CN115340738A - Polydicyclopentadiene resin composition material for wind driven generator blade - Google Patents

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

A kind of polydicyclopentadiene resin composition material for wind power generator blade

technical field

The invention relates to the field of wind power generators, in particular to a blade assembly of the wind power generator.

Background technique

With the introduction of zero-carbon targets in various countries, non-fossil energy such as wind power and photovoltaics has received more and more attention and attention. In particular, the development of wind power is changing with each passing day. The power of a single machine has grown from a few hundred kilowatts to more than a dozen megawatts, and the length of its key component blades has also exceeded 120m. At present, the wind turbine blade shell is mainly made of two-component epoxy resin system, which is poured into glass fiber fabric and core material under vacuum conditions and then cured. The commonly used epoxy infusion resin system for blades is composed of epoxy resin main agent, amine curing agent, diluent and so on. Epoxy resin has the characteristics of good process operability, good matching with fibers, good dimensional stability, low water absorption, low shrinkage, good chemical stability, and good fatigue resistance. The mechanical properties of the cured epoxy FRP composite material And thermal performance is excellent, the glass transition temperature is generally 80°C-90°C, the viscosity of the impregnated epoxy resin system for the blade is 200mPa.s-300mPa.s at room temperature, and the pouring time is longer in the thicker part of the blade shell , generally takes 1.5--3 hours. The post-curing cycle of epoxy resin is generally 6-7 hours at 70°C.

Since 2020, the prices of upstream chemical raw materials for epoxy resins such as bisphenol A, epichlorohydrin, hexylene glycol, etc., and polyether amine curing agents have risen sharply, resulting in the price of epoxy resin systems for wind turbine blades from the previous 25 yuan/kg, the highest rose to 40 yuan/kg, so the cost of fan blades has also risen sharply. At present, the price of epoxy infusion resin for wind power is still 31-32 yuan/kg, an increase of more than 20%.

At present, the longest onshore wind turbine blades made of epoxy fiberglass has exceeded 90m, and the length of offshore wind turbine blades has reached 120m. For such large blades, weight reduction and cost reduction are the main directions that the industry pays attention to. In recent years, with the advent of the era of wind power grid parity, all main engine manufacturers are facing huge cost pressures. How to reduce the cost of the whole machine and improve the market competitiveness of the whole machine has become the focus of the wind power industry. Since the cost of the blade accounts for about 25% of the cost of the whole machine, and advanced composite materials account for more than 90% of the weight of the entire blade, of which the weight of the resin material accounts for about 30%. Therefore, reducing the cost of the resin material will reduce the cost of the entire blade. Will have the effect of getting twice the result with half the effort.

Due to the high viscosity of epoxy resin at room temperature, about 200-300mPa.s, this will lead to a longer pouring time for the thick part of the blade, thus increasing the mold-taking time of the entire blade shell and restricting the production efficiency of the blade In addition, due to the impact of supply and demand in the entire chemical industry in recent years, raw materials such as bisphenol A and epichlorohydrin for matrix epoxy resin have continued to rise in price. As a result, the price of blade impregnation epoxy resin system has been rising all the way. Since the amount of resin accounts for about 25% of the weight of the blade, it directly leads to an increase in the cost of the blade, which is contrary to the constant pursuit of "wind and fire at the same price" in the field of wind power generation. Therefore, how to reasonably control and reduce the cost of blades through technical means is a technical problem that must be solved in the industry, and all parties in the supply chain are making continuous efforts in this regard.

Polydicyclopentadiene resin is a new type of resin, which is expected to replace epoxy resin in the field of wind power generators. However, there are few studies on making wind turbine blades from polydicyclopentadiene resins at present. Polydicyclopentadiene resin has a low viscosity at room temperature, only 10-30mPa.s. When it is used in the field of wind power generators, it does not meet the requirements of the blade vacuum infusion process for resin performance. Due to its low viscosity and strong fluidity, pure Polydicyclopentadiene resin is easy to be pumped away during the vacuuming process, which is not conducive to the infiltration of fibers, resulting in defects such as poor infiltration and whitening.

Contents of the invention

The invention aims at the problems of large weight and high cost of fan blades in the prior art, and provides a weight-reducing and cost-reducing polydicyclopentadiene resin composite material as a raw material for preparing a wind turbine blade shell. The polydicyclopentadiene resin combination material prepared by the invention has low cost, low viscosity and fast pouring rate, and can significantly improve the production efficiency of fan blades and reduce costs.

The purpose of the present invention is achieved through the following technical solutions:

A polydicyclopentadiene resin combination material is used to prepare wind turbine blade shells, and the polydicyclopentadiene resin part is mixed with the epoxy resin part in proportion, wherein the mass percentage of the polydicyclopentadiene resin part is 20-90%, the mass percentage of the epoxy resin part is 10%-80%.

Preferably, the polydicyclopentadiene resin part also includes a catalyst, and the catalyst is one of a single-component catalyst, a two-component catalyst, a molybdenum phenol catalyst, a tungsten-triphenylphosphine series complex, and the catalyst and The mass percentage of the polydicyclopentadiene resin is 0.01-0.5%.

Preferably, the single-component catalyst is a ruthenium catalyst, which is one of Grubbs first generation or Grubbs second generation.

Preferably, 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 aluminum, magnesium, tin, zinc, silicon A metal organic compound in

The molybdenum phenol catalyst is tri-p-methylphenoxy molybdenum dichloride, tris(2,4-di-tert-butyl-6-methylphenoxy) molybdenum dichloride, trinonylphenoxy dichloride One of the molybdenum oxides.

Preferably, the epoxy resin part includes an epoxy resin base and a curing agent.

Preferably, the mass percentage of epoxy resin main agent and curing agent is 100:30～100:40;

Preferably, the curing agent includes 44-90% polyetheramine curing agent, 5-16% isophorone diamine and 5-40% modified amine in terms of mass fraction.

Preferably, the epoxy resin main agent includes epoxy resin and reactive diluent.

Preferably, the mass fraction of epoxy resin is 75%-95%, and the mass fraction of reactive diluent is 5%-25%;

Preferably, the reactive diluent is 1,6-hexanediol diglycidyl ether.

Compared with the prior art, the present invention has the following advantages:

(1) the composition of polydicyclopentadiene resin and epoxy resin involved in the present invention, its viscosity is relatively low, between 50-200mPa.s, only the viscosity 30-60% of epoxy resin, so perfusion The speed is fast, it is easy to infiltrate the fiber, which can improve the production efficiency and reduce the mold time by 1-1.5 hours; the mechanical properties and fatigue properties of the composite material are equivalent to those of epoxy resin, and the process can be used the same as epoxy resin infusion craft.

(2) The cost of the composition is 5%-15% lower than the currently commonly used perfusion epoxy resin system, so the cost of the blade can be effectively reduced, and the problem of cost increase caused by the price increase of epoxy raw materials can be solved, and it is also for the blade. Infusion resin systems add an option.

(3) The above composition is used to prepare shell parts of blades of wind power generators through a vacuum infusion process, which can shorten the infusion time, improve production efficiency, and reduce the weight of the shell parts by about 2%.

(4) the dicyclopentadiene resin composition system that the present invention relates to has synthesized the advantage of dicyclopentadiene and epoxy resin, the performance of the composite material made is better than pure dicyclopentadiene resin system, has both increased composite material Toughness, and solve the problem of the slightly lower modulus of the pure polydicyclopentadiene resin system.

(5) The present invention can reduce the influence of price fluctuation and supply of epoxy resin and curing agent.

Other advantages, objectives and characteristics of the present invention will partly be embodied through the following embodiment description, and part will also be understood by those skilled in the art through the research and practice of the present invention, the present invention will be further done below in conjunction with accompanying drawing and embodiment instruction of.

Description of drawings

Figure 1 is a schematic diagram of the integrated filling system of the blade shell, 1 is the integrated filling equipment, 2 is the vacuum system, 3 is the mold forming system of the blade shell, 4 is the sensor, 5 is the valve 1, and 6 is the valve 2.

Detailed ways

(1) The resin system involved in the present invention is the proportional mixture of polydicyclopentadiene resin and epoxy resin, wherein the mass percent of polydicyclopentadiene resin (containing catalyst) is 20-90%, epoxy resin ( The mass percent of the mixing ratio including curing agent, diluent, etc.) is 10%-80%.

The chemical structure of polydicyclopentadiene resin is as follows. The catalyst used in conjunction with it can be the ruthenium catalyst adopted, which can be Grubbs first generation or Grubbs second generation; other types of catalysts can also be used, including classic two-component catalysts, the first group The first component (main catalyst) is a complex of W, Mo, Ru, Ti, Re, etc.; the second component is a metal organic compound such as Al, Mg, Sn, Zn, Si, etc. Or use molybdenum phenolic compound catalysts, such as tri-p-methylphenoxy molybdenum dichloride; tri(2,4-di-tert-butyl-6-methylphenoxy) molybdenum dichloride; trinonylbenzene Oxymolybdenum dioxide, etc., or tungsten-triphenylphosphine series complexes, etc., the mass percentage of catalyst and polydicyclopentadiene resin is 0.01-0.5%.

The Chinese name of the first-generation Grubbs catalyst is dichloro(o-isopropoxyphenylmethylene)(tricyclohexylphosphine)ruthenium, and its molecular formula is C ₂₈ H ₄₅ C _l2 OPRu, and its chemical structure is shown below.

The Chinese name of the second-generation Grubbs catalyst is (1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene) dichloro(o-isopropoxybenzylidene) Ruthenium, the molecular formula is C ₃₁ H ₃₈ C ₁₂ N ₂ ORu, and its chemical structure is shown below.

The epoxy resin part mainly consists of epoxy resin main agent and curing agent (including diluent). The epoxy resin is generally a general-purpose bisphenol A or F epoxy resin with an epoxy value of 0.5-0.7. The curing agent is modified The diluent is a reactive polyether amine. Epoxy resin main agent (including active diluent, epoxy resin content is 75-95%, diluent is 5-25%) and curing agent (including modifier, polyetheramine curing agent 44-90%; Alone diamine 5-16%; Modified amine 5-40%) The mass percentage is 100:(30-40).

The chemical name of isophoronediamine (IPDA) is 3-aminomethyl-3,5,5-trimethylcyclohexylamine, C ₉ H ₂₀ N ₂ O, is a cycloaliphatic diamine, is The mixture formed by the two isomers of 3-aminomethyl-3,5,5-trimethylcyclohexylamine has the following chemical structure.

The reactive diluent for epoxy resin is 1,6-hexanediol diglycidyl ether, the molecular formula is O(CH ₂ CH)CH ₂ O(CH ₂ ) ₆ OCH ₂ (CHCH ₂ )O.

(2) The combined material provided by the present invention is poured into the wind turbine blade shell by using the equipment in the accompanying drawing 1 of the specification. The equipment in accompanying drawing 1 is made up of integral pouring equipment, vacuum system and blade shell mold forming system.

3. In the blade shell mold forming system, the single-layer thickness of 5mm glass fiber or carbon fiber pultruded board laminate (or the beam cap prefabricated part prepared by vacuum infusion process) is placed in the shell, and the upper and lower layers of pultruded board Put a layer of 200-300g/ ^m2 glass fiber or carbon fiber or carbon glass hybrid mesh cloth between them, and then according to the design requirements of the blade structure, general-purpose glass fiber such as epoxy sizing agent or dicyclopentadiene resin sizing agent ( Fabric) and structural core material PET (polyethylene terephthalate) foam, PVC (polyvinyl chloride) foam and balsa wood, etc. are placed in the shell mold, and finally a vacuum bag is made, which is composed of a guide net, a It is composed of auxiliary materials such as porous film, release cloth and vacuum bag film, and the specific layering sequence is carried out in accordance with the requirements of the specific blade structure design drawings. During the laying process of glass fiber and core material, the mold needs to have a heating function, and the maximum heating temperature is ≥80°C. It is recommended to use thicker (85-150g/m ² ) nylon release cloth. The release cloth can be dried before use, or unsaturated polyester release cloth can be used. The moisture content of glass fiber fabric is required to be ≤0.1%.

(3) 2 Vacuum system means that the vacuum degree of the material in the mold is reduced to less than 10mbar through the compressor and the pipeline system, and at the same time, the material system in the mold is kept in a vacuum state during the vacuum infusion process.

(4) In the present invention, 1 integrated perfusion equipment refers to adopting the principle of separate degassing of two components and automatically mixing the resin into the vacuum bag system under a certain pressure through a fixed pipeline to ensure that there are no air bubbles in the resin and the temperature inside the resin Controllable, on-line infusion process refers to the method of directly connecting the injection equipment with the injection port of the mold, and directly outputting the resin for infusion. Different from the traditional manual infusion method, the integrated infusion system does not need to degas the resin separately in advance, which avoids the temperature rise of the resin caused by degassing after mixing, and also reduces the air bubbles introduced by repeated pouring of the resin. Online perfusion can better control the quality of resin defoaming, prolong the use time of resin, reduce the whitening of perfusion caused by air bubbles, and improve the perfusion quality.

The requirements for integrated perfusion equipment are as follows:

4.1 With online perfusion function, it can automatically start and stop switching, and the flow rate can be automatically adjusted according to the demand of resin consumption;

4.2 With temperature control function, control the temperature of the resin at the discharge port to 16-30°C and keep it stable;

4.3 It has the functions of resin stirring and separate defoaming, and the defoaming pressure is ≤3mBar;

4.4 The mixing ratio requires a weight ratio of 100: (0.1-40);

4.5 The mixing ratio is accurate, the mass deviation is ≤1%, and the output is ≥20kg/min;

4.6 It has a full Chinese operation interface, the menu setting is simple and clear, and the fault alarm can be coordinated with sound and light.

(5) In the present invention, 4 is the pressure sensor of the integrated pouring equipment. Its form is to be embedded next to the glue injection port of the mold vacuum system, and its function is to feed back the pressure of the glue injection port to the integral pouring equipment in real time through the circuit, thereby dynamically adjusting The pressure of the glue injection pipeline indirectly controls the pouring rate of the resin glue in the shell mold to ensure the pouring quality.

(6) When the surface temperature of the glass fiber laminate in the vacuum bag reaches 28-30°C, start pouring, and gradually open the injection port during the pouring process to ensure that the resin completely infiltrates the fiber.

(7) After the pouring is completed, start to heat up according to the curing requirements. First, keep the temperature at 40-60°C for 1-3 hours, then raise the temperature to 65-85°C (preferably 70°C), keep it warm for 2-4 hours, and wait for the mold to After cooling down to room temperature, the demoulding of the shell is completed.

Example 1

The shell forming process of the blade SS surface (pressure surface) above 80 meters:

1. The formula ratio of the resin composition in this case is as follows: 60 parts of polydicyclopentadiene resin, 0.012 parts of Grubbs second-generation ruthenium catalyst, 25.2 parts of E-51 epoxy resin, and 1,6 hexanediol diglycidol diluent 4.4 parts of ether, 8.32 parts of polyether amine curing agent, 1.04 parts of IPDA isophorone diamine, 1.04 parts of cardanol modified amine curing agent (also known as natural long-chain substituted phenalkamine curing agent).

2. The components are mixed and stirred according to the proportion requirements through the integrated infusion equipment after separate defoaming to form a uniform glue.

3. Lamination: According to the lamination requirements of the SS surface blade shell structure design and the requirements of the process documents, the glass fiber pultruded board with a single layer thickness of 5mm is laminated into the shell mold (the upper and lower layers of the pultruded board are laminated). Put a layer of 200-300g/ ^m2 glass fiber mesh cloth between them), carry out the sequential lamination of glass fiber cloth and core material and make vacuum bags, the glass fiber can use epoxy sizing agent or dicyclopentadiene resin sizing agent The base of the shell is made of PET200 foam or balsa 150-density structural core material, and the shell is made of PET150 foam and PVC60 foam or HP110E foam.

4. When the temperature of the uppermost layer of the glass fiber laminate reaches 25°C, the resin infusion is performed. Due to the low viscosity, the infusion time is generally completed in 1 hour, which is at least 1 hour shorter than that of the pure epoxy resin system.

5. Polydicyclopentadiene resin composition composite shell curing:

5.1 After the filling is completed, set the mold heating program at 50°C for 1 hour while maintaining a vacuum pressure, and then raise the temperature to 80°C for 4 hours.

5.2 During the curing process, cover the surface of the product with insulation cotton, remove it when the surface exceeds 70°C, and dissipate heat, and cover it again after the exothermic peak passes.

5.3 During the pre-curing process, avoid covering the injection port and the injection pipeline with insulation cotton.

5.4 Corresponding post-curing is also required in the later stage, and the post-curing cycle is 70°C×6hr.

5.5 After the curing is completed, after the temperature is naturally lowered to room temperature, the demoulding is carried out, and the blade shell is taken out.

Resin system provided by the present invention is compared with the mechanical properties of pure polybicyclodipentene and pure epoxy resin system as follows:

The resin system provided by the present invention is compared with the mechanical properties of pure polybicyclodipentene and pure epoxy resin system uniaxial glass fiber composite material UD1250 (Zhejiang Jushi 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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