CN111732838A - Anti-aging wood-plastic composite material for wood-like furniture and preparation method thereof - Google Patents
Anti-aging wood-plastic composite material for wood-like furniture and preparation method thereof Download PDFInfo
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- CN111732838A CN111732838A CN202010626919.7A CN202010626919A CN111732838A CN 111732838 A CN111732838 A CN 111732838A CN 202010626919 A CN202010626919 A CN 202010626919A CN 111732838 A CN111732838 A CN 111732838A
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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
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses an anti-aging wood-plastic composite material for wood-like furniture, which comprises the following components: polypropylene, straw, an initiator, an adhesive, petroleum asphalt, an acid catalyst, a silane coupling agent, silanized glass fiber and a filler. The aging-resistant wood-plastic composite material disclosed by the invention is used for silanizing and modifying glass fibers, so that the effect of the participation of the glass fibers in a reaction can be obviously improved; petroleum asphalt is added, and the penetration degree and the softening point of the petroleum asphalt are limited, so that the finally obtained composite material is ensured to have very good antique wood grains, and the economic value of the prepared antique furniture is obviously improved; the adopted petroleum asphalt also has the effect of an organic solvent, and the addition of the initiator and the acid catalyst can effectively improve the connection effect among the raw materials, so that the strength of the composite material is effectively enhanced. The aging resistance of the wood-plastic composite material can be effectively improved by adding the large-diameter flaky calcium carbonate doped with a small amount of bonite.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to an anti-aging wood-plastic composite material for wood-like furniture and a preparation method thereof.
Background
The wood-plastic composite material is a new type of material which is briskly developed at home and abroad, and is generally prepared by mixing plastics such as polyethylene, polypropylene, polyvinyl chloride and the like instead of common resin adhesives with more than 50% of waste plant fibers such as wood flour, rice hulls, straws and the like to form a new wood material, and then carrying out plastic processing processes such as extrusion, mould pressing, injection molding and the like to produce plates, wherein the wood-plastic composite material is mainly used in industries such as building materials, furniture, logistics packaging and the like.
At present, the preparation method of the wood-plastic composite material mainly comprises three methods: the first is that the solid wood is added with plastic or phenolic resin, urea-formaldehyde resin and polyester resin type composite material; the second is a composite material prepared by mixing wood fiber and thermoplastic high molecular polymer, namely, wood powder and high molecular polymer are fully mixed under the heating condition and then injected into a mould for hot pressing to prepare a finished product. The third one is prepared through mixing wood powder, plastic, modifier or compatilizer and grafting reaction to certain degree. For example, in chinese patent CN1227297C, wood flour and plastic or waste plastic are used as main raw materials, a small amount of additives and special grafting agents are added to graft-modify the surfaces of the wood flour and plastic, and a continuous extrusion process is adopted to extrude various high-performance composite materials by using molds with various cross-sectional shapes, but such wood flour and plastic composite materials have the defects of monotonous color, non-bright color, non-uniform color, and the like, and thus an ideal color wood-plastic composite material cannot be obtained.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides an anti-aging wood-plastic composite material for wood-like furniture and a preparation method thereof.
The technical scheme of the invention is as follows:
an anti-aging wood-plastic composite material for wood-like furniture comprises the following components: 100-200 parts of polypropylene, 300-500 parts of straw, 1-3 parts of initiator, 2-5 parts of adhesive, 50-80 parts of petroleum asphalt, 3-6 parts of acid catalyst, 10-18 parts of silane coupling agent, 20-30 parts of silanized glass fiber and 300 parts of filler.
Preferably, the average particle size of the polypropylene is 20-80 μm, and the standard deviation is 5-12 μm.
Preferably, the initiator is a peroxide initiator, preferably benzoyl peroxide.
Preferably, the binder is a phenolic resin.
Preferably, the petroleum asphalt has a penetration degree of 25-55(1/10mm, 25 ℃) and a softening point of 55-65 ℃.
Preferably, the acid catalyst is an inorganic acid catalyst, and more preferably dilute sulfuric acid or dilute hydrochloric acid.
Preferably, the silane coupling agent is KH550 or KH 570.
Preferably, the preparation method of the silanized glass fiber comprises the following steps: dropwise adding 10-40 parts by weight of hydrogen peroxide into 1 part by weight of raw material glass fiber, uniformly stirring, heating to 105 ℃, refluxing for 3-6 hours, filtering and drying to obtain hydroxylated glass fiber; adding 20 weight parts of acetone and 5-20 weight parts of gamma-aminopropyltriethoxysilane into the hydroxylated glass fiber, heating to 80 ℃, reacting for 4-10 hours, filtering and drying to obtain the silanized glass fiber.
Preferably, the filler is light calcium carbonate doped with a small amount of bonite; the light calcium carbonate is large-diameter flaky calcium carbonate.
More preferably, the large-diameter flaky calcium carbonate has a diameter of 4-10 μm and a ratio of diameter to thickness of (20-50): 1.
A preparation method of an anti-aging wood-plastic composite material for wood-like furniture comprises the following steps:
A. sequentially putting polypropylene, straws, an adhesive, petroleum asphalt, a silane coupling agent, silanized glass fiber and a filler into a high-speed mixer for mixing treatment, and uniformly stirring;
B. heating the mixture obtained in the step A to 185-210 ℃, then slowly adding an initiator and an acid catalyst, stirring for 20-30min after the addition is finished, and putting the mixture into a double-screw extruder for melt blending and extrusion;
C. and D, drawing out the mixture obtained in the step B through a machine head of an extruder, cooling, blow-drying and dicing to obtain the material.
Bonite is a new synthetic dense refractory aggregate based on a mineral phase of calcium hexaluminate (CA 6). CA6 has the following main properties: high refractoriness; low solubility in iron-containing slag; high stability in reducing atmosphere (such as carbon monoxide); the chemical stability in alkaline environment is good; low wettability to molten metal and slag (steel and non-ferrous metals).
The Bonit is widely reported as an aggregate applied to refractory materials so as to improve the corrosion resistance of the refractory materials, and the aging resistance of the wood-plastic composite material can be obviously improved by utilizing the characteristics of high melting point and low expansion coefficient of the Bonit; however, since calcium hexaluminate in bornite is likely to form a lamellar structure or equiaxed crystals, and the lamellar structure is more beneficial to improving the aging resistance and impact resistance of the material, it is necessary to prevent the particles of calcium hexaluminate from agglomerating to form equiaxed crystals. The invention is beneficial to forming the calcium hexaluminate with a flaky structure by combining the calcium hexaluminate with large-diameter flaky calcium carbonate.
The invention has the advantages that: the invention relates to an anti-aging wood-plastic composite material for wood-like furniture, which comprises the following components: 100-200 parts of polypropylene, 300-500 parts of straw, 1-3 parts of initiator, 2-5 parts of adhesive, 50-80 parts of petroleum asphalt, 3-6 parts of acid catalyst, 10-18 parts of silane coupling agent, 20-30 parts of silanized glass fiber and 300 parts of filler. Compared with the traditional wood-plastic composite material, the aging-resistant wood-plastic composite material for the wood-like furniture mainly has the following differences: firstly, the silanization modification is carried out on the glass fiber, so that the effect of the glass fiber participating in the reaction can be obviously improved; secondly, petroleum asphalt is added, and the penetration degree and the softening point of the petroleum asphalt are limited, so that the finally obtained composite material is ensured to have very good antique wood grains, and the economic value of the prepared antique furniture is obviously improved; and thirdly, the petroleum asphalt also has the effect of an organic solvent, and the initiator and the acid catalyst are added, so that the connection effect among the raw materials can be effectively improved, and the strength of the composite material is effectively enhanced. Fourthly, a small amount of large-diameter flaky calcium carbonate doped with bonite is added, calcium hexaluminate in the bonite is distributed on the surface of the large-diameter flaky calcium carbonate in a flaky manner, the dispersing effect is good, and the particle agglomeration of the calcium hexaluminate is effectively prevented, so that the aging resistance of the wood-plastic composite material can be effectively improved.
Detailed Description
Example 1
An anti-aging wood-plastic composite material for wood-like furniture comprises the following components: 180 parts of polypropylene, 350 parts of straw, 1.5 parts of initiator, 3 parts of adhesive, 70 parts of petroleum asphalt, 5 parts of acid catalyst, 12 parts of silane coupling agent, 25 parts of silanized glass fiber and 220 parts of filler.
The average particle size of the polypropylene is 20-80 μm, and the standard deviation is 5-12 μm.
The initiator is benzoyl peroxide.
The adhesive is phenolic resin.
The petroleum asphalt has a penetration degree of 25-55(1/10mm, 25 ℃), and a softening point of 55-65 ℃.
The acid catalyst is dilute sulfuric acid.
The silane coupling agent is KH 550.
The preparation method of the silanized glass fiber comprises the following steps: dropwise adding 20 parts by weight of hydrogen peroxide into 1 part by weight of raw material glass fiber, uniformly stirring, heating to 105 ℃, refluxing for 5 hours, filtering and drying to obtain hydroxylated glass fiber; adding 20 parts by weight of acetone and 12 parts by weight of gamma-aminopropyltriethoxysilane into the hydroxylated glass fiber, heating to 80 ℃, reacting for 6 hours, filtering and drying to obtain the silanized glass fiber.
The filler is light calcium carbonate doped with 1.5% of bornite in mass ratio; the light calcium carbonate is large-diameter flaky calcium carbonate; the diameter of the large-diameter flaky calcium carbonate is 4-10 mu m, and the diameter-thickness ratio is (20-50): 1.
Example 2
An anti-aging wood-plastic composite material for wood-like furniture comprises the following components: 200 parts of polypropylene, 300 parts of straw, 1 part of initiator, 2 parts of adhesive, 80 parts of petroleum asphalt, 3 parts of acidic catalyst, 18 parts of silane coupling agent, 20 parts of silanized glass fiber and 300 parts of filler.
The average particle size of the polypropylene is 20-80 μm, and the standard deviation is 5-12 μm.
The initiator is benzoyl peroxide.
The adhesive is phenolic resin.
The petroleum asphalt has a penetration degree of 25-55(1/10mm, 25 ℃), and a softening point of 55-65 ℃.
The acid catalyst is dilute hydrochloric acid.
The silane coupling agent is KH 570.
The preparation method of the silanized glass fiber comprises the following steps: dropwise adding 40 parts by weight of hydrogen peroxide into 1 part by weight of raw material glass fiber, uniformly stirring, heating to 105 ℃, refluxing for 3 hours, filtering and drying to obtain hydroxylated glass fiber; adding 20 parts by weight of acetone and 20 parts by weight of gamma-aminopropyltriethoxysilane into the hydroxylated glass fiber, heating to 80 ℃, reacting for 4 hours, filtering and drying to obtain the silanized glass fiber.
The filler is light calcium carbonate doped with 1.7% of bornite in mass ratio; the light calcium carbonate is large-diameter flaky calcium carbonate; the diameter of the large-diameter flaky calcium carbonate is 4-10 mu m, and the diameter-thickness ratio is (20-50): 1.
Example 3
An anti-aging wood-plastic composite material for wood-like furniture comprises the following components: 100 parts of polypropylene, 500 parts of straw, 3 parts of initiator, 5 parts of adhesive, 80 parts of petroleum asphalt, 3 parts of acidic catalyst, 18 parts of silane coupling agent, 20 parts of silanized glass fiber and 300 parts of filler.
The average particle size of the polypropylene is 20-80 μm, and the standard deviation is 5-12 μm.
The initiator is benzoyl peroxide.
The adhesive is phenolic resin.
The petroleum asphalt has a penetration degree of 25-55(1/10mm, 25 ℃), and a softening point of 55-65 ℃.
The acid catalyst is dilute sulfuric acid.
The silane coupling agent is KH 570.
The preparation method of the silanized glass fiber comprises the following steps: dropwise adding 10 parts by weight of hydrogen peroxide into 1 part by weight of raw material glass fiber, uniformly stirring, heating to 105 ℃, refluxing for 6 hours, filtering and drying to obtain hydroxylated glass fiber; adding 20 parts by weight of acetone and 5 parts by weight of gamma-aminopropyltriethoxysilane into the hydroxylated glass fiber, heating to 80 ℃, reacting for 10 hours, filtering and drying to obtain the silanized glass fiber.
The filler is light calcium carbonate doped with 1.2% of bornite in mass ratio; the light calcium carbonate is large-diameter flaky calcium carbonate; the diameter of the large-diameter flaky calcium carbonate is 4-10 mu m, and the diameter-thickness ratio is (20-50): 1.
Example 4
An anti-aging wood-plastic composite material for wood-like furniture comprises the following components: 175 parts of polypropylene, 485 parts of straw, 3 parts of initiator, 2 parts of adhesive, 60 parts of petroleum asphalt, 5 parts of acidic catalyst, 12 parts of silane coupling agent, 27 parts of silanized glass fiber and 215 parts of filler.
The average particle size of the polypropylene is 20-80 μm, and the standard deviation is 5-12 μm.
The initiator is benzoyl peroxide.
The adhesive is phenolic resin.
The petroleum asphalt has a penetration degree of 25-55(1/10mm, 25 ℃), and a softening point of 55-65 ℃.
The acid catalyst is dilute hydrochloric acid.
The silane coupling agent is KH 570.
The preparation method of the silanized glass fiber comprises the following steps: dropwise adding 35 parts by weight of hydrogen peroxide into 1 part by weight of raw material glass fiber, uniformly stirring, heating to 105 ℃, refluxing for 3 hours, filtering and drying to obtain hydroxylated glass fiber; adding 20 parts by weight of acetone and 20 parts by weight of gamma-aminopropyltriethoxysilane into the hydroxylated glass fiber, heating to 80 ℃, reacting for 4 hours, filtering and drying to obtain the silanized glass fiber.
The filler is light calcium carbonate doped with 1.6% of bornite in mass ratio; the light calcium carbonate is large-diameter flaky calcium carbonate; the diameter of the large-diameter flaky calcium carbonate is 4-10 mu m, and the diameter-thickness ratio is (20-50): 1.
Example 5
An anti-aging wood-plastic composite material for wood-like furniture comprises the following components: 100 parts of polypropylene, 500 parts of straw, 1.2 parts of initiator, 4.5 parts of adhesive, 65 parts of petroleum asphalt, 3.5 parts of acid catalyst, 18 parts of silane coupling agent, 20 parts of silanized glass fiber and 250 parts of filler.
The average particle size of the polypropylene is 20-80 μm, and the standard deviation is 5-12 μm.
The initiator is benzoyl peroxide.
The adhesive is phenolic resin.
The petroleum asphalt has a penetration degree of 25-55(1/10mm, 25 ℃), and a softening point of 55-65 ℃.
The acid catalyst is dilute sulfuric acid.
The silane coupling agent is KH 570.
The preparation method of the silanized glass fiber comprises the following steps: dropwise adding 18 parts by weight of hydrogen peroxide into 1 part by weight of raw material glass fiber, uniformly stirring, heating to 105 ℃, refluxing for 4.5 hours, filtering and drying to obtain hydroxylated glass fiber; adding 20 parts by weight of acetone and 15 parts by weight of gamma-aminopropyltriethoxysilane into the hydroxylated glass fiber, heating to 80 ℃, reacting for 10 hours, filtering and drying to obtain the silanized glass fiber.
The filler is light calcium carbonate doped with 1.5% of bornite in mass ratio; the light calcium carbonate is large-diameter flaky calcium carbonate; the diameter of the large-diameter flaky calcium carbonate is 4-10 mu m, and the diameter-thickness ratio is (20-50): 1.
Comparative example 1
The petroleum asphalt in the example 1 is replaced by the petroleum asphalt with the softening point of 75 ℃, and the rest proportion and the preparation method are not changed.
Comparative example 2
The petroleum asphalt in the example 1 is replaced by the petroleum asphalt with the softening point of 45 ℃, and the rest proportion and the preparation method are not changed.
Comparative example 3
The silanized glass fiber in the example 1 is replaced by unmodified conventional glass fiber, and the rest proportion and the preparation method are unchanged.
Comparative example 4
The large-diameter platy calcium carbonate in the embodiment 1 is replaced by the conventional light calcium carbonate with the particle size of 5-10 microns, and the rest proportion and the preparation method are unchanged.
The preparation methods of the aging-resistant wood-plastic composite materials for the wood-like furniture of the above examples 1 to 5 and comparative examples 1 to 4 include the following steps:
A. sequentially putting polypropylene, straws, an adhesive, petroleum asphalt, a silane coupling agent, silanized glass fiber and a filler into a high-speed mixer for mixing treatment, and uniformly stirring;
B. heating the mixture obtained in the step A to 195 ℃, then slowly adding an initiator and an acid catalyst, stirring for 25min after the addition is finished, and putting the mixture into a double-screw extruder for melt blending extrusion;
C. and D, drawing out the mixture obtained in the step B through a machine head of an extruder, cooling, blow-drying and dicing to obtain the material.
Test example
Performance tests tensile strength, notched impact strength and flexural strength performance tests were carried out on the wood-plastic composite material prepared above using ASTM (american society for testing and materials) standards:
1. tensile strength: the tensile strength of the material is measured by using the method of ASTM D638;
2. notched impact strength: determining the notch impact strength of the material by using an ASTM D256 method;
3. bending strength: the flexural strength and flexural modulus of the material were determined using the method of ASTM D790.
The aging-resistant wood-plastic composite materials for the wood-like furniture prepared in examples 1 to 5 and comparative examples 1 to 4 were tested (average value of 5 data) to obtain the following test data, and the specific data are shown in table 1.
Remarking: the test data after aging are the test results of the wood-plastic composite material after being aged in hot air at 100 ℃ for 24 hours.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. The anti-aging wood-plastic composite material for the wood-like furniture is characterized by comprising the following components: 100-200 parts of polypropylene, 300-500 parts of straw, 1-3 parts of initiator, 2-5 parts of adhesive, 50-80 parts of petroleum asphalt, 3-6 parts of acid catalyst, 10-18 parts of silane coupling agent, 20-30 parts of silanized glass fiber and 300 parts of filler.
2. The aging-resistant wood-plastic composite material for wood-like furniture according to claim 1, wherein the polypropylene has an average particle diameter of 20 to 80 μm and a standard deviation of 5 to 12 μm.
3. The aging-resistant wood-plastic composite material for wood-like furniture according to claim 1, wherein the initiator is a peroxide initiator; the adhesive is phenolic resin.
4. The aging-resistant wood-plastic composite material for wood-like furniture according to claim 1, wherein the petroleum asphalt has a penetration degree of 25-55(1/10mm, 25 ℃) and a softening point of 55-65 ℃.
5. The aging-resistant wood-plastic composite material for wood-like furniture according to claim 1, wherein the acid catalyst is an inorganic acid catalyst.
6. The aging-resistant wood-plastic composite material for wood-like furniture according to claim 1, wherein the silane coupling agent is KH550 or KH 570.
7. The aging-resistant wood-plastic composite material for wood-like furniture according to claim 1, wherein the preparation method of the silanized glass fiber comprises the following steps: dropwise adding 10-40 parts by weight of hydrogen peroxide into 1 part by weight of raw material glass fiber, uniformly stirring, heating to 105 ℃, refluxing for 3-6 hours, filtering and drying to obtain hydroxylated glass fiber; adding 20 weight parts of acetone and 5-20 weight parts of gamma-aminopropyltriethoxysilane into the hydroxylated glass fiber, heating to 80 ℃, reacting for 4-10 hours, filtering and drying to obtain the silanized glass fiber.
8. The aging-resistant wood-plastic composite material for wood-like furniture according to claim 1, wherein the filler is light calcium carbonate doped with a small amount of bonite; the light calcium carbonate is large-diameter flaky calcium carbonate.
9. The aging-resistant wood-plastic composite material for wood-like furniture according to claim 1, wherein the large-diameter platy calcium carbonate has a diameter of 4 to 10 μm and a diameter-thickness ratio of (20 to 50): 1.
10. The aging-resistant wood-plastic composite material for wood-like furniture according to any one of claims 1 to 9, wherein the preparation method comprises the following steps:
A. sequentially putting polypropylene, straws, an adhesive, petroleum asphalt, a silane coupling agent, silanized glass fiber and a filler into a high-speed mixer for mixing treatment, and uniformly stirring;
B. heating the mixture obtained in the step A to 185-210 ℃, then slowly adding an initiator and an acid catalyst, stirring for 20-30min after the addition is finished, and putting the mixture into a double-screw extruder for melt blending and extrusion;
C. and D, drawing out the mixture obtained in the step B through a machine head of an extruder, cooling, blow-drying and dicing to obtain the material.
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| CN202010626919.7A CN111732838B (en) | 2020-07-01 | 2020-07-01 | Anti-aging wood-plastic composite material for wood-like furniture and preparation method thereof |
| PCT/CN2021/083723 WO2022001244A1 (en) | 2020-07-01 | 2021-03-30 | Aging-resistant wood-plastic composite material for faux wood furniture and preparation method therefor |
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| CN202010626919.7A CN111732838B (en) | 2020-07-01 | 2020-07-01 | Anti-aging wood-plastic composite material for wood-like furniture and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112175274A (en) * | 2020-11-03 | 2021-01-05 | 浙江尚元塑木制品有限公司 | Outdoor plastic-wood floor with good antifouling effect in oil pollution environment |
| WO2022001244A1 (en) * | 2020-07-01 | 2022-01-06 | 杨曦 | Aging-resistant wood-plastic composite material for faux wood furniture and preparation method therefor |
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- 2020-07-01 CN CN202010626919.7A patent/CN111732838B/en active Active
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- 2021-03-30 WO PCT/CN2021/083723 patent/WO2022001244A1/en active Application Filing
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| CN101747639A (en) * | 2008-12-12 | 2010-06-23 | 比亚迪股份有限公司 | Wood plastic composite composition, wood plastic composite and preparation method thereof |
| US20180201813A1 (en) * | 2017-01-19 | 2018-07-19 | Harry Kim | Self-adhesive waterproof sheet with modified synthetic rubber |
| CN108841060A (en) * | 2018-06-25 | 2018-11-20 | 浙江温州轻工研究院 | A kind of calcium sulfate crystal whiskers/styrene-butadiene latex composite foam material and preparation method thereof |
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| WO2022001244A1 (en) * | 2020-07-01 | 2022-01-06 | 杨曦 | Aging-resistant wood-plastic composite material for faux wood furniture and preparation method therefor |
| CN112175274A (en) * | 2020-11-03 | 2021-01-05 | 浙江尚元塑木制品有限公司 | Outdoor plastic-wood floor with good antifouling effect in oil pollution environment |
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| WO2022001244A1 (en) | 2022-01-06 |
| CN111732838B (en) | 2021-08-17 |
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