CN103937388A - Weather-resistant nano-composite gel coat and preparation method thereof - Google Patents
Weather-resistant nano-composite gel coat and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a weather-resistant nano-composite gel coat. The weather-resistant nano-composite gel coat consists of the following components in parts by weight: 100 parts of unsaturated polyester resin, 10-30 parts of styrene, 10-25 parts of modified nano ZnO, 5-8 parts of talcum powder, 3-5 parts of titanium dioxide, 1-3 parts of thixotropic agent, 0.1-0.2 part of thixotropic stabilizer, 0.4-1 part of surface additive, 0-10 parts of mill base and 0.1-0.4 part of accelerant. The invention also provides a preparation method of the weather-resistant nano-composite gel coat. The method comprises the following step of 1) adding the talcum powder, the titanium dioxide, the thixotropic stabilizer and the thixotropic agent sequentially to the unsaturated polyester resin; 2), adding the modified nano ZnO into styrene, dispersing at a high speed and adding to the mixture obtained in the step 1); and 3), adding the mill base, the surface additive and the accelerant into the mixture obtained in the step 2). The weather resistant nano-composite gel coat is mainly used for the surface of the glass reinforced plastics of the cooling tower.
Description
Technical field
This invention relates to nano combined gel coat of a kind of weather resistant and preparation method thereof, and the nano combined gel coat of this weather resistant is mainly used in cooling tower glass fiber reinforced plastic surface.
Background technology
Cooling tower is equipment conventional in industrial circulating water, is usually used in the fields such as Steel Plant, printing and dyeing mill, Medicine Factory, nuclear power plant, air-conditioning, freezer and chemical fibre, oil.Conventional cooling tower tower body is generally glass reinforced plastic at present, and for the material of improving glass reinforced plastic visual appearance and protective glass steel construction layer is not subject to extraneous dielectric corrosion, the glass fiber reinforced plastic surface of being everlasting applies one deck gel coat.Gel coat is the kind of a kind of special applications in unsaturated polyester resin, its chief component thing is macromolecular material, therefore when it is often exposed in the various environment such as sunlight, wind and rain, high temperature, severe cold, As time goes on, its weathering resistance can decline, thereby causes the phenomenon such as efflorescence, variable color.For improving gel coat weather resistance, one method is to use the better unsaturated polyester resin of weather resistance, another kind method is that the filler in gel coat is carried out preferably, because filler can improve the physical strength of gel coat, wear-resisting, water-fast and weather resistance (Cao Xin, the research of weather resistant fire retardant glue coating resin, fibre composite, 2005,1:10-11; Zhang Huijuan, the impact of the each component of gel coat on gel coat aging resistance, East China University of Science,, Engineering Master paper in 2011).
Nano-ZnO is a kind of polyfunctional new oxide, and it has the features such as surface effects, volume effect, quantum size effect and macroscopical tunnel effect that macro object do not have and high-clarity, polymolecularity.In addition, nano-ZnO also has and covers preferably ultraviolet performance, and its UV-preventing rate is up to 98%.But while use nano-ZnO as filler at present, also there are following two problems:
1), nano-ZnO surface can be high, easily reunites, bad with matrix resin consistency, for addressing this problem, normal coupling agent or the tensio-active agent of using carries out surface modification to nano-ZnO at present, but this method of modifying can use a large amount of organic solvents conventionally, as ethanol, toluene etc., their contaminate environment, poisonous to human body, also can increase and reclaim or destroy cost (Shi Zhen etc., the Research on Surface Modification of nano-ZnO, Shanghai coating, 2008,46 (5) 1-3; Wu Wenming, Pan Lei etc., the preparation of the surface modification of nano-ZnO and ZnO/UPR matrix material, thermosetting resin, 2009,24 (5): 44).
2) its addition in matrix resin of nanoparticle after modification is at present little, otherwise can play opposite effect to the performance of resin, as reduce mechanical property, increase dope viscosity cause can not moulding etc. (Wu Wenming, Pan Lei etc., the preparation of the surface modification of nano-ZnO and ZnO/UPR matrix material, thermosetting resin, 2009,24 (5): 44; Wang Haifeng, Xu Yi etc., nanometer Al
2o
3the preparation and property research of Filled PTEF matrix material, plastics industry, 2012,40 (6): 88; Bauer F, et al.Preparation of sctrach and abrasion resistant polymeric nanocomposites by monoer grafting onto nanoparticles, effect of filler partilces and grafting agents, Macromol.Mater.Eng.2002,287,546-552.).Such problem also there will be in the gel coat after ZnO Modified, therefore in gel coat, the addition of nano-ZnO can not be too many, otherwise can cause gel coat viscosity to increase (thickening power), but also the weather resistance of gel coat not had to remarkable enhancement like this.
Summary of the invention
The technical problem to be solved in the present invention is to provide nano combined gel coat of a kind of weather resistant and preparation method thereof; The nano combined gel coat of this weather resistant is mainly used in cooling tower glass fiber reinforced plastic surface.
In order to solve the problems of the technologies described above, the invention provides the nano combined gel coat of a kind of weather resistant, be grouped into by the one-tenth of following weight part: 100 parts of unsaturated polyester resins, vinylbenzene 10-30 part, nano-ZnO 10-25 part after modification, talcum powder 5-8 part, titanium dioxide 3-5 part, thixotropic agent 1-3 part, thixotroping stablizer 0.1-0.2 part, surface modifier 0.4-1 part, mill base 0-10 part, promotor 0.1-0.4 part.
Improvement as the nano combined gel coat of weather resistant of the present invention: the preparation method of the nano-ZnO after modification is:
The nano-ZnO that is 10～60nm by 1 part of particle diameter is added in the deionized water of 1.5～2.5 parts (being preferably 2 parts), after high-speed stirring 10～30 minutes, add again 0.2～0.5 part of properties-correcting agent, then regulating pH is 3～5 (being for example 4), be warming up to again 50～70 DEG C, insulation (50～70 DEG C) stirring reaction 1～3 hour, filters, gained filter cake under room temperature environment vacuum-drying to constant weight; Obtain the nano-ZnO after modification;
Described properties-correcting agent is γ-methacryloxypropyl trimethoxy silane or vinyltriethoxysilane;
Above-mentioned part is weight part.
Remarks explanation: regulate pH to adopt usual manner to carry out, for example, can adopt 10% (weight ratio) HCl solution to regulate.
γ-methacryloxypropyl trimethoxy silane is γ-(methacryloxypropyl) propyl trimethoxy silicane.
Further improvement as the nano combined gel coat of weather resistant of the present invention:
Described unsaturated polyester resin is adjacent benzene-neopentyl glycol type unsaturated polyester resin, isophthalic-neopentyl glycol type unsaturated polyester resin;
Thixotropic agent is gas phase SiO
2, specific surface area is 150～380m
2/ g;
Thixotroping stablizer is the PR600 type thixotroping stablizer that Ke Laien (Clariant) company produces;
Surface modifier is any three kinds or four kinds in BYK-A515, BYK-A555, BYK-S706 and JS-V966;
Mill base is azo pigment class, color lake class, copper phthalocyanine class, condensed ring class and organic macromolecule pigment;
Promotor is cobalt iso-octoate.
The present invention also provides the preparation method of the nano combined gel coat of above-mentioned weather resistant simultaneously, comprises the steps:
1), first unsaturated polyester resin is put into Scattered Kettle, stir and successively adds talcum powder, titanium dioxide, thixotroping stablizer and thixotropic agent down, be uniformly dispersed;
2), in vinylbenzene, add the nano-ZnO after modification, after high speed dispersion, join step 1) in the mixture that forms; Evenly mix;
3), to step 2) gains in add mill base, surface modifier and promotor, after uniform stirring, obtain the nano combined gel coat of weather resistant.
In the present invention, room temperature refers to 15～25 DEG C; High-speed stirring is the rotating speed of 1000-2000rpm; All the other stirrings are the rotating speed of 500～800rpm.
In view of the existing technological deficiency of above-mentioned prior art, the present invention is the nano combined gel coat of a kind of weather resistant of exploitation, will use the nano-ZnO after modification, as a kind of filler, gel coat is carried out to modification.The preparation method of the nano-ZnO after modification of the present invention (, nano-ZnO is carried out to the method for surface modification) taking water as solvent, pollution-free, little to human injury, properties-correcting agent is the silane coupling agent with two keys simultaneously, its can with unsaturated polyester resin generation copolyreaction, therefore can reinforcing filler and matrix between bonding force, can reduce nano-ZnO gel coat mechanical property is produced and destroyed.In addition, the above-mentioned method of modifying setting due to the present invention can carry out good modification to nano-ZnO, therefore its adding proportion in gel coat is higher, can not increase the viscosity of gel coat, therefore it can significantly improve the weather resistance of gel coat on the one hand, also can strengthen on the other hand the performances such as wear-resisting, the hardness of gel coat, thereby reduce the interpolation of other hard filler.
In sum, the present invention is directed to existing cooling tower glass fiber reinforced plastic surface gel coat weather resistance bad, easily efflorescence, this present situation easy to change, by add the nano-ZnO after the modification with good ultraviolet line function of shielding in gel coat, prepared the nano combined gel coat of weather resistant.
The nano combined gel coat of weather resistant prepared by the present invention adopts the artificially-aged method of acceleration of the current international practice and uses standard convention to carry out experimental evaluation with reference to U.S. ASTM-G154 non-metallic material ultraviolet ray fluorescence equipment, the artificial accelerated aging time is 1000 hours, then use full-automatic color difference meter (SC-80C, Beijing Kang Guang opticinstrument company limited) colourimetric number that characterizes aging front and back coating changes (△ E) and yellow value degree variation (△ Yid), and the coating that detects by an unaided eye has or not efflorescence.Experimental result shows, the nano combined gel coat artificial accelerated aging of weather resistant of the present invention is after 1000 hours, its △ E≤1.5, and △ Yid≤1.5, coatingsurface is without efflorescence.
Embodiment
Embodiment 1,
1), the surface modification of nano-ZnO (, the preparation method of the nano-ZnO after modification):
Taking 100g nano-ZnO (particle diameter 20nm) is added in 200g deionized water, high-speed stirring adds γ-methacryloxypropyl trimethoxy silane of 20g after 10 minutes, and to use 10% (weight ratio) HCl regulation system pH be 4, be warming up to subsequently 50 DEG C, and keep this temperature stirring reaction 3 hours, filter, gained filter cake in vacuum-drying under room temperature environment to constant weight; Obtain the nano-ZnO after modification.
2), the preparation of the nano combined gel coat of weather resistant
(1), 100 parts of adjacent benzene-neopentyl glycol type unsaturated polyester resins are added in Scattered Kettle, under stirring, add 8 parts of talcum powder, 5 parts of titanium dioxides, thixotropic agent--gas phase SiO
2(specific surface area 150m
2/ g) 3 parts, thixotroping stablizer---PR6000.2 part; Stir 30 minutes; Be uniformly dispersed thereby realize.
(2), 10 parts of the nano-ZnOs after modification are joined in 10 parts of vinylbenzene, high speed dispersion joins after 30 minutes in the mixture that step (1) forms, uniform stirring 0.5 hour; Mix thereby realize evenly;
(3) in the mixture, forming to step (2), add 0 part of mill base, surface modifier 0.5 part of (being obtained by mixing according to the weight ratio of 1:1:1 by BYK-A515, BYK-A555, BYK-S706) and promotor---0.1 part of cobalt iso-octoate, after uniform stirring 0.5 hour, obtain the nano combined gel coat of weather resistant.
Comparative example 1-1,
By embodiment 1 step 1) in " adding γ-methacryloxypropyl trimethoxy silane of 20g " make " adding γ-methacryloxypropyl trimethoxy silane of 15g ", the other the same as in Example 1 into.
Comparative example 1-2,
By embodiment 1 step 1) in " adding 20g γ-methacryloxypropyl trimethoxy silane " make " adding 60g γ-methacryloxypropyl trimethoxy silane ", the other the same as in Example 1 into.
Comparative example 1-3,
By embodiment 1 step 1) in " adding 20g γ-methacryloxypropyl trimethoxy silane " make " adding 20g3-aminopropyltriethoxywerene werene ", the other the same as in Example 1 into.
Comparative example 1-4,
In embodiment 1, " add 20g γ-methacryloxypropyl trimethoxy silane " and make " adding 20g γ-glycidyl ether oxygen propyl trimethoxy silicane ", the other the same as in Example 1 into.
Comparative example 1-5,
By embodiment 1 step 1) in reaction be modified to " 40 DEG C stirring reaction 4 hours " by " 50 DEG C stirring reaction 3 hours "; The other the same as in Example 1.
Comparative example 1-6,
By embodiment 1 step 1) in reaction be modified to " 80 DEG C stirring reaction 3 hours " by " 50 DEG C stirring reaction 3 hours "; The other the same as in Example 1.
Comparative example 1-7,
Through embodiment 1 step 2) in modification after the consumption of nano-ZnO make 8 parts into by 10 parts; The other the same as in Example 1.
After nano combined gel coat film-forming prepared by above-described embodiment 1 and comparative example 1-1～1-7, artificial accelerated aging 1000h, its performance is in table 1 (detection method is as described above).
Table 1
| ? | △E | △Yid | Have or not efflorescence |
| Embodiment 1 | 1.5 | 1.5 | Nothing |
| Comparative example 1-1 | 1.7 | 2.0 | Have |
| Comparative example 1-2 | 1.8 | 1.9 | Nothing |
| Comparative example 1-3 | 2.8 | 2.9 | Have |
| Comparative example 1-4 | 2.5 | 2.6 | Have |
| Comparative example 1-5 | 2.1 | 2.0 | Nothing |
| Comparative example 1-6 | 2.0 | 2.2 | Have |
| Comparative example 1-7 | 1.6 | 2.0 | Nothing |
Embodiment 2,
1), the surface modification of nano-ZnO
Taking 100g nano-ZnO (particle diameter 40nm) is added in 200g deionized water, high-speed stirring adds γ-methacryloxypropyl trimethoxy silane of 50g after 20 minutes, and to use 10% (weight ratio) HCl regulation system pH be 4, be warming up to subsequently 70 DEG C, and keep this temperature stirring reaction 1 hour, filter, gained filter cake under room temperature environment vacuum-drying to constant weight; Obtain the nano-ZnO after modification.
2), the preparation of the nano combined gel coat of weather resistant
(1), 100 parts of isophthalic-neopentyl glycol type unsaturated polyester resins are added in Scattered Kettle, under stirring, add 6 parts of talcum powder, 4 parts of titanium dioxides, thixotropic agent---gas phase SiO
2(specific surface area 380m
2/ g) 2 parts, thixotroping stablizer----PR6000.1 part; Stir 30 minutes, be uniformly dispersed thereby realize;
(2), 15 parts of the nano-ZnOs after modification are joined in 15 parts of vinylbenzene, high speed dispersion joins after 30 minutes in the mixture that step (1) forms, uniform stirring 0.5 hour; Mix thereby realize evenly;
(3)---5 parts of azo pigment, surface modifier 1 part of (being obtained by mixing according to the mass ratio of 1:1:1 by BYK-A515, BYK-A555, BYK-S706) and promotor---0.1 part of the cobalt iso-octoate that adds mill base in the mixture, forming to step (2), after uniform stirring 0.5 hour, obtain the nano combined gel coat of weather resistant.
Comparative example 2-1,
By embodiment 2 steps 2) in the consumption of " nano-ZnO after modification " make 0 part into by 15 parts, that is, cancel the use of " nano-ZnO after modification "; All the other are with embodiment 2.
Comparative example 2-2,
By embodiment 2 steps 2) in the consumption of " nano-ZnO after modification " make 3 parts into by 15 parts, all the other are with embodiment 2.
Comparative example 2-3,
By embodiment 2 steps 2) in the consumption of " nano-ZnO after modification " make 30 parts into by 15 parts, all the other are with embodiment 2.
After nano combined gel coat film-forming prepared by embodiment 2 and comparative example 2-1～2-3, artificial accelerated aging 1000h, its performance is in table 2.
Table 2
| ? | △E | △Yid | Have or not efflorescence |
| Embodiment 2 | 1.2 | 1.4 | Nothing |
| Comparative example 2-1 | 3.7 | 3.8 | Have |
| Comparative example 2-2 | 1.8 | 2.4 | Nothing |
| Comparative example 2-3 | 1.2 | 1.4 | Nothing |
Embodiment 3.
1), the surface modification of nano-ZnO:
Take 100g nano-ZnO (particle diameter 60nm) in 200g deionized water, high-speed stirring adds 50g vinyltriethoxysilane after 20 minutes, and to use 10% (weight ratio) HCl regulation system pH be 4, be warming up to subsequently 50 DEG C, and keep this temperature stirring reaction 2 hours, filter, gained filter cake under room temperature environment vacuum-drying to constant weight; Obtain the nano-ZnO after modification.
2), the preparation of the nano combined gel coat of weather resistant
(1), 100 parts of isophthalic-neopentyl glycol type unsaturated polyester resins are added in Scattered Kettle, under stirring, add 5 parts of talcum powder, 3 parts of titanium dioxides, thixotropic agent---gas phase SiO
2(specific surface area 250m
2/ g) 1 part, thixotroping stablizer---PR6000.2 part; Churning time 30 minutes, is uniformly dispersed thereby realize;
(2), 25 parts of the nano-ZnOs after modification are joined in 25 parts of vinylbenzene, high speed dispersion joins after 30 minutes in the mixture that step (1) forms, uniform stirring 0.5 hour; Mix thereby realize evenly;
(3)---1 part of copper phthalocyanine class pigment, surface modifier 0.5 part of (being obtained by mixing by weight ratios such as BYK-A515, BYK-A555, BYK-S706, JS-V966) and promotor---0.4 part of the cobalt iso-octoate that adds mill base in the mixture, forming to step (2), after uniform stirring 0.5 hour, obtain the nano combined gel coat of weather resistant.
Comparative example 3-1,
By embodiment 3 steps 1) in the consumption of vinyltriethoxysilane make 60g into by 50g; The other the same as in Example 3.
Comparative example 3-2,
By embodiment 3 steps 1) in the consumption of vinyltriethoxysilane make 15g into by 50g; The other the same as in Example 3.
Comparative example 3-3,
By embodiment 3 steps 2) in modification after the consumption of nano-ZnO make 8 parts into by 25 parts; The other the same as in Example 3.
Comparative example 3-4,
Cancel the step 2 of embodiment 3) (2), that is, step (3) is made into:
(2) in the mixture, forming to step (1), first add 25 parts and the 25 parts vinylbenzene of nano-ZnO after modification;---1 part of copper phthalocyanine class pigment, surface modifier 0.5 part of (being obtained by mixing by weight ratios such as BYK-A515, BYK-A555, BYK-S706, JS-V966) and promotor---0.4 part of the cobalt iso-octoate that adds again mill base, after uniform stirring 0.5 hour, obtain the nano combined gel coat of weather resistant.
After nano combined gel coat film-forming prepared by embodiment 3 and comparative example 3-1～3-4, artificial accelerated aging 1000h, its performance is in table 3.
Table 3
| ? | △E | △Yid | Have or not efflorescence |
| Embodiment 3 | 1.1 | 1.2 | Nothing |
| Comparative example 3-1 | 1.7 | 1.4 | Nothing |
| Comparative example 3-2 | 1.9 | 2.0 | Nothing |
| Comparative example 3-3 | 2.2 | 2.4 | Have |
| Comparative example 3-4 | 2.8 | 2.9 | Have |
Find by above-described embodiment and comparative example, the nano combined gel coat of weather resistant prepared by the present invention has better weather resistance, therefore can use at cooling tower glass fiber reinforced plastic surface.
Finally, what more than enumerate is only several specific embodiments of the present invention, obviously, the invention is not restricted to above embodiment, can also have many distortion.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (4)
1. the nano combined gel coat of weather resistant, it is characterized in that being grouped into by the one-tenth of following weight part: 100 parts of unsaturated polyester resins, vinylbenzene 10-30 part, the nano-ZnO 10-25 part after modification, talcum powder 5-8 part, titanium dioxide 3-5 part, thixotropic agent 1-3 part, thixotroping stablizer 0.1-0.2 part, surface modifier 0.4-1 part, mill base 0-10 part, promotor 0.1-0.4 part.
2. the nano combined gel coat of weather resistant according to claim 1, is characterized in that:
The preparation method of the nano-ZnO after modification is:
The nano-ZnO that is 10～60nm by 1 part of particle diameter is added in the deionized water of 1.5～2.5 parts, after high-speed stirring 10～30 minutes, add again 0.2～0.5 part of properties-correcting agent, then regulating pH is 3～5, be warming up to again 50～70 DEG C, insulated and stirred reaction 1～3 hour, filters, gained filter cake under room temperature environment vacuum-drying to constant weight; Obtain the nano-ZnO after modification;
Described properties-correcting agent is γ-methacryloxypropyl trimethoxy silane or vinyltriethoxysilane;
Above-mentioned part is weight part.
3. the nano combined gel coat of weather resistant according to claim 2, is characterized in that:
Described unsaturated polyester resin is adjacent benzene-neopentyl glycol type unsaturated polyester resin, isophthalic-neopentyl glycol type unsaturated polyester resin;
Thixotropic agent is gas phase SiO
2, specific surface area is 150～380m
2/ g;
Thixotroping stablizer is PR600 type thixotroping stablizer;
Surface modifier is any three kinds or four kinds in BYK-A515, BYK-A555, BYK-S706 and JS-V966;
Mill base is azo pigment class, color lake class, copper phthalocyanine class, condensed ring class and organic macromolecule pigment;
Promotor is cobalt iso-octoate.
4. the preparation method of the nano combined gel coat of weather resistant as described in as arbitrary in claim 1～3, is characterized in that comprising the steps:
1), first unsaturated polyester resin is put into Scattered Kettle, stir and successively adds talcum powder, titanium dioxide, thixotroping stablizer and thixotropic agent down, be uniformly dispersed;
2), in vinylbenzene, add the nano-ZnO after modification, after high speed dispersion, join step 1) in the mixture that forms; Evenly mix;
3), to step 2) gains in add mill base, surface modifier and promotor, after uniform stirring, obtain the nano combined gel coat of weather resistant.
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| CN105400388A (en) * | 2015-12-18 | 2016-03-16 | 福建梭罗复合材料研究有限公司 | Colorful gel coat and preparation method thereof |
| CN105440897A (en) * | 2015-12-19 | 2016-03-30 | 福建梭罗复合材料研究有限公司 | Flame retardant black gel coat for piano and preparation method thereof |
| CN106881881A (en) * | 2017-03-29 | 2017-06-23 | 重庆海庆新材料有限公司 | Weather resistant glass fiber reinforced plastics product vacuum imports processing method |
| CN109321102A (en) * | 2018-10-11 | 2019-02-12 | 上海众挚化工科技有限公司 | A kind of gel coat and its preparation method and application for epoxy resin composite material surface |
| CN110724446A (en) * | 2019-11-26 | 2020-01-24 | 常熟市建安玻璃钢制品有限公司 | Glass fiber reinforced plastic product gel coat for automobile parts and preparation method thereof |
| CN111019494A (en) * | 2019-12-31 | 2020-04-17 | 南京德嘉玻璃钢材料有限公司 | High-weather-resistance gel coat and preparation method thereof |
| CN113004600A (en) * | 2021-02-25 | 2021-06-22 | 浙江金菱制冷工程有限公司 | Cooling tower filler and preparation process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105400388A (en) * | 2015-12-18 | 2016-03-16 | 福建梭罗复合材料研究有限公司 | Colorful gel coat and preparation method thereof |
| CN105440897A (en) * | 2015-12-19 | 2016-03-30 | 福建梭罗复合材料研究有限公司 | Flame retardant black gel coat for piano and preparation method thereof |
| CN106881881A (en) * | 2017-03-29 | 2017-06-23 | 重庆海庆新材料有限公司 | Weather resistant glass fiber reinforced plastics product vacuum imports processing method |
| CN106881881B (en) * | 2017-03-29 | 2019-06-07 | 重庆海庆新材料有限公司 | Weather-proof glass fiber reinforced plastics product vacuum imports processing method |
| CN109321102A (en) * | 2018-10-11 | 2019-02-12 | 上海众挚化工科技有限公司 | A kind of gel coat and its preparation method and application for epoxy resin composite material surface |
| CN110724446A (en) * | 2019-11-26 | 2020-01-24 | 常熟市建安玻璃钢制品有限公司 | Glass fiber reinforced plastic product gel coat for automobile parts and preparation method thereof |
| CN111019494A (en) * | 2019-12-31 | 2020-04-17 | 南京德嘉玻璃钢材料有限公司 | High-weather-resistance gel coat and preparation method thereof |
| CN111019494B (en) * | 2019-12-31 | 2021-10-01 | 南京德嘉玻璃钢材料有限公司 | High-weather-resistance gel coat and preparation method thereof |
| CN113004600A (en) * | 2021-02-25 | 2021-06-22 | 浙江金菱制冷工程有限公司 | Cooling tower filler and preparation process thereof |
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| CN103937388B (en) | 2016-01-20 |
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