CN113214622B - Alloy resin and glass fiber reinforced plastic plate using same - Google Patents
Alloy resin and glass fiber reinforced plastic plate using same Download PDFInfo
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Abstract
The application relates to the field of glass fiber reinforced plastic plates, in particular to an alloy resin and a glass fiber reinforced plastic plate using the same. The alloy resin raw materials comprise thermoplastic resin powder: 5-35 parts; silane crosslinking agent: 5-20 parts of a solvent; the thermoplastic resin powder adopts one of PE powder and PP powder or a composition thereof. In addition, the preparation method of the alloy resin comprises the following steps: mixing maleic anhydride, phthalic anhydride, propylene glycol and diethylene glycol with resin powder according to the weight part ratio, heating, raising the temperature, fully reacting, adding styrene and a silane crosslinking agent, and mixing and reacting to obtain the alloy resin. Compared with the conventional unsaturated polyester resin, the alloy resin prepared by the method has more excellent elasticity and toughness, so that the impact toughness of the glass fiber reinforced plastic plate can be effectively improved.
Description
Technical Field
The application relates to the field of glass fiber reinforced plastic plates, in particular to an alloy resin and a glass fiber reinforced plastic plate using the same.
Background
The glass fiber reinforced plastic plate is a fiber resin mixed matrix which is formed by reinforcing unsaturated resin, epoxy resin and phenolic resin by inorganic fibers. The composite material has the advantages of light weight, hardness, non-conductivity, high mechanical strength, corrosion resistance and the like, and is widely applied to automobiles, boats, building materials, corrosion-resistant products and the like.
The unsaturated polyester resin has excellent wettability, extremely simple and convenient molding and curing process and strong applicability, so the unsaturated polyester resin is a common glass steel plate resin raw material in the market. However, the inventors believe that the unsaturated polyester resin has high rigidity and low toughness, so that the glass fiber reinforced plastic plate made of the unsaturated polyester resin has low impact toughness, and the application of the glass fiber reinforced plastic plate in fields with high safety requirements, such as automobiles and boats, is limited.
Content of application
In order to solve the problems that the traditional unsaturated resin has poor toughness, and the glass steel plate has insufficient tensile property and low impact resistance, the application provides the alloy resin and the glass steel plate using the alloy resin.
In a first aspect, the present application provides an alloy resin, which adopts the following technical scheme:
the alloy resin is prepared from the following raw materials in parts by weight:
phthalic anhydride: 22-28 parts;
maleic anhydride: 25-33 parts;
propylene glycol: 6-10 parts of a solvent;
diethylene glycol: 10-19 parts;
styrene: 22-35 parts.
Thermoplastic resin powder: 5-35 parts;
silane crosslinking agent: 5-20 parts of a solvent;
the thermoplastic resin powder adopts one of PE powder and PP powder or a composition thereof.
By adopting the technical scheme, the PE and the PP added in the application have excellent thermoplasticity, and have excellent toughness and tensile property compared with unsaturated resin. Meanwhile, the dibasic acid such as maleic anhydride, acid anhydride and the like in the raw materials can perform polycondensation reaction with dihydric alcohol such as propylene glycol and the like to generate polyester, and the polyester, PE and PP form resin with a three-dimensional network structure under the crosslinking action of a styrene crosslinking monomer and a silane crosslinking agent. Compared with the conventional unsaturated polyester resin, the alloy resin with better toughness and tensile property can be obtained by adopting the thermoplastic resin powder and the raw materials. In addition, the silane crosslinking agent is beneficial to improving the compatibility of PE resin, PP resin and polyester.
Preferably, the preparation method of the alloy resin comprises the following operations:
mixing maleic anhydride, phthalic anhydride, propylene glycol and diethylene glycol with resin powder according to the weight part ratio, heating, raising the temperature, fully reacting, adding styrene and a silane crosslinking agent, and mixing and reacting to obtain the alloy resin.
By adopting the technical scheme, the dibasic acid such as maleic anhydride, anhydride and the like and the dihydric alcohol such as propylene glycol and the like can be subjected to polycondensation reaction under the heating condition to generate polyester, and if styrene is added as a crosslinking agent, unsaturated polyester can be prepared. According to the preparation method, resin powder is added before polyester is generated, and then the styrene cross-linking agent and the silane cross-linking agent are added together, wherein the styrene can enable polyester molecules to be cross-linked with each other, and the silane cross-linking agent can be polyester, PE and PP, so that the alloy resin with higher toughness and a three-dimensional network structure is obtained, and finally, the impact toughness of the glass steel plate can be enhanced.
In a second aspect, the present application provides a glass fiber reinforced plastic plate, which adopts the following technical scheme:
the glass fiber reinforced plastic plate comprises at least one fiber resin mixing layer and resin coatings arranged on one side or two side surfaces of the fiber resin mixing layer, and is characterized in that raw materials in at least one layer of the resin coatings and the fiber resin mixing layer comprise any one of the alloy resins.
By adopting the technical scheme, the impact toughness of the glass steel plate can be obviously improved and the applicability can be improved by adding the alloy resin into the glass steel plate matrix or the coating.
Preferably, the fiber-resin mixed layer is prepared from the following raw materials in parts by weight:
alloy resin: 90-120 parts;
fiber fabric: 20-70 parts;
curing agent: 1-3 parts;
accelerator (b): 0.1-0.8 part;
polymerization inhibitor: 0.01-0.3 part;
defoaming agent: 0.1 to 0.2 portion.
The fiber fabric in the application can be made of inorganic fibers such as glass fibers, basalt fibers, carbon fibers and polyester fibers, and the alloy resin is soaked on the surface of the fiber fabric, so that the high-strength and high-toughness glass steel plate matrix is obtained. Meanwhile, the curing agent and the accelerator are added, so that the curing of the alloy resin is facilitated, and the defoaming agent can reduce bubbles in the resin and increase the strength of the matrix.
Preferably, the resin coating is prepared from the following raw materials in parts by weight:
alloy resin: 90-120 parts;
elastic resin: 10-50 parts;
curing agent: 1-3 parts;
polymerization inhibitor: 0.01-0.3 part;
defoaming agent: 0.1-2 parts;
leveling agent: 0.1-2 parts;
toughening agent: 0.5-5 parts;
anti-ultraviolet agent: 0.3-1 part;
acid and alkali resistant auxiliary agent: 0.5-10 parts.
By adopting the technical scheme, the resin coating with excellent impact toughness is obtained by adopting the elastic resin and the alloy resin with high elasticity and high toughness, and finally, the impact toughness of the glass steel plate is remarkably improved. In addition, the anti-ultraviolet agent can effectively improve the anti-ultraviolet performance of the glass steel plate, and the glass steel plate is not easy to age under outdoor illumination conditions.
Preferably, the raw material of the resin coating further comprises 4-9 parts by weight of aluminum sol.
By adopting the technical scheme, the aluminum sol not only has an adhesive effect, but also has a tip effect because the aluminum sol contains a large amount of nano aluminum oxide particles which are distributed in the resin coating and can play a role in inhibiting the generation and growth of cracks, thereby improving the impact toughness of the glass steel plate; in addition, the aluminum sol has an anti-ultraviolet effect, and can improve the aging resistance of the glass steel plate.
Preferably, aluminum chloride is dissolved in water to prepare an aluminum chloride solution with the concentration of 0.4-1 mol/L, then ammonia water with the concentration of 20-30% is dripped until the pH value is 8-9, the mixture is heated to 80-90 ℃, the heat preservation reaction is carried out for 1-2 h, then citric acid is added until the pH value is 4-5, the mixture is uniformly mixed, and then the heat preservation reaction is carried out for 6-12 h at the temperature of 80-90 ℃, so that the alumina sol is prepared.
By adopting the technical scheme, in the process of preparing the aluminum sol, the pH value of the system can be adjusted to be acidic by adding citric acid, and the generation of nano alumina gel particles is promoted.
Preferably, the toughening agent is a composition of PU elastomer and nano zinc oxide in a weight ratio of (1.5-3): 1.
By adopting the technical scheme, the PU elastomer has excellent toughening effect, the nano zinc oxide has higher rigidity, and the nano zinc oxide and the resin coating are mixed in the resin coating, so that the impact toughness of the resin coating can be effectively enhanced. In addition, the nano zinc oxide has an anti-ultraviolet effect, and is beneficial to improving the aging resistance of the glass steel plate.
Preferably, the preparation method of the glass fiber reinforced plastic plate comprises the following steps:
s1, fully mixing alloy resin, an accelerator, a polymerization inhibitor, a defoaming agent and a curing agent in the raw materials of the fiber resin mixing layer to obtain a resin raw material, coating the resin raw material on the surface of the fiber material, and drying and curing at the temperature of 70-90 ℃ to obtain the fiber resin mixing layer;
s2, fully mixing the raw materials of the resin coating layer to obtain the resin coating, coating the resin coating on the surface of the fiber resin mixing layer to form the resin coating layer, drying and curing at 70-90 ℃ to obtain the glass fiber reinforced plastic plate
By adopting the technical scheme, the method has the advantages that,
in summary, the present application has the following beneficial effects:
1. according to the preparation method, the PE powder, the PP powder and the silane cross-linking agent are added into the raw materials of the unsaturated resin, so that the alloy resin with excellent toughness and tensile property can be prepared, and the glass steel plate with higher impact toughness can be prepared.
2. According to the preparation method of the alloy resin, the PE powder and the PP powder are added before polyester synthesis, so that a three-dimensional cross-linked structure with higher elasticity and toughness is obtained, and the impact toughness of the glass steel plate can be effectively improved.
3. The aluminum sol is preferably adopted in the resin coating, so that the ultraviolet resistance and the aging resistance of the glass steel plate can be improved while the impact toughness of the glass steel plate is improved.
Detailed Description
The present application will be described in further detail with reference to examples.
Preparation examples
Preparation example 1, an alumina sol was prepared as follows:
weighing 0.2mol of aluminum chloride, adding water to dissolve 0.4L of the aluminum chloride to prepare 0.5mol/L aluminum chloride solution, then dropwise adding 25% ammonia water, adjusting the pH value to 8.2, heating to 85 ℃, carrying out heat preservation reaction for 2h, then adding citric acid until the pH value is 4.5, uniformly mixing, and carrying out heat preservation reaction for 10h at the temperature of 85 ℃ to prepare the aluminum sol.
Preparation example 2, an aluminum sol, was different from preparation example 1 in that the concentration of aluminum chloride produced was 1 mol/L.
Preparation example 3, an aluminum sol, was different from preparation example 1 in that the concentration of aluminum chloride produced was 0.4 mol/L.
Preparation example 4, an aluminum sol, was different from preparation example 1 in that nitric acid was used instead of citric acid, and the pH was adjusted to 4.5.
Examples
Example 1, an alloy resin, the selection of the raw material components and their respective amounts are shown in table 1 and was prepared according to the following steps:
under the protection of nitrogen, maleic anhydride, phthalic anhydride, propylene glycol, diethylene glycol and thermoplastic resin powder are added into a reaction kettle, stirred and mixed uniformly, heated to 192 ℃, cooled to 90 ℃ when the acid value in the reaction kettle reaches 40 +/-2 mgKOH/g, then simultaneously added with styrene and a silane cross-linking agent, stirred and reacted for 0.5 hour under heat preservation, and cooled to room temperature, thus obtaining the alloy resin.
Examples 2 to 3, an alloy resin, differs from example 1 in the selection of each raw material component and the corresponding amount thereof are shown in table 1.
Example 4, an alloy resin, differs from example 1 in that it is prepared as follows:
under the protection of nitrogen, adding maleic anhydride, phthalic anhydride, propylene glycol and diethylene glycol into a reaction kettle, stirring and mixing uniformly, heating to 192 ℃, cooling to 90 ℃ when the acid value in the reaction kettle reaches 40 +/-2 mgKOH/g, then adding styrene, stirring and carrying out heat preservation reaction for 0.5h, then adding thermoplastic resin powder and a silane cross-linking agent, continuing the heat preservation reaction for 0.5h, and cooling to room temperature to obtain the alloy resin.
Comparative example
Comparative examples 1 to 3, an alloy resin, differs from example 1 in the selection of each raw material component and the corresponding amount thereof are shown in table 1.
Table 1 selection of feed components and their respective consumption per kg for each of the examples and comparative examples
TABLE 2 manufacturer model information of each raw material component of alloy resin
Application example
Application example 1, a glass fiber reinforced plastic plate, the selection of each raw material component and the corresponding amount are shown in table 1, and the glass fiber reinforced plastic plate is prepared according to the following steps:
s1, uniformly stirring alloy resin, an accelerant, a polymerization inhibitor, a defoaming agent and a curing agent in the raw materials of the fiber resin mixing layer to obtain a resin raw material, then scraping the resin raw material on the surface of a glass fiber felt with the gram weight of 200 g/square meter, and drying and curing at the temperature of 80 ℃ for 2 hours to obtain the fiber resin mixing layer;
and S2, uniformly stirring the raw materials of the resin coating layer to obtain the resin coating, scraping the resin coating on the upper and lower side surfaces of the fiber-resin mixed layer to form the resin coating layer, and drying and curing at the temperature of 80 ℃ for 3 hours to obtain the glass fiber reinforced plastic plate.
Application examples 2 to 7, namely a glass fiber reinforced plastic plate, are different from application example 1 in that the selection of each raw material component and the corresponding use amount are shown in table 3.
Table 3 selection of raw material components and their respective consumption per kg of sheet glass material in application examples 1 to 7
Wherein the aluminum sol in table 1 is the aluminum sol prepared in preparation example 1; alloy resin the alloy resin prepared in example 1 was used.
TABLE 4 manufacturer model information of raw material components in glass fiber reinforced plastic panels
Application example 8, a glass fiber reinforced plastic plate, was different from application example 1 in that the aluminum sol in the resin coating raw material was the aluminum sol prepared in preparation example 2.
Application example 9, a glass fiber reinforced plastic sheet, was different from application example 1 in that the aluminum sol in the resin coating raw material was the aluminum sol prepared in preparation example 3.
Application example 10, a glass fiber reinforced plastic plate, was different from application example 1 in that the aluminum sol in the resin coating raw material was the aluminum sol prepared in preparation example 4.
Application example 11, a glass fiber reinforced plastic plate, was different from application example 1 in that the alloy resin in the fiber resin mixed layer and the resin coating raw material was the alloy resin obtained in example 2.
Application example 12, a glass fiber reinforced plastic plate, differs from application example 1 in that the alloy resin in the fiber resin mixed layer and the resin coating raw material is the alloy resin prepared in example 3.
Application example 13, a glass fiber reinforced plastic plate, was different from application example 1 in that the alloy resin in the fiber resin mixed layer and the resin coating raw material was the alloy resin obtained in example 4.
Comparative example
Comparative example 1, a glass fiber reinforced plastic plate, and the difference from application example 1, are that the alloy resin in the fiber resin mixed layer and the resin coating raw material is the alloy resin prepared in comparative example 1.
Comparative example 2, a glass fiber reinforced plastic plate, was different from application example 1 in that the alloy resin in the fiber resin mixed layer and the resin coating raw material was the alloy resin prepared in comparative example 2.
Comparative example 3, a glass fiber reinforced plastic plate, was different from application example 1 in that the alloy resin in the fiber resin mixed layer and the resin coating raw material was the alloy resin prepared in comparative example 3.
Performance test
Test 1: testing impact resistance and tensile property of glass fiber reinforced plastic plate
The test method comprises the following steps: 1. referring to the test standard in GB/T1451-2005 "method for testing impact toughness of simply-supported Beam of fiber reinforced Plastic", 3 test specimens with a length of 120cm, a width of 10cm and a thickness of 6mm were cut out from the glass fiber reinforced plastics in the above application examples and comparative examples, the impact velocity during the test was 3.8M/s and the span was 70mm, and the impact toughness was measured and recorded as M 0 The test results are shown in table 5.
2. The tensile properties of the fiber reinforced plastics are tested according to GB/T1447-2005, 3I-type test samples are cut from the glass fiber reinforced plastics in the application examples and the comparative examples according to the detection standard, the breaking elongation of the samples is tested by adopting a loading rate of 10mm/min, and the test results are shown in Table 5.
TABLE 5 impact toughness and elongation at break test results for glass fiber reinforced plastic panels
Test 2: testing ultraviolet resistance of glass fiber reinforced plastic plate
Sample preparation: the test was carried out according to the test standard of GB/T1451-2005 "method for testing impact toughness of simply-supported Beam of fiber reinforced plastics", and 3 test specimens having a length of 120cm, a width of 10cm and a thickness of 7mm were cut out from the glass fiber reinforced plastic sheet sampled in the above test 1 again.
The test method comprises the following steps: referring to the laboratory light source exposure test method and standard in GB/T16422.2, after a sample is exposed for 2000 hours under a xenon arc lamp, the impact toughness of the sample is tested by adopting the sample method and standard in test 1 and is recorded as M 1 ，M 1 /M 0 The test results are shown in table 6.
TABLE 6 ultraviolet resistance test results of glass fiber reinforced plastic plate
And (3) analyzing test results:
(1) by combining application examples 1 to 13 and comparative examples 1 to 3 and combining table 5, it can be seen that the alloy resin prepared by adding the thermoplastic resin powder and the silane crosslinking agent in the preparation process of the unsaturated resin can significantly improve the elongation at break and the impact toughness of the glass fiber reinforced plastic plate.
(2) By combining application example 1 with comparative examples 1-3 and table 5, it can be seen that the elongation at break and impact toughness of the glass fiber reinforced plastic plate cannot be effectively improved by using the thermoplastic resin powder or the alloy resin prepared by using the silane crosslinking agent alone. The reason for this may be that the compatibility between PP and PE and unsaturated polyester resin is poor, so that the toughening effect of PP and PEDE is difficult to exert; the silane cross-linking agent can promote the PP and the PE to form cross-linking with unsaturated resin, and alloy resin with a three-dimensional network structure is obtained, and the alloy resin has toughening and buffering effects and can reduce impact energy; on the other hand, the three-dimensional network structure can play a role in stress dispersion, the resin fracture caused by local stress concentration of alloy resin is avoided, and the impact toughness and the elongation at break of the glass fiber reinforced plastic plate are improved.
(3) As can be seen by combining application example 1 with application example 13 and table 5, in application example 1, the thermoplastic resin powder and the raw material of the polyester resin are simultaneously mixed and added; in application example 13, the thermoplastic resin powder is added after the unsaturated polyester resin is prepared, and the impact toughness and the elongation at break of application example 1 are obviously higher than those of application example 13. The reason for this may be that, in application example 1, when the thermoplastic resin powder is added, the dibasic acid and the diol have not been polycondensed to form polyester, and the styrene crosslinking agent has not been added, and thus the unsaturated polyester resin has not been prepared; in application example 1, polyester is mixed with PP and PE, and then a styrene crosslinking agent and a silane crosslinking agent are added, wherein the styrene crosslinking agent promotes the polyester molecules to be crosslinked, and the silane crosslinking agent promotes the polyester molecules to be crosslinked with the PP and PE, so that an elastic three-dimensional network structure is formed.
In application example 14, after polyester is obtained by polycondensation of dibasic acid and dihydric alcohol, unsaturated polyester resin is obtained by crosslinking under the action of styrene, and then PP, PE and a silane crosslinking agent are added, the obtained crosslinked structure has a poor stress dispersion effect, so that the impact toughness of the glass fiber reinforced plastic plate of application example 14 is lower than that of application example 1.
(4) Combining application example 1 with application example 4 and combining tables 5 and 6, it can be seen that in application example 1, the aluminum sol is added to the resin coating of the glass fiber reinforced plastic plate, while in application example 4, the aluminum sol is not added, and the impact toughness, elongation at break and ultraviolet resistance of the glass fiber reinforced plastic plate in application example 1 are significantly higher than those of application example 4. The aluminum sol contains more nano alumina sol particles, so that the particles have a bonding effect, and when the glass fiber reinforced plastic plate is impacted, the particles can reduce the tip effect and inhibit the generation and the expansion of cracks, thereby improving the impact toughness of the plate; in addition, the light-resistant and anti-aging plate also has the functions of reflecting ultraviolet light and improving the light-resistant and anti-aging performance of the plate.
(5) By combining application examples 1 and 5-7 and combining tables 5 and 6, it can be seen that the toughening agent adopts nano zinc oxide and PU elastomer, which is beneficial to improving the impact toughness of the glass fiber reinforced plastic plate, and the combination of the two has more excellent effect. The reason for this may be that the nano zinc oxide can increase the rigidity of the alloy resin, while the PU elastomer can increase the toughness of the alloy resin, and the two cooperate with each other to improve the impact toughness of the plate.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (4)
1. The glass fiber reinforced plastic plate is characterized by comprising at least one fiber resin mixing layer and resin coatings arranged on one side or two side surfaces of the fiber resin mixing layer, wherein the fiber resin mixing layer is prepared from the following raw materials in parts by weight:
alloy resin: 90-120 parts;
fiber fabric: 20-70 parts of a solvent;
curing agent: 1-3 parts;
accelerator (b): 0.1-0.8 part;
polymerization inhibitor: 0.01-0.3 part;
defoaming agent: 0.1-0.2 parts;
the resin coating is prepared from the following raw materials in parts by weight:
alloy resin: 90-120 parts;
elastic resin: 10-50 parts;
curing agent: 1-3 parts;
polymerization inhibitor: 0.01-0.3 part;
defoaming agent: 0.1-2 parts;
leveling agent: 0.1-2 parts;
a toughening agent: 0.5-5 parts;
anti-ultraviolet agent: 0.3-1 part;
acid and alkali resistant auxiliary agent: 0.5-10 parts;
the toughening agent is a composition of a PU elastomer and nano zinc oxide, wherein the weight ratio of the PU elastomer to the nano zinc oxide is (1.5-3): 1;
the alloy resin is prepared from the following raw materials in parts by weight:
phthalic anhydride: 22-28 parts;
maleic anhydride: 25-33 parts;
propylene glycol: 6-10 parts of a solvent;
diethylene glycol: 10-19 parts;
styrene: 22-35 parts of a solvent;
thermoplastic resin powder: 5-35 parts;
silane crosslinking agent: 5-20 parts of a stabilizer;
the thermoplastic resin powder adopts one or the combination of PE powder and PP powder,
the preparation method of the alloy resin comprises the following operations:
mixing maleic anhydride, phthalic anhydride, propylene glycol and diethylene glycol with thermoplastic resin powder according to the weight part ratio, heating, raising the temperature, fully reacting, adding styrene and a silane crosslinking agent, and mixing and reacting to obtain the alloy resin.
2. The glass fiber reinforced plastic plate as claimed in claim 1, wherein the resin coating layer further comprises 4-9 parts by weight of aluminum sol.
3. The glass fiber reinforced plastic plate as claimed in claim 2, wherein the aluminum sol is prepared by the following method:
dissolving aluminum chloride in water to prepare an aluminum chloride solution with the concentration of 0.4-1 mol/L, then dropwise adding ammonia water with the concentration of 20-30% until the pH value is 8-9, heating to 80-90 ℃, carrying out heat preservation reaction for 1-2 h, then adding citric acid until the pH value is 4-5, uniformly mixing, and carrying out heat preservation reaction for 6-12 h at the temperature of 80-90 ℃ to prepare the aluminum sol.
4. The glass fiber reinforced plastic sheet according to any one of claims 1 to 3, wherein the preparation method of the glass fiber reinforced plastic sheet comprises the following steps:
s1, fully mixing alloy resin, an accelerator, a polymerization inhibitor, a defoaming agent and a curing agent in the raw materials of the fiber resin mixing layer to obtain a resin raw material, coating the resin raw material on the surface of a fiber material, and drying and curing at the temperature of 70-90 ℃ to obtain the fiber resin mixing layer;
and S2, fully mixing the raw materials of the resin coating layer to obtain a resin coating, coating the resin coating on the surface of the fiber resin mixing layer to form the resin coating layer, and drying and curing at the temperature of 70-90 ℃ to obtain the glass fiber reinforced plastic plate.
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Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1601926A (en) * | 1978-05-23 | 1981-11-04 | Uop Inc | Manufacture of alumina sols |
| JPS5580423A (en) * | 1978-12-13 | 1980-06-17 | Hitachi Chem Co Ltd | Low shrinkage unsaturated polyester resin composition |
| JPS5723615A (en) * | 1980-07-17 | 1982-02-06 | Nippon Oil & Fats Co Ltd | Unsaturated polyester resin composition |
| CN1261355C (en) * | 2003-03-20 | 2006-06-28 | 淄博市临淄正华助剂有限公司 | Technique for preparing aluminium sol |
| CN100519154C (en) * | 2005-05-10 | 2009-07-29 | 西北工业大学 | Mehtod for preparing composite material contg. nano-silicon dioxide, polyurethane and cyanate resin |
| CN101280080B (en) * | 2008-05-23 | 2011-07-20 | 中山大学 | Inorganic nano-particle/urethane elastomer/polymer composite material and preparation thereof |
| CN101367973A (en) * | 2008-10-09 | 2009-02-18 | 上海交通大学 | Preparation method for high-strength heat-proof polythene composite material |
| CN102603993A (en) * | 2012-03-09 | 2012-07-25 | 宜兴市兴合树脂有限公司 | Unsaturated polyester resin for winding and method for preparing same |
| CN110527266A (en) * | 2019-08-19 | 2019-12-03 | 浙江衡昶科技有限公司 | A method of improving unsaturated polyester resin glass-reinforced plastic material pultrusion |
| CN112608417A (en) * | 2020-12-17 | 2021-04-06 | 苏州瀚海新材料有限公司 | Low-dielectric-constant polyester material and preparation method thereof |
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