CN105153679A - TPU (thermoplastic polyurethane) composite membrane used for fan blades and preparation method for TPU composite membrane - Google Patents
TPU (thermoplastic polyurethane) composite membrane used for fan blades and preparation method for TPU composite membrane Download PDFInfo
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Abstract
The invention provides a TPU (thermoplastic polyurethane) composite membrane used for fan blades and a preparation method for the TPU composite membrane. The TPU composite membrane is prepared from the following raw materials in parts by weight: 70 to 90 parts of TPU particles, 10 to 25 parts of glass fiber reinforced polybutylene terephthalate, 2 to 10 parts of PVDF (polyvinylidene fluoride), 3 to 8 parts of compatilizer, 1 to 5 parts of pore-foaming agent, 1 to 3 parts of antioxygen and 0.5 to 1 parts of ultraviolet light absorber. The TPU composite membrane provided by the invention is high in strength (the tensile strength can reach 85.1mpa) and high in heat resistance (the maximum vicat softening temperature is 128 DEG C), has good heat insulation property (the minimum heat conductivity coefficient is 0.012w/(m.k)), and is not is easy to separate from adhesive; when the TPU composite membrane is used for the fan blades, the fan blades can be protected to prolong the service life of the fan blades; moreover, the preparation method for the TPU composite membrane is simple.
Description
Technical field
The invention belongs to technical field of polymer materials, particularly relate to a kind of fan blade TPU composite membrane and preparation method thereof.
Background technology
Under current Nonrenewable energy resources day by day shortage, weather sharply changes, environment goes from bad to worse global context, wind energy is subject to various countries as renewable, the environmental protection energy and shows great attention to, also will being the Main way of the current utilization of new energy resources of China, be also the advanced productivity of future electrical energy.In exchange, account for 1/4 pricing by blade cost, the domestic market scale of following 15 years Chinese fan blades will more than 50,000,000,000 yuan.Eleventh Five-Year Plan clearly proposes, and the localization rate of parts and components of the wind power equipments such as the fan blade of newly-built wind energy turbine set must reach more than 70%, and therefore, only in the more than ten years, wind power generation has sizable development space in China, defines the wind electric heating of Present Domestic.
In the course of the work, fan blade will bear the external influences such as powerful wind loading, air scour, sandstone particle impacting, uviolizing to blower fan.The general glass fiber compound material blade adopting the epoxy resin of glass fiber reinforcement at present.
Thermoplastic polyurethane (TPU) is environmental protection macromolecule polymkeric substance, which overcome many defects of PVC and PU skin, not only have most of characteristic of rubber and common plastics, but also have excellent comprehensive physical and chemical property, so the following material that is otherwise known as.TPU film adopts TPU pellet, and the film made by special process, it inherits the outstanding physical property of TPU, and range of application is very extensive.
But TPU film is used for the film on fan blade surface, its thermotolerance, erosion resistance, intensity and desirable not enough with the binding property of sizing agent, be therefore necessary to study a kind of novel TPU laminated film.
Summary of the invention
The object of the present invention is to provide a kind of fan blade TPU composite membrane and preparation method thereof, described TPU compound film strength is high, and thermotolerance is strong; heat transfer coefficient is low; not easily be separated with sizing agent, can fan blade be protected for fan blade surface, extend its duration of service.
For reaching this object, the present invention by the following technical solutions:
On the one hand, the invention provides a kind of fan blade TPU composite membrane, described TPU composite membrane prepares primarily of following raw material by weight:
Glass fiber reinforced polybutylene terephthalate (PBT), its mechanical property and thermotolerance significantly improve relative to polybutylene terephthalate, its tensile strength can reach 135MPa, heat-drawn wire is up to 210 DEG C, exceed the nylon-6 of glass fiber reinforcement, used as the raw material of TPU composite membrane, be conducive to improving TPU compound film strength and thermotolerance.
The F atom contained in the molecular chain of polyvinylidene difluoride (PVDF) (PVDF) and H atom can form hydrogen bond, have good stability, the advantages such as good corrosion resistance.
Experimental result shows, the glass fiber reinforced polybutylene terephthalate (PBT) added in TPU particle and polyvinylidene difluoride (PVDF) (PVDF) can play synergy, substantially increase thermotolerance and the intensity of TPU film.
Described fan blade TPU composite membrane mainly comprises following raw material by weight: TPU particle 70-90 part, as 72 parts, 75 parts, 78 parts, 80 parts, 82 parts, 83 parts, 85 parts or 88 parts etc.; Glass fiber reinforced polybutylene terephthalate 10-25 part, as 12 parts, 13 parts, 15 parts, 16 parts, 18 parts, 20 parts, 22 parts or 24 parts etc.; PVDF2-10 part, as 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts or 9 parts etc.; Compatilizer 3-8 part, as 3 parts, 4 parts, 5 parts, 6 parts or 7 parts etc.; Pore-creating agent 1-5 part, as 2 parts, 3 parts, 4 parts or 5 parts etc.; Oxidation inhibitor 1-3 part, as 1 part, 2 parts or 3 parts; UV light absorber 0.5-1 part, as 0.6 part, 0.7 part, 0.8 part, 0.9 part or 1 part etc.
As preferred technical scheme, described TPU composite membrane prepares primarily of following raw material by weight:
As preferred technical scheme, described TPU composite membrane prepares primarily of following raw material by weight:
Described TPU particle prepares primarily of following raw material by weight: polycaprolactone diols 42-48 part, as 43 parts, 44 parts, 45 parts, 46 parts or 47 parts etc.; PCDL 30-36 part, as 32 parts, 33 parts, 35 parts or 36 parts etc.; Chainextender 8-12 part, as 8 parts, 9 parts, 10 parts, 11 parts or 12 parts etc.; Aliphatic diisocyanate 43-50 part, as 45 parts, 46 parts, 47 parts, 48 parts or 49 parts etc.; Catalyzer 0.005-0.012 part, as 0.006 part, 0.007 part, 0.008 part, 0.01 part or 0.011 part etc.
The number-average molecular weight of described polycaprolactone diols is 2000-5500, as 2200,2300,2500,2700,3000,3500,3800,4000,4500 or 5000 etc.
Preferably, the number-average molecular weight of described PCDL is 1500-3500, as 1800,2000,2500,2800,3000 or 3200 etc.
Preferably, the molecular weight of described aliphatic diisocyanate is 100-500, as 200,300,400 or 500 etc.
Preferably, described chainextender is ethylene glycol, Isosorbide-5-Nitrae butyleneglycol, the combination of 1,6-hexylene glycol ethylene glycol, 1,2-PD, methyl propanediol, 1,3 butylene glycol, glycol ether, 1,6-hexylene glycol or neopentyl glycol a kind of or at least two kinds.
Preferably, described catalyzer is the combination of a kind of in organotin, organo-bismuth or organic zinc or at least two kinds.
Adopt the thermoplastic polyurethane that the polyester type dibasic alcohol of macromolecule, more small molecule chain extender and aliphatic diisocyanate are obtained, its intensity is high with degree of crystallinity, and hardness is large, inter-molecular binding force comparatively greatly, Heat stability is good.
Described pore-creating agent is Cellmic C 121.
Pore-creating agent add the hole making to form uniform 3-5 μm in TPU composite membrane, described hole makes TPU composite membrane have very strong heat-insulating capability.Because the sizing agent of composite membrane used on current fan blade is generally pressure sensitive adhesive, its thermotolerance is poor, easy and composite membrane departs from, therefore, improve the heat-insulating capability of TPU composite membrane, contribute to the tack time improving TPU composite membrane and sizing agent, TPU composite membrane is unlikely to come off after long-time use.Described pore-creating agent is not limited only to Cellmic C 121, also can select other pore-creating agent.
Described compatilizer is the combination of a kind of in SMA resin (phenylethylene-maleic anhydride segmented copolymer), chromium of organic acid complex compound, organic coupling agent, titanate coupling agent or aluminate coupling agent or at least two kinds.
Preferably, described oxidation inhibitor is the combination of a kind of in Hinered phenols antioxidant, suffocated amine antioxidant or phosphite ester kind antioxidant or at least two kinds.
Described ultraviolet absorbers is without particular requirement, and those skilled in the art can select different ultraviolet absorbers as required.Typical but non-limiting ultraviolet absorbers is as salicylate class, benzophenone class, benzotriazole category, group-substituted acrylonitrile, triazines or hindered amines ultraviolet absorbers etc.
On the other hand, the invention provides the preparation method of TPU composite membrane as above, described preparation method comprises the steps:
1) take the TPU particle of formula ratio, glass fiber reinforced polybutylene terephthalate, PVDF, compatilizer, pore-creating agent, oxidation inhibitor and UV light absorber, and mix, obtain mixture;
2) by after mixture drying, through casting machine extrusion moulding, TPU composite membrane is namely obtained.
Step 2) described in drying temperature be 80-90 DEG C, as 82 DEG C, 83 DEG C, 84 DEG C, 85 DEG C, 86 DEG C or 88 DEG C etc., time of drying is 2-3h, as 2h, 2.5h or 3h etc.
Step 2) described in the temperature extruded be 190-195 DEG C, as 192 DEG C, 193 DEG C, 194 DEG C or 195 DEG C etc.
Compared with prior art, beneficial effect of the present invention is:
TPU compound film strength provided by the invention high (tensile strength can reach 85.1MPa), thermotolerance strong (vicat softening temperature is up to 128 DEG C), thermal insulation good (heat transfer coefficient is minimum is 0.012W/ (mK)), not easily be separated with sizing agent, can fan blade be protected for fan blade surface, extend its duration of service; And described TPU composite membrane preparation method is simple.
Embodiment
Technical scheme of the present invention is further illustrated below by embodiment.
Embodiment 1
A kind of fan blade TPU composite membrane, described TPU composite membrane prepares primarily of following raw material by weight:
Described TPU particle is prepared by following raw material by weight:
Wherein, the number-average molecular weight of described polycaprolactone diols is 2000-2500.The number-average molecular weight of described PCDL is 1500-2000.The molecular weight of described aliphatic diisocyanate is 100-200.Described chainextender is ethylene glycol.Described catalyzer is organotin catalysts.
Described pore-creating agent is Cellmic C 121.Described compatilizer is SMA resin.Described oxidation inhibitor is Hinered phenols antioxidant.
The preparation method of described TPU composite membrane is:
1) take the TPU particle of formula ratio, glass fiber reinforced polybutylene terephthalate, PVDF, compatilizer, pore-creating agent, oxidation inhibitor and UV light absorber, and mix, obtain mixture;
2) by mixture after 80-90 DEG C of dry 2-3h, through casting machine extrusion moulding, the temperature extruded is 190-195 DEG C, namely obtains TPU composite membrane.
Embodiment 2
A kind of fan blade TPU composite membrane, described TPU composite membrane prepares primarily of following raw material by weight:
Described TPU particle is prepared by following raw material by weight:
Wherein, the number-average molecular weight of described polycaprolactone diols is 2500-3500.The number-average molecular weight of described PCDL is 2000-2500.The molecular weight of described aliphatic diisocyanate is 200-300.Described chainextender is the combination of Isosorbide-5-Nitrae butyleneglycol and 1,6-hexylene glycol ethylene glycol.Described catalyzer is organozinc catalyst.
Described pore-creating agent is Cellmic C 121.Described compatilizer is the combination of chromium of organic acid complex compound and organic coupling agent.Described oxidation inhibitor is suffocated amine antioxidant.
The preparation method of described TPU composite membrane is:
1) take the TPU particle of formula ratio, glass fiber reinforced polybutylene terephthalate, PVDF, compatilizer, pore-creating agent, oxidation inhibitor and UV light absorber, and mix, obtain mixture;
2) by mixture after 80-90 DEG C of dry 2-3h, through casting machine extrusion moulding, the temperature extruded is 190-195 DEG C, namely obtains TPU composite membrane.
Embodiment 3
A kind of fan blade TPU composite membrane, described TPU composite membrane prepares primarily of following raw material by weight:
Described TPU particle is prepared by following raw material by weight:
Wherein, the number-average molecular weight of described polycaprolactone diols is 3500-4500.The number-average molecular weight of described PCDL is 2500-3000.The molecular weight of described aliphatic diisocyanate is 300-500.Described chainextender is the combination of 1,3 butylene glycol, glycol ether, 1,6-hexylene glycol and neopentyl glycol.Described catalyzer is organic bismuth catalyst.
Described pore-creating agent is Cellmic C 121.Described compatilizer is the combination of titanate coupling agent and aluminate coupling agent.Described oxidation inhibitor is phosphite ester kind antioxidant.
The preparation method of described TPU composite membrane is:
1) take the TPU particle of formula ratio, glass fiber reinforced polybutylene terephthalate, PVDF, compatilizer, pore-creating agent, oxidation inhibitor and UV light absorber, and mix, obtain mixture;
2) by mixture after 80-90 DEG C of dry 2-3h, through casting machine extrusion moulding, the temperature extruded is 190-195 DEG C, namely obtains TPU composite membrane.
Embodiment 4
A kind of fan blade TPU composite membrane, described TPU composite membrane prepares primarily of following raw material by weight:
Wherein, the number-average molecular weight of described polycaprolactone diols is 4500-5500.The number-average molecular weight of described PCDL is 3000-3500.The molecular weight of described aliphatic diisocyanate is 200-400.Described chainextender is Isosorbide-5-Nitrae butyleneglycol.Described catalyzer is organotin catalysts.
Described pore-creating agent is Cellmic C 121.Described compatilizer is titanate coupling agent.Described oxidation inhibitor is Hinered phenols antioxidant.
The preparation method of described TPU composite membrane is:
1) take the TPU particle of formula ratio, glass fiber reinforced polybutylene terephthalate, PVDF, compatilizer, pore-creating agent, oxidation inhibitor and UV light absorber, and mix, obtain mixture;
2) by mixture after 80-90 DEG C of dry 2-3h, through casting machine extrusion moulding, the temperature extruded is 190-195 DEG C, namely obtains TPU composite membrane.
Comparative example 1
Do not contain except glass fiber reinforced polybutylene terephthalate except in the raw material of TPU composite membrane, all the other are identical with embodiment 3.
Comparative example 2
Do not contain except PVDF except in the raw material of TPU composite membrane, all the other are identical with embodiment 3.
Comparative example 3
Do not contain except pore-creating agent except in the raw material of TPU composite membrane, all the other are identical with embodiment 3.
The TPU composite membrane obtained to embodiment 1-4 and comparative example 1-3 carries out performance test, and test result is as shown in table 1.
Wherein, tensile strength test is carried out according to GB/T1040.3-2006; The test of microcaloire softening temperature is carried out according to GB/T1633-2000; Thermal conductivity is obtained by DRY-300F thermal conductivity measuring apparatus.
Table 1
Applicant states; the foregoing is only the specific embodiment of the present invention; but protection scope of the present invention is not limited thereto; person of ordinary skill in the field should understand; anyly belong to those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all drop within protection scope of the present invention and open scope.
Claims (10)
1. a fan blade TPU composite membrane, is characterized in that, described TPU composite membrane prepares primarily of following raw material by weight:
2. TPU composite membrane according to claim 1, is characterized in that, described TPU composite membrane prepares primarily of following raw material by weight:
3. TPU composite membrane according to claim 1 and 2, is characterized in that, described TPU composite membrane prepares primarily of following raw material by weight:
4. according to the TPU composite membrane one of claim 1-3 Suo Shu, it is characterized in that, described TPU particle prepares primarily of following raw material by weight:
5. TPU composite membrane according to claim 4, is characterized in that, the number-average molecular weight of described polycaprolactone diols is 2000-5500;
Preferably, the number-average molecular weight of described PCDL is 1500-3500;
Preferably, the molecular weight of described aliphatic diisocyanate is 100-500;
Preferably, described chainextender is ethylene glycol, Isosorbide-5-Nitrae butyleneglycol, the combination of 1,6-hexylene glycol ethylene glycol, 1,2-PD, methyl propanediol, 1,3 butylene glycol, glycol ether, 1,6-hexylene glycol or neopentyl glycol a kind of or at least two kinds;
Preferably, described catalyzer is the combination of a kind of in organotin, organo-bismuth or organic zinc or at least two kinds.
6. according to the TPU composite membrane one of claim 1-5 Suo Shu, it is characterized in that, described pore-creating agent is Cellmic C 121.
7. according to the TPU composite membrane one of claim 1-6 Suo Shu, it is characterized in that, described compatilizer is the combination of a kind of in SMA resin, chromium of organic acid complex compound, organic coupling agent, titanate coupling agent or aluminate coupling agent or at least two kinds;
Preferably, described oxidation inhibitor is the combination of a kind of in Hinered phenols antioxidant, suffocated amine antioxidant or phosphite ester kind antioxidant or at least two kinds.
8. according to the preparation method of the TPU composite membrane one of claim 1-7 Suo Shu, it is characterized in that, described preparation method comprises the steps:
1) take the TPU particle of formula ratio, glass fiber reinforced polybutylene terephthalate, PVDF, compatilizer, pore-creating agent, oxidation inhibitor and UV light absorber, and mix, obtain mixture;
2) by after mixture drying, through casting machine extrusion moulding, TPU composite membrane is namely obtained.
9. the preparation method of TPU composite membrane according to claim 8, is characterized in that, step 2) described in drying temperature be 80-90 DEG C, time of drying is 2-3h.
10. the preparation method of TPU composite membrane according to claim 8 or claim 9, is characterized in that, step 2) described in the temperature extruded be 195-200 DEG C.
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| CN105924941A (en) * | 2016-06-20 | 2016-09-07 | 苏州科斯曼照明工程有限公司 | Material for manufacturing neon lamp advertising panel |
| CN107099133A (en) * | 2017-04-18 | 2017-08-29 | 东莞市吉鑫高分子科技有限公司 | A kind of new TPU alloy materials and preparation method thereof |
| CN108587113A (en) * | 2018-03-20 | 2018-09-28 | 浙江工业大学 | A kind of preparation method of self-cleaning polyurethane elastomer film |
| WO2020011919A1 (en) * | 2018-07-12 | 2020-01-16 | Basf Se | Glassfiber-reinforced tpu |
| CN112341791A (en) * | 2020-09-21 | 2021-02-09 | 江苏鑫易达新材料科技有限公司 | TPU embossed film for high-temperature-resistant anti-sticking clothes and preparation method thereof |
| WO2021212901A1 (en) * | 2020-04-21 | 2021-10-28 | He Jianxiong | Tpu thin film for express packaging and preparation method therefor |
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| CN105924941A (en) * | 2016-06-20 | 2016-09-07 | 苏州科斯曼照明工程有限公司 | Material for manufacturing neon lamp advertising panel |
| CN107099133A (en) * | 2017-04-18 | 2017-08-29 | 东莞市吉鑫高分子科技有限公司 | A kind of new TPU alloy materials and preparation method thereof |
| CN108587113A (en) * | 2018-03-20 | 2018-09-28 | 浙江工业大学 | A kind of preparation method of self-cleaning polyurethane elastomer film |
| CN108587113B (en) * | 2018-03-20 | 2020-11-24 | 浙江工业大学 | Preparation method of self-cleaning polyurethane elastomer film |
| WO2020011919A1 (en) * | 2018-07-12 | 2020-01-16 | Basf Se | Glassfiber-reinforced tpu |
| WO2021212901A1 (en) * | 2020-04-21 | 2021-10-28 | He Jianxiong | Tpu thin film for express packaging and preparation method therefor |
| CN112341791A (en) * | 2020-09-21 | 2021-02-09 | 江苏鑫易达新材料科技有限公司 | TPU embossed film for high-temperature-resistant anti-sticking clothes and preparation method thereof |
| CN112341791B (en) * | 2020-09-21 | 2022-06-07 | 江苏鑫易达新材料科技有限公司 | TPU embossed film for high-temperature-resistant anti-sticking clothes and preparation method thereof |
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