CN113637130B - Modified polyurethane for wind power blade pultrusion plate - Google Patents
Modified polyurethane for wind power blade pultrusion plate Download PDFInfo
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- CN113637130B CN113637130B CN202110948098.3A CN202110948098A CN113637130B CN 113637130 B CN113637130 B CN 113637130B CN 202110948098 A CN202110948098 A CN 202110948098A CN 113637130 B CN113637130 B CN 113637130B
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- power blade
- phenolic resin
- polyurethane
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 58
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 56
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 229920005862 polyol Polymers 0.000 claims abstract description 27
- 150000003077 polyols Chemical class 0.000 claims abstract description 26
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 23
- 229920000570 polyether Polymers 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000004970 Chain extender Substances 0.000 claims abstract description 16
- 125000003158 alcohol group Chemical group 0.000 claims abstract description 12
- 239000006082 mold release agent Substances 0.000 claims abstract description 11
- 239000013530 defoamer Substances 0.000 claims abstract description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 43
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 24
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 17
- 229920002866 paraformaldehyde Polymers 0.000 claims description 17
- 239000008098 formaldehyde solution Substances 0.000 claims description 16
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims description 11
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 11
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims description 11
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 11
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
- CTNICFBTUIFPOE-UHFFFAOYSA-N 2-(4-hydroxyphenoxy)ethane-1,1-diol Chemical compound OC(O)COC1=CC=C(O)C=C1 CTNICFBTUIFPOE-UHFFFAOYSA-N 0.000 claims description 4
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 claims description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- WHMDKBIGKVEYHS-IYEMJOQQSA-L Zinc gluconate Chemical compound [Zn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O WHMDKBIGKVEYHS-IYEMJOQQSA-L 0.000 claims description 3
- CANRESZKMUPMAE-UHFFFAOYSA-L Zinc lactate Chemical compound [Zn+2].CC(O)C([O-])=O.CC(O)C([O-])=O CANRESZKMUPMAE-UHFFFAOYSA-L 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- 239000000600 sorbitol Substances 0.000 claims description 3
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 229960000314 zinc acetate Drugs 0.000 claims description 3
- 239000011746 zinc citrate Substances 0.000 claims description 3
- 235000006076 zinc citrate Nutrition 0.000 claims description 3
- 229940068475 zinc citrate Drugs 0.000 claims description 3
- 239000011670 zinc gluconate Substances 0.000 claims description 3
- 235000011478 zinc gluconate Nutrition 0.000 claims description 3
- 229960000306 zinc gluconate Drugs 0.000 claims description 3
- 239000011576 zinc lactate Substances 0.000 claims description 3
- 229940050168 zinc lactate Drugs 0.000 claims description 3
- 235000000193 zinc lactate Nutrition 0.000 claims description 3
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 3
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 3
- 229940077935 zinc phosphate Drugs 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 23
- 229920005989 resin Polymers 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 11
- 239000002131 composite material Substances 0.000 abstract description 10
- -1 phenolic aldehyde Chemical class 0.000 abstract description 2
- 229920001568 phenolic resin Polymers 0.000 description 18
- 239000005011 phenolic resin Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 230000018044 dehydration Effects 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 208000005156 Dehydration Diseases 0.000 description 6
- 229920005749 polyurethane resin Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- 229920013683 Celanese Polymers 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002888 oleic acid derivatives Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- ADJMNWKZSCQHPS-UHFFFAOYSA-L zinc;6-methylheptanoate Chemical compound [Zn+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O ADJMNWKZSCQHPS-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
- C08G8/30—Chemically modified polycondensates by unsaturated compounds, e.g. terpenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Wind Motors (AREA)
Abstract
The invention relates to modified polyurethane for a wind power blade pultrusion plate, in particular to a composite plate for a wind power blade girder, which is suitable for a pultrusion process, and belongs to the technical field of wind power. The invention solves the technical problem of providing phenolic aldehyde modified polyurethane for a wind power pultrusion plate, which comprises a component A and a component B, wherein the component A comprises the following components: 1 to 20 parts of 2-functionality polyether polyol, 70 to 90 parts of 3-functionality polyether polyol, 5 to 15 parts of modified phenolic resin, 1 to 5 parts of alcohol chain extender, 0.01 to 2 parts of defoamer, 0.001 to 1 part of gel catalyst and 1 to 3 parts of internal mold release agent; the B component comprises polymeric MDI. According to the invention, the modified phenolic resin is introduced into the polyurethane, so that the glass transition temperature of the resin is greatly improved, and the obtained pultruded polyurethane has the outstanding advantages of moderate gel time, low viscosity, high strength, high glass transition temperature and the like, completely meets the technical requirements of the wind power blade girder, and can be used as the pultruded polyurethane for the wind power blade girder.
Description
Technical Field
The invention relates to modified polyurethane for a wind power blade pultrusion plate, in particular to a composite material for a wind power blade girder, which is suitable for a pultrusion process, and belongs to the technical field of wind power.
Background
The preparation of the composite material mainly comprises the processes of vacuum pouring, mould pressing, winding, pultrusion and the like. The pultrusion process has the outstanding advantages of simple equipment, low manufacturing cost, high production efficiency and the like, is convenient for forming an automatic production line, and has stable product quality; the reinforced material can be fully exerted, and the mechanical property is high, in particular to the longitudinal strength and modulus; the effective utilization rate of raw materials is high, and no corner waste is generated basically; the longitudinal and transverse strength of the section bar can be adjusted to adapt to different use requirements, and the length of the section bar can be cut according to the requirements.
Compared with epoxy resin, vinyl and unsaturated resin in the traditional pultrusion process, the polyurethane resin has the outstanding advantages of low viscosity, high reaction speed, high strength, strong toughness, good fatigue and the like. As the length of wind power blades is longer and longer, weight reduction of the blades is also increasingly emphasized, and the preparation of the polyurethane pultrusion plate by adopting the pultrusion process replaces the traditional vacuum pouring process to prepare the blade girder, so that the wind power blades become a new trend. Although the application of the polyurethane in the fields of pultrusion doors and windows, shelves, cable bridges and the like is reported at present, no research report on the pultrusion polyurethane for wind power blade girders exists at present. The main problem of the polyurethane for the pultrusion process currently marketed is that the glass transition temperature is low (Tg is less than 100 ℃), the high strength and the high glass transition temperature cannot be unified, and the requirements of the wind power blade on matrix resin and the pultrusion FRP technology cannot be met completely.
Patent CN201910235171.5 reports that the reactive monomer with unsaturated double bond and polyether polyol are mixed as polyol component, free radical initiator and polymeric MDI are used as isocyanate component, and the main problem of the pultrusion polyurethane system formed by this scheme is that the glass transition temperature is low, which cannot be used in the field of wind power blade pultrusion composite material.
Patent CN202110005461.8 mainly reports that PM130, 2-functional and 3-functional polyether polyols and aliphatic polyols are used as chain extenders, gel catalysts, ultraviolet absorbers, internal mold release agents and the like to form a high-strength composite material pultrusion polyurethane system for vehicles, but the mechanical properties are poor and the glass transition temperature is low.
Patent CN201510795935.8 discloses a polyurethane resin system and a method for preparing a pultruded fiber composite material, which has short gel time and low glass transition temperature, and cannot be used for a pultruded plate of a wind power blade.
Patent CN201410057086.1 discloses a two-component polyurethane composition specially used for composite material pultrusion process, mainly composed of 100 parts of polyol, 1-10 parts of chain extender, 0.1-0.6 part of catalyst, 1-5 parts of release agent and 100-150 parts of mixture of polyisocyanate and modified isocyanate, etc., which still does not solve the problem of high glass transition temperature.
The phenolic resin has higher glass transition temperature and high-temperature heat resistance, and the glass transition temperature of the polyurethane system can be theoretically improved by adding the rigid structural phenolic with benzene rings into the polyurethane system. However, phenolic resins are various in types and mainly comprise thermosetting and thermoplastic phenolic resins, different phenolic molar ratios, catalyst types, reaction conditions and the like, various types of phenolic resins can be obtained, part of the phenolic resins are incompatible with a polyurethane system, layering is easy to carry out after the phenolic resins are added, the viscosity of the part of the phenolic resins is high, the viscosity of the system is greatly increased after the phenolic resins are added, the alkalinity of the part of the phenolic resins is high, the gel time is greatly shortened after the phenolic resins are added, the part of the phenolic resins are obtained by amine catalysis, the defects of a casting body and FRP products are caused after the phenolic resins are added, and the mechanical properties are reduced. The selection of a proper phenolic resin to improve the glass transition temperature on the premise of ensuring the mechanical strength of the phenolic resin is still a technical problem to be solved.
Patent CN201910021718.1 discloses a polyurethane/phenolic resin based high-temperature-resistant fireproof composite material and a preparation method thereof, wherein a polyurethane prepolymer and phenolic resin are added into a single-neck flask, then ethylenediamine is added, rapid stirring reaction is carried out, and then a char forming agent is added to obtain a glue solution for standby; mixing the glue solution, the corn stalk fiber and the fly ash, pouring into a mould, and curing and forming to obtain the polyurethane/phenolic resin-based high-temperature-resistant fireproof composite material, wherein the material has limited mechanical properties and cannot be used in wind power blades.
Disclosure of Invention
Aiming at the defects, the technical problem solved by the invention is to provide the modified phenolic resin, and the glass transition temperature of the modified phenolic resin can be improved by adding the modified phenolic resin into a polyurethane system, so that the modified phenolic resin is suitable for wind power blades.
The modified phenolic resin is prepared from the following components in parts by weight: 100-140 parts of paraformaldehyde, 80-120 parts of formaldehyde solution, 300-350 parts of phenol, 50-80 parts of cardanol, 30-70 parts of furfuryl alcohol and 5-10 parts of toluene.
In one specific embodiment of the invention, the modified phenolic resin is prepared from the following components in parts by weight: 120 parts of paraformaldehyde, 100 parts of formaldehyde solution, 310 parts of phenol, 70 parts of cardanol, 50 parts of furfuryl alcohol and 8 parts of toluene.
In one embodiment of the invention, the aldehyde content in the paraformaldehyde is more than or equal to 96wt% based on formaldehyde; the formaldehyde concentration in the formaldehyde solution is 35-40 wt%. In one embodiment of the invention, the aldehyde content in the paraformaldehyde is 96wt% in terms of formaldehyde, and the formaldehyde concentration in the formaldehyde solution is 37wt%.
In one embodiment of the invention, the modified phenolic resin has a viscosity of 300 to 500mpas, a moisture content of 0.1wt% or less, and a hydroxyl number of 200 to 300. In one embodiment of the invention, the modified phenolic resin has a viscosity of 450mpas, a moisture content of 0.07wt% and a hydroxyl number of 248.
In one specific embodiment of the invention, the modified phenolic resin is prepared by the following method: mixing paraformaldehyde, formaldehyde solution, phenol, cardanol and furfuryl alcohol, adding a catalyst, raising the temperature to 60-65 ℃ at the rate of 0.1-1 ℃ per minute, reacting for 60-70 min, removing water, adding toluene, continuously raising the temperature to 105-120 ℃, preserving heat, reacting for 20-40 min, and dehydrating (the dehydration at this time can also be called secondary dehydration) to obtain the modified phenolic resin.
In one embodiment of the invention, the temperature is raised to 60℃at a rate of 0.5℃per minute.
In some embodiments of the invention, the catalyst comprises at least one of zinc lactate, zinc acetate, zinc phosphate, zinc citrate, zinc sulfate, zinc gluconate, zinc nitrate, and zinc naphthenate.
The second technical problem to be solved by the invention is to provide modified polyurethane for a wind power blade pultrusion plate.
The invention relates to modified polyurethane for a wind power blade pultrusion plate, which comprises a component A and a component B, wherein,
The component A comprises the following components in parts by weight: 1 to 20 parts of 2-functionality polyether polyol, 70 to 90 parts of 3-functionality polyether polyol, 5 to 15 parts of modified phenolic resin, 1 to 5 parts of alcohol chain extender, 0.01 to 2 parts of defoamer, 0.001 to 1 part of gel catalyst and 1 to 3 parts of internal mold release agent; the modified phenolic resin is the modified phenolic resin of any one of claims 1 to 6;
The B component comprises polymeric MDI.
In some embodiments of the invention, the alcohol chain extender is at least one of 1, 4-butanediol, ethylene glycol, 1, 6-hexanediol, hydroquinone dihydroxyethyl ether, glycerol, trimethylolpropane, pentaerythritol, diethylene glycol, neopentyl glycol, sorbitol, and diethylaminoethanol.
In some embodiments of the invention, the gel catalyst comprises at least one of an organotin-based catalyst, an organobismuth-based catalyst, and an organozinc-based catalyst.
In some embodiments of the invention, the internal mold release agent comprises at least one of a zinc hard fatty acid and a polymeric silicone oil.
The invention also provides application of the modified polyurethane for the wind power blade pultrusion plate in preparing wind power blades.
The modified polyurethane for the wind power blade pultrusion plate has the advantages of low mixing viscosity, moderate gel time, high glass transition temperature (Tg) of more than 105 ℃, high glass transition temperature and good mechanical property, meets the technical requirements of the wind power blade on matrix resin and pultrusion FRP, and can be used as the pultrusion polyurethane for the wind power blade girder.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts specific raw materials to prepare the modified phenolic resin, and the modified phenolic resin can be used in a polyurethane system to improve the glass transition temperature, the tensile strength and the modulus of the resin.
According to the modified phenolic resin, the modified phenolic resin is introduced, the glass transition temperature of the resin is greatly improved under the condition that the physical and chemical properties and the mechanical strength of the resin are not affected, and the obtained modified polyurethane for the wind power blade pultrusion plate has the outstanding advantages of moderate gel time, low viscosity, excellent mechanical properties, high glass transition temperature and the like, completely meets the technical requirements of wind power blade girders, and can be used as the pultrusion polyurethane for the wind power blade girders.
Drawings
FIG. 1 is a schematic drawing of the polyurethane pultrusion process of example 4 of the present invention.
Detailed Description
The modified phenolic resin is prepared from the following components in parts by weight: 100-140 parts of paraformaldehyde, 80-120 parts of formaldehyde solution, 300-350 parts of phenol, 50-80 parts of cardanol, 30-70 parts of furfuryl alcohol and 5-10 parts of toluene.
The modified phenolic resin is prepared by adopting specific raw materials and proportions, can be used in a polyurethane system, is introduced into the polyurethane system, and greatly improves the glass transition temperature of the resin under the condition that the physicochemical property and mechanical strength of the resin are not affected.
In one specific embodiment of the invention, the modified phenolic resin is prepared from the following components in parts by weight: 120 parts of paraformaldehyde, 100 parts of formaldehyde solution, 310 parts of phenol, 70 parts of cardanol, 50 parts of furfuryl alcohol and 8 parts of toluene.
As the polymer of formaldehyde, commercially available one having CAS number 30125-89-4 can be used. In one embodiment of the invention, the aldehyde content in the paraformaldehyde is more than or equal to 96wt% based on formaldehyde; the formaldehyde concentration in the formaldehyde solution is 35-40 wt%. In one embodiment of the invention, the aldehyde content in the paraformaldehyde is 96wt% in terms of formaldehyde, and the formaldehyde concentration in the formaldehyde solution is 37wt%. The formaldehyde solution may be commercially available.
In one embodiment of the invention, the modified phenolic resin has a viscosity of 300 to 500mpas, a moisture content of 0.1wt% or less, and a hydroxyl number of 200 to 300. In one embodiment of the invention, the modified phenolic resin has a viscosity of 450mpas, a moisture content of 0.07wt% and a hydroxyl number of 248. The viscosity of the invention adopts a rotational viscometer method, the measurement standard is GB/T22235, the measurement temperature is 25 ℃, and a Brookfield U.S. Bowler fem DV-II+pro digital display viscometer is adopted. The modified phenolic resin of the present invention may be prepared by methods conventional in the art.
In one specific embodiment of the invention, the modified phenolic resin is prepared by the following method: mixing paraformaldehyde, formaldehyde solution, phenol, cardanol and furfuryl alcohol, adding a catalyst, raising the temperature to 60-65 ℃ at the rate of 0.1-1 ℃ per minute, reacting for 60-70 min, removing water, adding toluene, continuously raising the temperature to 105-120 ℃, preserving heat, reacting for 20-40 min, and dehydrating (the dehydration at this time can also be called secondary dehydration) to obtain the modified phenolic resin.
Wherein, when the reaction is carried out for 60-70 min at 60-65 ℃, the water is removed when the viscosity of the system reaches 75 mpas. The method of dehydrating may be conventional in the art including, but not limited to, turning on vacuum dehydration.
In one embodiment of the invention, the temperature is raised to 60℃at a rate of 0.5℃per minute.
After the temperature is raised to 105-120 ℃ and the reaction is carried out under the heat preservation, the dehydration is also needed until the moisture content is less than or equal to 0.1 percent. Methods of dewatering include, but are not limited to, vacuum dewatering.
The catalyst may employ a conventional phenol formaldehyde condensation catalyst, and in some embodiments of the invention, the catalyst comprises at least one of zinc lactate, zinc acetate, zinc phosphate, zinc citrate, zinc sulfate, zinc gluconate, zinc nitrate, and zinc naphthenate. The catalyst is used in an amount conventional in the art and will not be described in detail herein.
The invention relates to modified polyurethane for a wind power blade pultrusion plate, which comprises a component A and a component B, wherein,
The component A comprises the following components in parts by weight: 1 to 20 parts of 2-functionality polyether polyol, 70 to 90 parts of 3-functionality polyether polyol, 5 to 10 parts of modified phenolic resin, 1 to 5 parts of alcohol chain extender, 0.01 to 1 part of defoamer, 0.001 to 1 part of gel catalyst and 1 to 3 parts of internal mold release agent; the modified phenolic resin is the modified phenolic resin disclosed by the invention;
The B component comprises polymeric MDI.
In the component A, the polyether polyol with 2 functionality is polyether polyol with 2 functionality, the polyether polyol with 3 functionality is polyether polyol with 3 functionality, and both the polyether polyol with 2 functionality and the polyether polyol with 3 functionality can be commercially available.
In the present invention, the alcohol chain extender is a commonly used polyurethane chain extender for extending the molecular weight of polyurethane and increasing the molecular weight thereof. Polyfunctional alcohol chain extenders commonly used in the art are suitable for use in the present invention and include, but are not limited to, 1, 4-Butanediol (BDO), ethylene glycol, diethylene glycol, 1, 6-hexanediol, hydroquinone dihydroxyethyl ether (HQEE), glycerol, trimethylolpropane (TMP), pentaerythritol, diethylene glycol (DEG), neopentyl glycol (NPG), sorbitol, diethylaminoethanol (DEAE) and the like.
As the defoaming agent, those commonly used in the art, such as BYK088, BYK053, BYK1506, epiff card EFKA-2722, etc., can be used.
Gel catalysts may also be employed as commonly used in the art, including but not limited to one or more of organotin catalysts, organobismuth catalysts, and organozinc catalysts. Wherein the organotin catalyst includes, but is not limited to, stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, T9, T12, T131, etc.; the organobismuth catalysts include, but are not limited to, bismuth isooctanoate, DY-20, biCAT8118, biCAT8108, biCAT8124, biCAT8106, and the like; the organozinc catalysts include, but are not limited to, zinc isooctanoate, ZCAT-Y16, ZCAT-Y18, and the like.
The internal mold release agents described herein may be those known to those skilled in the art for use with polyurethanes, including but not limited to zinc hard fatty acids, oleic acid esters, polymeric silicone oils, and the like.
In component B, polymeric MDI may also be used commercially, including but not limited to the following brands of polymeric MDI: PM130, PM200, PM400, 5005, M20S, M R.
In a specific embodiment of the invention, the A component and the B component are mixed according to the mass ratio of 1:1-2 when in use, and the polyurethane can be obtained after curing.
The invention also provides application of the modified polyurethane for the wind power blade pultrusion plate in preparing wind power blades.
The modified polyurethane for the wind power blade pultrusion plate has the advantages of low mixing viscosity, moderate gel time, high glass transition temperature (Tg) of more than 105 ℃, high glass transition temperature and good mechanical property, meets the technical requirements of the wind power blade on matrix resin and pultrusion FRP, and can be used as the pultrusion polyurethane for the wind power blade girder.
The following describes the invention in more detail with reference to examples, which are not intended to limit the invention thereto. The raw materials used in the examples are as follows:
96% paraformaldehyde, celanese, 96.3% in content, is purchased from Shanghai Dongdi chemical industry Ind.
Liquid formaldehyde, available from Chengdu chemical Co., ltd, content 37%.
Phenol, purchased from beijing yanshan petrochemical industry, has a content of 99.99%.
Cardanol, model YLT-001, available from Tengzhou Yalante Inc., 97.8% content.
Furfuryl alcohol, available from Henan Corp Chemie Co., ltd, was 99.5% in water content, 0.03%.
2-Functionality polyether polyol, trade name PPG4000, molecular weight 4100, available from Shanghai chain collection chemical Co.
3 Functionality polyether polyol, brand DV125, molecular weight 350, available from Shandong blue Star east chemical Co., ltd.
Alcohol chain extenders, 1,4 Butanediol (BDO) species, were purchased from blue Star chemical New materials Co.
Gel catalyst, stannous octoate, type, commercially available from Dabco T9 defoamer, wittig, shanghai, inc., organosilicon BYK053, commercially available from Pick chemical Co.
Internal mold release agent, 1968RAC, available from acler, usa.
Example 1
Preparation of modified phenolic resin:
The specific weight proportions of 96% paraformaldehyde, 37% formaldehyde, phenol, cardanol and furfuryl alcohol are shown in Table 1 after the materials are added in proportion. Then adding zinc naphthenate catalyst, raising the temperature to 60 ℃ at the rate of 0.5 ℃ per minute, reacting at 60-65 ℃ for 60-70min, stopping the reaction when the viscosity reaches 75mpas, starting vacuum to remove water 1, adding toluene, continuously raising the temperature to 105-120 ℃, preserving heat for 30min, starting vacuum dehydration 2, and stopping dehydration when the water content is less than 0.1%. Pouring out the materials in the bottle to obtain the modified phenolic resin. The viscosity, moisture and hydroxyl number of the modified phenolic resin were measured, and the results are shown in Table 2.
TABLE 1
Wherein, the measurement of the viscosity adopts a Brookfield American Bowler fem DV-II+pro digital display viscometer, the measurement standard is GB/T22235, and the measurement temperature is 25 ℃.
The measurement of the hydroxyl value was carried out by the method specified in national standard GB/T7383-2007.
TABLE 2
| Numbering device | Viscosity, 25 ℃ (mpas) | Moisture (wt%) | Hydroxyl value |
| 1# | 450 | 0.07 | 248 |
| 2# | 479 | 0.05 | 225 |
| 3# | 397 | 0.08 | 267 |
| 4# | 465 | 0.06 | 232 |
| 5# | 414 | 0.05 | 238 |
Example 2
Preparation of polyurethane System:
And (3) preparing the component A, namely uniformly mixing the 2-functionality polyether polyol, the 3-functionality polyether polyol, the modified phenolic resin 1# prepared in the example 1, the alcohol chain extender, the defoamer, the gel catalyst and the internal mold release agent to obtain the component A, wherein the proportion of each component is shown in the table 3.
And the component B comprises the following components: commercially available polymeric MDI, trade name PM200 was used.
TABLE 3 Table 3
The component A and the component B are mixed according to 100:118, and measuring the mixing viscosity and gel time, and measuring the mechanical properties of casting materials, and the results are shown in tables 4 and 5. Because the polyurethane reaction speed is very fast, the polyurethane is reacted immediately after mixing, and the materials are stirred for 1min after the A, B components are mixed, and then vacuum defoamed for 1min, and the measurement is carried out.
Gel time was measured using a Gardco model GT-SHP-220 gel time measuring instrument, weighing 100g total of A/B components in proportion each time, placing into an aluminum foil cup, immersing the rotating rotor of the instrument into the reaction mixture, starting the device to record time, and starting to rotate by a motor-driven stirrer. When the specific maximum torque of the device is reached (when the mixed resin is present in a high viscosity or solid state at this time), the motor stops rotating and the corresponding gel time can be read on the device.
TABLE 4 Table 4
| Numbering device | Mixing viscosity, 25 ℃/mpas | Gel time, 25 ℃/min |
| 2-1 | 474.5 | 25 |
| 2-2 | 488.4 | 30 |
| 2-3 | 465.2 | 28 |
| 2-4 | 476.6 | 28 |
| 2-5 | 468.8 | 29 |
| Comparative example 1 | 481.3 | 22 |
| Comparative example 2 | 502.3 | 12 |
| Comparative example 3 | 577.5 | 12 |
Wherein, comparative example 2 was conducted as inventive example 2 in the method disclosed in patent CN 201080054523.4. Comparative example 3 a polyurethane system prepared according to the process of patent CN 201510795935.8. The preparation method comprises the following steps: the polyether polyol component (set as a) is: 2.55g of DL400, 63.81g of polyether polyol TEP330N, 18.71g of TMN450, 5.10g of alcohol chain extender DPG, 0.85g of alcohol chain extender TMP, 2.55g of amine chain extender, 0.829g of ultraviolet absorber 171, 0.29g of light stabilizer Lowilite94, 0.034g of antioxidant ANOX71, 0.0085g of bactericide, 5.19g of internal mold release agent 1948MCH, 0.017g of catalyst Bicat8/Dabot-T12, and the above materials are uniformly mixed according to the mass ratio of 2:1, and the polyether polyol component is obtained after the above materials are uniformly mixed, wherein the isocyanate component (set as B) is Vanhua PM130. The mixing mass ratio of the two is A, B=100:112.
TABLE 5
| Numbering device | Tensile Strength/MPa | Tensile modulus/GPa | Elongation at break/% | Tg/℃ |
| 2-1 | 74.5 | 2.91 | 7.82 | 109 |
| 2-2 | 73.5 | 3.02 | 7.53 | 115 |
| 2-3 | 71.2 | 2.84 | 6.88 | 108 |
| 2-4 | 75.2 | 2.95 | 6.42 | 112 |
| 2-5 | 72.3 | 2.87 | 6.77 | 108 |
| Comparative example 1 | 68.8 | 2.56 | 7.12 | 92 |
| Comparative example 2 | 67.5 | 2.62 | 6.52 | 88 |
| Comparative example 3 | 69.6 | 2.55 | 6.02 | 91 |
Wherein Tg is determined by ISO 11357-2-201, plastic Differential Scanning Calorimetry (DSC) part 2, determination of glass transition temperature and glass transition step height
Example 3
The properties of the modified phenolic resin prepared in example 1, which was replaced with the modified phenolic resin of different numbers using the polyurethane system ratio of 2-1 in example 2, were determined as shown in Table 6, and are specifically as follows:
TABLE 6
Example 4
With the polyurethane system of example 2-1 and comparative example 2, the glass fiber type was TMRII type of Chongqing International composite Co., ltd, the prepared polyol component and polymeric MDI were each placed in a heated A/B bucket of a glue injection machine, the addition of the A material (i.e., the A component) was set to 100, and the addition of the B material (i.e., the B component) was set to 118. The pultrusion line equipment is started, and the test is carried out on the machine, and the details are shown in figure 1. The temperature of the first area is set to 95 ℃, the temperature of the second area is set to 148 ℃, the temperature of the third area is set to 180 ℃, the initial starting speed is set to 0.5cm/min, the temperature is gradually increased to 1.5m/min after the temperature is stabilized, the temperature of the third area is 115 ℃ of the first area, the temperature of the second area is set to 165 ℃, the temperature of the third area is set to 190 ℃, and the continuous operation is carried out on the basis. Finally, a continuous composite board with the width of 105cm and the thickness of 4cm and without surface quality defects is obtained.
The obtained sheet was cut to prepare a sample, and the FRP performance was measured as shown in tables 7 and 8, wherein table 7 shows the performance measured in the 0 degree direction and table 8 shows the performance measured in the 90 degree direction.
TABLE 7
| Numbering device | Glass fiber content/% | Tensile Strength/MPa | Tensile modulus/GPa | Elongation at break/% | Tg/℃ |
| 2-1 | 82.5 | 1430 | 59.29 | 2.38 | 112 |
| Comparative example 2 | 82.8 | 1243 | 47.52 | 2.12 | 90 |
TABLE 8
| Numbering device | Glass fiber content/% | Tensile Strength/MPa | Tensile modulus/GPa | Elongation at break/% | Tg/℃ |
| 2-1 | 82.5 | 69.77 | 20.70 | 0.42 | 112 |
| Comparative example 2 | 82.8 | 55.68 | 14.66 | 0.33 | 90 |
Therefore, the polyurethane system provided by the invention introduces specific modified phenolic resin, has the advantages of high glass transition temperature, high mechanical strength, moderate gel time and low viscosity, completely meets the technical requirements of the wind power blade girder, and can be used as the pultrusion polyurethane for the wind power blade girder.
Claims (10)
1. The modified polyurethane for the wind power blade pultrusion plate is characterized in that: comprises a component A and a component B, wherein,
The component A comprises the following components in parts by weight: 1 to 20 parts of 2-functionality polyether polyol, 70 to 90 parts of 3-functionality polyether polyol, 5 to 15 parts of modified phenolic resin, 1 to 5 parts of alcohol chain extender, 0.01 to 2 parts of defoamer, 0.001 to 1 part of gel catalyst and 1 to 3 parts of internal mold release agent;
The component B comprises polymeric MDI;
the modified phenolic resin is prepared from the following components in parts by weight: 100-140 parts of paraformaldehyde, 80-120 parts of formaldehyde solution, 300-350 parts of phenol, 50-80 parts of cardanol, 30-70 parts of furfuryl alcohol and 5-10 parts of toluene;
The modified phenolic resin is prepared by the following method: mixing paraformaldehyde, formaldehyde solution, phenol, cardanol and furfuryl alcohol, adding catalyst, raising the temperature to 60-65 deg.c at the rate of 0.1-1 deg.c per minute, reaction for 60-70 min, eliminating water, adding toluene, heating to 105-120 deg.c, maintaining the temperature for 20-40 min, dewatering to obtain the modified phenolic resin.
2. The modified polyurethane for a wind power blade pultrusion panel according to claim 1, characterized in that: the modified phenolic resin is prepared from the following components in parts by weight: 120 parts of paraformaldehyde, 100 parts of formaldehyde solution, 310 parts of phenol, 70 parts of cardanol, 50 parts of furfuryl alcohol and 8 parts of toluene.
3. The modified polyurethane for a wind power blade pultrusion panel according to claim 1, characterized in that: the aldehyde content in the paraformaldehyde is more than or equal to 96wt% calculated by formaldehyde; the formaldehyde concentration in the formaldehyde solution is 35-40 wt%.
4. A modified polyurethane for a wind power blade pultrusion panel according to claim 3, characterized in that: the aldehyde content in the paraformaldehyde is 96wt% based on formaldehyde, and the formaldehyde concentration in the formaldehyde solution is 37wt%.
5. The modified polyurethane for a wind power blade pultrusion panel according to claim 1, characterized in that: the viscosity of the modified phenolic resin is 300-500 mpas, the moisture is less than or equal to 0.1wt percent, and the hydroxyl value is 200-300.
6. The modified polyurethane for a wind power blade pultrusion panel according to claim 5, characterized in that: the modified phenolic resin had a viscosity of 450mpas, a moisture content of 0.07wt% and a hydroxyl number of 248.
7. The modified polyurethane for a wind power blade pultrusion panel according to claim 1, characterized in that: the temperature was raised to 60℃at a rate of 0.5℃per minute.
8. The modified polyurethane for a wind power blade pultrusion panel according to claim 1, characterized in that: the catalyst comprises at least one of zinc lactate, zinc acetate, zinc phosphate, zinc citrate, zinc sulfate, zinc gluconate, zinc nitrate and zinc naphthenate.
9. The modified polyurethane for a wind power blade pultrusion panel according to claim 1, characterized in that: the alcohol chain extender is at least one of 1, 4-butanediol, ethylene glycol, 1, 6-hexanediol, hydroquinone dihydroxyethyl ether, glycerol, trimethylolpropane, pentaerythritol, diethylene glycol, neopentyl glycol, sorbitol and diethylaminoethanol;
The gel catalyst comprises at least one of an organotin catalyst, an organobismuth catalyst and an organozinc catalyst;
The internal mold release agent includes at least one of zinc hard fatty acids and polymeric silicone oils.
10. Use of the modified polyurethane for a wind power blade pultrusion panel according to any of claims 1-9 in the preparation of wind power blades.
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| CN110156946A (en) * | 2019-05-30 | 2019-08-23 | 哈尔滨工业大学 | A kind of shape memory phenolic resin and preparation method thereof |
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| CN102639314A (en) * | 2009-12-01 | 2012-08-15 | 巴斯夫欧洲公司 | Pultrusion resin system based on polyurethane |
| CN104744652A (en) * | 2013-12-26 | 2015-07-01 | 上海昊海化工有限公司 | Modified phenol formaldehyde resin and preparation method thereof |
| CN103756292A (en) * | 2014-01-08 | 2014-04-30 | 合肥杰事杰新材料股份有限公司 | Linear phenolic resin modified polyurethane composite flame-retardant foam and preparation method thereof |
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