CN110202804B - Polyurethane resin composite material for civil engineering and pultrusion process thereof - Google Patents
Polyurethane resin composite material for civil engineering and pultrusion process thereof Download PDFInfo
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- CN110202804B CN110202804B CN201910455207.0A CN201910455207A CN110202804B CN 110202804 B CN110202804 B CN 110202804B CN 201910455207 A CN201910455207 A CN 201910455207A CN 110202804 B CN110202804 B CN 110202804B
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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
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
- B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
- B29C70/521—Pultrusion, i.e. forming and compressing by continuously pulling through a die and impregnating the reinforcement before the die
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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
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
- B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
- B29C70/525—Component parts, details or accessories; Auxiliary operations
-
- 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
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
- B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
- B29C70/525—Component parts, details or accessories; Auxiliary operations
- B29C70/528—Heating or cooling
Abstract
The invention discloses a polyurethane resin composite material for civil engineering and a pultrusion process thereof, belonging to the preparation of large-scale composite sections. The resin is solidified by adopting sectional heating and pressurizing on the traditional extrusion forming process. The invention optimizes the pultrusion process, reduces the resin fluidity by changing the temperature and the pressure, ensures that the content distribution of the resin in the composite material is more uniform, reduces the void ratio in the composite material, and improves the mechanical property of the large composite material prepared by the pultrusion process.
Description
Technical Field
The invention belongs to the preparation of large-scale composite sections, and particularly relates to a polyurethane resin composite material for civil engineering and a pultrusion process thereof.
Background
The composite material is a multiphase material formed by combining two or more materials with different properties by using a specific forming process. The properties of the materials are made up for the deficiencies, and a synergistic effect is generated, so that the composite material has the properties better than the original components, and further, the composite material is widely applied. Particularly, in recent years, the use amount of composite materials in the fields of aerospace and wind power generation is increasing, and the composite materials are expected to be lighter in weight and better in durability on the premise of maintaining or improving the performance of parts.
The extrusion forming process adopts a method that different resin components are respectively placed in a glue injection box, then continuous fibers or fabrics thereof are soaked in the glue injection box under the traction of traction equipment, and a heating mould is used for heating to solidify resin so as to form the composite material. The existing pultrusion process is already applied to the processing and production of small-volume composite materials such as continuous yarns, but few composite materials are directly applied to the production of large-scale building sections in the field of civil engineering.
The applicant finds that the pultrusion process can perfectly overcome the two technical problems that the resin component and the moisture react with each other and the raw materials react too fast to cause the mold blockage in the production of the existing large-scale composite material. However, in the process of continuous research, the applicant finds that the mechanical properties of the large composite material prepared by the pultrusion process are far lower than those of the same type of small-volume composite material prepared by the same process in the using process.
Disclosure of Invention
The purpose of the invention is as follows: the polyurethane resin composite material for the civil engineering and the pultrusion process thereof are provided, so as to solve the problem that the mechanical properties of the large composite material prepared by the pultrusion process are far lower than those of the composite material with the same type and small volume prepared by the same process in the use process.
The technical scheme is as follows: a pultrusion process of a polyurethane resin composite material for civil engineering comprises the following specific pultrusion processes:
and S1, mixing the component A and the component B which are beaten out by the metering pump according to a preset proportion by the static mixer, and then feeding the mixture into a closed glue injection box of the two-component polyurethane pultrusion system.
And S2, drying and cooling the fabric board through a vacuum oven, and then, under the drive of a tractor, allowing the fabric board to enter the glue injection box at a certain tension and a certain speed until the whole hot-pressing glue injection box can be just fully paved.
S3, pulling the fabric board impregnated with the resin to enter the front section of the heating segmented heating mould, heating the front section of the segmented heating mould to 80-100 ℃, and keeping constant temperature for heating.
S4, applying a pressure to press the upper surface of the front section of the sectional heating mould and compacting the fabric plate while executing the step S3, so that the pressure of the whole resin impregnation system in front of the sectional heating mould is 0.1-0.2 MPa; on one hand, the whole fabric plate is kept flat; on the other hand, the fabric plate and the demoulding plate are better jointed. The viscosity of the mixture of the A component and the B component is rapidly increased at the temperature, the mixed resin material is not lost even in the presence of certain pressure, and the pressure can inhibit the growth of pores in the fabric plate.
S5, the fabric board enters the middle section of a segmented heating mold to be further pressurized and heated under the drive of a tractor, the pressure is increased to 0.5-0.8 MPa, and the temperature is increased to 120-150 ℃; at this time, the viscosity of the mixture is further increased, and the growth of pores can be inhibited, and even the pores in the fabric plate can be dissolved.
S6, the fabric board enters the tail section of the segmented heating mold under the drive of a tractor to be cured and heated, at the moment, the pressure is removed, meanwhile, the temperature is continuously raised to 180-250 ℃, and the resin is rapidly cured under the combined action of the temperature and the catalyst to form the composite material with the strength.
And S7, slightly shrinking the resin after curing, demolding at the tail section of the mold under the combined action of the mold release agent, and cutting and trimming the section.
In a further embodiment, the component B is prepared by vacuumizing polyol with a hydrophobic function at 120 ℃ for 2h, cooling to 80 ℃, adding excessive carbodiimide modified isocyanate, and reacting at the temperature for 2-3 h to obtain the polyurethane prepolymer with-NCO content.
In a further embodiment, the preparation of the A-component polyol crosslinking agent comprises the following components in parts by weight:
55-80 wt% of polyester polyol;
10-20 wt% of castor oil polyol;
2-8 wt% of a release agent;
2-5 wt% of a water removing agent;
0.2-1 wt% of a catalyst;
0-25 wt% of filler;
0.5-1 wt% of ultraviolet absorbent;
0.5-1 wt% of an anti-aging agent.
In a further embodiment, the pultrusion process employs a two-component pultrusion system comprising: modules such as a creel, a yarn guide device, a glue injection box, a segmented heating mould, a tractor and the like; wherein, supply gluey system and hot pressing injecting glue box airtight continuous, the segmentation heating die comprises forepart, middle section and three districts of tail end.
In a further embodiment, the traction speed of the tractor is 10-30 cm/min, wherein the total length of the segmented heating mold is 6-18 m, three sections of the front section, the middle section and the tail end respectively account for 1/3, and the three sections are isolated by adopting heat insulation materials. The temperatures in the three zones are kept relatively independent.
In a further embodiment, a glue injection device is arranged on the glue injection box of the two-component pultrusion system, and the glue injection device comprises: the device comprises a material tank A, a material tank B, two peristaltic pumps respectively connected with the lower parts of the material tank A and the material tank B, and modules such as a static mixer and the like for mixing a component A and a component B.
In a further embodiment, the glue injection frequency of the glue injection device is 0.2-2 Hz, the glue injection amount is 50-200 g/time, and the resin content in the composite material is controlled by adjusting the glue injection frequency and the glue injection amount.
Has the advantages that: the invention relates to a pultrusion process of a polyurethane resin composite material for civil engineering, which optimizes the pultrusion process, reduces the fluidity of the resin by changing the temperature and the pressure, ensures that the content distribution of the resin in the composite material is more uniform, reduces the void ratio in the composite material, and improves the mechanical property of a large-scale composite material prepared by the pultrusion process.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present invention. It will be apparent, however, to one skilled in the art, that the present invention may be practiced without one or more of these specific details. In other instances, well-known features have not been described in order to avoid obscuring the invention.
The applicant finds that the pultrusion process can perfectly overcome the two technical problems that the resin component and the moisture react with each other and the raw materials react too fast to cause the mold blockage in the production of the existing large-scale composite material. And then the pultrusion process is applied to the preparation of the large composite material, but in the using process and the performance testing process, the service life and the mechanical property of the large composite material produced by the pultrusion process are far lower than those of the composite material with the same type and small volume prepared by the same process and the composite material with large volume produced by the compression molding process.
The applicant advances the products produced by pultrusionWhen the performance detection is carried out for multiple times, the average density of the large composite material produced by the pultrusion process is 0.1-0.4 g/cm apart from that of the composite material with the same type and small volume prepared by the same process under the condition that the fiber and resin content are similar3Negative deviation of (3). Applicants suspect that there may be some correlation between the separation of the average densities and the properties of the composite, and further suspect that there may be some amount of gaps at the resin-fiber bonds, resulting in a reduction in the mechanical properties and useful life of the composite. To verify this hypothesis, the applicants consulted the data to find: when the polyurethane composite material is soaked in a high-temperature environment for a long time, bound water (bound water and polymer molecules are bound in a hydrogen bond mode) can be formed between the polyurethane composite material and water molecules. It is conjectured that if the gap is larger, the resistance to binding with water molecules is relatively smaller and the space for binding water molecules is larger.
Thus, further validation experiments were designed regarding water absorption by the composite. In the experimental process, a large composite material synthesized by an extrusion process is selected as a comparative example 1, and a small composite material (with the same resin content, the deviation of the resin content is not more than 1%) synthesized by the extrusion process is selected as a comparative example 2. And (3) drying the composite materials in the comparative example 1 and the comparative example 2, and soaking the composite materials in water environments in different environments. Wherein, the maximum water absorption refers to that the water absorption capacity of the composite material is balanced after the composite material is soaked for a long enough time, and the ratio of the water absorption capacity to the weight of the composite material before soaking is the maximum water absorption capacity, also called the balanced water absorption capacity; the weight change rate refers to the ratio of the weight of the composite material before soaking after the maximum water absorption is reached and the composite material is dried at low temperature to remove free water from the composite material. I.e. the content of bound water in the composite, the specific experimental data are as follows:
from comparative experiments, the hypothesis was further verified that large composites produced using the pultrusion process had a higher void fraction than similar small volume composites prepared using the same process. Among other things, porosity may be a factor that further affects the mechanical properties and service life of the composite. Therefore, the applicant hopes to reduce the fluidity of the resin by changing the temperature and the pressure, so that the content distribution of the resin in the composite material is more uniform, the void ratio in the composite material is reduced, and the mechanical property of the large-scale composite material prepared by adopting the pultrusion process is improved.
The following detailed description of embodiments of the invention is intended to be illustrative of the invention and is not to be construed as limiting the invention. The examples, where specific techniques and reaction conditions are not indicated, can be carried out according to the techniques or conditions or product specifications described in the literature in the field. Reagents and instruments of any manufacturer are commercially available.
Example 1
A pultrusion process of a polyurethane resin composite material for civil engineering comprises the following steps:
preparation of the component B: 93 kg of castor oil is weighed and added into a closed reaction kettle, the temperature is raised to 120 ℃, the stirring and the vacuumizing are carried out, the vacuumizing and the heating are stopped after 2h, the temperature is reduced to 80 ℃, 121.6 kg of carbodiimide modified MDI (Vanhua company) with the trade name of 100LL is added, and the reaction is continued for 2h to obtain the prepolymer with the NCO content of 27 percent.
Preparation of component A: 80 kg of polyester 2915 (Spodopan company), 10 kg of castor oil polyol, 8 kg of 550D mold release agent (Technick Products company), 2 kg of 3A activated molecular sieve which has been baked at high temperature, 1 kg of FOMREZ UL-28 and 0.5 kg of K-5218 which are used as catalysts, 1 kg of benzophenone serving as an ultraviolet absorbent and 1 kg of 2, 5-ditert-butylhydroquinone serving as an anti-aging agent are respectively weighed and added into a stirring kettle and stirred uniformly.
The fabric plate made of glass fiber is processed by adopting the following pultrusion process:
step one, mixing the component A and the component B which are beaten out by a metering pump according to a preset proportion by a static mixer, and then entering a closed glue injection box of a two-component polyurethane pultrusion system;
drying and cooling the fabric plate by a vacuum oven, and then, under the drive of a tractor, allowing the fabric plate to enter a glue injection box at a certain tension and a certain speed until the whole hot-pressing glue injection box can be properly paved;
step three, drawing the fabric plate impregnated with the resin into the front section of a heating sectional heating mould, heating the front section of the heating sectional mould to 100 ℃, and keeping constant temperature for heating;
step four, applying a pressure to press the upper surface of the front section of the sectional heating mould and compacting the fabric plate while executing the step S3, so that the pressure of the whole resin impregnation system in front of the sectional heating mould is 0.2 MPa; on one hand, the whole fabric plate is kept flat; on the other hand, the fabric plate and the demoulding plate are better jointed;
step five, the fabric plate enters the middle section of a segmented heating mold to be further pressurized and heated to 0.5MPa and heated to 150 ℃ under the drive of a tractor;
step six, the fabric plate enters the tail section of a segmented heating mold under the drive of a tractor to be cured and heated, at the moment, the pressure is removed, meanwhile, the temperature is continuously raised to 250 ℃, and the resin is rapidly cured under the combined action of the temperature and a catalyst to form a composite material with strength;
and seventhly, slightly shrinking the resin after curing, demolding at the tail section of the mold under the combined action of the mold release agent, and cutting and finishing the section.
And (3) testing mechanical properties: testing the tensile strength, the tensile modulus, the elongation at break, the bending strength and the bending modulus of the prepared composite material according to the national standard GB/T16421-1996;
example 2
In this example, the preparation of the component a and the component B was the same as in example 1, except that the textile sheet material was replaced with fiber yarns. The specific pultrusion process comprises the following steps:
step one, mixing the component A and the component B which are beaten out by a metering pump according to a preset proportion by a static mixer, and then entering a closed glue injection box of a two-component polyurethane pultrusion system;
drying and cooling the fiber yarns through a vacuum oven, and then, under the drive of a tractor, allowing the fiber yarns to enter a glue injection box at a certain tension and a certain speed until the whole hot-pressing glue injection box can be properly paved;
step three, drawing the fiber yarns impregnated with the resin into the front section of the heating sectional heating mould, heating the front section of the heating sectional mould to 100 ℃, and keeping constant temperature for heating;
step four, applying a pressure to press the upper surface of the front section of the sectional heating mould and compact the fiber yarns while executing the step S3, so that the pressure of the whole resin impregnation system before the sectional heating mould is 0.2 MPa; on one hand, the whole fiber yarn is kept flat; on the other hand, the fiber yarns are better attached to the demoulding plate;
step five, the fiber yarns enter the middle section of a segmented heating die to be further pressurized and heated to 0.5MPa and 150 ℃ under the drive of a tractor;
step six, the fiber yarns enter the tail section of the segmented heating mold under the drive of a tractor to be cured and heated, at the moment, the pressure is removed, meanwhile, the temperature is continuously raised to 250 ℃, and the resin is rapidly cured under the combined action of the temperature and the catalyst to form a composite material with strength;
and seventhly, slightly shrinking the resin after curing, demolding at the tail section of the mold under the combined action of the mold release agent, and cutting and finishing the section.
And (3) testing mechanical properties: the prepared composite material is tested for tensile strength, tensile modulus, elongation at break, flexural strength and flexural modulus according to the national standard GB/T16421-1996.
Example 3
The preparation process of the component a and the component B in this example is the same as that of example 1, except that the fabric sheet is processed by a conventional production process, and the specific pultrusion process is as follows: the component A and the component B are respectively led into a storage tank A and a storage tank B corresponding to a bi-component glue supply system, a fabric board made of glass fiber forms certain tension under the drive of a traction machine from a creel through a yarn guide plate, passes through a glue injection box connected with the bi-component glue supply system (the glue injection frequency of the bi-component glue supply system is 2Hz, the glue injection amount is 200g each time, and the weight ratio of the material B to the material A is 1: 1) at the speed of 280cm/min, is fully soaked with mixed resin of the component AB, enters a mold (the three-region temperature is 150 ℃, 180 ℃ and 160 ℃ respectively), and is cured and molded at high temperature and leaves the mold.
And (3) testing mechanical properties: the prepared composite material is tested for tensile strength, tensile modulus, elongation at break, flexural strength and flexural modulus according to the national standard GB/T16421-1996.
Example 4
The preparation of the component a and the component B in this example was the same as in example 3, except that the textile sheet was replaced with a fibre yarn. The specific pultrusion process comprises the following steps: respectively introducing the component A and the component B into a storage tank A and a storage tank B corresponding to a bi-component glue supply system, enabling glass fibers to form a certain tension from a creel through a yarn guide plate under the drive of a tractor, enabling the glass fibers to pass through a glue injection box connected with the bi-component glue supply system (the glue injection frequency of the bi-component glue supply system is 2Hz, the glue injection amount is 200g each time, the weight ratio of the material B to the material A is 1: 1) at a speed of 280cm/min, enabling the bi-component glue supply system and the material B to be fully soaked with mixed resin of the component AB, enabling the mixed resin to enter a mold (the three temperatures are respectively 150 ℃, 180 ℃ and 160 ℃), and enabling the resin to be cured and molded at a high temperature and to leave the mold.
And (3) testing mechanical properties: the prepared composite material is tested for tensile strength, tensile modulus, elongation at break, flexural strength and flexural modulus according to the national standard GB/T16421-1996.
Comparison of performance data between examples:
as can be seen from the data in the table above: the mechanical properties of the composite materials prepared in the examples 2 and 4 are basically equivalent, that is, the optimized process has no obvious influence on the preparation of the composite materials such as small-volume yarns; the composite material prepared in comparative example 1 has a larger difference than that prepared in example 3, but still cannot achieve the mechanical properties of examples 2 and 3, namely the mechanical properties of the optimized process for processing large-volume plates are obviously improved, but the mechanical properties of the composite material with small volume cannot be achieved, and the process optimization has further development space.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
Claims (2)
1. A pultrusion process of a polyurethane resin composite material for civil engineering is characterized in that the pultrusion process comprises the following steps:
s1, mixing the component A and the component B which are beaten out by a metering pump according to a preset proportion by a static mixer, and then feeding the mixture into a closed glue injection box of a two-component polyurethane pultrusion system;
the component A is prepared from a polyol cross-linking agent, and comprises the following components in parts by weight:
55-80 wt% of polyester polyol;
10-20 wt% of castor oil polyol;
2-8 wt% of a release agent;
2-5 wt% of a water removing agent;
0.2-1 wt% of a catalyst;
0-25 wt% of filler;
0.5-1 wt% of ultraviolet absorbent;
0.5-1 wt% of an anti-aging agent;
the component B is hydrolysis-resistant polyurethane prepolymer, and the preparation method comprises the steps of vacuumizing polyol with a hydrophobic function at 120 ℃ for 2 hours, cooling to 80 ℃, adding excessive carbodiimide modified isocyanate, and reacting at the temperature for 2-3 hours to obtain polyurethane prepolymer with-NCO content; s2, drying and cooling the fabric board through a vacuum oven, and then, under the drive of a tractor, entering a glue injection box at a certain tension and a certain speed until the whole hot-pressing glue injection box can be just fully paved;
s3, drawing the fabric board impregnated with the resin into the front section of the heating segmented heating mould, heating the front section of the segmented heating mould to 80-100 ℃, and keeping constant temperature for heating;
s4, applying a pressure to press the upper surface of the front section of the sectional heating mould and compacting the fabric plate while executing the step S3, so that the pressure of the whole resin impregnation system of the front section of the sectional heating mould is 0.1-0.2 MPa; on one hand, the whole fabric plate is kept flat; on the other hand, the fabric plate and the demoulding plate are better jointed;
s5, the fabric board enters the middle section of a segmented heating mold to be further pressurized and heated under the drive of a tractor, the pressure is increased to 0.5-0.8 MPa, and the temperature is increased to 120-150 ℃;
s6, enabling the fabric board to enter a tail section of a segmented heating mold under the drive of a tractor to be cured and heated, removing pressure at the moment, continuously heating to 180-250 ℃, and rapidly curing resin under the combined action of temperature and a catalyst to form a composite material with strength;
s7, slightly shrinking the resin after curing, demolding at the tail section of the mold under the combined action of the mold release agent, and cutting and finishing the section;
the two-component pultrusion system adopted by the pultrusion process comprises the following steps: the device comprises a creel, a yarn guide device, a glue injection box, a segmented heating mold and a tractor; the segmented heating mould consists of a front segment, a middle segment and a tail end three segments;
the traction speed of the tractor is 10-30 cm/min, wherein the total length of the segmented heating mould is 6-18 m, three sections of the front section, the middle section and the tail end respectively account for 1/3, and the three sections are isolated by adopting a heat insulating material;
two ingredient pultrusion system glue injection box is last to be set up the injecting glue device, the injecting glue device includes: the device comprises a material tank A, a material tank B, two peristaltic pumps respectively connected with the lower parts of the material tank A and the material tank B, and a static mixer for mixing AB materials;
the glue injection frequency of the glue injection device is 0.2-2 Hz, and the glue injection amount is 50-200 g/time.
2. A polyurethane resin composite material for civil engineering use characterized by being a composite fabric sheet obtained by the method as claimed in claim 1.
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| CN103568337B (en) * | 2012-07-25 | 2016-01-13 | 株洲柳龙复合新材有限公司 | The preparation method of contact moudling polyurethane or polyurea composite material member |
| CN105838020A (en) * | 2015-12-31 | 2016-08-10 | 苏州振瑞昌材料科技有限公司 | Bakelite corrugated plate and manufacturing method thereof |
| CN107793548A (en) * | 2017-10-31 | 2018-03-13 | 镇江利德尔复合材料有限公司 | A kind of dual-component polyurethane resin, its preparation method and use it for the technique for preparing polyurethane pultrusion composite materials |
| CN108943773A (en) * | 2018-06-11 | 2018-12-07 | 苏州恒川光伏科技有限公司 | The preparation method of pultrusion polyurethane fiber enhancing composite material |
| CN109438967A (en) * | 2018-11-07 | 2019-03-08 | 铁科腾跃科技有限公司 | Continuous glass fibre enhances compound polyurethane material foot plank and preparation method thereof |
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Inventor after: Ju Mingjie Inventor after: Deng Junfa Inventor after: Cheng Yuan Inventor after: Li Qiansheng Inventor before: Ju Mingjie Inventor before: Deng Junfa Inventor before: Cheng Yuan Inventor before: Ben Jin Inventor before: Li Qiansheng |