CN111875900A - Wood-plastic composite material prepared from modified ammonium polyphosphate and preparation method thereof - Google Patents
Wood-plastic composite material prepared from modified ammonium polyphosphate and preparation method thereof Download PDFInfo
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- CN111875900A CN111875900A CN202010641334.2A CN202010641334A CN111875900A CN 111875900 A CN111875900 A CN 111875900A CN 202010641334 A CN202010641334 A CN 202010641334A CN 111875900 A CN111875900 A CN 111875900A
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/18—Binary blends of expanding agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2497/00—Characterised by the use of lignin-containing materials
- C08J2497/02—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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- Polymers & Plastics (AREA)
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Abstract
A wood-plastic composite material prepared from modified ammonium polyphosphate and a preparation method thereof comprise the following substances in parts by weight: 35-60 parts of PVC resin powder; 15-30 parts of a filling agent; 20-30 parts of plant fiber powder; 1-5 parts of a foaming agent; 2-6 parts of an environment-friendly stabilizer; 5-10 parts of modified ammonium polyphosphate. Modified ammonium polyphosphate is prepared by alcohol amine, then the modified ammonium polyphosphate is added into a molten base material, the modified ammonium polyphosphate rapidly undergoes melt phase transition to form viscous liquid, and at the moment, due to the similar polarity of a flame retardant and wood fibers and the wetting effect of the liquid on the rough surfaces of the fibers, a large amount of modified ammonium polyphosphate tends to adhere to the surfaces of the fibers, namely, selective aggregation is realized. And then the irreversible exothermic reaction takes place, make liquid modified ammonium polyphosphate regenerate the more tiny modified ammonium polyphosphate solid of particle size, finally most modified ammonium polyphosphate gathering has realized a novel fire-retardant mode, and the addition is few, and fire-retardant efficient.
Description
Technical Field
The invention belongs to the field of flame-retardant wood-plastic composite materials, and particularly relates to a wood-plastic composite material prepared from modified ammonium polyphosphate and a preparation method thereof.
Background
Most of the existing flame retardants suitable for wood-plastic composite materials are general flame retardants, the flame retardants are added into the wood-plastic composite materials for volume flame retardance in a simple blending mode, and the general characteristics are that the flame retardance efficiency is low, the flame retardants are added in large quantities to improve the flame retardance, the physical and mechanical properties of the materials are seriously reduced, the cost is greatly improved, and the green development characteristics of the materials are reduced. According to the characteristic that the surfaces of the wood powder and the wood fiber are rich in hydroxyl, the flame retardant capable of being selectively dispersed on the surfaces of the wood powder or the fiber through chemical bonds or hydrogen bonds in the processing process is developed. In the combustion process, the flame retardant can be rapidly formed into charcoal and is enriched on the surface of wood powder or wood fiber, the combustion and the charcoal formation of the component are promoted, the high-thermal-conductivity combustion-supporting behavior of the component is inhibited, the generation of a combustion-supporting wick effect is inhibited, and the flame retardance of the wood powder and the wood fiber can be effectively realized in an interface charcoal-forming flame-retardant mode. Meanwhile, part of the flame retardant is dispersed in the resin, and the flame retardance of the wood-plastic composite material is realized in a volume flame retardant manner.
Disclosure of Invention
The invention provides a wood-plastic composite material prepared from modified ammonium polyphosphate, which is used for overcoming the defects in the prior art.
The invention is realized by the following technical scheme:
a wood-plastic composite material prepared from modified ammonium polyphosphate comprises the following substances in parts by weight:
the wood-plastic composite material prepared from the modified ammonium polyphosphate, wherein the filler is 800-1000 mesh active calcium carbonate.
The wood-plastic composite material prepared from the modified ammonium polyphosphate, wherein the environment-friendly stabilizer is a calcium-zinc composite environment-friendly stabilizer.
The wood-plastic composite material is prepared from the modified ammonium polyphosphate, and the foaming agent is a mixture of carbonate compounds and azo compounds in any proportion or a mixture of the carbonate compounds and the azo compounds in any proportion.
The preparation method of the modified ammonium polyphosphate for preparing the wood-plastic composite material comprises the following steps:
the method comprises the following steps: mixing a liquid alcohol compound and water according to a volume ratio of 100:1-20, introducing inert gas, adding ammonium polyphosphate and organic amine into a reaction vessel according to a molar ratio of 10:1-10 in an inert gas atmosphere, stirring and heating to 90-110 ℃, reacting for 1-3h, washing with ethanol, and drying to obtain the modified ammonium polyphosphate.
The wood-plastic composite material prepared from the modified ammonium polyphosphate, wherein the liquid alcohol compound is any one of methanol and ethanol.
The organic amine is any one of ethylenediamine, 1, 2-propanediamine, 1, 3-propanediamine, 1, 4-butanediamine, ethanolamine, diethanolamine and isopropanolamine.
A method for preparing a wood-plastic composite material by using modified ammonium polyphosphate comprises the following steps: comprises the following steps:
the method comprises the following steps: accurately weighing PVC resin powder, a filling agent, plant fiber powder, a foaming agent, an environment-friendly stabilizer and modified ammonium polyphosphate;
step two: firstly, drying the plant fiber powder at the temperature of 120-130 ℃ for 30-60min to ensure that the water content of the plant fiber is less than 1%;
step three: feeding the dried plant fiber powder, PVC resin powder, a filling agent, a foaming agent, an environment-friendly stabilizer and modified ammonium polyphosphate into a mixer, heating to 120 ℃ for 100-;
step four: adding the mixed raw materials into an extruder, heating to the temperature of 120-.
The invention has the advantages that:
1. modified ammonium polyphosphate is prepared by alcohol amine, then the modified ammonium polyphosphate is added into a molten base material, the modified ammonium polyphosphate rapidly undergoes melt phase transition to form viscous liquid, and at the moment, due to the similar polarity of a flame retardant and wood fibers and the wetting effect of the liquid on the rough surfaces of the fibers, a large amount of modified ammonium polyphosphate tends to adhere to the surfaces of the fibers, namely, selective aggregation is realized. And then the irreversible exothermic reaction takes place next, make liquid modified ammonium polyphosphate regenerate the more tiny modified ammonium polyphosphate solid of particle size, and finally most modified ammonium polyphosphate has gathered on the fibre surface, and a small amount of modified ammonium polyphosphate granule has dispersed to the resin substrate under violent shearing action, has realized a novel fire-retardant mode, and the addition is few, and fire-retardant efficient.
2. Because the modified ammonium polyphosphate particles are adhered to the surface of the fiber, the polarity of the surface of the fiber is improved, and compared with the traditional formula, the modified ammonium polyphosphate fiber does not need to be added with a coupling agent, a lubricating agent and a processing aid, so that the production cost is greatly reduced.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The method comprises the following steps: mixing a liquid alcohol compound and water according to a volume ratio of 100:20, introducing inert gas, adding ammonium polyphosphate and organic amine into a reaction vessel according to a molar ratio of 10:10 in an inert gas atmosphere, stirring and heating to 90 ℃, reacting for 3 hours, washing with ethanol, and drying to obtain modified ammonium polyphosphate;
step two: accurately weighing 35kg of PVC resin powder, 27kg of filler, 25.5kg of plant fiber powder, 2kg of foaming agent, 4kg of environment-friendly stabilizer and 6kg of modified ammonium polyphosphate;
step three: firstly, drying the plant fiber powder at 120 ℃ for 50min to ensure that the water content of the plant fiber is less than 1%;
step four: feeding the dried plant fiber powder, PVC resin powder, a filling agent, a foaming agent, an environment-friendly stabilizer and modified ammonium polyphosphate into a mixer, heating to 110 ℃, stirring for 10min, cooling to 50 ℃, and putting into a charging barrel;
step five: adding the mixed raw materials into an extruder, heating to 170 ℃ for extrusion, wherein the cylinder temperature of the extruder is 160 ℃, the die temperature is 170 ℃, the rotating speed of a main engine is 25r/min, the feeding rotating speed is 15r/min, and obtaining a product after extrusion through calendaring molding, traction and cutting, which is recorded as example 1.
Example 2
The method comprises the following steps: mixing a liquid alcohol compound and water according to a volume ratio of 100:15, introducing inert gas, adding ammonium polyphosphate and organic amine into a reaction vessel according to a molar ratio of 10:8 in an inert gas atmosphere, stirring and heating to 101 ℃, reacting for 2 hours, washing with ethanol, and drying to obtain modified ammonium polyphosphate;
step two: accurately weighing 40kg of PVC resin powder, 20kg of filler, 29kg of plant fiber powder, 1kg of foaming agent, 2kg of environment-friendly stabilizer and 8kg of modified ammonium polyphosphate;
step three: firstly, drying the plant fiber powder at 125 ℃ for 40min to ensure that the water content of the plant fiber is less than 1 percent;
step four: feeding the dried plant fiber powder, PVC resin powder, a filling agent, a foaming agent, an environment-friendly stabilizer and modified ammonium polyphosphate into a mixer, heating to 108 ℃, stirring for 10min, cooling to 55 ℃, and putting into a charging barrel;
step five: adding the mixed raw materials into an extruder, heating to 170 ℃ for extrusion, wherein the cylinder temperature of the extruder is 165 ℃, the die temperature is 178 ℃, the rotating speed of a main machine is 30r/min, the feeding rotating speed is 25r/min, and after extrusion, performing calendaring molding, traction and cutting to obtain a product, which is recorded as example 2.
Example 3
The method comprises the following steps: mixing a liquid alcohol compound and water according to a volume ratio of 100:8, introducing inert gas, adding ammonium polyphosphate and organic amine into a reaction vessel according to a molar ratio of 10:4 in an inert gas atmosphere, stirring and heating to 110 ℃, reacting for 1.5h, washing with ethanol, and drying to obtain modified ammonium polyphosphate;
step two: accurately weighing PVC resin powder, a filling agent, plant fiber powder, a foaming agent, an environment-friendly stabilizer and modified ammonium polyphosphate;
step three: firstly, drying the plant fiber powder at 127 ℃ for 43min to ensure that the water content of the plant fiber is less than 1 percent;
step four: feeding the dried plant fiber powder, PVC resin powder, a filling agent, a foaming agent, an environment-friendly stabilizer and modified ammonium polyphosphate into a mixer, heating to 109 ℃, stirring for 10min, cooling to 51 ℃, and putting into a charging barrel;
step five: adding the mixed raw materials into an extruder, heating to 175 ℃ for extrusion, wherein the cylinder temperature of the extruder is 176 ℃, the die temperature is 192 ℃, the rotating speed of a main machine is 20r/min, the feeding rotating speed is 20r/min, and after extrusion, performing calendaring molding, traction and cutting to obtain a product, which is recorded as example 3.
Example 4
The method comprises the following steps: mixing a liquid alcohol compound and water according to a volume ratio of 100:15, introducing inert gas, adding ammonium polyphosphate and organic amine into a reaction vessel according to a molar ratio of 10:8 in an inert gas atmosphere, stirring and heating to 105 ℃, reacting for 2 hours, washing with ethanol, and drying to obtain modified ammonium polyphosphate;
step two: accurately weighing PVC resin powder, a filling agent, plant fiber powder, a foaming agent, an environment-friendly stabilizer and modified ammonium polyphosphate;
step three: firstly, drying the plant fiber powder at 125 ℃ for 45min to ensure that the water content of the plant fiber is less than 1 percent;
step four: feeding the dried plant fiber powder, PVC resin powder, a filling agent, a foaming agent, an environment-friendly stabilizer and modified ammonium polyphosphate into a mixer, heating to 112 ℃, stirring for 10min, cooling to 52 ℃, and putting into a charging barrel;
step five: adding the mixed raw materials into an extruder, heating to 180 ℃ for extrusion, wherein the barrel temperature of the extruder is 1180 ℃, the die temperature is 200 ℃, the rotating speed of a main machine is 30r/min, the feeding rotating speed is 25r/min, and after extrusion, performing calendaring molding, traction and cutting to obtain a product, which is recorded as example 4.
The performance of examples 1-4 was tested and the results are shown in Table I, and the qualification criteria for each performance are shown in Table II:
watch 1
| Detecting items | Unit of | Standard requirements |
| Water content ratio | ％ | ≤2 |
| Bending strength | MPa | ≥20 |
| Elasticity in bendingModulus of elasticity | MPa | ≥1800 |
| Water absorption thickness expansion rate | ％ | ≤0.5 |
| Dimensional stability | ％ | ≤1.5 |
| Formaldehyde emission | mg/m3 | ≤0.124 |
| Flame retardant properties | Stage | ≤2 |
Watch two
According to the data, the product prepared by the invention has good physical and mechanical properties while ensuring the fireproof and flame-retardant performance, so that the problem that the physical and mechanical properties are seriously reduced due to excessive addition of the flame retardant at present is solved, and a high-flame-retardant and high-performance double-high product can be provided.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. A wood-plastic composite material prepared from modified ammonium polyphosphate is characterized in that: the composition comprises the following substances in parts by weight:
2. the wood-plastic composite material prepared from modified ammonium polyphosphate according to claim 1, wherein: the filler is 800-1000 mesh active calcium carbonate.
3. The wood-plastic composite material prepared from modified ammonium polyphosphate according to claim 1, wherein: the environment-friendly stabilizer is a calcium-zinc composite environment-friendly stabilizer.
4. The wood-plastic composite material prepared from modified ammonium polyphosphate according to claim 1, wherein: the foaming agent is a mixture of carbonate compounds and azo compounds or a mixture of the carbonate compounds and the azo compounds mixed in any proportion.
5. The wood-plastic composite material prepared from modified ammonium polyphosphate according to claim 1, wherein: the preparation method of the modified ammonium polyphosphate comprises the following steps:
the method comprises the following steps: mixing a liquid alcohol compound and water according to a volume ratio of 100:1-20, introducing inert gas, adding ammonium polyphosphate and organic amine into a reaction vessel according to a molar ratio of 10:1-10 in an inert gas atmosphere, stirring and heating to 90-110 ℃, reacting for 1-3h, washing with ethanol, and drying to obtain the modified ammonium polyphosphate.
6. The wood-plastic composite material prepared from modified ammonium polyphosphate according to claim 1, wherein: the liquid alcohol compound is any one of methanol and ethanol.
7. The wood-plastic composite material prepared from modified ammonium polyphosphate according to claim 1, wherein: the organic amine is any one of ethylenediamine, 1, 2-propanediamine, 1, 3-propanediamine, 1, 4-butanediamine, ethanolamine, diethanolamine and isopropanolamine.
8. A method for preparing a wood-plastic composite material by using modified ammonium polyphosphate comprises the following steps: the method is characterized in that: comprises the following steps:
the method comprises the following steps: accurately weighing PVC resin powder, a filling agent, plant fiber powder, a foaming agent, an environment-friendly stabilizer and modified ammonium polyphosphate;
step two: firstly, drying the plant fiber powder at the temperature of 120-130 ℃ for 30-60 min;
step three: feeding the dried plant fiber powder, PVC resin powder, a filling agent, a foaming agent, an environment-friendly stabilizer and modified ammonium polyphosphate into a mixer, heating to 120 ℃ for 100-;
step four: adding the mixed raw materials into an extruder, heating to the temperature of 120-.
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| CN202010641334.2A CN111875900A (en) | 2020-07-06 | 2020-07-06 | Wood-plastic composite material prepared from modified ammonium polyphosphate and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113637269A (en) * | 2021-07-28 | 2021-11-12 | 山东霞光集团有限公司 | High-performance wood-plastic composite material prepared from poplar fibers |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4254177A (en) * | 1979-05-07 | 1981-03-03 | W. R. Grace & Co. | Fire-retardant product and method of making |
| CN103396623A (en) * | 2013-07-15 | 2013-11-20 | 安徽济峰节能材料有限公司 | PVC (polyvinyl chloride) micro-foam floor and preparation method thereof |
| CN103756013A (en) * | 2013-12-25 | 2014-04-30 | 四川大学 | Flame-retardant modified ammonium polyphosphate and preparation method and application thereof |
-
2020
- 2020-07-06 CN CN202010641334.2A patent/CN111875900A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4254177A (en) * | 1979-05-07 | 1981-03-03 | W. R. Grace & Co. | Fire-retardant product and method of making |
| CN103396623A (en) * | 2013-07-15 | 2013-11-20 | 安徽济峰节能材料有限公司 | PVC (polyvinyl chloride) micro-foam floor and preparation method thereof |
| CN103756013A (en) * | 2013-12-25 | 2014-04-30 | 四川大学 | Flame-retardant modified ammonium polyphosphate and preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113637269A (en) * | 2021-07-28 | 2021-11-12 | 山东霞光集团有限公司 | High-performance wood-plastic composite material prepared from poplar fibers |
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Effective date of registration: 20211123 Address after: 277600 intersection of Jianshe Road and 104 National Road, Weishan Economic Development Zone, Jining City, Shandong Province Applicant after: SHANDONG ENJOY ADVANCED MATERIAL CO.,LTD. Address before: 277600 Weishan Economic Development Zone, Jining City, Shandong Province Applicant before: SHANDONG XIAGUANG GROUP Co.,Ltd. |
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Application publication date: 20201103 |