solvent, [ AB ]]As solvent concentration, [ M ]]Cs is the initiator chain transfer constant, is the monomer concentration.
(5) The decomposition temperature of the benzoyl peroxide is 105 ℃, the polymerization temperature is too high in the polymerization process, the polymerization crystallinity of the vinyl acetate is low, and the hot water resistance of the vinyl acetate is poor, so that the polymerization crystallinity can be improved and the hot water resistance of the vinyl acetate can be improved by adopting a lower polymerization temperature in the invention.
(6) In the invention, by adding the reactive dye, the molecules of the reactive dye react with hydroxyl in the wood and amino in protein fiber, and the reactive group in the reactive material and the fiber generate covalent bonds during dyeing to generate dye-fiber, so that the reactive dye can not only add color to the wood, but also increase the interior and exterior of the colored wood, and simultaneously, the reactive dye can act with the wood, thereby further improving the performance of the wood.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
The manufacturing method of the colored ceramic wood comprises the following steps:
(1) a reservoir is prepared and acetic acid is added to the reservoir.
(2) Putting the wood into a storage container with acetic acid, sealing the storage container at normal temperature for 10-24 hours, and allowing the acetic acid to enter the wood.
(3) And (3) taking out the wood after the step (2) is finished, putting the wood into a stainless steel closed storage, controlling the pressure in the stainless steel closed storage to be 0.5-1MPa, controlling the temperature in the stainless steel closed storage to be 140-180 ℃, then introducing ethylene and oxygen into the stainless steel closed storage, and introducing the ethylene and the oxygen into the wood under the action of the pressure to generate vinyl acetate in the wood.
(4) And (4) putting the wood in the step (3) into a mixed solution of a reactive dye, a solvent with a chain transfer constant less than 5 and an initiator, and soaking the wood for 8-10 hours in an environment with the pressure of 2-4MPa and the temperature of 30-50 ℃.
(5) Taking out the wood, generating a high molecular weight polymer at normal temperature, forming a net structure by the high molecular weight polymer and wood fibers, reacting molecules of the reactive dye with hydroxyl in the wood and amino in protein fibers, generating covalent bonds between active groups in the reactive material and the fibers during dyeing, generating dye-fibers, and dyeing the wood.
The solvent is one of chloroform, dichloromethane, methyl acetate and vinyl acetate. The initiator is benzoyl peroxide.
The percentage usage of the raw materials in each example is as follows:
raw materials EXAMPLE 1 Example 2 Example 3
Acetic acid 30% 20% 28%
Ethylene 25% 17.5% 16%
Oxygen gas 9.9% 12% 7%
Solvent(s) 35% 50% 48.7%
Initiator 0.1% 0.5% 0.3%
In the above embodiment, the reactive colorant is 10-20% by weight of the above raw materials.
Wood is a naturally growing organic material, consisting of high molecular substances and low molecular substances. The main substances forming the wood cell wall are three high polymers, wherein the three high polymers are cellulose, hemicellulose and lignin respectively and account for 97-99% of the weight of the wood.
Cellulose is a linear natural high molecular compound formed by connecting a plurality of D-grape pond groups through l, 4-beta-glucoside bonds, plays a role of a skeleton in the wood cell wall, generally accounts for more than 40% of the wood components, and accounts for about 50% of the wood cells. Its chemical properties and supramolecular structure have important influence on wood properties and processability.
The hemicellulose is a substance tightly connected with cellulose in the wood cell wall, plays a role of bonding, mainly consists of five neutral monosaccharides such as hexose, mannose, galactose, pentose and an arable leveler, and has a molecular chain far shorter than that of the cellulose and a certain branching degree.
Lignin is an aromatic compound consisting of phenylpropane units, the last high polymer deposited in the cell wall during cell formation, which interpenetrates cellulose and serves to strengthen the cell wall.
Based on the structure, the wood has a plurality of gaps.
In the invention:
(1) according to the manufacturing method, in the wood, the high molecular weight polymer and the wood fiber form a net structure, the high molecular weight polymer fills gaps in the wood, the original internal structure of the wood is changed, the wood is good in waterproof, mildew-proof, anticorrosion and mothproof performances, and the ceramic wood is good in size stability because no gap exists in the ceramic wood. Because the high molecular weight polymer is filled in the wood instead of the surface layer, the inner layer and the outer layer of the ceramic wood are consistent, and the ceramic wood is not different from the inner layer of the ceramic wood after the outer layer of the ceramic wood is polished. For the above reasons, the ceramic wood of the present invention is durable and has a long life.
(2) In the ceramic wood manufacturing process, firstly, acetic acid enters the wood, and a vinyl acetate monomer is formed in the wood, the reason for adopting the mode is that the acetic acid is easier to enter the wood than the vinyl acetate, the technical problem of incomplete filling of wood gaps is avoided, in addition, because the vinyl acetate easily generates polymerization reaction, and before the vinyl acetate does not enter the wood, the vinyl acetate needs to be controlled to generate polymerization reaction, therefore, the acetic acid with stable performance is adopted as one of the raw materials, and the vinyl acetate is formed in the wood. The reaction formula is mainly
(1) Principal reaction formula for vinyl acetate formation
C2H4+1/2O2+ CH3COOH = CH3COOCHCH2+ H2O + 35Kcal/molVAC
(2) Formation of CO2Is of the main reaction formula
C2H4+ 3O2= 2CO2+ 2H2O + 320Kcal/molC2H4
（3） CH3COOH combustion reaction
CH3COOH + 2O2= 2CO2+ 2H2O
(4) Reaction to acrolein
2C2H4+ 2CH3COOH + 3O2= 2CH2CHCHO + 4H2O + 2CO2
(5) Reaction for generating methyl acetate
2C2H4+ 2CH3COOH + 3O2= 2CH3COOCH3+ 2H2O + 2CO2
(6) Reaction to form ethyl acetate
C2H4+ CH3COOH = CH3COOC2H3
(7) Reaction to form acetaldehyde
C2H4+ 1/2O2= CH3CHO
(8) Reaction to form ethylene diacetate
2C2H4+ 4CH3COOH + O2= 2（CH3COO）2C2H4+ 2H2O
(3) In order to reduce the chance of vinyl acetate polymerization during the formation of vinyl acetate in the wood, the reservoir was closed with stainless steel.
(4) After vinyl acetate is formed in the wood, a solvent and initiator are added in order to form a high molecular weight polymer. In addition to three fractions of chain initiation, chain extension and chain termination, vinyl acetate polymerization reactions in which chain transfer should be minimized, such as to form high molecular weight polymers, are also known to occur due to RCH2CHOCOCH3The growing active chain is easily transferred to the solvent, to the monomer and to the polymer macromolecule already formed. For transfer to the solvent, see the following equation:
Mn+HA→MnH+A
if A is.Inactive, non-reactive with the monomer, or having a very low reaction rate if A.Is very active and has the advantages of high activity,the monomers are easily reacted to re-initiate the polymerization reaction, and therefore, it is very important to control the chain transfer reaction solvent, the choice of solvent includes the amount and type of the solvent, and the amount of the solvent is [ AB ]]/[M]Ratio determination according to the formula
Figure 993329DEST_PATH_IMAGE003
It can be seen that the degree of polymerization is determined primarily by the Cs of the solvent, but also by the amount of solvent used, whereas in the present invention it is desired to obtain a material with a higher degree of polymerization, and therefore the initiator and amount used in the present invention. DP of the above formula is the degree of polymerization, DP0The average polymerization degree of the polymer in the absence of a solvent, [ AB ]]As solvent concentration, [ M ]]Cs is the initiator chain transfer constant, is the monomer concentration.
(5) The decomposition temperature of the benzoyl peroxide is 105 ℃, the polymerization temperature is too high in the polymerization process, the polymerization crystallinity of the vinyl acetate is low, and the hot water resistance of the vinyl acetate is poor, so that the polymerization crystallinity can be improved and the hot water resistance of the vinyl acetate can be improved by adopting a lower polymerization temperature in the invention.
(6) In the invention, by adding the reactive dye, the molecule of the reactive dye reacts with the hydroxyl in the wood and the amino in the protein fiber, and the reactive group in the active material and the fiber generate covalent bonds during dyeing to generate dye-fiber, so that the reactive dye can not only add color to the wood, but also increase the interior and exterior of the colored wood, and simultaneously, the reactive dye can act with the wood, thereby further improving the performance of the wood.

Claims (6)

1. The manufacturing method of the colored ceramic wood is characterized by comprising the following steps:
(1) preparing a storage, and adding acetic acid into the storage;
(2) putting the wood into a storage with acetic acid, sealing the storage for 10-24 hours at normal temperature, and allowing the acetic acid to enter the wood;
(3) taking out the wood after the step (2) is finished, putting the wood into a stainless steel closed storage, controlling the pressure in the stainless steel closed storage to be 0.5-1MPa, controlling the temperature in the stainless steel closed storage to be 140-180 ℃, then introducing ethylene and oxygen into the stainless steel closed storage, and introducing the ethylene and the oxygen into the wood under the action of the pressure to generate vinyl acetate in the wood;
(4) putting the wood in the step (3) into a mixed solution of a reactive dye, a solvent with a chain transfer constant less than 5 and an initiator, and soaking the wood for 8-10 hours in an environment with the pressure of 2-4MPa and the temperature of 30-50 ℃;
(5) taking out the wood, generating a high molecular weight polymer at normal temperature, forming a net structure by the high molecular weight polymer and wood fibers, reacting molecules of the reactive dye with hydroxyl in the wood and amino in protein fibers, generating covalent bonds between active groups in the reactive material and the fibers during dyeing, generating dye-fibers, and dyeing the wood;
the weight percentages of the acetic acid, the ethylene, the oxygen, the solvent and the initiator relative to the total weight of the acetic acid, the ethylene, the oxygen, the solvent and the initiator are as follows:
20 to 30 percent of acetic acid
16 to 25 percent of ethylene
7 to 12 percent of oxygen
35 to 50 percent of solvent
0.1 to 0.5 percent of initiator.
2. The method for manufacturing a colored ceramic wood according to claim 1, characterized in that: the solvent is one of chloroform, dichloromethane, methyl acetate and vinyl acetate.
3. The method for manufacturing a colored ceramic wood according to claim 1, characterized in that: the initiator is benzoyl peroxide.
4. A colored ceramic wood manufactured by the method for manufacturing a colored ceramic wood according to claim 1, characterized in that: the gaps of the wood are filled with high molecular weight polymers to form a net structure with wood fibers, and the reactive dye and the fibers generate covalent bonds during dyeing to generate dye-fibers.
5. The colored ceramic wood according to claim 4, wherein: the solvent is one of chloroform, dichloromethane, methyl acetate and vinyl acetate.
6. The colored ceramic wood according to claim 4, wherein: the initiator is benzoyl peroxide.
CN201810375455.XA 2018-04-24 2018-04-24 Colored ceramic wood and manufacturing method thereof Active CN108582355B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2900465B2 (en) * 1990-01-19 1999-06-02 日立化成工業株式会社 Resin composition for woody decorative material, treated woody decorative material and composite board
US20150174785A1 (en) * 2013-12-20 2015-06-25 Armstrong World Industries, Inc. Wood products impregnated with water based compositions
CN105382896A (en) * 2015-11-15 2016-03-09 浙江大学自贡创新中心 Low-water-absorption sleeper with chemical treatment layer
CN106493811B (en) * 2016-11-02 2018-11-09 广州精点高分子材料制品有限公司 A kind of ceramic wooden and its manufacturing method

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Effective date of registration: 20211026

Address after: 274000 No. 1, North medical device Industrial Park, 500m west of the intersection of Yanhe Road and Lanzhou Road, high tech Zone, Heze City, Shandong Province

Patentee after: Zhongjiya (Shandong) New Materials Co.,Ltd.

Address before: No.5-2 Furong Xinhua Road, Shiling Town, Guangzhou, Guangdong 510850

Patentee before: GUANGZHOU GENIUS FOCUS HIGH MOLECULE PRODUCTS Co.,Ltd.