CN108264730B - Preparation method of solid buoyancy section bar - Google Patents
Preparation method of solid buoyancy section bar Download PDFInfo
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- CN108264730B CN108264730B CN201710003606.4A CN201710003606A CN108264730B CN 108264730 B CN108264730 B CN 108264730B CN 201710003606 A CN201710003606 A CN 201710003606A CN 108264730 B CN108264730 B CN 108264730B
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92514—Pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92904—Die; Nozzle zone
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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
Abstract
The embodiment of the invention provides a preparation method of a solid buoyancy section bar, which comprises the following steps: (1) mixing a resin system weighed in advance with the hollow glass beads to obtain a mixture; the resin system comprises: a thermosetting resin having a viscosity of not more than 50 pas, a curing agent, a catalyst and an accelerator; the hydrostatic pressure resistance strength of the hollow glass beads is not lower than 30 MPa; (2) extruding and molding the mixture through a vacuum extruder to obtain a profile blank; wherein, the ratio of the sectional area of the shaping section of the extrusion head of the vacuum extruder to the sectional area of the extruder cylinder is between 0.02 and 0.8; the extrusion pressure is between 0.5MPa and 15 MPa; (3) and curing the blank of the profile to obtain the solid buoyancy profile. The preparation method of the solid buoyancy section provided by the embodiment of the invention can omit the steps of demoulding and the like, does not need the work of disassembling, assembling, cleaning and the like of the die, improves the production efficiency and reduces the labor intensity.
Description
Technical Field
The invention relates to the technical field of material preparation, in particular to a preparation method of a solid buoyancy section bar.
Background
With the rise and development of ocean development science, human beings have more and more exploration on the seabed world, the submergence depth is deeper and deeper, and a buoyancy material which can be applied to deep sea is urgently needed to ensure the safe use of deep water equipment. Therefore, since the 60 s of the 20 th century, research on high-strength buoyancy materials has been started at home and abroad.
Patent 200610043524.4 discloses a machinable deep sea buoyant material and a method for making the same. The method comprises the steps of stirring and mixing hollow glass beads and epoxy resin in a kneader at the temperature of 80-100 ℃, putting the mixture into a mold, pressurizing, heating and curing, wherein the applicable depth is 4000 meters.
Patent 200910174576.9 discloses a machinable solid buoyant material and a method of making the same. Mixing epoxy resin, curing agent and the like with the hollow glass microspheres under the heating condition, mixing and filling into a mould for curing, wherein the curing time is 40 hours.
In the above methods for preparing the buoyancy material, the kneaded material is transferred to a mold for molding; putting the material belt molds into an oven together for heating and curing; after curing, a demolding operation is also required. Because the mould is needed for molding and curing, the preparation steps are more, and the production efficiency is low. Moreover, the preparation process also relates to the operations of disassembling, assembling, cleaning and the like of the die, so that the production efficiency is further reduced, and the labor intensity is increased. More importantly, these processes are difficult to automate.
Disclosure of Invention
The embodiment of the invention aims to provide a preparation method of a solid buoyancy section, which is used for improving the production efficiency of a buoyancy material. The specific technical scheme is as follows:
a preparation method of the solid buoyancy section bar comprises the following steps:
(1) mixing a resin system weighed in advance with the hollow glass beads to obtain a mixture; the resin system comprises: a thermosetting resin having a viscosity of not more than 50 pas, a curing agent, a catalyst and an accelerator; the hydrostatic pressure resistance strength of the hollow glass beads is not lower than 30MPa, preferably not lower than 40 MPa;
(2) extruding and molding the mixture through a vacuum extruder to obtain a profile blank; wherein, the ratio of the sectional area of the shaping section of the extrusion head of the vacuum extruder to the sectional area of the extruder cylinder is between 0.02 and 0.8; the extrusion pressure is between 0.5MPa and 15 MPa;
(3) and curing the blank of the profile to obtain the solid buoyancy profile.
In one embodiment of the present invention, the mass ratio of the hollow glass microspheres to the resin system is 1: (1.0-2.0), preferably (1.2-1.8).
In one embodiment of the present invention, the thermosetting resin includes at least one of epoxy resin, polyurethane and unsaturated polyester, and preferably epoxy resin.
In one embodiment of the invention, the viscosity of the thermosetting resin is not more than 20Pa · s.
In one embodiment of the invention, the viscosity of the thermosetting resin is not greater than 10Pa · s.
In one embodiment of the present invention, the hollow glass microspheres have a particle size of 40 to 120 μm.
In one embodiment of the invention, the vacuum extruder is a vacuum screw extruder or a vacuum hydraulic extruder.
In one embodiment of the invention, the ratio of the cross-sectional area of the shaping section of the extrusion head of the vacuum extruder to the cross-sectional area of the barrel of the extruder is between 0.09 and 0.5; the extrusion pressure is between 2MPa and 10 MPa.
In one embodiment of the present invention, in step (1), the mixing is accomplished by a stirrer or kneader.
In one embodiment of the invention, the density of the solid buoyant profile is from 0.55 to 0.70g/cm3(ii) a Under a pressure condition of 30MPa or less, preferably 70MPa or less, more preferably 100MPa or less, the water absorption rate in 1 week is less than 1%.
According to the preparation method of the solid buoyancy section bar, the mold is not needed to be used for molding and curing in the preparation process, the steps of demolding and the like can be omitted, the work of disassembling, assembling, cleaning and the like of the mold is not needed, the production efficiency is improved, and the labor intensity is reduced.
Furthermore, due to the fact that the vacuum extruder is used for extrusion molding, compared with die molding, the extrusion molding continuity degree is higher, and continuous production of the solid buoyancy section bar is facilitated.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a profile prepared in example 2;
FIG. 2 is a section bar prepared in comparative example 1
FIG. 3 is a profile prepared in comparative example 2.
Detailed Description
The invention provides a preparation method of a solid buoyancy section bar, which comprises the following steps:
(1) mixing a resin system weighed in advance with the hollow glass beads to obtain a mixture; the resin system comprises: a thermosetting resin having a viscosity of not more than 50 pas, a curing agent, a catalyst and an accelerator; the hydrostatic pressure resistance strength of the hollow glass beads is not lower than 30 MPa; preferably not less than 40 MPa;
(2) extruding and molding the mixture through a vacuum extruder to obtain a profile blank; wherein, the ratio of the sectional area of the shaping section of the extrusion head of the vacuum extruder to the sectional area of the extruder cylinder is between 0.02 and 0.8; the extrusion pressure is between 0.5MPa and 15 MPa;
(3) and curing the blank of the profile to obtain the solid buoyancy profile.
In order to realize the preparation of the solid buoyancy section bar through the extrusion process, the inventor carries out extensive research and a large number of experiments, and finally, the inventor does not limit any theory to discover that the hydrostatic pressure strength of the hollow glass microspheres and the ratio of the sectional area of the shaping section of the extrusion head of the vacuum extruder to the sectional area of the extruder barrel play a very key role in realizing the technical scheme of the invention, namely successfully preparing the solid buoyancy section bar with low density and low water absorption. Specifically, the hydrostatic pressure resistance strength of the hollow glass beads is not lower than 30MPa, preferably not lower than 40 MPa; meanwhile, the ratio of the sectional area of the shaping section of the extrusion head of the vacuum extruder to the sectional area of the extruder cylinder is 0.02-0.8; the extrusion pressure is between 0.5MPa and 15MPa, and the ratio of the sectional area of the shaping section of the extrusion head of the vacuum extruder to the sectional area of the extruder barrel is preferably between 0.09 and 0.5; the extrusion pressure is between 2MPa and 10 MPa. Otherwise, even if the extrusion pressure and the sectional area ratio both satisfy the above conditions, the hollow glass beads may be damaged during the extrusion process due to insufficient compressive strength of the beads themselves, resulting in a profile density much higher than the theoretical density. When the extrusion pressure is too high, for example, more than 15MPa, even when the ratio of the sectional area of the shaping section of the extrusion head to the sectional area of the extruder barrel of the vacuum extruder is in the above range, the problems such as collapse and deformation of the shape and breakage of the hollow glass beads occur during the curing process. When the ratio of the sectional area of the shaping section of the extrusion head of the vacuum extruder to the sectional area of the extruder barrel is too large, for example, exceeds 0.8, cracks occur in the profile even if the extrusion pressure is appropriate, and the water absorption rate and voids are large.
It should be noted that the term "sectional area" as used herein refers to a cross-sectional area of the relevant component perpendicular to the axial direction thereof. For example, the cross-sectional area of the extruder barrel means the cross-sectional area of the extruder barrel, which is perpendicular to the axial direction of the extruder barrel.
The resin system used in the invention can adopt the thermosetting resin types commonly used by the existing solid buoyancy materials and the curing agent, the catalyst, the accelerator and the like matched with the thermosetting resin types. Specifically, the thermosetting resin may include at least one of epoxy resin, polyurethane, and unsaturated polyester, preferably epoxy resin. It is to be noted that the viscosity of the thermosetting resin in the present invention should be not more than 50 pas, preferably not more than 20 pas, more preferably not more than 10 pas. It is understood that the thermosetting resin in step (1) refers to a thermosetting resin before curing, and may also be referred to as a resin monomer.
As used herein, the term "viscosity" refers to the viscosity at 25 ℃.
In the specific implementation, when epoxy resin is used, high temperature curing epoxy resin such as TTA21, ERL4221, UVR6110, UVR6105, CEL2021P, etc; room temperature curing epoxy resins such as E44 and the like may also be used. Since the curing agent, catalyst, accelerator, etc. used in combination with the epoxy resin are conventional in the art, the present invention is not limited thereto.
In the specific implementation process of the technical scheme of the invention, the mass ratio of the hollow glass beads to the resin system is 1: (1.5-2.0), preferably (1.5-1.8). The density, strength, water absorption and other properties of the obtained solid buoyancy sectional material can be adjusted by changing the mass ratio of the hollow glass beads to the resin system. Typically, the hollow glass microspheres employed in the present invention have a particle size of 40 to 120 microns.
In the above step (2), the vacuum extruder used may be, alternatively, a vacuum screw extruder or a vacuum hydraulic extruder. By changing the shape and structure of the extrusion head, the obtained solid buoyancy section bar can be a cylinder, a circular tube, a square column, a square tube, a rectangular column, a rectangular tube, a plate, or a round, square or rectangular honeycomb structure. The vacuum extruder is conventional in itself, the invention is not limited thereto, and the terms "extrusion head", "extrusion head shaping section" and "extruder barrel" are used herein as part of a vacuum extruder and have their ordinary meaning, and the structure of which can be determined without any doubt by a person of ordinary skill in the art.
In the specific implementation process of the technical scheme of the invention, before the extrusion molding is carried out, generally, the resin system and the hollow glass beads need to be preliminarily mixed, and the mixing can be completed by a stirrer or a kneader. More specifically, when a vacuum screw extruder is used for extrusion molding, the mixing process is simpler, and generally only the resin system and the hollow glass beads need to be mixed together. More elaborate mixing processes can be carried out in a vacuum screw extruder. Therefore, when a vacuum screw extruder is used for extrusion molding, the continuity of feeding, mixing and extrusion can be basically realized. When the vacuum hydraulic extruder is used, the mixing function of the vacuum screw extruder is not provided, so that the mixture needs to be mixed uniformly before extrusion, and a kneader or equipment with the same function is required for the mixing process.
The curing process in step (3) can be determined according to the thermosetting resin used and the curing agent, catalyst, accelerator, etc. associated therewith, which are conventional techniques, and the invention is not limited thereto.
The density of the solid buoyancy section bar prepared by the method is 0.55-0.70g/cm3(ii) a Preferably, the water absorption rate is less than 1% at a pressure of 70MPa or less, more preferably 100MPa or less, for 1 week, and the method is suitable for use in deep sea having a maximum depth of 3000 m, preferably 7000 m.
In the present invention, particularly in the examples of the present invention, the density and the water absorption can be measured by the following methods.
Density testing method
The product was cut into rectangular samples with a precision cutter. The length, width and height values are measured by a vernier caliper to obtain the volume. The sample mass was weighed with a one-ten-thousandth electronic analytical balance. The sample density was calculated from the mass and volume. At least three samples were cut out for each product and averaged.
Water absorption testing method
Firstly, weighing the sample mass of the cut sample, and recording the mass as m0To the nearest 0.0001 g. And (4) putting the weighed sample into a deep sea pressure simulator, and maintaining the pressure for one week under the required pressure. Wiping off the water on the surface of the sample by using cotton cloth after pressure maintaining, and weighing the mass m of the sample after pressure maintaining1. The water absorption of the sample was calculated according to the following formula.
Water absorption rate of (m)1-m0)/m0×100％
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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
Weighing and mixing epoxy resin monomer (TTA21), curing agent (tetrahydrophthalic anhydride), catalyst (KH560) and accelerator (N, N-dimethylbenzylamine) according to the mass ratio of 100:40:1.5:1 to prepare an epoxy resin system with the total weight of 6kg, wherein the volume of the epoxy resin system is 5L (the density of the epoxy system is 1.2 g/c)m3)。
Hollow glass microspheres (3M company, U.S. HGS8000X, hydrostatic strength 50MPa, density 0.42 g/cm) were weighed3)4.9kg, volume 11.7L. At the moment, the mass ratio of the hollow glass beads to the epoxy resin system is 1: 1.2. the volume ratio is 70: 30.
The hollow glass beads and the epoxy resin system are initially mixed by a stirrer and then are put into a vacuum screw extruder. Mixing and extruding under the vacuum condition (the vacuum degree is between-0.085 and-0.1 MPa). The extrusion head is square column shaped. The ratio of the sectional area of the shaping section of the extrusion head to the sectional area of the extruder cylinder is 0.2, and the extrusion pressure is 8 MPa.
And (3) transversely placing the extruded square column section blank on a tray, placing the tray in an oven, precuring for 3h at 90 ℃, and then curing for 3h at 160 ℃ to obtain the section.
The density of the section bar is 0.59g/cm3(since the packing coefficient of the hollow glass microsphere beads is 65% and below 70%, the volume of the hollow glass microsphere beads which are not filled with epoxy in the section is larger, so that the density of the section is less than the theoretical density of 0.624g/cm3) And the water absorption rate at 30MPa for 1 week is less than 1%.
Example 2
Weighing and mixing epoxy resin monomer (TTA21), curing agent (tetrahydrophthalic anhydride), curing agent (dodecenylsuccinic anhydride), catalyst (KH560) and accelerator (N, N-dimethylbenzylamine) according to the mass ratio of 100:40:140:1.5:1 to prepare an epoxy resin system with the total weight of 7.04kg, wherein the volume of the epoxy resin system is 6.4L (the density of the epoxy resin system is 1.1 g/cm)3)。
Hollow glass microspheres (3M Co., USA, XLD6000, hydrostatic strength 40MPa, density 0.32 g/cm) were weighed3)4.35kg, volume 13.6L. At the moment, the mass ratio of the hollow glass beads to the epoxy resin system is 1: 1.62. the volume ratio was 68: 32.
The hollow glass beads and the epoxy resin system are initially mixed and then are put into a vacuum screw extruder. Mixing and extruding under vacuum condition. The extrusion head is in a circular tube shape. The ratio of the sectional area of the shaping section of the extrusion head to the sectional area of the extruder cylinder is 0.09, and the extrusion pressure is 5 MPa.
Placing the extruded profile blank in a baking ovenIn the oven, precured at 90 ℃ for 3h and then cured at 160 ℃ for 3h to give a profile (see FIG. 1). The density of the section bar is 0.56g/cm3(since the packing factor of the microbeads is 65%, lower than 68%, the volume between the microbeads in the profile, which is not filled with epoxy, is large, the density of the profile is less than the theoretical density of 0.55g/cm3) And the water absorption rate at 30MPa for 1 week is less than 1%.
Example 3
Example 3 differs from example 1 in that an epoxy resin system of a total weight of 7.35kg is formulated, i.e. the mass ratio of hollow glass microspheres to epoxy resin system is 1: 1.5. the volume ratio was 66: 34.
The density of the obtained profile was 0.64g/cm3And the water absorption rate under 70MPa for 1 week is less than 1%.
Example 4
Example 4 differs from example 1 in that an epoxy resin system of a total weight of 8.8kg is formulated, i.e. the mass ratio of hollow glass microspheres to epoxy resin system is 1: 1.8. the volume ratio is 62: 38. The extrusion pressure was 5 MPa.
The density of the obtained section bar was 0.68g/cm3And the water absorption rate at 100MPa for 1 week is less than 1%.
Example 5
Example 5 differs from example 1 in that the ratio of the cross-sectional area of the shaping zone of the extrusion head to the cross-sectional area of the barrel of the extruder is 0.02 and the extrusion pressure is 15 MPa.
The density of the obtained profile was 0.61g/cm3And the water absorption rate at 30MPa for 1 week is less than 1%.
Example 6
Example 6 differs from example 1 in that the ratio of the cross-sectional area of the shaping stage of the extrusion head to the cross-sectional area of the barrel of the extruder was 0.8 and the extrusion pressure was 0.5 MPa.
The density of the obtained section bar was 0.58g/cm3And the water absorption rate at 30MPa for 1 week is less than 1%.
Comparative example 1
Comparative example 1 differs from example 1 in that the extrusion pressure of comparative example 1 is 17 MPa. The resulting profile is shown in FIG. 2. As can be seen in fig. 2, when the extrusion pressure is too high, the profile collapses and deforms when cured.
Comparative example 2
Comparative example 2 differs from example 1 in that the ratio of the cross-sectional area of the shaping section of the extrusion head to the cross-sectional area of the barrel of the extruder of comparative example 2 is 0.9. The resulting profile is shown in FIG. 3. As can be seen in fig. 3, the profile surface has large cracks.
Comparative examples 3 to 8
The profiles were prepared according to the method of example 1 using XLD3000 glass beads (3M company, hydrostatic strength 20MPa) using the process parameters given in Table 1. The resulting profile densities are set forth in table 1.
As can be seen from the density data in Table 1, although the extrusion pressure and the cross-sectional area ratio both meet the conditions, the glass beads are not enough in hydrostatic pressure resistance, the beads are damaged in the extrusion process, and the product density is far higher than the theoretical density.
TABLE 1 Process parameters and Density data for comparative examples 3-7
Note: the mass ratio in table 1 refers to the mass ratio of the hollow glass microspheres to the epoxy resin system; the cross-sectional area ratio refers to the ratio of the cross-sectional area of the shaping section of the extrusion head to the cross-sectional area of the barrel of the extruder.
The preparation method of the solid buoyancy section provided by the invention is described in detail above. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its central concept. It should be noted that it would be apparent to those skilled in the art that various changes and modifications can be made in the invention without departing from the principles of the invention, and such changes and modifications are intended to be covered by the appended claims.
Claims (12)
1. The preparation method of the solid buoyancy section bar is characterized by comprising the following steps:
(1) mixing a resin system weighed in advance with the hollow glass beads to obtain a mixture; the resin system comprises: a thermosetting resin having a viscosity of not more than 50 pas, a curing agent, a catalyst and an accelerator; the hydrostatic pressure resistance strength of the hollow glass beads is not lower than 40 MPa; the mass ratio of the hollow glass beads to the resin system is 1: (1.0-2.0);
(2) extruding and molding the mixture through a vacuum extruder to obtain a profile blank; wherein the ratio of the sectional area of the shaping section of the extrusion head of the vacuum extruder to the sectional area of the extruder cylinder is 0.09-0.5; the extrusion pressure is between 2MPa and 10 MPa;
(3) and curing the blank of the profile to obtain the solid buoyancy profile.
2. The method of claim 1, wherein the mass ratio of hollow glass microspheres to resin system is 1: (1.2-1.8).
3. The method of claim 1, wherein the thermosetting resin comprises at least one of an epoxy, a polyurethane, and an unsaturated polyester.
4. The method of claim 3, wherein the thermosetting resin is an epoxy resin.
5. The method of claim 1, wherein the viscosity of the thermosetting resin is no greater than 20 Pa-s.
6. The method of claim 5, wherein the viscosity of the thermosetting resin is no greater than 10 Pa-s.
7. The method of claim 1, wherein the hollow glass microspheres have a particle size of 40 to 120 microns.
8. The method of claim 1, wherein the vacuum extruder is a vacuum screw extruder or a vacuum hydraulic extruder.
9. The method of claim 1, wherein in step (1), the mixing is accomplished by a blender or kneader.
10. The method of any one of claims 1 to 9, wherein the density of the solid buoyant profile is from 0.55 to 0.70g/cm3(ii) a Under the pressure condition of less than 30MPa, the water absorption rate in 1 week is less than 1%.
11. The method of claim 10, wherein the solid buoyancy profile has a water absorption of less than 1% at 1 week under pressure conditions of 70MPa or less.
12. The method of claim 11, wherein the solid buoyancy profile has a water absorption of less than 1% at 1 week under pressure conditions of 100MPa or less.
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| JP2007191540A (en) * | 2006-01-18 | 2007-08-02 | Nissan Motor Co Ltd | Thermoplastic resin composition and its manufacturing method |
| CN105038130A (en) * | 2015-07-31 | 2015-11-11 | 苏州天健竹业科技有限公司 | Preparation method of light composite for bicycle wheel frame |
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| CN102532722A (en) * | 2011-12-25 | 2012-07-04 | 江苏金波新材料科技有限公司 | Special material for polypropylene pipe |
| CN102757656B (en) * | 2012-07-20 | 2014-04-23 | 鑫盛(湖州)塑木科技有限公司 | Elastomer modified plastic-wood composite board and preparation method thereof |
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| JP2007191540A (en) * | 2006-01-18 | 2007-08-02 | Nissan Motor Co Ltd | Thermoplastic resin composition and its manufacturing method |
| CN105038130A (en) * | 2015-07-31 | 2015-11-11 | 苏州天健竹业科技有限公司 | Preparation method of light composite for bicycle wheel frame |
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| "深海地震仪浮力材料成型工艺研究";陈江等;《科技创新导报》;20160211;第13卷(第5期);第168页 * |
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