CN108610593A - A kind of polymer membranes and preparation method thereof - Google Patents
A kind of polymer membranes and preparation method thereof Download PDFInfo
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- CN108610593A CN108610593A CN201810357587.XA CN201810357587A CN108610593A CN 108610593 A CN108610593 A CN 108610593A CN 201810357587 A CN201810357587 A CN 201810357587A CN 108610593 A CN108610593 A CN 108610593A
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- Prior art keywords
- polymer membranes
- hours
- fluorine
- parts
- containing propene
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- 229920005597 polymer membrane Polymers 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 46
- 239000011737 fluorine Substances 0.000 claims abstract description 46
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical class CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920000554 ionomer Polymers 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000835 fiber Substances 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- 238000001125 extrusion Methods 0.000 claims abstract description 8
- 239000004800 polyvinyl chloride Substances 0.000 claims description 26
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 15
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 15
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 15
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 229920002521 macromolecule Polymers 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- ITUNZCVRYICLQM-UHFFFAOYSA-N 1-ethenyl-1,2,4-triazole Chemical class C=CN1C=NC=N1 ITUNZCVRYICLQM-UHFFFAOYSA-N 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- QMOKQVPITLXHJM-UHFFFAOYSA-N n,n-dimethylpent-3-en-1-amine Chemical group CC=CCCN(C)C QMOKQVPITLXHJM-UHFFFAOYSA-N 0.000 claims description 8
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004255 Butylated hydroxyanisole Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 235000019282 butylated hydroxyanisole Nutrition 0.000 claims description 4
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 claims description 4
- 229940043253 butylated hydroxyanisole Drugs 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 claims description 3
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 3
- 238000007046 ethoxylation reaction Methods 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims 1
- 230000001476 alcoholic effect Effects 0.000 claims 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims 1
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical group CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 claims 1
- 239000001294 propane Substances 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000010276 construction Methods 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- VBHXIMACZBQHPX-UHFFFAOYSA-N 2,2,2-trifluoroethyl prop-2-enoate Chemical compound FC(F)(F)COC(=O)C=C VBHXIMACZBQHPX-UHFFFAOYSA-N 0.000 description 6
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 6
- 235000006708 antioxidants Nutrition 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000004078 waterproofing Methods 0.000 description 5
- 239000010426 asphalt Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- -1 polyethylene terephthalate Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- NNNLYDWXTKOQQX-UHFFFAOYSA-N 1,1-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OC(CC)(OC(=O)C=C)OC(=O)C=C NNNLYDWXTKOQQX-UHFFFAOYSA-N 0.000 description 1
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical class CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 240000006927 Foeniculum vulgare Species 0.000 description 1
- 235000004204 Foeniculum vulgare Nutrition 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000002243 cyclohexanonyl group Chemical group *C1(*)C(=O)C(*)(*)C(*)(*)C(*)(*)C1(*)* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003852 triazoles Chemical group 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
- C08F259/02—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine
- C08F259/04—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine on to polymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a kind of polymer membranes, are made of the component of following parts by weight：100 parts of fluorine-containing propene acids ionomer, 10 15 parts of modified montmorillonoid, 15 parts of organic fiber, 13 parts of antioxidant.The preparation method of the polymer membranes, includes the following steps：S1, by fluorine-containing propene acids ionomer, modified montmorillonoid, organic fiber, antioxidant is proportionally added into mixer and is uniformly mixed, and obtains mixture；S2, the mixture being prepared by step S1 is added twin-screw extrude into extrusion molding, obtains polymer membranes.Polymer membranes environmental protection disclosed by the invention, economical, weatherability and water resistance are better.
Description
Technical field
The invention belongs to waterproof material technical fields, are related to a kind of high molecular material, specifically, being related to a kind of macromolecule
Waterproof roll and preparation method thereof.
Background technology
In recent years, with the development and the improvement of people's living standards of society, miscellaneous high buildings and large mansions, bridging tunnel
It emerges in large numbers like the mushrooms after rain.These buildings can cause leakage, mouldy etc. to be asked in the long-term use, if waterproof is improper
Topic, to seriously affect people’s lives.Therefore, building waterproof problem can not despise.
Currently, waterproof material category is various, construction technology is irregular, and the selection of waterproof material and waterproof technology is still perhaps
The waterproof material of a great problem of more families, mainstream includes mainly waterproof roll, polyurethanes water-repellent paint, polyalcohol cement basis
Waterproof material and cementitious capillary waterproofing material.Wherein, waterproof roll is most widely used a kind of material, is
For construction wall, roofing and tunnel, highway, refuse landfill etc., plays and resist extraneous rainwater, underground water leaks
A kind of rollable flexible water building material product at web-like.Product mainly has asphalt water-proof coiled material and polymer membranes.It passes
The asphalt water-proof coiled material peel strength of system is low, and water resistance is insufficient, and with the extension of usage time, water resistance weakens, and
Since pitch has carcinogenesis, threat is caused using the health to environment and construction personnel.Traditional macromolecule
Waterproof roll quality is harder, and construction ride comfort is poor, and due to equipment complexity, passability is poor in the welding process, and waterproofing node is applied
Work difficulty is higher, and there are security risks.
Chinese invention patent 201410161404.9 discloses a kind of non-bituminous waterproof material system that nano-sized filler changes
Method is made, is made of by weight following component：25-45 parts of rubber oil, 1-5 parts of hot melt adhesive grade elastomer, styrene-butadiene-
1-11 parts of styrene block copolymer, 1-8 parts of tackified rubber, 4-16 parts of devulcanized rubber, 5-8 parts of high-temperature resin, tackifying resin 10-
25 parts, 4-35 parts of nanoscale talcum powder, 1-2 parts of white carbon powder, have good self-healing ability and stripping ability.However its ingredient
It is complicated with preparation method, and the requirement to raw material is stringent, production cost is higher, hinders its extensive use.
Therefore, exploitation is a kind of environment friendliness, and weatherability and stripping are rolled up with the excellent macromolecule waterproof of water resistance
Material accords with the demands of the market, and has a very important significance.
Invention content
In order to overcome the defects of the prior art, a kind of polymer membranes of present invention offer and preparation method thereof, should
Preparation method is simple for process, and raw material is easy to get, cheap, of less demanding to equipment and reaction condition, is suitble to extensive raw
Production；The polymer membranes being prepared by the preparation method overcomes traditional asphalt waterproof roll water resistance not
Foot, with the extension of usage time, water resistance weakens, and the technical issues of pollution environment, also overcomes conventional polymer
Waterproof roll quality is harder, and construction ride comfort is poor, and due to equipment complexity, passability is poor in the welding process, and waterproofing node is applied
Work difficulty is higher, there is technical issues that, has environmental protection, economical, weatherability and the superior spy of water resistance
Sign.
To achieve the above object of the invention, the technical solution adopted by the present invention is a kind of polymer membranes, by weighing as follows
The component of amount part is made：100 parts of fluorine-containing propene acids ionomer, 10-15 parts of modified montmorillonoid, 1-5 parts of organic fiber are anti-oxidant
1-3 parts of agent.
Preferably, the organic fiber is polyphenylene sulfide fibre, polyetheretherketonefiber fiber, polyethylene terephthalate fibre
Dimension, at least one of plant fiber.
Preferably, the antioxidant is in di-tert-butyl p-cresol, butylated hydroxy anisole, dibutyl hydroxy toluene
One or more.
Preferably, the preparation method of the fluorine-containing propene acids ionomer, includes the following steps：
1) polyvinyl chloride, 2- (dimethylamino) ethyl propylene acid esters are dissolved in organic solvent, and are stirred at room temperature anti-
Answer 4-6 hours, after settle out in methylene chloride, after centrifugation revolving remove solvent, obtain modified polyvinyl chloride；
2) will pass through step 1) be prepared modified polyvinyl chloride, 2,2,2- trifluoroethyls acrylate, ethoxylation
Trimethylolpropane trimethacrylate, 1- vinyl -1,2,4- triazoles are dissolved in high boiling solvent, and are added cause thereto
Agent is stirred to react 2-3 hours under 55-65 DEG C of nitrogen of temperature or atmosphere of inert gases, after settle out in water, and be dried in vacuo
It is dried 10-15 hours at 95-105 DEG C of case, obtains fluorine-containing propene acid copolymer；
3) it is by the mass fraction that the fluorine-containing propene acid copolymer being prepared by step 2) is immersed at 50-60 DEG C
18-24 hours in the aqueous solution of the sodium hexafluorisilicate of 10-20%, after impregnate in water 10-15 hours, it is rear to take out that be placed in vacuum dry
It is dried 10-15 hours at 95-105 DEG C of dry case, obtains fluorine-containing propene acids ionomer.
Preferably, the mass ratio of polyvinyl chloride described in step 1), 2- (dimethylamino) ethyl propylenes acid esters, organic solvent
For (1-2):1:(10-15).
Preferably, the organic solvent is selected from one or more of cyclohexanone, dichloroethanes, tetrahydrofuran.
Preferably, modified polyvinyl chloride described in step 2), 2,2,2- trifluoroethyl acrylate, three hydroxyl first of ethoxylation
Base propane triacrylate, 1- vinyl -1,2,4- triazoles, high boiling solvent, initiator mass ratio be (1-2):1:(0.3-
0.5):0.3:(5-10):(0.02-0.05)。
Preferably, the high boiling solvent is selected from cyclohexanone, dimethyl sulfoxide, n,N-Dimethylformamide, N- methylpyrroles
One or more of alkanone.
Preferably, the initiator is selected from one or both of azodiisobutyronitrile, azobisisoheptonitrile.
Preferably, the inert gas is selected from one or more of helium, neon, argon gas.
Preferably, the mass ratio of the aqueous solution of fluorine-containing propene acid copolymer described in step 3), sodium hexafluorisilicate, water is
1:(80-120):100。
Preferably, the preparation method of the modified montmorillonoid, includes the following steps：Montmorillonite is placed in round-bottomed flask,
And mechanical agitation 25-30 minutes at 70-80 DEG C, after be added dropwise mass fraction be 5-10% silane coupling agent ethyl alcohol it is molten
Liquid drips off in 2 hours, after continue stirring 2-4 hour, take out and be placed at 80-90 DEG C of vacuum drying chamber and dry 8-12 hours, obtain
Modified montmorillonoid.
Preferably, the montmorillonite, silane coupling agent ethanol solution mass ratio be (3-5):(1-5).
Further, the silane coupling agent is selected from Silane coupling agent KH550, silane coupling agent KH560, silane coupling agent
One or more of KH570.
Preferably, the preparation method of the polymer membranes, includes the following steps：
S1, by fluorine-containing propene acids ionomer, modified montmorillonoid, organic fiber, antioxidant is proportionally added into mixer
In be uniformly mixed, obtain mixture；
S2, the mixture being prepared by step S1 is added twin-screw extrude into extrusion molding, obtains macromolecule
Waterproof roll.
It is using advantageous effect caused by above-mentioned technical proposal：
1) preparation method of polymer membranes provided by the invention, simple for process, raw material is easy to get, and price is low
It is honest and clean, it is of less demanding to equipment and reaction condition, it is suitble to large-scale production.
2) polymer membranes provided by the invention, it is low to overcome traditional asphalt waterproof roll peel strength, water proofing property
Can be insufficient, with the extension of usage time, water resistance weakens, and the technical issues of pollution environment, also overcomes traditional height
Molecule waterproof roll quality is harder, and construction ride comfort is poor, and due to equipment complexity, passability is poor in the welding process, waterproof section
Point difficulty of construction is higher, there is technical issues that, has environmental protection, economical, weatherability and water resistance are better
Feature.
3) polymer membranes provided by the invention contains triazole structure in molecular structure, is conducive to improve material
Resistance to UV aging introduces quaternary ammonium salt structure, and hexafluorosilicic acid root is fixed by ionic bond, is conducive to improve macromolecule waterproof volume
Material water resistance and weatherability, each component and monomer synergistic effect so that the polymer membranes being prepared has more
Excellent heat resistance, weatherability, water proofing property and mechanical mechanics property.
4) polymer membranes provided by the invention, is modified polyvinyl chloride, then is connect with polymerisable monomer
Branch reaction forms three-dimensional net structure by polymerization, the advantages of with pvc material and acrylic resin material, has
Conducive to the comprehensive performance of raising polymer membranes；Introducing montmorillonite, organic fiber are enhanced, and are conducive to improve mechanical property
Energy；Contain ethoxylated trimethylolpropane triacrylate in monomer, be easily formed cross-linked structure, improves water resistance.
Specific implementation mode
In order to make those skilled in the art more fully understand technical scheme of the present invention, and make the present invention features described above,
Purpose and advantage are more clear understandable, and with reference to embodiment, the present invention is described further.Embodiment is only used for
It is bright the present invention rather than limit the scope of the invention.
Raw material used in the following embodiments of the present invention is purchased from shellfish store of rubbing.
Embodiment 1
A kind of polymer membranes is made of the component of following parts by weight：100 parts of fluorine-containing propene acids ionomer, changes
10 parts of montmorillonite of property, 1 part of polyphenylene sulfide fibre, 1 part of di-tert-butyl p-cresol.
The preparation method of the fluorine-containing propene acids ionomer, includes the following steps：
1) polyvinyl chloride 10g, 2- (dimethylamino) ethyl propylene acid esters 10g is dissolved in cyclohexanone 100g, and in room temperature
Under be stirred to react 4 hours, after settle out in methylene chloride, after centrifugation revolving remove solvent, obtain modified polyvinyl chloride；
2) modified polyvinyl chloride 10g, 2,2,2- trifluoroethyl acrylate 10g, the second that step 1) is prepared will be passed through
Oxygroup trimethylolpropane trimethacrylate 3g, 1- vinyl -1,2,4- triazoles 3g are dissolved in cyclohexanone 80g, and thereto
Azodiisobutyronitrile 0.2g is added, is stirred to react 2 hours under 55 DEG C of nitrogen atmospheres of temperature, after settle out in water, and in vacuum
It is dried 10 hours at 95 DEG C of drying box, obtains fluorine-containing propene acid copolymer；
3) it is by the fluorine-containing propene acid copolymer 10g being prepared by the step 2) mass fractions being immersed at 50 DEG C
18 hours in the aqueous solution 800g of 10% sodium hexafluorisilicate, after impregnated 10 hours in water 1000g, it is rear to take out that be placed in vacuum dry
It is dried 10 hours at 95 DEG C of dry case, obtains fluorine-containing propene acids ionomer.
The preparation method of the modified montmorillonoid, includes the following steps：Montmorillonite 30g is placed in round-bottomed flask, and
Mechanical agitation 25 minutes at 70 DEG C, after be added dropwise the ethanol solution 10g of the Silane coupling agent KH550 that mass fraction is 5%, 2
Dripped off in hour, after continue stirring 2 hours, taking-up is placed at 80 DEG C of vacuum drying chamber and dries 8 hours, obtains modified montmorillonoid.
The preparation method of the polymer membranes, includes the following steps：
S1, by fluorine-containing propene acids ionomer, modified montmorillonoid, polyphenylene sulfide fibre, di-tert-butyl p-cresol is in proportion
It is added in mixer and is uniformly mixed, obtain mixture；
S2, the mixture being prepared by step S1 is added twin-screw extrude into extrusion molding, obtains macromolecule
Waterproof roll.
Embodiment 2
A kind of polymer membranes is made of the component of following parts by weight：100 parts of fluorine-containing propene acids ionomer, changes
12 parts of montmorillonite of property, 2 parts of polyetheretherketonefiber fiber, 2 parts of butylated hydroxy anisole.
The preparation method of the fluorine-containing propene acids ionomer, includes the following steps：
1) polyvinyl chloride 13g, 2- (dimethylamino) ethyl propylene acid esters 10g is dissolved in dichloroethanes 115g, and in room
Be stirred to react under temperature 4.5 hours, after settle out in methylene chloride, after centrifugation revolving remove solvent, obtain modified polyvinyl chloride；
2) modified polyvinyl chloride 13g, 2,2,2- trifluoroethyl acrylate 10g, the second that step 1) is prepared will be passed through
Oxygroup trimethylolpropane trimethacrylate 3.5g, 1- vinyl -1,2,4- triazoles 3g are dissolved in dimethyl sulfoxide 65g, and to
Wherein be added azobisisoheptonitrile 0.25g, be stirred to react 2.2 hours under 58 DEG C of helium atmosphere of temperature, after settle out in water, and
It is dried 12 hours at 98 DEG C of vacuum drying chamber, obtains fluorine-containing propene acid copolymer；
3) it is by the fluorine-containing propene acid copolymer 10g being prepared by the step 2) mass fractions being immersed at 53 DEG C
20 hours in the aqueous solution 900g of 13% sodium hexafluorisilicate, after impregnated 12 hours in water 1000g, it is rear to take out that be placed in vacuum dry
It is dried 12 hours at 99 DEG C of dry case, obtains fluorine-containing propene acids ionomer.
The preparation method of the modified montmorillonoid, includes the following steps：Montmorillonite 35g is placed in round-bottomed flask, and
Mechanical agitation 27 minutes at 73 DEG C, after be added dropwise the ethanol solution 15g of the silane coupling agent KH560 that mass fraction is 6%, 2
Dripped off in hour, after continue stirring 2.5 hours, taking-up is placed at 83 DEG C of vacuum drying chamber and dries 9.5 hours, obtains modified cover and takes off
Soil.
The preparation method of the polymer membranes, includes the following steps：
S1, by fluorine-containing propene acids ionomer, modified montmorillonoid, polyetheretherketonefiber fiber, butylated hydroxy anisole is in proportion
It is added in mixer and is uniformly mixed, obtain mixture；
S2, the mixture being prepared by step S1 is added twin-screw extrude into extrusion molding, obtains macromolecule
Waterproof roll.
Embodiment 3
A kind of polymer membranes is made of the component of following parts by weight：100 parts of fluorine-containing propene acids ionomer, changes
13 parts of montmorillonite of property, 3 parts of pet fiber, 2 parts of dibutyl hydroxy toluene.
The preparation method of the fluorine-containing propene acids ionomer, includes the following steps：
1) polyvinyl chloride 15g, 2- (dimethylamino) ethyl propylene acid esters 10g is dissolved in tetrahydrofuran 135g, and in room
Be stirred to react under temperature 5 hours, after settle out in methylene chloride, after centrifugation revolving remove solvent, obtain modified polyvinyl chloride；
2) modified polyvinyl chloride 15g, 2,2,2- trifluoroethyl acrylate 10g, the second that step 1) is prepared will be passed through
Oxygroup trimethylolpropane trimethacrylate 4g, 1- vinyl -1,2,4- triazoles 3g is dissolved in N,N-dimethylformamide 75g
In, and thereto be added azodiisobutyronitrile 0.3g, be stirred to react under temperature 60 C neon atmosphere 2.5 hours, after in water
It settles out, and is dried 13.5 hours at 100 DEG C of vacuum drying chamber, obtain fluorine-containing propene acid copolymer；
3) it is by the fluorine-containing propene acid copolymer 10g being prepared by the step 2) mass fractions being immersed at 55 DEG C
21 hours in the aqueous solution 1000g of 15% sodium hexafluorisilicate, after impregnated 13 hours in water 1000g, rear take out is placed in vacuum
It is dried 12.5 hours at 100 DEG C of drying box, obtains fluorine-containing propene acids ionomer.
The preparation method of the modified montmorillonoid, includes the following steps：Montmorillonite 40g is placed in round-bottomed flask, and
Mechanical agitation 27 minutes at 75 DEG C, after be added dropwise the ethanol solution 35g of the silane coupling agent KH570 that mass fraction is 7%, 2
Dripped off in hour, after continue stirring 3 hours, taking-up is placed at 86 DEG C of vacuum drying chamber and dries 10 hours, obtains modified montmorillonoid.
The preparation method of the polymer membranes, includes the following steps：
S1, by fluorine-containing propene acids ionomer, modified montmorillonoid, pet fiber, dibutyl hydroxyl
Base toluene is proportionally added into mixer and is uniformly mixed, and obtains mixture；
S2, the mixture being prepared by step S1 is added twin-screw extrude into extrusion molding, obtains macromolecule
Waterproof roll.
Embodiment 4
A kind of polymer membranes is made of the component of following parts by weight：100 parts of fluorine-containing propene acids ionomer, changes
14 parts of montmorillonite of property, 4 parts of plant fiber, 3 parts of antioxidant；The antioxidant is di-tert-butyl p-cresol, butylhydroxy fennel
Fragrant ether in mass ratio 2:3 mixtures mixed.
The preparation method of the fluorine-containing propene acids ionomer, includes the following steps：
1) polyvinyl chloride 18g, 2- (dimethylamino) ethyl propylene acid esters 10g is dissolved in dichloroethanes 140g, and in room
Be stirred to react under temperature 5.5 hours, after settle out in methylene chloride, after centrifugation revolving remove solvent, obtain modified polyvinyl chloride；
2) modified polyvinyl chloride 18g, 2,2,2- trifluoroethyl acrylate 10g, the second that step 1) is prepared will be passed through
Oxygroup trimethylolpropane trimethacrylate 4.5g, 1- vinyl -1,2,4- triazoles 3g is dissolved in N-Methyl pyrrolidone 90g
In, and thereto be added initiator 0.45g, be stirred to react 2.8 hours under 63 DEG C of argon atmospheres of temperature, after settle out in water,
And dried 14.5 hours at 103 DEG C of vacuum drying chamber, obtain fluorine-containing propene acid copolymer；The initiator is two isobutyl of azo
Nitrile, azobisisoheptonitrile in mass ratio 2:5 mixtures mixed；
3) it is by the fluorine-containing propene acid copolymer 10g being prepared by the step 2) mass fractions being immersed at 58 DEG C
23 hours in the aqueous solution 1150g of 18% sodium hexafluorisilicate, after impregnated 14 hours in water 1000g, rear take out is placed in vacuum
It is dried 14.5 hours at 103 DEG C of drying box, obtains fluorine-containing propene acids ionomer.
The preparation method of the modified montmorillonoid, includes the following steps：Montmorillonite 45g is placed in round-bottomed flask, and
Mechanical agitation 29 minutes at 79 DEG C, after be added dropwise the ethanol solution 40g of the Silane coupling agent KH550 that mass fraction is 9%, 2
Dripped off in hour, after continue stirring 3.5 hours, taking-up is placed at 89 DEG C of vacuum drying chamber and dries 11 hours, obtains modified cover and takes off
Soil.
The preparation method of the polymer membranes, includes the following steps：
S1, by fluorine-containing propene acids ionomer, modified montmorillonoid, plant fiber, antioxidant is proportionally added into mixer
In be uniformly mixed, obtain mixture；
S2, the mixture being prepared by step S1 is added twin-screw extrude into extrusion molding, obtains macromolecule
Waterproof roll.
Embodiment 5
A kind of polymer membranes is made of the component of following parts by weight：100 parts of fluorine-containing propene acids ionomer, changes
15 parts of montmorillonite of property, 5 parts of polyphenylene sulfide fibre, 3 parts of di-tert-butyl p-cresol.
The preparation method of the fluorine-containing propene acids ionomer, includes the following steps：
1) polyvinyl chloride 20g, 2- (dimethylamino) ethyl propylene acid esters 10g is dissolved in tetrahydrofuran 150g, and in room
Be stirred to react under temperature 6 hours, after settle out in methylene chloride, after centrifugation revolving remove solvent, obtain modified polyvinyl chloride；
2) modified polyvinyl chloride 20g, 2,2,2- trifluoroethyl acrylate 10g, the second that step 1) is prepared will be passed through
Oxygroup trimethylolpropane trimethacrylate 5g, 1- vinyl -1,2,4- triazoles 3g are dissolved in cyclohexanone 100g, and thereto
Azobisisoheptonitrile 0.5g is added, is stirred to react 3 hours under 65 DEG C of nitrogen atmospheres of temperature, after settle out in water, and in vacuum
It is dried 15 hours at 105 DEG C of drying box, obtains fluorine-containing propene acid copolymer；
3) it is by the fluorine-containing propene acid copolymer 10g being prepared by the step 2) mass fractions being immersed at 60 DEG C
24 hours in the aqueous solution 1200g of 20% sodium hexafluorisilicate, after impregnated 15 hours in water 1000g, rear take out is placed in vacuum
It is dried 15 hours at 105 DEG C of drying box, obtains fluorine-containing propene acids ionomer.
The preparation method of the modified montmorillonoid, includes the following steps：Montmorillonite 50g is placed in round-bottomed flask, and
Mechanical agitation 30 minutes at 80 DEG C, after be added dropwise the ethanol solution 50g of the silane coupling agent KH570 that mass fraction is 10%, 2
Dripped off in hour, after continue stirring 4 hours, taking-up is placed at 90 DEG C of vacuum drying chamber and dries 12 hours, obtains modified montmorillonoid.
The preparation method of the polymer membranes, includes the following steps：
S1, by fluorine-containing propene acids ionomer, modified montmorillonoid, polyphenylene sulfide fibre, di-tert-butyl p-cresol is in proportion
It is added in mixer and is uniformly mixed, obtain mixture；
S2, the mixture being prepared by step S1 is added twin-screw extrude into extrusion molding, obtains macromolecule
Waterproof roll.
Comparative example
This example provides a kind of polymer membranes, according to 1 method system of Chinese invention patent CN105331002A embodiments
It is standby to obtain.
Polymer membranes described in embodiment 1-5 and comparative example is tested for the property, test method refers to GB/
T328-2007, test result are shown in Table 1.
1 polymer membranes performance parameter of table
As seen from Table 1, polymer membranes disclosed by the embodiments of the present invention is rolled up with macromolecule waterproof in the prior art
Material is compared, and has more excellent water resistance, mechanical property and heat resistance.
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (10)
1. a kind of polymer membranes, which is characterized in that be made of the component of following parts by weight：Fluorine-containing propene acids ionomer
100 parts, 10-15 parts of modified montmorillonoid, 1-5 parts of organic fiber, 1-3 parts of antioxidant.
2. polymer membranes according to claim 1, which is characterized in that the organic fiber is that polyphenylene sulfide is fine
At least one of dimension, polyetheretherketonefiber fiber, pet fiber, plant fiber；The antioxidant is selected from
One or more of di-tert-butyl p-cresol, butylated hydroxy anisole, dibutyl hydroxy toluene.
3. polymer membranes according to claim 1, which is characterized in that the system of the fluorine-containing propene acids ionomer
Preparation Method includes the following steps：
1) polyvinyl chloride, 2- (dimethylamino) ethyl propylene acid esters are dissolved in organic solvent, and reaction 4-6 is stirred at room temperature
Hour, after settle out in methylene chloride, after centrifugation revolving remove solvent, obtain modified polyvinyl chloride；
2) modified polyvinyl chloride, 2,2,2- trifluoroethyls acrylate, three hydroxyl of ethoxylation that step 1) is prepared will be passed through
Propane tri, 1- vinyl -1,2,4- triazoles are dissolved in high boiling solvent, and initiator is added thereto,
Be stirred to react under 55-65 DEG C of nitrogen of temperature or atmosphere of inert gases 2-3 hours, after settle out in water, and in vacuum drying chamber 95-
It is dried 10-15 hours at 105 DEG C, obtains fluorine-containing propene acid copolymer；
3) it is 10- the fluorine-containing propene acid copolymer being prepared by step 2) to be immersed in the mass fraction at 50-60 DEG C
18-24 hours in the aqueous solution of 20% sodium hexafluorisilicate, after impregnate in water 10-15 hours, rear take out is placed in vacuum drying
It is dried 10-15 hours at 95-105 DEG C of case, obtains fluorine-containing propene acids ionomer.
4. polymer membranes according to claim 3, which is characterized in that polyvinyl chloride described in step 1), 2- (two
Methyl ammonia) ethyl propylene acid esters, organic solvent mass ratio be (1-2):1:(10-15).
5. polymer membranes according to claim 3, which is characterized in that modified polyvinyl chloride described in step 2),
2,2,2- trifluoroethyls acrylate, ethoxylated trimethylolpropane triacrylate, 1- vinyl -1,2,4- triazoles, height
Boiling point solvent, initiator mass ratio be (1-2):1:(0.3-0.5):0.3:(5-10):(0.02-0.05).
6. polymer membranes according to claim 3, which is characterized in that the high boiling solvent be selected from cyclohexanone,
One or more of dimethyl sulfoxide, N,N-dimethylformamide, N-Methyl pyrrolidone；It is different that the initiator is selected from azo two
One or both of butyronitrile, azobisisoheptonitrile；The inert gas is selected from one or more of helium, neon, argon gas；
The organic solvent is selected from one or more of cyclohexanone, dichloroethanes, tetrahydrofuran.
7. polymer membranes according to claim 3, which is characterized in that fluorine-containing propene acids described in step 3) is total
Polymers, the aqueous solution of sodium hexafluorisilicate, water mass ratio be 1:(80-120):100.
8. polymer membranes according to claim 1, which is characterized in that the preparation method of the modified montmorillonoid,
Include the following steps：Montmorillonite is placed in round-bottomed flask, and mechanical agitation 25-30 minutes at 70-80 DEG C, after be added dropwise
Mass fraction be 5-10% silane coupling agent ethanol solution, dripped off in 2 hours, after continue stirring 2-4 hour, taking-up juxtaposition
It is dried 8-12 hours at 80-90 DEG C of vacuum drying chamber, obtains modified montmorillonoid.
9. polymer membranes according to claim 8, which is characterized in that the montmorillonite, silane coupling agent second
The mass ratio of alcoholic solution is (3-5):(1-5；The silane coupling agent be selected from Silane coupling agent KH550, silane coupling agent KH560,
One or more of silane coupling agent KH570.
10. a kind of preparation method according to claim 1-9 any one of them polymer membranes, which is characterized in that packet
Include following steps：
S1, by fluorine-containing propene acids ionomer, modified montmorillonoid, organic fiber, antioxidant is proportionally added into mixer and mixes
It closes uniformly, obtains mixture；
S2, the mixture being prepared by step S1 is added twin-screw extrude into extrusion molding, obtains macromolecule waterproof
Coiled material.
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| JP2002179922A (en) * | 2000-12-07 | 2002-06-26 | Asahi Glass Co Ltd | Curable composition |
| CN103410276A (en) * | 2013-08-22 | 2013-11-27 | 烟台斯坦普精工建设有限公司 | Roof photovoltaic waterproof coiled material and preparation method thereof |
| CN107286501A (en) * | 2017-06-07 | 2017-10-24 | 广东大禹九鼎防水科技有限公司 | A kind of high intensity high rush-resistant polyvinyl chloride waterproof roll and preparation method thereof |
| CN107828349A (en) * | 2017-11-30 | 2018-03-23 | 湖南神宇新材料有限公司 | A kind of preparation method of composite type self-adhesion waterproof roll |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002179922A (en) * | 2000-12-07 | 2002-06-26 | Asahi Glass Co Ltd | Curable composition |
| CN103410276A (en) * | 2013-08-22 | 2013-11-27 | 烟台斯坦普精工建设有限公司 | Roof photovoltaic waterproof coiled material and preparation method thereof |
| CN107286501A (en) * | 2017-06-07 | 2017-10-24 | 广东大禹九鼎防水科技有限公司 | A kind of high intensity high rush-resistant polyvinyl chloride waterproof roll and preparation method thereof |
| CN107828349A (en) * | 2017-11-30 | 2018-03-23 | 湖南神宇新材料有限公司 | A kind of preparation method of composite type self-adhesion waterproof roll |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110551256A (en) * | 2019-09-06 | 2019-12-10 | 山东建筑大学 | Preparation method of composite plant fiber molding decorative building material |
| CN110551256B (en) * | 2019-09-06 | 2021-10-15 | 山东建筑大学 | Preparation method of composite plant fiber molding decorative building material |
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