CN115340738A - Polydicyclopentadiene resin composition material for wind driven generator blade - Google Patents
Polydicyclopentadiene resin composition material for wind driven generator blade Download PDFInfo
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- CN115340738A CN115340738A CN202211082331.5A CN202211082331A CN115340738A CN 115340738 A CN115340738 A CN 115340738A CN 202211082331 A CN202211082331 A CN 202211082331A CN 115340738 A CN115340738 A CN 115340738A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/70—Wind energy
- Y02E10/72—Wind turbines with rotation axis in wind direction
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Abstract
The invention relates to the field of wind driven generators, in particular to a blade assembly of a wind driven generator. The material of the wind driven generator blade shell is a polydicyclopentadiene composite material which consists of a polydicyclopentadiene resin part and an epoxy resin part, wherein the polydicyclopentadiene resin part accounts for 20-90% by mass, and the epoxy resin part accounts for 10-80% by mass. The polydicyclopentadiene has lower viscosity, so the perfusion speed is higher and the production efficiency is improved. The cost is lower than that of a common blade epoxy resin system in the market, and the weight of the shell component can be reduced by about 2 percent. The dicyclopentadiene resin composition system provided by the invention integrates the advantages of polydicyclopentadiene and epoxy resin, the performance of the prepared composition material is superior to that of a pure dicyclopentadiene perfusion resin system, the toughness of the composite material is increased, the problem that the modulus of the pure dicyclopentadiene resin system is slightly low is solved, the dicyclopentadiene resin composition system can be directly matched with an epoxy sizing agent glass fiber fabric on the current market for use, the existing blade perfusion process does not need to be changed or adjusted, and cost reduction and weight reduction of a blade material can be effectively realized.
Description
Technical Field
The invention relates to the field of wind driven generators, in particular to a blade assembly of a wind driven generator.
Background
With the zero carbon target of each country, non-fossil energy such as wind power and photovoltaic has received more and more attention and attention. Especially, the development of wind power generation is more and more advanced, the single machine power is developed from hundreds of kilowatts to tens of megawatts at present, and the length of the blade of the key part of the single machine power also breaks through 120m. At present, a blade shell of a wind generating set is mainly formed by pouring glass fiber fabrics and core materials into a two-component epoxy resin system under a vacuum condition and then curing the glass fiber fabrics and the core materials. The epoxy resin system for blade consists of main epoxy resin agent, amine curing agent, diluent, etc. The epoxy resin has the characteristics of good process operability, good matching property with fibers, good dimensional stability, low water absorption, low shrinkage rate, good chemical stability, good fatigue resistance and the like, the cured epoxy glass fiber reinforced plastic composite material has excellent mechanical property and thermal property, the glass transition temperature is generally 80-90 ℃, the viscosity of a perfusion epoxy resin system for the blade is 200mPa.s-300mPa.s at room temperature, the perfusion time at a thicker part of the blade shell is longer, and the perfusion time is generally 1.5-3 hours. The post-cure cycle for epoxy resins is generally 6-7 hours at 70 ℃.
Since 2020, the prices of upstream chemical raw materials of epoxy resin, such as bisphenol a, epichlorohydrin, hexanediol and the like, and polyetheramine curing agent and the like, have greatly increased, so that the price of an epoxy resin system for wind power blades has increased from the former 25 yuan/kg to the highest 40 yuan/kg, and thus the cost of fan blades has also greatly increased, and the price of epoxy potting resin for wind power is still 31-32 yuan/kg at present, and the increase is more than 20%.
At present, the longest land fan blade made of epoxy glass fiber reinforced plastics exceeds 90m, and the length of the offshore wind power blade reaches 120m. Weight reduction and cost reduction are major concerns for such large blades. With the arrival of the wind power flat-price internet era in recent years, each host manufacturer faces huge cost pressure, so that how to reduce the cost of the whole machine and improve the market competitiveness of the whole machine become the key points of attention of the wind power industry. Because the cost of the blade accounts for about 25 percent of the cost of the whole blade, the advanced composite material accounts for more than 90 percent of the weight of the whole blade, and the weight of the resin material accounts for about 30 percent, the cost of the resin material is reduced, and the effect of reducing the cost of the whole blade with half effort is achieved.
The viscosity of the epoxy resin is higher at room temperature and is about 200-300mPa.s, so that the pouring time of the large-thickness part of the blade is longer, the mold occupying time of the whole blade shell is increased, the improvement of the production efficiency of the blade is restricted, and the risk of poor pouring caused by local gel is easy to occur; in addition, in recent years, due to the influence of supply and demand relationship of the whole chemical industry, the price of a blade-infused epoxy resin system is increased all the way due to the continuous price increase of raw materials such as bisphenol A, epichlorohydrin and the like of the matrix epoxy resin, and the cost of the blade is directly increased because the resin consumption accounts for about 25% of the weight of the blade, which is contrary to the constant price of wind and fire in the field of wind power generation, so how to reasonably control and reduce the cost of the blade through technical means is a technical problem which needs to be solved in the industry, and all parties in a supply chain make continuous efforts in this respect.
The polydicyclopentadiene resin is a novel resin and is expected to replace epoxy resin to be applied to the field of wind driven generators. However, the research on the polydicyclopentadiene resin for manufacturing the wind driven generator blade is less at present. The polydicyclopentadiene resin has low viscosity of only 10-30mPa.s at room temperature, does not meet the requirements of a blade vacuum infusion process on the resin process performance when applied to the field of wind driven generators, and is not beneficial to fiber infiltration due to low viscosity and strong fluidity, and pure polydicyclopentadiene resin is easy to pump away in the vacuum pumping process, so that the defects of poor infiltration, whitening and the like are caused.
Disclosure of Invention
Aiming at the problems of heavy weight, high cost and the like of a fan blade in the prior art, the invention provides a weight-reducing and cost-reducing preparation raw material taking polydicyclopentadiene resin composite material as a wind driven generator blade shell. The polydicyclopentadiene resin composite material prepared by the method is low in cost, low in viscosity and high in pouring speed, and can be used for remarkably improving the production efficiency of fan blades and reducing the cost.
The purpose of the invention is realized by the following technical scheme:
a polydicyclopentadiene resin composite material is used for preparing a wind driven generator blade shell, and is prepared by mixing a polydicyclopentadiene resin part and an epoxy resin part in proportion, wherein the mass percent of the polydicyclopentadiene resin part is 20-90%, and the mass percent of the epoxy resin part is 10-80%.
Preferably, the polydicyclopentadiene resin part also comprises a catalyst, the catalyst is one of a single-component catalyst, a double-component catalyst, a molybdenum phenol catalyst and a tungsten-triphenylphosphine series complex, and the mass percentage of the catalyst and the polydicyclopentadiene resin is 0.01-0.5%.
Preferably, the one-component catalyst is a ruthenium catalyst, which is one of a first generation Grubbs or a second generation Grubbs.
Preferably, the first component of the bi-component catalyst is a main catalyst which is a complex of one of tungsten, molybdenum, ruthenium, titanium and rhenium, and the second component is a metal organic compound of aluminum, magnesium, tin, zinc and silicon;
the molybdenum phenol catalyst is one of tri-p-methyl phenoxy molybdenum dichloride, tri (2, 4-di-tert-butyl-6-methyl phenoxy) molybdenum dichloride and trinonyl phenoxy molybdenum dioxide.
Preferably, the epoxy resin part includes an epoxy resin main agent and a curing agent.
Preferably, the mass percentage of the epoxy resin main agent to the curing agent is 100;
preferably, the curing agent comprises 44-90% of polyether amine curing agent, 5-16% of isophorone diamine and 5-40% of modified amine by mass.
Preferably, the epoxy resin main agent comprises an epoxy resin and a reactive diluent.
Preferably, the mass fraction of the epoxy resin is 75-95%, and the mass fraction of the reactive diluent is 5-25%;
preferably, the reactive diluent is 1, 6-hexanediol diglycidyl ether.
Compared with the prior art, the invention has the following advantages:
(1) The viscosity of the composition of polydicyclopentadiene resin and epoxy resin is lower, between 50 and 200mPa.s, and is only 30 to 60 percent of that of the epoxy resin, so the perfusion rate is high, the fiber is easy to infiltrate, the production efficiency can be improved, and the mold occupying time is reduced by 1 to 1.5 hr; the mechanical property and fatigue property of the prepared composite material are equivalent to those of epoxy resin, and the process can be the same as that of epoxy resin infusion.
(2) The cost of the composition is 5-15% lower than that of the prior common epoxy resin infusion system, so that the cost of the blade can be effectively reduced, the problem of cost increase caused by price rise of epoxy raw materials can be solved, and a choice is added to the blade epoxy resin infusion system.
(3) The shell component of the wind generating set blade is prepared by the composition through a vacuum infusion process, so that the infusion time can be shortened, the production efficiency can be improved, and the weight of the shell component can be reduced by about 2%.
(4) The dicyclopentadiene resin composition system provided by the invention integrates the advantages of dicyclopentadiene and epoxy resin, the performance of the prepared composite material is superior to that of a pure dicyclopentadiene resin system, the toughness of the composite material is improved, and the problem of slightly low modulus of a pure dicyclopentadiene resin system is solved.
(5) The invention can reduce the influence of price fluctuation and supply of the epoxy resin and the curing agent.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention as set forth hereinafter in connection with the accompanying drawings and examples.
Drawings
Fig. 1 is a schematic diagram of an integrated blade shell filling system, wherein 1 is an integrated filling device, 2 is a vacuum system, 3 is a blade shell mold forming system, 4 is a sensor, 5 is a valve 1, and 6 is a valve 2.
Detailed Description
(1) The resin system related by the invention is a mixture of polydicyclopentadiene resin and epoxy resin according to a proportion, wherein the mass percent of the polydicyclopentadiene resin (containing a catalyst) is 20-90%, and the mass percent of the epoxy resin (containing a curing agent, a diluent and the like) is 10-80%.
The chemical structure of the polydicyclopentadiene resin can be the ruthenium catalyst adopted by the following catalyst which is matched with the polydicyclopentadiene resin, and the polydicyclopentadiene resin can be Grubbs I or Grubbs II; other types of catalysts may also be employed, including classical two-component catalysts, the first component (the main catalyst) being a complex of W, mo, ru, ti, re, etc.; the second component is metal organic compound of Al, mg, sn, zn, si, etc. Or catalysts employing molybdenum phenolic compounds, such as tri-p-methylphenoxy molybdenum dichloride; tris (2, 4-di-tert-butyl-6-methylphenoxy) molybdenum dichloride; molybdenum trisnonylphenoxy oxide or tungsten-triphenylphosphine series complex, and the mass percent of the catalyst and the polydicyclopentadiene resin is 0.01-0.5%.
The Grubbs catalyst generation 1 is named as dichloro (o-isopropoxyphenylmethylene) (tricyclohexylphosphine) ruthenium, having the molecular formula C 28 H 45 C l2 OPRu has a chemical structural formula shown below.
The Chinese name of the 2 nd generation Grubbs catalyst is (1, 3-bis- (2, 4, 6-trimethylphenyl) -2-imidazolidinylidene) dichloro (o-isopropoxybenzylidene) ruthenium, and the molecular formula is C 31 H 38 C l2 N 2 ORu, chemical structural formula is shown below.
The epoxy resin part mainly comprises an epoxy resin main agent and a curing agent (containing a diluent), wherein the epoxy resin is general bisphenol A or F epoxy resin, the epoxy value is 0.5-0.7, the curing agent is modified amine, and the diluent is reactive polyether amine. The mass percentage of the main agent of the epoxy resin (containing reactive diluent, the content of the epoxy resin is 75-95 percent, the diluent is 5-25 percent) and the curing agent (containing modifier, polyether amine curing agent 44-90 percent, isophorone diamine 5-16 percent, modified amine 5-40 percent) is 100 (30-40).
The chemical name of isophorone diamine (IPDA) is 3-aminomethyl-3, 5-trimethylcyclohexylamine, C 9 H 20 N 2 O, an alicyclic diamine, is a mixture formed by two isomers of 3-aminomethyl-3, 5-trimethylcyclohexylamine, and has the following chemical structural formula.
The epoxy resin reactive diluent is 1, 6-hexanediol diglycidyl ether with a molecular formula of O (CH) 2 CH)CH 2 O(CH 2 ) 6 OCH 2 (CHCH 2 )O。
(2) The combined material provided by the invention is poured into a wind driven generator blade shell by adopting the equipment shown in the attached figure 1 of the specification. The apparatus of figure 1 consists of an integrated infusion apparatus, vacuum system and blade shell mould forming system.
In the 3-blade shell mold forming system, single-layer glass fiber or carbon fiber pultruded plate lamination (or beam cap prefabricated part prepared by adopting vacuum infusion process) with the thickness of 5mm is placed in a shell, and a layer of 200-300g/m is placed between an upper pultruded plate and a lower pultruded plate 2 Then according to the design requirements of blade structure, spreading epoxy sizing agent or dicyclopentadiene resin sizing agent and other general glass fiber (fabric), structural core material PET (polyethylene terephthalate) foam, PVC (polyvinyl chloride) foam and balsawood and the like on the glass fiber or carbon glass mixed mesh clothAnd finally manufacturing a vacuum bag in the shell mold, wherein the vacuum bag is composed of auxiliary materials such as a flow guide net, a porous film, demolding cloth, a vacuum bag film and the like, and the specific layering sequence is carried out according to the specific blade structure design drawing requirements. In the laying process of the glass fibers and the core materials, the mold has a heating function, and the maximum heating temperature is more than or equal to 80 ℃. It is recommended to use a thicker (85-150 g/m) 2 ) The nylon release fabric can be dried before use, and can also be unsaturated polyester release fabric. The water content of the glass fiber fabric is required to be less than or equal to 0.1 percent.
(3) The vacuum system 2 is that the vacuum degree of the material in the mould is reduced to be within 10mbar through a compressor and a pipeline system, and meanwhile, the vacuum state of the material system in the mould is continuously kept in the vacuum infusion process.
(4) The integrated infusion device 1 adopts a two-component independent defoaming principle, automatically mixes the two components, inputs resin into a vacuum bag system through a fixed pipeline under certain pressure, ensures that no bubbles exist in the resin and the temperature in the resin is controllable, and adopts an online infusion process, namely a mode of directly connecting an injection device with an injection port of a mold and directly outputting the resin for infusion. Different from the traditional manual perfusion mode, the integrated perfusion system does not need to defoam the resin independently in advance, so that the temperature rise of the resin caused by defoaming after mixing is avoided, and the bubbles caused by repeatedly pouring the resin are reduced. The on-line pouring can better control the defoaming quality of the resin, prolong the service time of the resin, reduce the pouring blush caused by bubbles and improve the pouring quality.
The requirements for an integrated perfusion apparatus are as follows:
4.1, the system has an online perfusion function, can be automatically started and stopped for switching, and can automatically adjust the flow according to the resin dosage requirement;
4.2, the temperature control function is realized, the resin temperature at the discharge port is controlled to be 16-30 ℃, and the stability is maintained;
4.3 has the functions of resin stirring and single defoaming, and the defoaming pressure is less than or equal to 3mBar;
4.4 the mixing ratio requires the weight ratio of 100 (0.1-40);
4.5 the mixing proportion is accurately measured, the mass deviation is less than or equal to 1 percent, and the discharge amount is more than or equal to 20kg/min;
4.6 has a full Chinese operation interface, the menu setting is simple and clear, and the fault alarm can be in acousto-optic cooperation.
(5) The invention 4 relates to a pressure sensor of an integrated pouring device, which is embedded beside a glue injection port of a vacuum system of a mould and has the function of feeding back the pressure of the glue injection port to the integrated pouring device in real time through a line, thereby dynamically adjusting the pressure of a glue injection pipeline, indirectly controlling the pouring rate of resin glue solution in a shell mould and ensuring the pouring quality.
(6) When the surface temperature of the glass fiber lamination layer of the vacuum bag reaches 28-30 ℃, the infusion is started, and the glue injection port is gradually opened in the infusion process to ensure that the resin completely infiltrates the fibers.
(7) After pouring, heating according to the curing requirement, keeping the temperature at 40-60 ℃ for 1-3 hours, then heating to 65-85 ℃ (preferably 70 ℃), keeping the temperature for 2-4 hours, and after the mold is cooled to room temperature, demolding the shell.
Example 1
The forming process of the blade SS surface (pressure surface) shell with more than 80 meters:
1. the formulation ratio of the resin composition of this case was as follows: 60 parts of polydicyclopentadiene resin, 0.012 part of Grubbs second-generation ruthenium catalyst, 25.2 parts of E-51 epoxy resin, 4.4 parts of 1,6 parts of hexanediol diglycidyl ether serving as a diluent, 8.32 parts of a polyether amine curing agent, 1.04 parts of IPDA isophorone diamine and 1.04 parts of an anacardol modified amine curing agent (also called natural long-chain substituted phenol aldehyde amine curing agent).
2. The components are mixed and stirred after being defoamed separately according to the proportion requirement by an integrated filling device to form uniform and consistent glue solution.
3. Layering: according to the layering requirement and the process file requirement of the structural design of the SS-surface blade shell, firstly, the glass fiber pultrusion plates with the single-layer thickness of 5mm are placed into a shell mold (a layer of 200-300g/m is placed between an upper layer of pultrusion plate and a lower layer of pultrusion plate) 2 Glass fiber gridding cloth) and sequentially laying glass fiber cloth and core materials and manufacturing a vacuum bag, wherein the glass fiber can adopt a fabric of epoxy sizing agent or dicyclopentadiene resin sizing agent, and the root of the shell adopts PET200 foam or a 150-density structure core of balsawoodThe shell is made of PET150 foam and PVC60 foam or HP110E foam.
4. When the temperature of the uppermost layer of the glass fiber lamination reaches 25 ℃, resin infusion is carried out, and because the viscosity is low, the infusion time is generally finished within 1 hour, which is shortened by at least 1 hour compared with a pure epoxy resin system.
5. Curing the polydicyclopentadiene resin composition composite shell:
5.1 after the completion of the infusion, the mold heating program was set to 50 ℃ with 1 vacuum pressure and the temperature was maintained for 1 hour, and then the temperature was raised to 80 ℃ and maintained for 4 hours.
5.2 in the curing process, covering heat preservation cotton on the surface of the product, removing the product when the temperature of the surface exceeds 70 ℃, dissipating heat, and covering again after an exothermic peak.
5.3 in the pre-curing process, the glue injection port and the glue injection pipeline are prevented from being covered with heat insulation cotton.
5.4 later stage, corresponding post-curing is required, and the post-curing period is 70 ℃ multiplied by 6hr.
And 5.5, after the solidification is finished, naturally cooling to room temperature, demolding, and taking out the blade shell.
The mechanical properties of the resin system provided by the invention are compared with those of pure poly-dicyclopentene and pure epoxy resin systems as follows:
the mechanical properties of the resin system provided by the invention are compared with those of a pure poly-dicyclopentene and pure epoxy resin system uniaxial glass fiber composite material UD1250 (Zhejiang jumbo E7 glass fiber, epoxy sizing agent type) as follows:
Claims (10)
1. the polydicyclopentadiene resin composite material is used for preparing a wind driven generator blade shell and is characterized in that a polydicyclopentadiene resin part and an epoxy resin part are mixed in proportion, wherein the mass percent of the polydicyclopentadiene resin part is 20-90%, and the mass percent of the epoxy resin part is 10-80%.
2. The combined material as claimed in claim 1, wherein the polydicyclopentadiene resin part further comprises a catalyst, the catalyst is one of a single-component catalyst, a bi-component catalyst, a molybdenum phenol catalyst and a tungsten-triphenylphosphine series complex, and the mass percentage of the catalyst to the polydicyclopentadiene resin is 0.01-0.5%.
3. The composition of claim 2, wherein the one-component catalyst is a ruthenium catalyst that is one of Grubbs one generation or Grubbs two generation.
4. The composition according to claim 3, wherein the first component of the two-component catalyst is a main catalyst which is a complex of one of tungsten, molybdenum, ruthenium, titanium and rhenium, and the second component is a metal organic compound of aluminum, magnesium, tin, zinc and silicon.
The molybdenum phenol catalyst is one of tri-p-methyl phenoxy molybdenum dichloride, tri (2, 4-di-tert-butyl-6-methyl phenoxy) molybdenum dichloride and trinonyl phenoxy molybdenum dioxide.
5. The composition of claim 1, wherein the epoxy resin portion comprises an epoxy resin base and a curing agent.
6. The composition according to claim 5, wherein the mass percentages of the epoxy resin main agent and the curing agent are 100.
7. The composition according to claim 5 or 6, wherein the curing agent comprises 44-90% by mass of polyether amine curing agent, 5-16% by mass of isophorone diamine, and 5-40% by mass of modified amine.
8. The composition of claim 5 or 6, wherein the epoxy resin host comprises an epoxy resin and a reactive diluent.
9. The composition according to claim 8, wherein the mass fraction of the epoxy resin is 75-95% and the mass fraction of the reactive diluent is 5-25%.
10. The composition of claim 9, wherein the reactive diluent is 1, 6-hexanediol diglycidyl ether.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211082331.5A CN115340738A (en) | 2022-09-06 | 2022-09-06 | Polydicyclopentadiene resin composition material for wind driven generator blade |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211082331.5A CN115340738A (en) | 2022-09-06 | 2022-09-06 | Polydicyclopentadiene resin composition material for wind driven generator blade |
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