CN101805494B - Natural fiber resin composite material and preparation method thereof - Google Patents
Natural fiber resin composite material and preparation method thereof Download PDFInfo
- Publication number
- CN101805494B CN101805494B CN2010101262450A CN201010126245A CN101805494B CN 101805494 B CN101805494 B CN 101805494B CN 2010101262450 A CN2010101262450 A CN 2010101262450A CN 201010126245 A CN201010126245 A CN 201010126245A CN 101805494 B CN101805494 B CN 101805494B
- Authority
- CN
- China
- Prior art keywords
- water
- resin
- natural fiber
- parts
- aqueous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 62
- 239000000805 composite resin Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 title abstract description 43
- 239000003822 epoxy resin Substances 0.000 claims abstract description 79
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 79
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 33
- 239000000945 filler Substances 0.000 claims abstract description 20
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 18
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 66
- -1 phenol aldehyde Chemical class 0.000 claims description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 239000003351 stiffener Substances 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 15
- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical class N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 claims description 12
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 235000013312 flour Nutrition 0.000 claims description 12
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229920002472 Starch Polymers 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 239000008107 starch Substances 0.000 claims description 11
- 235000019698 starch Nutrition 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 6
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 5
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 5
- LCJRHAPPMIUHLH-UHFFFAOYSA-N 1-$l^{1}-azanylhexan-1-one Chemical compound [CH]CCCCC([N])=O LCJRHAPPMIUHLH-UHFFFAOYSA-N 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 229920002292 Nylon 6 Polymers 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 229950001919 policapram Drugs 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229920003987 resole Polymers 0.000 claims description 3
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 3
- WIHIUTUAHOZVLE-UHFFFAOYSA-N 1,3-diethoxypropan-2-ol Chemical compound CCOCC(O)COCC WIHIUTUAHOZVLE-UHFFFAOYSA-N 0.000 claims description 2
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical group NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 2
- NFVPEIKDMMISQO-UHFFFAOYSA-N 4-[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC=C(O)C=C1 NFVPEIKDMMISQO-UHFFFAOYSA-N 0.000 claims description 2
- LWRNVMALNXWNRW-UHFFFAOYSA-N 4-cyanopentanoic acid;sodium Chemical compound [Na].N#CC(C)CCC(O)=O LWRNVMALNXWNRW-UHFFFAOYSA-N 0.000 claims description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 241001330002 Bambuseae Species 0.000 claims description 2
- 241001474374 Blennius Species 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 229920002396 Polyurea Polymers 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 229920006387 Vinylite Polymers 0.000 claims description 2
- WONCHGDEGMFLPR-UHFFFAOYSA-N [Cl-].[NH4+].CC(CCCCCCC)P(CCCCCCCC)CCCCCCCC Chemical compound [Cl-].[NH4+].CC(CCCCCCC)P(CCCCCCCC)CCCCCCCC WONCHGDEGMFLPR-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical class [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 230000031709 bromination Effects 0.000 claims description 2
- 238000005893 bromination reaction Methods 0.000 claims description 2
- 150000003983 crown ethers Chemical class 0.000 claims description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- 229940089401 xylon Drugs 0.000 claims description 2
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims 1
- 239000004848 polyfunctional curative Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 26
- 239000002023 wood Substances 0.000 description 9
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 239000004567 concrete Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 229920001342 Bakelite® Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N Methyl ethyl ketone Natural products CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 208000034189 Sclerosis Diseases 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000004637 bakelite Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000002118 epoxides Chemical group 0.000 description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- QRFALSDGOMLVIR-UHFFFAOYSA-N 1,2,3,4-tetrabromobenzene Chemical compound BrC1=CC=C(Br)C(Br)=C1Br QRFALSDGOMLVIR-UHFFFAOYSA-N 0.000 description 1
- JBHRGAHUHVVXQI-UHFFFAOYSA-N 1-triethoxysilylpropan-1-amine Chemical compound CCO[Si](OCC)(OCC)C(N)CC JBHRGAHUHVVXQI-UHFFFAOYSA-N 0.000 description 1
- OWOCLFMXKYUTDH-UHFFFAOYSA-N 1-trimethoxysilylpropane-1-thiol Chemical compound CCC(S)[Si](OC)(OC)OC OWOCLFMXKYUTDH-UHFFFAOYSA-N 0.000 description 1
- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 0.000 description 1
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- QXONIHMUSQFKJU-UHFFFAOYSA-N 2-(prop-1-enoxymethyl)oxirane Chemical compound CC=COCC1CO1 QXONIHMUSQFKJU-UHFFFAOYSA-N 0.000 description 1
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 description 1
- IYAYDWLKTPIEDC-UHFFFAOYSA-N 2-[2-hydroxyethyl(3-triethoxysilylpropyl)amino]ethanol Chemical compound CCO[Si](OCC)(OCC)CCCN(CCO)CCO IYAYDWLKTPIEDC-UHFFFAOYSA-N 0.000 description 1
- OXGOEZHUKDEEKS-UHFFFAOYSA-N 3-tert-butylperoxy-1,1,5-trimethylcyclohexane Chemical compound CC1CC(OOC(C)(C)C)CC(C)(C)C1 OXGOEZHUKDEEKS-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 1
- KVSUZLUXHBKXDF-UHFFFAOYSA-N C1(=O)OOOOC(O1)=O.CCCC Chemical compound C1(=O)OOOOC(O1)=O.CCCC KVSUZLUXHBKXDF-UHFFFAOYSA-N 0.000 description 1
- FVLVWBKHSDWKMM-UHFFFAOYSA-N CC(C)(C)OO.CCCCC(CC)C(O)=O Chemical compound CC(C)(C)OO.CCCCC(CC)C(O)=O FVLVWBKHSDWKMM-UHFFFAOYSA-N 0.000 description 1
- NOKXNDKMAPFVBB-UHFFFAOYSA-N CC(C)[Ti] Chemical class CC(C)[Ti] NOKXNDKMAPFVBB-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920002449 FKM Polymers 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- KRJRKEPWQOASJN-UHFFFAOYSA-N aniline;trimethoxy(methyl)silane Chemical compound NC1=CC=CC=C1.CO[Si](C)(OC)OC KRJRKEPWQOASJN-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000008953 bacterial degradation Effects 0.000 description 1
- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 description 1
- OWDKTRHHVBNMED-UHFFFAOYSA-N bis(ethenyl)-(2-methoxyethoxy)silane Chemical compound COCCO[SiH](C=C)C=C OWDKTRHHVBNMED-UHFFFAOYSA-N 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- UPIWXMRIPODGLE-UHFFFAOYSA-N butyl benzenecarboperoxoate Chemical compound CCCCOOC(=O)C1=CC=CC=C1 UPIWXMRIPODGLE-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- WCPWDLUDOOCKTH-UHFFFAOYSA-N cyanamide urea Chemical compound NC(=O)N.NC(=O)N.NC(=O)N.NC(=O)N.N#CN WCPWDLUDOOCKTH-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- XMQYIPNJVLNWOE-UHFFFAOYSA-N dioctyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OCCCCCCCC XMQYIPNJVLNWOE-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- QDXBVEACAWKSFL-UHFFFAOYSA-N ethenethiol Chemical compound SC=C QDXBVEACAWKSFL-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical group CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000012802 nanoclay Substances 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004978 peroxycarbonates Chemical class 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- ALHBQZRUBQFZQV-UHFFFAOYSA-N tin;tetrahydrate Chemical compound O.O.O.O.[Sn] ALHBQZRUBQFZQV-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- WCAGGTLUGWSHOV-UHFFFAOYSA-N tris(tert-butylperoxy)-ethenylsilane Chemical compound CC(C)(C)OO[Si](OOC(C)(C)C)(OOC(C)(C)C)C=C WCAGGTLUGWSHOV-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 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
- 238000004078 waterproofing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a natural fiber resin composite material and a preparation method thereof, wherein the natural fiber resin composite material is prepared from the following components in parts by weight: 10-50 parts of water-based resin, 10-50 parts of non-water-based epoxy resin, 50-200 parts of natural fiber, 3-15 parts of water-soluble hardener, 6-15 parts of phase transfer catalyst, 50-150 parts of filler and 100-200 parts of water. The natural fiber resin composite material has the characteristics of high strength and low cost.
Description
Technical field
The present invention relates to a kind of natural fiber resin composite and preparation method thereof.
Background technology
Matrix material is defined as two or more materials and closes assembly and become a kind of brand-new material; Advantage with former two kinds of materials, the fiber that is used for matrix material at present mainly contains spun glass and thomel, though thomel has the performance of excellence; But its production sequence is complicated, so cost is very high; And the spun glass performance is than thomel difference, and its quality is heavier than thomel, though production sequence is simpler than thomel, but still very complicated.
Compare with above-mentioned two kinds of fibers, natural fiber have easily obtain, characteristics that price is cheap, but natural fiber is not water-fast, easily by bacterial degradation, has therefore limited to its purposes.In order to improve the These characteristics of natural fiber; People begin to attempt in natural fiber to add and have HS, the good macromolecular material of water resistance like epoxy resin, unsaturated polyester and resol etc.; The processing but the resin of high viscosity must add solvent; And solvent is harmful material, in the course of processing, possibly disengage, and harm constructor or user's is healthy; Or the adding reactive thinner is processed solventfree resin in resin; But some reactive thinner has volatility, and it has the same with solvent even more serious hazardness, and solventfree resin is used for matrix material; Fiber is not easy wetting; Therefore in order to reach the ideal effect, the resin usage quantity must be very many, and the integral material cost is increased.Therefore, in order to solve solvent and reactive thinner evaporable problem, reaching the problem of fiber wettability, is that the water-base resin of solvent is able to development with water.But the water-base resin character that the technology of preparing of present most water-base resin is produced is crisp, and is not suitable for the manufacturing of high definition matrix material.
Summary of the invention
The purpose of this invention is to provide a kind of HS, natural fiber resin composite cheaply.
In order to reach above-mentioned purpose, solution of the present invention is:
A kind of natural fiber resin composite; It is characterized in that it is by mainly comprising the preparation of following components in weight portions: 100～200 parts in 10～50 parts of water-base resins, 10～50 parts of non-aqueous epoxy resin (being water-insoluble epoxy resin), 50～200 parts in natural fiber, 3～15 parts of water-soluble stiffening agents, 6～15 parts of phase-transfer catalysts, 50～150 parts of fillers and water.
In a preferred embodiment of the present invention, said water-base resin is by mainly comprising following components in weight portions preparation: 4～20 parts of 10～100 parts of non-aqueous resins and water-based initiators.The concrete preparation method of water-base resin is following: the non-aqueous resin of said ratio is put into reaction kettle with the water-based initiator mix, obtained in 1～2 hour at 120～160 ℃ of compressive reactions.This part content has been open in detail in 200910310409.2 the patented claim at the patentee's number of patent application, no longer carefully states at this.Said non-aqueous resin is selected from least a in epoxy resin, unsaturated polyester resin, resol, urea-formaldehyde resin or the Vinylite, and makes aqueous epoxy resins, water-based unsaturated polyester resin, aqueous phenolic aldehyde resin, water-based urea-formaldehyde resin or aqueous vinyl resin or other relevant water-base resins respectively.Preferably, said water-base resin is an aqueous epoxy resins, and said aqueous epoxy resins is at least a in Water-borne modification bisphenol A epoxide resin, Water-borne modification phenol aldehyde type epoxy resin or the Water-borne modification dilution type epoxy resin.Further preferably, said Water-borne modification bisphenol A epoxide resin is at least a in E51, E20, E44, E41, Epon828, BE188, CYD128 or other the relevant epoxy resin; Said Water-borne modification phenol aldehyde type epoxy resin is at least a in F51, F20, F44, F41 or other the relevant epoxy resin; Said Water-borne modification dilution type epoxy resin is at least a in ethylene glycol bisthioglycolate glycidyl ester, butyleneglycol 2-glycidyl ester, Ucar 35 2-glycidyl ester, USP Kosher 2-glycidyl ester or the glycidyl allyl ether.Further preferably, said aqueous epoxy resins is water-based bisphenol A epoxide resin BE188.Said water-based initiator is selected from Sodium Persulfate, Potassium Persulphate, 4; 4-azo two (4-cyanopentanoic acid), 4; 4-azo two (4-cyanopentanoic acid sodium), 4, at least a in 4-azo two (4-cyanic acid amylalcohol), methylethyl ketone peroxides, cyclohexanone peroxide or other the relevant initiators.The effect of water-based initiator is that hydrophilic radical is introduced non-aqueous resin, and it is water-soluble to make that non-aqueous resin becomes.Preferably, aforementioned water-based initiator is 4,4-azo two (4-cyanopentanoic acid).
Said non-aqueous epoxy resin (being water-insoluble epoxy resin) is selected from least a in bisphenol A epoxide resin or the phenol aldehyde type epoxy resin.Said bisphenol A epoxide resin is at least a in E51, E20, E44, E41, Epon828, BE188, CYD128 or other the relevant epoxy resin, said phenol aldehyde type epoxy resin be in F51, F20, F44, F41 or other the relevant epoxy resin at least a-.
Described natural fiber is selected from least a in xylon, flaxen fiber, cotton fibre, bamboo fibers, vine fiber ti, straw fiber, sea-weed fibre or other the relevant natural fibers.Among the present invention, natural fiber need be ground into powder in advance, then uses again.
Said water-soluble stiffening agent is the stiffening agent of aqueous epoxy resins; It is only be restricted to must have water-soluble; And can with the epoxy resin commissure; Specifically can be selected from trolamine, quadrol, NSC 446, Triethylenetetramine (TETA), tetren, polyvinylamine, phenolic aldehyde amine, 2; 4,6-three (dimethylamino methyl) phenol ,-aqueous polyamide, policapram, dicyanamide, boron trifluoride-amine complex ,-at least a in propylamine, water-soluble aromatic amine, isophorone diamine, thiocarbamide, mercaptan amine, thiocarbamide-polyamine condenses or other the relevant stiffening agents of water-based polyureas, polyetheramine (Jeffamine), hexanediamine, amine end-blocking water-based polyimide, ammoniacal liquor, diethylin.Preferably, aforesaid water-soluble stiffening agent is at least a of NSC 446, polyvinylamine, mercaptan amine or policapram.Because in the aqueous epoxy resin emulsion, epoxide functional groups is at oil phase, and the functional group of water-based stiffening agent is at water, carries out two catalysis between mutually because of needing phase-transfer catalyst a bit.The epoxide functional groups that act as the catalysis oil phase of phase-transfer catalyst and the reaction of the stiffening agent of water are " oil-in-water " state with " water-in-oil " state-transition.Among the present invention, said phase-transfer catalyst is at least a in crown ether, polyoxyethylene glycol, quaternary amine 、 quaternary alkylphosphonium salt, sulfonium salt, arsenic salt, cave ether or other related compound.Preferably, said quaternary ammonium salt is Tetrabutyl amonium bromide and methyl trioctylphosphine ammonium chloride, and said quaternary alkylphosphonium salt is bromination Shi six alkyl San Ding Ji Phosphonium; Further preferably, said phase-transfer catalyst is a polyoxyethylene glycol.
Described filler is silica flour, stone flour, native powder, starch, white titanium pigment, clay powder, carbon black, nano-carbon powder, carbon fiber powder, glass fiber powder, nanoclay, Graphite Powder 99, Graphene, red phosphorus, White tin oxide, aluminium hydrate powder, Marinco H powder, stannic hydroxide, Antimony Trioxide: 99.5Min, molybdenum oxide, ammonium molybdate, zinc borate, barium metaborate, boron oxide, gathers and accompany half siloxanes, three (2; 3-two chloropropyls) at least a in SULPHOSUCCINIC ACID ESTER, vinylchlorid, SE, chlorine alkylphosphonic acid carboxylic acid glycidyl ester, amido SULPHOSUCCINIC ACID ESTER, phosphagel phosphaljel, trimeric cyanamide urea hydrochlorate, two (2, the 3-dibromopropyl) fumarate, tetrabromo-benzene dicarboxylic acid anhydride, tetrabromo-bisphenol, clorafin, hexachloro endoethylene tetrahydrophthalic acid acid anhydride, Fluroplast-4, viton, paraffin, softening agent, toughner, tributyl phosphate, triethyl phosphate, triphenylphosphate, Witcizer 300, dimethyl phthalate, diethyl phthalate, glass powder, jade powder, animal excrement, glass powder, sand, glass fiber powder, carbon fiber powder, plastic waste powder, cement, rubble, useless foaming rubber powder, wax powder, mica, asphalt powder or other associated materials.Among the present invention, above-mentioned filler need be ground into powder in advance, then uses again.
In the further embodiment of the present invention; Also comprise 1～10 part of monomer in the above-mentioned water-base resin, described monomer is at least a of vinylbenzene, vinyl cyanide, divinyl, butylene, vinylformic acid, methylacrylic acid, TEB 3K, methyl acrylate, ethyl propenoate, propyl acrylate, Bing Xisuandingzhi, the different monooctyl ester of propylene, Jia Jibingxisuanyizhi, propyl methacrylate, NSC 20956, toxilic acid, maleic anhydride or other relevant monomer.The monomeric lifting water-based free radical initiator that act as grafts on the efficient in the epoxy resin, increases material filming property, improves the material waterproofing performance, and reduces cost.Preferably, aforesaid monomer is at least a in vinylbenzene, TEB 3K, vinylformic acid, vinyl mercaptan, propenyl glycidyl ether, vinyl cyanide or the divinyl.
In the further embodiment of the present invention; Also comprise 1～2 part non-aqueous initiator in the said aqueous epoxy resins; Said non-aqueous initiator is selected from 4,4-azo two (4-cyanic acid butane peroxy dicarbonate two-2-phenoxy ester), peroxy dicarbonates two (4-tertiary butyl hexanaphthene), 2,5-two (2-ethyl hexanoyl peroxide)-2; 5-dimethyl-ethane, Lucidol, tert-butyl hydroperoxide-2-ethylhexanoate, 2-tertiary butyl azo-2-dicyanopropane, 2-tertiary butyl azo-dicyanobutane, 1; 1-two (t-butyl peroxy) 3,3,5-trimethyl-cyclohexane, 1; 1-two (t-butyl peroxy) hexanaphthene, 1-tertiary butyl azo-1-cyanocyclohexanoic alkane, 0; The 0-tertiary butyl-0-sec.-propyl list peroxycarbonates, butyl perbenzoate, ethyl-3,3-two (tert-butyl peroxide) butyric ester, Di Cumyl Peroxide 99, peroxo-LAURIC ACID 99 MIN, 2,5-dimethylhexane-2; 5-diperoxy ethylhexoate, peroxide-2-ethyl hexanoic acid tert-butyl, peroxide acid tert-butyl, 3, at least a in 3-two (t-butyl peroxy) ethyl n-butyrate or other the relevant initiators.Non-aqueous initiator can increase the hydrophobicity behind the hardened material, itself and the acting in conjunction of water-based initiator, regulate material can be in water before sclerosis dispersion and emulsion, then have certain hydrophobicity after the sclerosis.
A further embodiment of the invention, it further comprises 1 to 5 parts (by weight ratio) of the coupling, the coupling agent is selected from vinyltriethoxysilane, divinyl (β-methoxy- ethoxy) silane, γ-methacryloxypropyl trimethoxy silane, β-(3,4 - epoxycyclohexyl) ethyl trimethoxysilane, glycidoxypropyl trimethoxysilane, α - aminopropyl triethoxy silane, n-β-(aminoethyl)-α-aminopropyl trimethoxysilane, α-chloro-trimethoxysilane, α-mercaptopropyl trimethoxy silane, vinyl-tris - (t-butylperoxy) silane, methyl triethoxysilane anilino, diethylenetriaminepentaacetic aminopropyl triethoxysilane, methyltrimethoxysilane aniline, α-(methyl acryloyloxy group) methyl triethoxysilane, N, N-bis - (β-hydroxyethyl)-γ-aminopropyl triethoxysilane, n-butyl titanate, isopropyl titanium esters, tetraethyl titanate, 3,3,4 - tris (dioctyl phosphate acyloxy) titanate, isopropyl, 3,3,6 - tris (dioctyl pyrophosphate Ang oxy) titanium isopropyl, 3,3,7 - four octyloxy titanium (dodecyl phosphite), 3,3,12 - two (dioctyl phosphite ester) tetraisopropyl titanate or three , 3,10 - tris (acyloxy-phosphorus) titanate, at least one of ethylene.
Another object of the present invention provides the preparation method of natural fiber resin composite.
The preparation method of natural fiber resin composite is characterized in that, comprises following step:
1) water-base resin, non-aqueous epoxy resin, natural fiber, water-soluble stiffening agent, phase-transfer catalyst, filler and water are got the raw materials ready by aforementioned weight proportion;
2) in aqueous epoxy resins, sneak into non-aqueous epoxy resin, then add natural fiber, phase-transfer catalyst, filler and water, mix with kneader; Then add water-soluble stiffening agent again; Mix with kneader, do hydraulic pressure, be heated to 150～180 ℃ and form natural fiber resin composite.
Only if name especially, the implication of employed here all technology and scientific terminology is identical with the affiliated common implication of understanding of technical field those skilled in the art of the present invention.Equally, all introduce the present invention as a reference at this publication of mentioning, patented claim, patent and other bibliographys.
Compared with prior art, the present invention has following characteristics:
1) the present invention uses less resin to have good wetting effect to natural fiber; Coat performance resins material cheap, that do not absorb water at natural fiber, improve the water tolerance and the anti-bacterial degradation performance of natural fiber, it is suitable that its prepared product and traditional bakelite are compared performance; And cost of manufacture is lower than traditional bakelite; Compare as the wad of tackiness agent with urea-formaldehyde resin with tradition and then to have preferable water-repellancy, and do not contain formaldehyde fully, have plasticity-; Be not limited to sheet material, can be processed into Any shape;
2) the non-aqueous epoxy resin that adds is used for improving the fragility of water-base resin, obtains high-strength natural fibre resin matrix material.
Embodiment
Embodiment 1
By weight water intaking property bisphenol A epoxide resin BE188 (aqueous epoxy resins) 40g, bisphenol A epoxide resin BE188 (non-aqueous epoxy resin is produced by Changchun, Taiwan chemical industry group) 20g, wood powder (natural fiber) 100g, NSC 446 (water-soluble stiffening agent) 5g, polyoxyethylene glycol (phase-transfer catalyst) 10g, starch (filler) 5g, silica flour (filler) 100g and water 100g.
This wherein; Water-based bisphenol A epoxide resin BE188 obtains through following mode: other gets bisphenol A epoxide resin BE18830g and 4; Two (4-cyanopentanoic acid) 10g of 4-azo get the raw materials ready; With bisphenol A epoxide resin BE188 and 4,4-azo two (4-cyanopentanoic acid) is put into reaction kettle and is mixed, and obtains after 1 hour at 150 ℃ of compressive reactions.
In water-based bisphenol A epoxide resin BE188, sneak into bisphenol A epoxide resin BE188; Then add wood powder, polyoxyethylene glycol, starch, silica flour and water; Mix with kneader, then add NSC 446 again, mix with kneader; Do hydraulic pressure, be heated to 150 ℃ and form natural fiber resin composite sheet material.
Detection method and result:
1) sheet material was steeped in the entry 10 days, sheet material does not still scatter;
2) highly drop is to concrete floor from 2m with sheet material, and sheet material does not still break.
Embodiment 2
By weight water intaking property bisphenol A epoxide resin BE188 (aqueous epoxy resins) 14g, bisphenol A epoxide resin BE188 (non-aqueous epoxy resin is produced by Changchun, Taiwan chemical industry group) 50g, wood powder (natural fiber) 50g, NSC 446 (water-soluble stiffening agent) 3g, polyoxyethylene glycol (phase-transfer catalyst) 6g, starch (filler) 5g, silica flour (filler) 45g and water 200g.
This wherein; Water-based bisphenol A epoxide resin BE188 obtains through following mode: other gets bisphenol A epoxide resin BE18810g and 4; Two (4-cyanopentanoic acid) 4g of 4-azo get the raw materials ready; With bisphenol A epoxide resin BE188 and 4,4-azo two (4-cyanopentanoic acid) is put into reaction kettle and is mixed, and obtains after 1 hour at 150 ℃ of compressive reactions.
In water-based bisphenol A epoxide resin BE188, sneak into bisphenol A epoxide resin BE188; Then adding wood powder, terepthaloyl moietie, starch, silica flour and water mixes with kneader; Then add NSC 446 again; Mix with kneader, do hydraulic pressure, be heated to 180 ℃ and form natural fiber resin composite sheet material.
Detection method and result:
1) sheet material was steeped in the entry 10 days, sheet material does not still scatter;
2) highly drop is to concrete floor from 2m with sheet material, and sheet material does not still break.
Embodiment 3
Water intaking property bisphenol A epoxide resin BE188 (aqueous epoxy resins) 50g, bisphenol A epoxide resin BE188 (non-aqueous epoxy resin is produced by Changchun, Taiwan chemical industry group) 10g, wood powder (natural fiber) 200g, NSC 446 (water-soluble stiffening agent) 15g, polyoxyethylene glycol (phase-transfer catalyst) 15g, starch (filler) 50g, silica flour (filler) 100g and water 150g.
This wherein; Water-based bisphenol A epoxide resin BE188 obtains through following mode: other gets bisphenol A epoxide resin BE18830g and 4; Two (4-cyanopentanoic acid) 20g of 4-azo get the raw materials ready; With bisphenol A epoxide resin BE188 and 4,4-azo two (4-cyanopentanoic acid) is put into reaction kettle and is mixed, and obtains after 1 hour at 150 ℃ of compressive reactions.
In water-based bisphenol A epoxide resin BE188, sneak into bisphenol A epoxide resin BE188; Then add wood powder, polyoxyethylene glycol, starch, silica flour and water; Mix with kneader, then add NSC 446 again, mix with kneader; Do hydraulic pressure, be heated to 180 ℃ and form natural fiber resin composite sheet material.
Detection method and result:
1) sheet material was steeped in the entry 10 days, sheet material does not still scatter;
2) highly drop is to concrete floor from 2m with sheet material, and sheet material does not still break.
Reference examples 1
By weight water intaking property bisphenol A epoxide resin BE188 (aqueous epoxy resins) 50g, wood powder (natural fiber) 100g, NSC 446 (water-soluble stiffening agent) 5g, polyoxyethylene glycol (phase-transfer catalyst) 10g, starch (filler) 5g, silica flour (filler) 100g and water 100g.
This wherein; Water-based bisphenol A epoxide resin BE188 obtains through following mode: get bisphenol A epoxide resin BE18830g and 4; Two (4-cyanopentanoic acid) 20g of 4-azo get the raw materials ready; With bisphenol A epoxide resin BE188 and 4,4-azo two (4-cyanopentanoic acid) is put into reaction kettle and is mixed, and obtains after 1 hour at 150 ℃ of compressive reactions.
In water-based bisphenol A epoxide resin BE188, add wood powder, polyoxyethylene glycol, starch, silica flour and water; Mix with kneader, then add NSC 446 again, mix with kneader; Do hydraulic pressure, be heated to 150 ℃ and form natural fiber resin composite sheet material.
Detection method and result:
1) sheet material was steeped in the entry 10 days, sheet material does not still scatter;
2) highly drop is to concrete floor from 1m with sheet material, and sheet material breaks.
Reference examples 2
By weight getting urea-formaldehyde resin 40g, wood powder (natural fiber) 100g, ammoniacal liquor 30g, polyoxyethylene glycol (phase-transfer catalyst) 10g, starch (filler) 5g, silica flour (filler) 100g and water 200g; Then above-mentioned materials being added kneader mixes; Do hydraulic pressure, be heated to 150 ℃ and form sheet material.
Detection method and result:
1) sheet material was steeped in the entry after 3 days, sheet material scatters;
2) highly drop is to concrete floor from 1m with sheet material, and sheet material breaks.
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (6)
1. natural fiber resin composite; It is characterized in that it is by mainly comprising the preparation of following components in weight portions: 100～200 parts in 10～50 parts of water-base resins, 10～50 parts of non-aqueous epoxy resin, 50～200 parts in natural fiber, 3～15 parts of water-soluble stiffening agents, 6～15 parts of phase-transfer catalysts, 50～150 parts of fillers and water; Said water-base resin is by mainly comprising following components in weight portions preparation: 4～20 parts of 10～100 parts of non-aqueous resins and water-based initiators; Said non-aqueous resin is selected from least a in epoxy resin, unsaturated polyester resin, resol, urea-formaldehyde resin or the Vinylite; Said water-based initiator is selected from Sodium Persulfate, Potassium Persulphate, 4,4-azo two (4-cyanopentanoic acids), 4,4-azo two (4-cyanopentanoic acid sodium), 4, at least a in 4-azo two (4-cyanic acid amylalcohol), methylethyl ketone peroxide or the cyclohexanone peroxide; Said natural fiber is selected from least a in xylon, flaxen fiber, cotton fibre, bamboo fibers, vine fiber ti, straw fiber or the sea-weed fibre; Described filler is the combination of silica flour and starch.
2. according to the natural fiber resin composite described in the claim 1, it is characterized in that:
Said non-aqueous epoxy resin is selected from least a in bisphenol A epoxide resin or the phenol aldehyde type epoxy resin;
Said water-soluble stiffening agent is selected from trolamine, quadrol, NSC 446, Triethylenetetramine (TETA), tetren, polyvinylamine, phenolic aldehyde amine, 2; 4,6-three (dimethylamino methyl) phenol,, aqueous polyamide, policapram, dicyanamide, boron trifluoride-amine complex ,-at least a in propylamine, water-soluble aromatic amine, isophorone diamine, thiocarbamide, mercaptan amine or thiocarbamide-polyamine condenses of water-based polyureas, polyetheramine, hexanediamine, amine end-blocking water-based polyimide, ammoniacal liquor, diethylin;
Said phase-transfer catalyst is at least a in crown ether, polyoxyethylene glycol, quaternary amine 、 quaternary alkylphosphonium salt, sulfonium salt, arsenic salt or the cave ether.
3. according to the natural fiber resin composite described in the claim 2, it is characterized in that:
Said bisphenol A epoxide resin is at least a among E51, E20, E44, E41, Epon828, BE188 or the CYD128, and said phenol aldehyde type epoxy resin is at least a among F51, F20, F44 or the F41;
Aforesaid water-soluble stiffening agent is at least a of NSC 446, polyvinylamine, mercaptan amine or policapram;
Said phase-transfer catalyst is a polyoxyethylene glycol.
4. according to the natural fiber resin composite described in the claim 2, it is characterized in that: said quaternary ammonium salt is Tetrabutyl amonium bromide and methyl trioctylphosphine ammonium chloride, and said quaternary alkylphosphonium salt is bromination Shi six alkyl San Ding Ji Phosphonium.
5. according to the natural fiber resin composite described in the claim 1, it is characterized in that: the said non-aqueous resin that reaction forms water-base resin is preferably epoxy resin; Said water-based initiator is preferably 4,4-azo two (4-cyanopentanoic acid).
6. the preparation method of a natural fiber resin composite is characterized in that, comprises following step:
1) with water-base resin, non-aqueous epoxy resin, natural fiber, water-soluble stiffening agent, phase-transfer catalyst, filler and water by getting the raw materials ready by the weight proportion in claim 1 or 2 or 3;
2) in aqueous epoxy resins, sneak into non-aqueous epoxy resin, then add natural fiber, phase-transfer catalyst, filler and water, mix with kneader; Then add water-soluble stiffening agent again; Mix with kneader, do hydraulic pressure, be heated to 150～180 ℃ and form natural fiber resin composite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101262450A CN101805494B (en) | 2010-03-16 | 2010-03-16 | Natural fiber resin composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101262450A CN101805494B (en) | 2010-03-16 | 2010-03-16 | Natural fiber resin composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101805494A CN101805494A (en) | 2010-08-18 |
| CN101805494B true CN101805494B (en) | 2012-05-23 |
Family
ID=42607458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101262450A Expired - Fee Related CN101805494B (en) | 2010-03-16 | 2010-03-16 | Natural fiber resin composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101805494B (en) |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX2010013211A (en) * | 2010-12-01 | 2012-06-08 | Urbanizaciones Inmobiliarias Del Ct S A De C V | Compound material based on rice husk and binder, modified with carbon nanostructures. |
| CN103476803B (en) * | 2011-04-04 | 2016-03-16 | 日本电气株式会社 | Celluosic resin and manufacture method thereof |
| CN103421372A (en) * | 2013-08-22 | 2013-12-04 | 海安县亚太助剂有限公司 | Epoxy propane butyl ether anti-aging coating |
| CN103509384A (en) * | 2013-09-04 | 2014-01-15 | 安徽祈艾特电子科技有限公司 | Pearlescent powder paint |
| CN103865460B (en) * | 2014-03-13 | 2016-01-20 | 漳州市奈特新型建材有限责任公司 | Resin combination and its preparation method and application |
| CN104131494B (en) * | 2014-07-29 | 2016-03-09 | 哈尔滨理工大学 | A kind of preparation method of the non-linear dielectric cardboard based on nano modification |
| CN104212281B (en) * | 2014-09-22 | 2016-08-24 | 句容亿格纳米材料厂 | A kind of nanometer decorative coveringn and preparation method thereof |
| CN104356597A (en) * | 2014-10-31 | 2015-02-18 | 合肥鼎雅家具有限责任公司 | Composite material with bagasse and modified solid epoxy resin and production method thereof |
| CN104674376A (en) * | 2015-03-06 | 2015-06-03 | 苏州爱立方服饰有限公司 | Natural fiber composite material and preparation method thereof |
| CN104844242A (en) * | 2015-04-13 | 2015-08-19 | 安徽省含山瓷业股份有限公司 | High strength carbon fiber reinforced yttrium aluminum garnet ceramic matrix composite material and preparation method thereof |
| CN105273412B (en) * | 2015-10-18 | 2017-07-28 | 北京化工大学 | The anti-rubber plastizing agent and preparation method thereof of moving out of one kind |
| CN105462177B (en) * | 2016-01-07 | 2018-02-06 | 广东美特家家居用品有限公司 | A kind of heat-resistant fireproof bamboo-plastic composite material and preparation method thereof |
| CN105802201A (en) * | 2016-05-16 | 2016-07-27 | 苏州新区华士达工程塑胶有限公司 | Modified polyamide flame-retardant plastic |
| CN106277927A (en) * | 2016-08-18 | 2017-01-04 | 张振堂 | A kind of heat-preservation cotton Modified soil material and preparation method thereof |
| CN106366566A (en) * | 2016-08-27 | 2017-02-01 | 安徽天瞳智能科技有限公司 | Epoxy resin composition for flexible wiring board |
| CN106479115A (en) * | 2016-11-08 | 2017-03-08 | 郑州诚合信息技术有限公司 | A kind of electromagnetic shielding plastic and preparation method thereof |
| CN106496951B (en) * | 2016-11-25 | 2018-06-15 | 西华大学 | A kind of halogen-free flame-retardant composite material and preparation method thereof |
| CN107640527A (en) * | 2017-10-26 | 2018-01-30 | 安徽锐视光电技术有限公司 | A kind of wear-resisting material conveying bucket body that shakes applied to bulky grain ore separator |
| CN108158197A (en) * | 2017-12-19 | 2018-06-15 | 马斌祥 | A kind of Clean- electrostatic precipitation roller of sofa rug |
| CN109251549A (en) * | 2018-08-31 | 2019-01-22 | 安徽省新兴纸业有限责任公司 | A kind of preparation method of tear-resistant paper disc |
| CN109227863A (en) * | 2018-09-30 | 2019-01-18 | 湖州市南浔三亚家私有限公司 | Composite fibre plate and its manufacturing method |
| CN109504086A (en) * | 2018-10-10 | 2019-03-22 | 安徽省科晟生态木装饰材料有限公司 | A kind of preparation method of bamboo carbon fibre composite polyimide material |
| CN111348863A (en) * | 2020-01-16 | 2020-06-30 | 华中科技大学 | Graphene/stone composite board and preparation method thereof |
| CN111648163B (en) * | 2020-05-12 | 2022-02-15 | 仙鹤股份有限公司 | Preparation method of high-tightness process packaging base paper |
| CN114854172B (en) * | 2022-03-22 | 2024-11-12 | 中国林业科学研究院林产化学工业研究所 | A natural plant fiber/waterborne epoxy resin composite material and a manufacturing method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1594427A (en) * | 2004-06-29 | 2005-03-16 | 中国科学院广州化学研究所 | Process for preparing water soluble epoxy resin grouting agent |
| CA2584888A1 (en) * | 2006-05-05 | 2007-11-05 | Ghaus M. Rizvi | Wood/plastic composites with glass fiber reinforcement |
| WO2007144984A1 (en) * | 2006-06-14 | 2007-12-21 | Sanyo Chemical Industries, Ltd. | Method for producing resin dispersion and resin particle |
| CN101234505A (en) * | 2008-02-29 | 2008-08-06 | 上海大学 | Waterborne polymer, polyisocyanate and straw fiber composite material and preparation method thereof |
| CN101265364A (en) * | 2007-07-27 | 2008-09-17 | 张国栋 | Thermoset plastics infiltration strengthened powdery plant fiber material and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2461558T3 (en) * | 2004-06-08 | 2014-05-20 | The Procter & Gamble Company | Hot melt adhesive polymeric compositions for sustained release of volatile materials |
| US7994241B2 (en) * | 2008-01-15 | 2011-08-09 | Innovative Plastics and Molding RNE Tech | Wood composite alloy composition having a compatibilizer that improves the ability to process and compress cellulosic fiber |
-
2010
- 2010-03-16 CN CN2010101262450A patent/CN101805494B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1594427A (en) * | 2004-06-29 | 2005-03-16 | 中国科学院广州化学研究所 | Process for preparing water soluble epoxy resin grouting agent |
| CA2584888A1 (en) * | 2006-05-05 | 2007-11-05 | Ghaus M. Rizvi | Wood/plastic composites with glass fiber reinforcement |
| WO2007144984A1 (en) * | 2006-06-14 | 2007-12-21 | Sanyo Chemical Industries, Ltd. | Method for producing resin dispersion and resin particle |
| CN101265364A (en) * | 2007-07-27 | 2008-09-17 | 张国栋 | Thermoset plastics infiltration strengthened powdery plant fiber material and preparation method thereof |
| CN101234505A (en) * | 2008-02-29 | 2008-08-06 | 上海大学 | Waterborne polymer, polyisocyanate and straw fiber composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101805494A (en) | 2010-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101805494B (en) | Natural fiber resin composite material and preparation method thereof | |
| CN101798466B (en) | Natural fiber composite material and preparation method thereof | |
| CN100509890C (en) | Organosilicon epoxide acrylate water dispersion, preparation method and application thereof | |
| CN101445637B (en) | Preparation method of nano SiO2/ACR composite particles and application thereof | |
| CN102775861B (en) | Hollow hiding coating as well as preparation method and application thereof | |
| CN102161736B (en) | Method for preparing micro/nanocomposite photocurable resin | |
| CN106010046B (en) | It is a kind of aluminum paint, aqueous and preparation method thereof | |
| CN105819709B (en) | A kind of glass fiber treating compound being quickly impregnated with and its application in production roving | |
| CN102485790B (en) | Method for preparing SiO2/ACR nano composite material | |
| CN105907192A (en) | Water-based damping paint for automobile | |
| CN105237777A (en) | Preparation method of silicon modified waterborne epoxy resin | |
| CN109777232A (en) | A kind of watersoluble modified acrylic acid anticorrosive paint and preparation method thereof | |
| CN102140217B (en) | Preparation method and use of polyacrylate/silica solution composite material | |
| CN103387645B (en) | Fluorinated copolymer Grafted Nano-scale TiO 2composite particles and preparation method thereof | |
| CN101597453A (en) | Emulsion paint of a kind of high dirt resistance and preparation method thereof and application | |
| CN107141930A (en) | A kind of aqueous antistripping acrylic resin paint and preparation method thereof | |
| CN101600738B (en) | Silica sol having reactive monomer dispersed therein, method for producing the silica sol, curing composition, and cured article produced from the curing composition | |
| CN108912929B (en) | Preparation method of flame-retardant antibacterial water-based core-shell acrylate resin coating and paint | |
| CN106085083A (en) | A kind of aqueous composite paint of environmental protection and preparation method thereof | |
| CN106977663A (en) | A kind of special styrene-acrylic latex of wallpaper | |
| CN109735210A (en) | A kind of ultraviolet-curing paint containing modified carbon nano-tube | |
| CN105602425A (en) | High-refraction reflective paint and preparation method | |
| CN103289002B (en) | Connecting resin for water paint and preparation method of connecting resin | |
| CN101735408B (en) | High-decoration alcohol acid-organosilicon crylic acid composite waterborne resin | |
| CN104327659B (en) | A kind of earth building wall reinforcement protection agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB02 | Change of applicant information |
Address after: 363000, No. 168, ridge village, nine Lake Town, Longhai, Fujian, Zhangzhou Applicant after: Zhangzhou Night Star New Building Material Co., Ltd. Address before: 363000, No. 168, ridge village, nine Lake Town, Longhai, Fujian, Zhangzhou Applicant before: Longhai Naite Chemical Industry Co., Ltd. |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: LONGHAI NAITE CHEMICAL CO., LTD. TO: ZHANGZHOU NAITE NEW BUILDING MATERIALS CO., LTD. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120523 Termination date: 20180316 |