CN107880435B - PVC sheet pile for foundation resistance support and preparation method thereof - Google Patents
PVC sheet pile for foundation resistance support and preparation method thereof Download PDFInfo
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- 239000012467 final product Substances 0.000 claims description 10
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- -1 polyethylene Polymers 0.000 claims description 10
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- 239000008117 stearic acid Substances 0.000 claims description 10
- 230000001050 lubricating effect Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 26
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 20
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 10
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- 239000012965 benzophenone Substances 0.000 description 2
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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
- C08L27/00—Compositions 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; Compositions of derivatives of such polymers
- C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—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
- 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
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明提供了土木工程技术领域内的一种基抗支护用PVC板桩及其制备方法，本发明的PVC板桩由以下质量配比的原料制成：PVC100份、碳酸钙20‑40份、润滑剂1‑2份、增韧剂4‑10份、Ca‑Zn复合稳定剂4‑8份、光稳定剂0‑2份；本发明提升板桩的刚度，提高耐紫外老化性能，成本低下。
The invention provides a PVC sheet pile for foundation resistance support in the technical field of civil engineering and a preparation method thereof. The PVC sheet pile of the present invention is made of the following raw materials in the following mass ratios: 100 parts of PVC and 20-40 parts of calcium carbonate , 1-2 parts of lubricant, 4-10 parts of toughening agent, 4-8 parts of Ca-Zn composite stabilizer, and 0-2 parts of light stabilizer; the present invention improves the rigidity of sheet piles, improves ultraviolet aging resistance, and costs low.
Description
Technical Field
The invention belongs to the technical field of civil engineering, and particularly relates to a PVC sheet pile for foundation resistance support and a preparation method thereof.
Background
China is a country with a great natural disaster, and the sheet piles are applied to the aspects of diking and dam protection, wind and sand resistance, debris flow resistance, flood prevention, landslide prevention, avalanche prevention and the like, so that the loss of human beings caused by disasters can be effectively reduced.
The traditional sheet pile can be divided into a wooden sheet pile, a steel sheet pile, a reinforced concrete sheet pile and the like according to materials, the materials have certain defects, the wooden sheet pile is low in strength and easy to degrade under the attack of microorganisms, the steel sheet pile and the reinforced concrete sheet pile are high in manufacturing cost, and the manpower and mechanical force cost is high and the corrosion is easy.
In the prior art, a sheet pile made of PVC (polyvinyl chloride) serving as a main raw material has the problems of high cost and low rigidity.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to overcome the defects in the prior art, and provides the PVC sheet pile for the foundation resistance support and the preparation method thereof, so that the technical problems of high cost and low rigidity are solved, and the sheet pile prepared by the invention has high rigidity and low cost.
The purpose of the invention is realized as follows: a PVC sheet pile for foundation resistance support is prepared from the following raw materials in parts by mass:
in order to improve the friction between the PVC resins and the extruder, the lubricant is a compound of internal lubricating stearic acid and external lubricating polyethylene wax; the lubricant prevents the PVC from being locally decomposed due to overheating in the process of extruding the PVC resin by the extruder.
In order to further improve the shock resistance of the prepared sheet pile, the toughening agent is a MBS and CPE compound; the addition of the toughening agent improves the toughness of the sheet pile and improves the impact resistance of the sheet pile.
In order to further improve the ultraviolet aging resistance of the sheet pile, the light stabilizer is etoricine.
The preparation method of the PVC sheet pile for foundation resistance support comprises the following steps:
(1) mixing the raw materials, heating to 120-;
(2) single screw extrusion: the material in the storage bin is extruded by a single screw, shaped in vacuum, shaped in a water cooling way and cut to obtain a final product, wherein the single screw extrusion molding control condition is that,
the temperature of the 1 area is 195 +/-5 ℃, the temperature of the 2 area is 190 +/-5 ℃, the temperature of the 3 area is 190 +/-5 ℃, the temperature of the 4 area is 190 +/-5 ℃, the temperature of the 5 area is 185 +/-5 ℃, the temperature of the connecting section is 165 +/-5 ℃, the temperature of the neck mold is 180 plus and minus 200 ℃, the feeding speed is 860 +/-20 r/min, the extrusion speed is 500 +/-10 r/min, the traction speed is 175 +/-5 r/min, the vacuum degree of the vacuum shaping section is 0.5-0.7Mpa, and the temperature of the cooling water is 15-20 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the PVC sheet pile for foundation resistance support mainly takes PVC as a main material, the impact toughness of the PVC sheet pile is improved by adding the toughening agent, and the ultraviolet aging resistance of the PVC sheet pile is improved by adding the light stabilizer, so that the PVC sheet pile has a reinforcing effect on the mechanical strength of the PVC sheet pile; the sheet pile prepared by the method has higher rigidity, is non-toxic and environment-friendly, has good ultraviolet light resistance, can be used outdoors for a long time, and is added with more calcium carbonate, so that the cost is reduced; the method can be applied to support work with low strength, low stress and high rigidity requirements, such as the fields of farmland hydraulic engineering, municipal engineering and the like.
Drawings
FIG. 1 is a graph showing the change in tensile strength before and after aging of PVC prepared with different amounts of etoricine added.
FIG. 2 is a graph showing the change in the PVC elastic modulus before and after aging under different amounts of etoricine added.
FIG. 3 is a graph showing the change of the elongation at break of PVC before and after aging under different amounts of etoricine added.
Detailed Description
The present invention is illustrated below by way of specific examples, but is not limited to the specific examples given below.
Example 1
The raw material formula for preparing the PVC sheet pile is as follows: 100 parts of PVC, 20 parts of calcium carbonate, 0.5 part of stearic acid, 0.5 part of polyethylene wax, 2 parts of CPE, 2 parts of MBS and 4 parts of Ca-Zn composite stabilizer.
The method for preparing the PVC sheet pile comprises the following steps:
(1) mixing a PVC substrate and corresponding auxiliaries in a high-speed stirrer, heating to 120 ℃, discharging into a mixer with jacket water cooling, continuously mixing until the temperature is reduced to 40 ℃, and discharging into a storage bin;
(2) single screw extrusion: extruding the materials in the storage bin by a single screw, carrying out vacuum shaping, carrying out water-cooling shaping and cutting to obtain a final product, wherein the extrusion shaping control conditions are as follows:
the temperature of the 1 area is 190 ℃, the temperature of the 2 area is 185 ℃, the temperature of the 3 area is 185 ℃, the temperature of the 4 area is 185 ℃, the temperature of the 5 area is 180 ℃, the temperature of the connecting section is 160 ℃, the temperature of the neck mold is 180 ℃, the feeding speed is 840r/min, the extrusion speed is 490r/min, the traction speed is 170r/min, the vacuum degree of the vacuum shaping section is 0.5Mpa, and the temperature of the cooling water is 15 ℃.
Example 2
The raw material formula for preparing the PVC sheet pile is as follows: 100 parts of PVC, 40 parts of calcium carbonate, 0.5 part of stearic acid, 0.5 part of polyethylene wax, 6 parts of CPE, 4 parts of MBS, 8 parts of Ca-Zn composite stabilizer and 2 parts of etoricine.
The method for preparing the PVC sheet pile comprises the following steps:
(1) mixing a PVC substrate and corresponding auxiliaries in a high-speed stirrer, heating to 120 ℃, discharging into a mixer with jacket water cooling, continuously mixing until the temperature is reduced to 40 ℃, and discharging into a storage bin;
(2) single screw extrusion: extruding the materials in the storage bin by a single screw, carrying out vacuum shaping, carrying out water-cooling shaping and cutting to obtain a final product, wherein the extrusion shaping control conditions are as follows:
the temperature of the 1 area is 200 ℃, the temperature of the 2 area is 195 ℃, the temperature of the 3 area is 195 ℃, the temperature of the 4 area is 195 ℃, the temperature of the 5 area is 190 ℃, the temperature of the connecting section is 170 ℃, the temperature of the neck mold is 200 ℃, the feeding speed is 880r/min, the extrusion speed is 510r/min, the traction speed is 180r/min, the vacuum degree of the vacuum shaping section is 0.7Mpa, and the temperature of the cooling water is 20 ℃.
Example 3
The raw material formula for preparing the PVC sheet pile is as follows: 100 parts of PVC, 35 parts of calcium carbonate, 1.5 parts of stearic acid, 0.5 part of polyethylene wax, 6 parts of CPE, 4 parts of MBS, 6 parts of Ca-Zn composite stabilizer and 1.5 parts of etoricine.
The method for preparing the PVC sheet pile comprises the following steps:
(1) mixing a PVC substrate and corresponding auxiliaries in a high-speed stirrer, heating to 130 ℃, discharging to a mixer with jacket water cooling, continuously mixing until the temperature is reduced to 45 ℃, and discharging to a storage bin;
(2) single screw extrusion: extruding the materials in the storage bin by a single screw, carrying out vacuum shaping, carrying out water-cooling shaping and cutting to obtain a final product, wherein the extrusion shaping control conditions are as follows:
the temperature of the 1 area is 195 ℃, the temperature of the 2 area is 190 ℃, the temperature of the 3 area is 190 ℃, the temperature of the 4 area is 190 ℃, the temperature of the 5 area is 185 ℃, the temperature of the connecting section is 165 ℃, the temperature of the neck mold is 190 ℃, the feeding speed is 860r/min, the extrusion speed is 500r/min, the traction speed is 175r/min, the vacuum degree of the vacuum shaping section is 0.6Mpa, and the temperature of the cooling water is 18 ℃.
Example 4
The raw material formula for preparing the PVC sheet pile is as follows: 100 parts of PVC, 30 parts of calcium carbonate, 1.2 parts of stearic acid, 0.5 part of polyethylene wax, 4 parts of CPE, 2 parts of MBS, 6 parts of Ca-Zn composite stabilizer and 1 part of etoricine.
The method for preparing the PVC sheet pile comprises the following steps:
(1) mixing a PVC substrate and corresponding auxiliaries in a high-speed stirrer, heating to 130 ℃, discharging to a mixer with jacket water cooling, continuously mixing until the temperature is reduced to 45 ℃, and discharging to a storage bin;
(2) single screw extrusion: extruding the materials in the storage bin by a single screw, carrying out vacuum shaping, carrying out water-cooling shaping and cutting to obtain a final product, wherein the extrusion shaping control conditions are as follows:
the temperature of the 1 area is 190 ℃, the temperature of the 2 area is 188 ℃, the temperature of the 3 area is 188 ℃, the temperature of the 4 area is 188 ℃, the temperature of the 5 area is 183 ℃, the temperature of the connecting section is 165 ℃, the temperature of the neck mold is 185 ℃, the feeding speed is 870r/min, the extrusion speed is 510r/min, the traction speed is 177r/min, the vacuum degree of the vacuum shaping section is 0.6Mpa, and the cooling water temperature is 18 ℃.
Example 5
The raw material formula for preparing the PVC sheet pile is as follows: 100 parts of PVC, 20 parts of calcium carbonate, 1.5 parts of stearic acid, 0.5 part of polyethylene wax, 2 parts of CPE, 2 parts of MBS, 4 parts of Ca-Zn composite stabilizer and 1.5 parts of etoricine.
The method for preparing the PVC sheet pile comprises the following steps:
(1) mixing a PVC substrate and corresponding auxiliaries in a high-speed stirrer, heating to 140 ℃, discharging to a mixer with jacket water cooling, continuously mixing until the temperature is reduced to 45 ℃, and discharging to a storage bin;
(2) single screw extrusion: extruding the materials in the storage bin by a single screw, carrying out vacuum shaping, carrying out water-cooling shaping and cutting to obtain a final product, wherein the extrusion shaping control conditions are as follows:
the temperature of the 1 area is 190 ℃, the temperature of the 2 area is 192 ℃, the temperature of the 3 area is 191 ℃, the temperature of the 4 area is 190 ℃, the temperature of the 5 area is 185 ℃, the temperature of the connecting section is 165 ℃, the temperature of the neck mold is 190 ℃, the feeding speed is 860r/min, the extrusion speed is 500r/min, the traction speed is 175r/min, the vacuum degree of the vacuum shaping section is 0.6Mpa, and the temperature of the cooling water is 17 ℃.
Example 6
The raw material formula for preparing the PVC sheet pile is as follows: 100 parts of PVC, 25 parts of calcium carbonate, 1 part of stearic acid, 0.5 part of polyethylene wax, 6 parts of CPE, 2 parts of MBS, 6 parts of Ca-Zn composite stabilizer and 1.5 parts of etoricine.
The method for preparing the PVC sheet pile comprises the following steps:
(1) mixing a PVC substrate and corresponding auxiliaries in a high-speed stirrer, heating to 125 ℃, discharging to a mixer with jacket water cooling, continuously mixing until the temperature is reduced to 45 ℃, and discharging to a storage bin;
(2) single screw extrusion: extruding the materials in the storage bin by a single screw, carrying out vacuum shaping, carrying out water-cooling shaping and cutting to obtain a final product, wherein the extrusion shaping control conditions are as follows:
the temperature of the 1 area is 197 ℃, the temperature of the 2 area is 193 ℃, the temperature of the 3 area is 193 ℃, the temperature of the 4 area is 192 ℃, the temperature of the 5 area is 186 ℃, the temperature of the connecting section is 168 ℃, the temperature of the neck ring mold is 198 ℃, the feeding speed is 865r/min, the extrusion speed is 510r/min, the traction speed is 177r/min, the vacuum degree of the vacuum shaping section is 0.6Mpa, and the temperature of the cooling water is 19 ℃.
Example 7
The raw material formula for preparing the PVC sheet pile is as follows: 100 parts of PVC, 35 parts of calcium carbonate, 1.5 parts of stearic acid, 0.5 part of polyethylene wax, 5 parts of CPE, 3 parts of MBS, 8 parts of Ca-Zn composite stabilizer and 1.2 parts of etoricine.
The method for preparing the PVC sheet pile comprises the following steps:
(1) mixing a PVC substrate and corresponding auxiliaries in a high-speed stirrer, heating to 130 ℃, discharging into a mixer with jacket water cooling, continuously mixing until the temperature is reduced to 50 ℃, and discharging into a storage bin;
(2) single screw extrusion: extruding the materials in the storage bin by a single screw, carrying out vacuum shaping, carrying out water-cooling shaping and cutting to obtain a final product, wherein the extrusion shaping control conditions are as follows:
the temperature of the 1 zone is 190 ℃, the temperature of the 2 zone is 187 ℃, the temperature of the 3 zone is 188 ℃, the temperature of the 4 zone is 189 ℃, the temperature of the 5 zone is 187 ℃, the temperature of the connecting section is 167 ℃, the temperature of the neck mold is 192 ℃, the feeding speed is 860r/min, the extrusion speed is 500r/min, the traction speed is 175r/min, the vacuum degree of the vacuum shaping section is 0.5Mpa, and the temperature of the cooling water is 20 ℃.
Example 8
The raw material formula for preparing the PVC sheet pile is as follows: 100 parts of PVC, 40 parts of calcium carbonate, 1.6 parts of stearic acid, 0.4 part of polyethylene wax, 6 parts of CPE, 2 parts of MBS, 6 parts of Ca-Zn composite stabilizer and 1.5 parts of etoricine.
The method for preparing the PVC sheet pile comprises the following steps:
(1) mixing a PVC substrate and corresponding auxiliaries in a high-speed stirrer, heating to 135 ℃, discharging to a mixer with jacket water cooling, continuously mixing until the temperature is reduced to 50 ℃, and discharging to a storage bin;
(2) single screw extrusion: extruding the materials in the storage bin by a single screw, carrying out vacuum shaping, carrying out water-cooling shaping and cutting to obtain a final product, wherein the extrusion shaping control conditions are as follows:
the temperature of the 1 area is 195 ℃, the temperature of the 2 area is 192 ℃, the temperature of the 3 area is 189 ℃, the temperature of the 4 area is 189 ℃, the temperature of the 5 area is 187 ℃, the temperature of the connecting section is 167 ℃, the temperature of the neck mold is 190 ℃, the feeding speed is 865r/min, the extrusion speed is 505r/min, the traction speed is 175r/min, the vacuum degree of the vacuum shaping section is 0.7Mpa, and the temperature of the cooling water is 17 ℃.
Table 1: mechanical property test results of the products of examples
Table 2: ultraviolet light aging test performance data of products of some examples
Ultraviolet light aging conditions: the ultraviolet radiation intensity is 0.76W/m2@340nm, and the test temperature is 60 ℃.
Comparing example 1 with example 5, it can be found that the anti-ultraviolet agent etoricine not only has good anti-ultraviolet aging effect, but also has reinforcing effect on the mechanical strength of PVC.
In all the products of the above examples, the synthesis method of etoricine is as follows:
installing a thermometer, a water separator and a condenser on a 100mL three-neck flask, adding 6mL (56 mmol) of ethyl cyanoacetate and 5mL of prepared catalyst solution (prepared by using acetic acid and ammonium acetate), stirring for 0.5 hour, then adding 10.9g (60 mmol) of benzophenone and 40mL of n-heptane, slowly heating and stirring to completely dissolve the benzophenone, refluxing and dividing water for 3 hours, then dropwise adding 5mL of catalyst solution by using an automatic injector, after dropwise adding for 2 hours, continuing to reflux and react overnight; and (3) carrying out TLC monitoring reaction (a developing agent V ethyl acetate: V petroleum ether =1: 10), after the reaction is finished, naturally cooling the reaction liquid to room temperature, adding 30mL of ice-water mixture into the reaction system, standing to separate out crystals, carrying out suction filtration to obtain a crude product, then recrystallizing with absolute ethyl alcohol, carrying out suction filtration and drying to obtain the product of the etoricine.
The synthetic route of etoricine is as follows:
the aging performance of PVC added with etoricine is tested as follows:
the anti-aging test was carried out according to the national standard GB/T16422.3-1997. The PVC plastic is filled, irradiation is carried out under an ultraviolet lamp, the tensile property change of the PVC plastic is tested, and the influence of the filling amount on the aging resistance of the PVC is compared before and after filling so as to evaluate the ultraviolet resistance effect of the etoricine.
And (3) carrying out two-roll milling at 130 ℃, cutting after a PVC is held by a roll, carrying out open milling for 3-5 times, carrying out hot pressing on the milled sheet at 200 ℃ under 15MPa for 5min, and carrying out cold pressing under 15MPa for 5min to obtain the PVC sheet.
The prepared PVC plate is irradiated for 24 hours (one turn over for 12 hours) under 365nm ultraviolet rays, and then the change of the mechanical property of the PVC plate is tested.
The raw material composition of the PVC sheet pile in the aging property test is shown in table 3:
TABLE 3 composition of raw materials
Performing a tensile test on the PVC sheet pile by using a tensile testing machine to obtain different effect graphs shown in figures 1-3; as shown in figure 1, the tensile strength before and after aging of PVC prepared under different addition amounts of etoricine is given, and as can be seen from figure 1, the tensile strength gradually increases with the increase of the addition amount of the etoricine, when the addition amount of the etoricine is 2.0 parts, the maximum value is 38.51MPA, which shows that the addition of the etoricine has a certain reinforcing effect on the strength of a PVC material, after ultraviolet aging, the tensile strength is greater than that before aging due to crosslinking generated in the PVC degradation process, and in addition, as the addition amount of the etoricine increases, the variation of the tensile strength before and after PVC ultraviolet light aging is gradually reduced, which shows that after the addition of the etoricine, the PVC degradation and crosslinking process is inhibited, namely after the addition of the etoricine, the aging degradation of PVC is inhibited to a certain extent.
As can be seen from the graph 2, before aging, the elastic model is obviously increased along with the increase of the addition amount of the etoricine, the rigidity is increased, and when the addition amount of the etoricine is 2.0 parts, the maximum value is 1975.58 Mpa; after ultraviolet aging, on one hand, the hardening effect of the etoricine on PVC is weakened due to the structural change of the etoricine under ultraviolet irradiation, so that the elastic modulus of the PVC is reduced; on the other hand, the PVC is partially degraded to generate crosslinking and cause the elastic modulus to rise, and the comprehensive effect result of the two factors shows that the PVC degradation crosslinking dominates when the content of the etoricine is low, and finally the modulus of the aging sample is increased; when the addition amount of the etoricine is high, the PVC softening is dominant due to the consumption of the etoricine, and finally, the elastic modulus after aging is reduced compared with that before aging.
As can be seen from FIG. 3, before and after aging, the elongation at break of PVC is basically stable with the increase of the addition amount of etoricine, which indicates that the addition of the etoricine and the consumption of the etoricine in the aging process do not bring large influence on the interaction of the whole high molecular chain of PVC, the main chain structure of the PVC is not changed, and the etoricine is blended and dispersed in the same; in addition, the generation and the content of the PVC cross-linked structure after aging are increased, so that the elongation at break after aging is obviously reduced compared with that after aging.
The experiment of the Etorilin as the light stabilizer shows that: by adding the etoricine, the ultraviolet light aging resistance of the PVC is effectively improved; etorilin can form a good anti-aging auxiliary agent system aiming at hard PVC through compounding and content optimization.
The present invention is not limited to the above embodiments, and based on the technical solutions disclosed in the present invention, those skilled in the art can make some substitutions and modifications to some technical features without creative efforts based on the disclosed technical solutions, and these substitutions and modifications are all within the protection scope of the present invention.
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| CN102850699A (en) * | 2012-09-28 | 2013-01-02 | 北京奥宇模板有限公司 | Modified polyvinyl chloride (PVC) for producing building template |
| CN103242197A (en) * | 2013-05-24 | 2013-08-14 | 安徽圣诺贝化学科技有限公司 | Preparation method of ultraviolet absorbent intermediate etocrilene (ETO) |
| CN106632871A (en) * | 2017-01-04 | 2017-05-10 | 广东锦绣天地市政工程有限公司 | High-strength anti-breaking plastic steel sheet pile |
| CN106633578A (en) * | 2017-01-03 | 2017-05-10 | 广东护城高新建材股份有限公司 | High-polymer plastic steel composite board pile |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102850699A (en) * | 2012-09-28 | 2013-01-02 | 北京奥宇模板有限公司 | Modified polyvinyl chloride (PVC) for producing building template |
| CN103242197A (en) * | 2013-05-24 | 2013-08-14 | 安徽圣诺贝化学科技有限公司 | Preparation method of ultraviolet absorbent intermediate etocrilene (ETO) |
| CN106633578A (en) * | 2017-01-03 | 2017-05-10 | 广东护城高新建材股份有限公司 | High-polymer plastic steel composite board pile |
| CN106632871A (en) * | 2017-01-04 | 2017-05-10 | 广东锦绣天地市政工程有限公司 | High-strength anti-breaking plastic steel sheet pile |
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