CN104371625A - High-performance epoxy adhesive for wind power equipment - Google Patents
High-performance epoxy adhesive for wind power equipment Download PDFInfo
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- CN104371625A CN104371625A CN201410727268.5A CN201410727268A CN104371625A CN 104371625 A CN104371625 A CN 104371625A CN 201410727268 A CN201410727268 A CN 201410727268A CN 104371625 A CN104371625 A CN 104371625A
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Abstract
The invention discloses a high-performance epoxy adhesive for wind power equipment. The high-performance epoxy adhesive is formed by uniformly mixing a component A and a component B, the component A is resin, the component B is a curing agent, the component A and the component B are different in color, weight mixing ratio of the component A and the component B is 100:(45-55), and mixing temperature is 20-30 DEG C. The high-performance epoxy adhesive is wide in application range, a workpiece formed by bonding through the adhesive is high in fatigue resistance and weather resistance, the wind power equipment can be ensured to normally run for a long time in severe weather conditions, and the high-performance epoxy adhesive is excellent in using effect. TG value of the epoxy adhesive after curing is 80-85, tensile strength is larger than or equal to 70MPa, bending strength is larger than or equal to 105MPa, and the epoxy adhesive is excellent in performance; the epoxy adhesive does not contain solvent-class components, adhesive layer shrinkage rate after curing is 0.1-0.8% only, and both expansion coefficient and internal stress of the epoxy adhesive are small.
Description
Technical field
The present invention relates to a kind of epoxy resin glue, be specifically related to a kind of wind power equipment high-performance epoxy adhesive.
Background technology
Wind energy is the new forms of energy that a kind of potentiality are very large, and the wind resource that the earth can be used to every year generate electricity about has 10,000,000,000 kilowatts, is almost 10 times of present whole world water power amount.The energy that the annual coal combustion in the current whole world obtains, only have wind-force in 1 year 1/3rd of energy is provided.Therefore, all take much count of both at home and abroad utilizing wind-force to generate electricity, tap a new source of energy.
China is in August, 2008, and Wind Power In China installation total amount just reaches 7,000,000 kilowatts, and account for 1% of China's generating total installation of generating capacity, occupy the world the 5th, this also means that wind-power electricity generation has entered renewable energy source ranks.
The existing tackiness agent be used on wind power equipment of China, there is cohesive force deficiency, the shortcomings such as anti-weather, fatigue resistance difference, so cause the phenomenons such as the assemblies such as time limit of service is short, blade damage easily under severe weather conditions, be a large problem for most domestic wind power equipment manufacturing factory.
For above produced problem, need to research and develop a wind power equipment high-performance epoxy adhesive, this tackiness agent can be widely used in the field such as Aeronautics and Astronautics, wind-powered electricity generation, and the workpiece that bonding is formed has good fatigue resistance, weather resistance, can ensure that wind power equipment can normally run in inclement weather for a long time.Not only cohesive strength is high for this wind power installation epoxy adhesive, and excellent performance, mainly due to the good stability of epoxy adhesive own, when bonding blade, not producing the sagging of vertical surface, can well fill wide gap.Largely avoided the internal stress because heat release produces, improve antifatigue effect.There is splendid result of use.
Summary of the invention
The technical issues that need to address of the present invention are just the defect overcoming prior art, a kind of wind power equipment high-performance epoxy adhesive is provided, this adhesive applications is in extensive range, and the workpiece that bonding is formed has good fatigue resistance, weather resistance, can ensure that wind power equipment can normally run in inclement weather for a long time; This tackiness agent, when bonding blade, does not produce the sagging of vertical surface, can well fill wide gap, largely avoided the internal stress because heat release produces, and improves antifatigue effect, has splendid result of use; This epoxy adhesive TG value after hardening stretches Qiang Du≤70MPa at 80 ~ 85, La, and bent Qiang Du≤105 MPa of Wan, lap shear strength can reach 12 ~ 30 N/mm according to thickness 0.5 ~ 3mm
2, there is splendid performance; Epoxy adhesive is not containing solvent based component, and cured glue layer shrinking percentage only has 0.1 ~ 0.8%, and its coefficient of expansion and internal stress are all very little; Epoxy adhesive cohesive strength is high, and bonding strength reaches 18-25MPa, and T-shaped stripping strength reaches 28-50N/cm, can ensure best adhesiveproperties.
For solving the problem, the present invention adopts technical scheme to be:
Wind power equipment high-performance epoxy adhesive, described epoxy adhesive mixes rear use by first component and component B;
First component is resin, and component B is solidifying agent; First component and component B have distinct colors, so that distinguish two kinds of components in married operation, avoid mixing and consumption mistake;
The Mixing ratio by weight of first component and component B is 100:(40 ~ 55), mixing temperature is 20 ~ 30 DEG C;
The temperature of described epoxy adhesive mixing after fixing is 20 ~ 30 DEG C; during solidification accompanying by the surface temperature of gluing object lower than 35 DEG C; during solidification solidifying agent be less than 1 DEG C/min by the ramp rates of gluing object; thus guarantee the solidification effect of epoxy adhesive the best, obtain best bonding strength.
Preparation method as the first component of resin is:
The first step: synthesizing linear resol, by formaldehyde and phenol according to (0.5 ~ 0.8): the volume ratio of 1 is placed in three-necked bottle, stirs 0.5 hour at 80 DEG C of temperature, then to add salt acid for adjusting pH value be 1, then keeps 80 DEG C of temperature to continue reactions 2 ~ 3 hours; React rear cooling, vacuumized dehydration 2 ~ 6 hours under keeping 60 ~ 80mmHg vacuum pressure, obtain the resol of light yellow viscous liquid shape;
Second step: introduce epoxide group, the epoxy chloropropane of 1.15 ~ 1.20 of the amount of substance of the first step phenol times is added in the phenolic resin product of upper step gained, be warming up to 110 ~ 130 DEG C and material held stationary is refluxed, reacting and add NaOH solution after 1 ~ 3 hour;
The amount of substance of NaOH solution is equal with the amount of substance of epoxy chloropropane; NaOH solution successively adds at twice, and when first time drips NaOH solution, first drip 70 ~ 85% of NaOH solution total amount, the mass concentration of the NaOH solution now dripped is 40 ~ 45%, the NaOH solution of first part is adjusted to this concentration dilution and uses; Dripped off in 2 ~ 2.5 hours, transfer pale yellow color cloud liquid to the system in three-necked bottle, then decompression dehydration; Second time drips NaOH solution, continues to drip remaining NaOH solution, and the mass concentration of the NaOH solution now dripped is adjusted to 6 ~ 8%, and keeps backflow, drips off NaOH solution, be incubated 2h more afterwards in 0.5 ~ 1h; Then use vacuum pump to keep vacuum tightness 1 ~ 4 millibar removing moisture, ensure best in quality and the performance of resin, product is pale yellow transparent thick liquid, namely obtains the first component as resin.
As the component B of solidifying agent, it is the mixture of 3 kinds in triethylene tetramine, diethylenetriamine, tetraethylene pentamine, trimethylhexamethylenediamine, polyetheramine, N-aminoethyl piperazine, isophorone diamine, 4 kinds or 5 kinds.Mixed solidifying agent component effectively can improve the temperature because of the exothermal peak in solidification process, improves its toughness, guarantees the glueability of tackiness agent the best.
Advantage of the present invention and beneficial effect are:
Wind power equipment high-performance epoxy adhesive of the present invention, this adhesive applications is in extensive range, and the workpiece that bonding is formed has good fatigue resistance, weather resistance, can ensure that wind power equipment can normally run in inclement weather for a long time;
Wind power equipment high-performance epoxy adhesive of the present invention, this tackiness agent, when bonding blade, does not produce the sagging of vertical surface, can well fill wide gap, largely avoided the internal stress because heat release produces, improve antifatigue effect, there is splendid result of use;
Wind power equipment high-performance epoxy adhesive of the present invention, this epoxy adhesive TG value after hardening stretches Qiang Du≤70MPa at 80 ~ 85, La, and bent Qiang Du≤105 MPa of Wan, lap shear strength can reach 12 ~ 30 N/mm according to thickness 0.5 ~ 3mm
2, there is splendid performance;
Wind power equipment high-performance epoxy adhesive of the present invention, epoxy adhesive is not containing solvent based component, cured glue layer shrinking percentage only has 0.1 ~ 0.8%, its coefficient of expansion and internal stress are all very little, there is splendid adhesiveproperties and environmental-protecting performance, the volatility that the physical safety of available protecting operator and product are extremely low;
Wind power equipment high-performance epoxy adhesive of the present invention, epoxy adhesive cohesive strength is high, and bonding strength reaches 18-25MPa, and T-shaped stripping strength reaches 28-50N/cm, can ensure best adhesiveproperties.
Embodiment
The following example will further illustrate the present invention.
embodiment 1
The present invention adopts technical scheme to be wind power equipment high-performance epoxy adhesive, and described epoxy adhesive mixes rear use by first component and component B;
First component is resin, and component B is solidifying agent; First component and component B have distinct colors, so that distinguish two kinds of components in married operation, avoid mixing and consumption mistake;
The Mixing ratio by weight of first component and component B is 100:48, and mixing temperature is 20 ~ 30 DEG C;
The temperature of described epoxy adhesive mixing after fixing is 20 ~ 30 DEG C; during solidification accompanying by the surface temperature of gluing object lower than 35 DEG C; during solidification solidifying agent be less than 1 DEG C/min by the ramp rates of gluing object; thus guarantee the solidification effect of epoxy adhesive the best, obtain best bonding strength.
Preparation method as the first component of resin is:
The first step: synthesizing linear resol, is placed in three-necked bottle by formaldehyde and phenol according to the volume ratio of 0.7:1, stir 0.5 hour, then to add salt acid for adjusting pH value is 1 at 80 DEG C of temperature, then keeps 80 DEG C of temperature to continue reactions 2 ~ 3 hours; React rear cooling, vacuumized dehydration 2 ~ 6 hours under keeping 60 ~ 80mmHg vacuum pressure, obtain the resol of light yellow viscous liquid shape;
Second step: introduce epoxide group, the epoxy chloropropane of 1.17 of the amount of substance of the first step phenol times is added in the phenolic resin product of upper step gained, is warming up to 110 ~ 130 DEG C and material held stationary is refluxed, react and add NaOH solution after 1 ~ 3 hour;
The amount of substance of NaOH solution is equal with the amount of substance of epoxy chloropropane; NaOH solution successively adds at twice, and when first time drips NaOH solution, first drip 78% of NaOH solution total amount, the mass concentration of the NaOH solution now dripped is 43%, the NaOH solution of first part is adjusted to this concentration dilution and uses; Dripped off in 2 ~ 2.5 hours, transfer pale yellow color cloud liquid to the system in three-necked bottle, then decompression dehydration; Second time drips NaOH solution, continues to drip remaining NaOH solution, and the mass concentration of the NaOH solution now dripped is adjusted to 7%, and keeps backflow, drips off NaOH solution, be incubated 2h more afterwards in 0.5 ~ 1h; Then use vacuum pump to keep vacuum tightness 1 ~ 4 millibar removing moisture, ensure best in quality and the performance of resin, product is pale yellow transparent thick liquid, namely obtains the first component as resin.
As the component B of solidifying agent, it is the mixture of triethylene tetramine, diethylenetriamine, tetraethylene pentamine, trimethylhexamethylenediamine, polyetheramine 5 kinds.Mixed solidifying agent component effectively can improve the temperature because of the exothermal peak in solidification process, improves its toughness, guarantees the glueability of tackiness agent the best.
embodiment 2
On the basis of embodiment 1, the Mixing ratio by weight of first component and component B is 100:40;
Preparation method as the first component of resin is:
The first step: synthesizing linear resol, is placed in three-necked bottle by formaldehyde and phenol according to the volume ratio of 0.5:1;
Second step: introduce epoxide group, the epoxy chloropropane of 1.15 of the amount of substance of the first step phenol times is added in the phenolic resin product of upper step gained;
First time, when dripping NaOH solution, first drip 70% of NaOH solution total amount, the mass concentration of the NaOH solution now dripped was 40%; Second time drips NaOH solution, continues to drip remaining NaOH solution, and the mass concentration of the NaOH solution now dripped is adjusted to 6%.
As the component B of solidifying agent, it is the mixture of 3 kinds in polyetheramine, N-aminoethyl piperazine, isophorone diamine.
Other parts are identical with embodiment 1.
embodiment 3
On the basis of embodiment 1, the Mixing ratio by weight of first component and component B is 100:55;
Preparation method as the first component of resin is:
The first step: synthesizing linear resol, is placed in three-necked bottle by formaldehyde and phenol according to the volume ratio of 0.8:1;
Second step: introduce epoxide group, the epoxy chloropropane of 1.20 of the amount of substance of the first step phenol times is added in the phenolic resin product of upper step gained;
First time, when dripping NaOH solution, first drip 85% of NaOH solution total amount, the mass concentration of the NaOH solution now dripped was 45%; Second time drips NaOH solution, continues to drip remaining NaOH solution, and the mass concentration of the NaOH solution now dripped is adjusted to 8%.
As the component B of solidifying agent, it is the mixture of triethylene tetramine, trimethylhexamethylenediamine, polyetheramine, N-aminoethyl piperazine 4 kinds.
Other parts are identical with embodiment 1.
embodiment 4
On the basis of embodiment 1, the Mixing ratio by weight of first component and component B is 100:43;
Preparation method as the first component of resin is:
The first step: synthesizing linear resol, is placed in three-necked bottle by formaldehyde and phenol according to the volume ratio of 0.6:1;
Second step: introduce epoxide group, the epoxy chloropropane of 1.16 of the amount of substance of the first step phenol times is added in the phenolic resin product of upper step gained;
First time, when dripping NaOH solution, first drip 73% of NaOH solution total amount, the mass concentration of the NaOH solution now dripped was 41%; Second time drips NaOH solution, continues to drip remaining NaOH solution, and the mass concentration of the NaOH solution now dripped is adjusted to 6.5%.
As the component B of solidifying agent, it is the mixture of 4 kinds in diethylenetriamine, tetraethylene pentamine, polyetheramine, isophorone diamine.
Other parts are identical with embodiment 1.
embodiment 5
On the basis of embodiment 1, the Mixing ratio by weight of first component and component B is 100:52;
Preparation method as the first component of resin is:
The first step: synthesizing linear resol, is placed in three-necked bottle by formaldehyde and phenol according to the volume ratio of 0.75:1;
Second step: introduce epoxide group, the epoxy chloropropane of 1.19 of the amount of substance of the first step phenol times is added in the phenolic resin product of upper step gained;
First time, when dripping NaOH solution, first drip 83% of NaOH solution total amount, the mass concentration of the NaOH solution now dripped was 44%; Second time drips NaOH solution, continues to drip remaining NaOH solution, and the mass concentration of the NaOH solution now dripped is adjusted to 7.5%.
As the component B of solidifying agent, it is the mixture of 3 kinds in triethylene tetramine, trimethylhexamethylenediamine, isophorone diamine.
Other parts are identical with embodiment 1.
embodiment 6
On the basis of embodiment 1, the Mixing ratio by weight of first component and component B is 100:47;
Preparation method as the first component of resin is:
The first step: synthesizing linear resol, is placed in three-necked bottle by formaldehyde and phenol according to the volume ratio of 0.72:1;
Second step: introduce epoxide group, the epoxy chloropropane of 1.18 of the amount of substance of the first step phenol times is added in the phenolic resin product of upper step gained;
First time, when dripping NaOH solution, first drip 76% of NaOH solution total amount, the mass concentration of the NaOH solution now dripped was 42%; Second time drips NaOH solution, continues to drip remaining NaOH solution, and the mass concentration of the NaOH solution now dripped is adjusted to 7%.
As the component B of solidifying agent, it is the mixture of 5 kinds in diethylenetriamine, trimethylhexamethylenediamine, polyetheramine, N-aminoethyl piperazine, isophorone diamine.
Other parts are identical with embodiment 1.
comparative example 1
On the basis of embodiment 1,
First time, when dripping NaOH solution, drip whole NaOH solution, the mass concentration of the NaOH solution now dripped was 43%; Do not carry out the dropping of second time NaOH solution.
Other parts are identical with embodiment 1.
Structure after being solidified by the epoxy adhesive of embodiment 1-3, comparative example 1 carries out Performance Detection, and concrete examination criteria and method are:
(1) the TG value after solidification: adopt GB/T22567-2008 standard, carry out second-order transition temperature test with the differential scanning calorimetry of model DSC200F3;
(2) tensile strength after solidification: adopt ISO 527 standard, carry out the test of tensile strength with microcomputer control electronic universal tester (twin columns flooring machine) model UTM5205;
(3) flexural strength after solidification: adopt ISO 178 standard microcomputer control high/low temperature universal testing machine, model QJ211B-30KN carries out the test of flexural strength;
(4) lap shear strength after solidification: adopt GB7124-2007 standard microcomputer control high/low temperature universal testing machine, model QJ211B-30KN carries out the test of flexural strength;
(5) cured glue layer shrinking percentage: test by GB GB-T 13519-1992 percent thermal shrinkage tester;
(6) epoxy adhesive bonding strength: GB7124-2007 microcomputer control high/low temperature universal testing machine, model QJ211B-30KN carries out the test of cohesive strength;
(7) the T-shaped stripping strength of epoxy adhesive: by GB GB/T 2791 is that DLS-2 electron detachment trier (vertical) is tested by model;
(8) environmental-protecting performance: adopt baking oven BGF-140 to measure inner VOC content according to GB GB/T15022.2-2007.
According to above detection method and standard, that carries out Performance Detection to the structure after the epoxy adhesive of embodiment 1-3, comparative example 1 and solidification thereof the results are shown in Table 1.
Table 1:
| Test item | Embodiment 1 product | Embodiment 2 product | Embodiment 3 product | Comparative example 1 product |
| TG value | 81 | 84 | 85 | 72 |
| Tensile strength (MPa) | 73 | 71 | 76 | 66 |
| Flexural strength (MPa) | 107 | 112 | 109 | 95 |
| Lap shear strength (N/mm 2） | 19 | 26 | 31 | 11 |
| Glue-line shrinking percentage (%) | 0.22 | 0.45 | 0.12 | 0.96 |
| Bonding strength (MPa) | 22 | 21 | 27 | 16 |
| T-shaped stripping strength (N/cm) | 47 | 33 | 42 | 21 |
| Environmental-protecting performance VOC content (%) | 0.008 | 0.011 | 0.010 | 0.008 |
Can draw according to the detection data in table 1, epoxy adhesive prepared by the present invention, there is splendid TG value, tensile strength, flexural strength, lap shear strength, glue-line shrinking percentage, bonding strength, T-shaped stripping strength and environmental-protecting performance, there is extremely low volatile matter content, ensure that its security used and the feature of environmental protection.This adhesive applications is in extensive range, and the workpiece that bonding is formed has good fatigue resistance, weather resistance, can ensure that wind power equipment can normally run in inclement weather for a long time; This tackiness agent, when bonding blade, does not produce the sagging of vertical surface, can well fill wide gap, largely avoided the internal stress because heat release produces, and improves antifatigue effect, has splendid result of use.
Last it is noted that obviously, above-described embodiment is only for example of the present invention is clearly described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of amplifying out or variation be still among protection scope of the present invention.
Claims (3)
1. wind power equipment high-performance epoxy adhesive, is characterized in that, described epoxy adhesive mixes rear use by first component and component B;
First component is resin, and component B is solidifying agent; First component and component B have distinct colors;
The Mixing ratio by weight of first component and component B is 100:(40 ~ 55), mixing temperature is 20 ~ 30 DEG C;
The temperature of described epoxy adhesive mixing after fixing is 20 ~ 30 DEG C, during solidification accompanying by the surface temperature of gluing object lower than 35 DEG C, during solidification solidifying agent be less than 1 DEG C/min by the ramp rates of gluing object.
2. wind power equipment high-performance epoxy adhesive as claimed in claim 1, it is characterized in that, the preparation method as the first component of resin is:
The first step: synthesizing linear resol, by formaldehyde and phenol according to (0.5 ~ 0.8): the volume ratio of 1 is placed in three-necked bottle, stirs 0.5 hour at 80 DEG C of temperature, then to add salt acid for adjusting pH value be 1, then keeps 80 DEG C of temperature to continue reactions 2 ~ 3 hours; React rear cooling, vacuumized dehydration 2 ~ 6 hours under keeping 60 ~ 80mmHg vacuum pressure, obtain the resol of light yellow viscous liquid shape;
Second step: introduce epoxide group, the epoxy chloropropane of 1.15 ~ 1.20 of the amount of substance of the first step phenol times is added in the phenolic resin product of upper step gained, be warming up to 110 ~ 130 DEG C and material held stationary is refluxed, reacting and add NaOH solution after 1 ~ 3 hour;
The amount of substance of NaOH solution is equal with the amount of substance of epoxy chloropropane; First drip 70 ~ 85% of NaOH solution total amount, the mass concentration of the NaOH solution now dripped is 40 ~ 45%; Dripped off in 2 ~ 2.5 hours, transfer pale yellow color cloud liquid to the system in three-necked bottle, then decompression dehydration; Then continue to drip remaining NaOH solution, the mass concentration of the NaOH solution now dripped is adjusted to 6 ~ 8%, and keeps backflow, drips off NaOH solution, be incubated 2h more afterwards in 0.5 ~ 1h; Then use vacuum pump to keep vacuum tightness 1 ~ 4 millibar removing moisture, product is pale yellow transparent thick liquid, namely obtains the first component as resin.
3. wind power equipment high-performance epoxy adhesive as claimed in claim 1, it is characterized in that, as the component B of solidifying agent, it is the mixture of 3 kinds in triethylene tetramine, diethylenetriamine, tetraethylene pentamine, trimethylhexamethylenediamine, polyetheramine, N-aminoethyl piperazine, isophorone diamine, 4 kinds or 5 kinds.
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| CN201410727268.5A CN104371625A (en) | 2014-12-04 | 2014-12-04 | High-performance epoxy adhesive for wind power equipment |
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| CN201410727268.5A CN104371625A (en) | 2014-12-04 | 2014-12-04 | High-performance epoxy adhesive for wind power equipment |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105732954A (en) * | 2016-04-18 | 2016-07-06 | 武汉理工大学 | Epoxy resin containing phenolic hydroxyl groups and preparation method of fire-retardant foam material based on epoxy resin |
| CN106467714A (en) * | 2015-08-18 | 2017-03-01 | 意禾新材料科技（常州）有限公司 | Sheet material production adhesive and apply this adhesive sheet material production method |
| CN106497466A (en) * | 2015-09-06 | 2017-03-15 | 意禾新材料科技（常州）有限公司 | Compact grade laminate production adhesive and the production method of compact grade laminate |
| CN106497467A (en) * | 2015-09-06 | 2017-03-15 | 意禾新材料科技（常州）有限公司 | Sheet material production adhesive and apply the adhesive sheet material production method |
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| CN102329586A (en) * | 2010-07-14 | 2012-01-25 | 烟台德邦科技有限公司 | Epoxy structure adhesive for rotor blades and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106467714A (en) * | 2015-08-18 | 2017-03-01 | 意禾新材料科技（常州）有限公司 | Sheet material production adhesive and apply this adhesive sheet material production method |
| CN106497466A (en) * | 2015-09-06 | 2017-03-15 | 意禾新材料科技（常州）有限公司 | Compact grade laminate production adhesive and the production method of compact grade laminate |
| CN106497467A (en) * | 2015-09-06 | 2017-03-15 | 意禾新材料科技（常州）有限公司 | Sheet material production adhesive and apply the adhesive sheet material production method |
| CN105732954A (en) * | 2016-04-18 | 2016-07-06 | 武汉理工大学 | Epoxy resin containing phenolic hydroxyl groups and preparation method of fire-retardant foam material based on epoxy resin |
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Application publication date: 20150225 |