CN117565526B - High-strength TPO waterproof coiled material and preparation method thereof - Google Patents
High-strength TPO waterproof coiled material and preparation method thereof Download PDFInfo
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- CN117565526B CN117565526B CN202311520956.XA CN202311520956A CN117565526B CN 117565526 B CN117565526 B CN 117565526B CN 202311520956 A CN202311520956 A CN 202311520956A CN 117565526 B CN117565526 B CN 117565526B
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- CN
- China
- Prior art keywords
- tpo
- coiled material
- poe
- strength
- waterproof coiled
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- 239000000463 material Substances 0.000 title claims abstract description 130
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000004744 fabric Substances 0.000 claims abstract description 33
- 230000008569 process Effects 0.000 claims abstract description 29
- -1 imide siloxane Chemical class 0.000 claims abstract description 27
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 25
- 239000000945 filler Substances 0.000 claims abstract description 23
- 229960003656 ricinoleic acid Drugs 0.000 claims abstract description 22
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 claims abstract description 21
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- DVGKTVKVVIFKFP-UHFFFAOYSA-N stk396681 Chemical compound O=C1OC(=O)C2=CC=CC3=C2C1=CC=C3C(=O)O DVGKTVKVVIFKFP-UHFFFAOYSA-N 0.000 claims abstract description 18
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920000728 polyester Polymers 0.000 claims abstract description 13
- 238000013329 compounding Methods 0.000 claims abstract description 11
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920002397 thermoplastic olefin Polymers 0.000 claims description 156
- 238000002156 mixing Methods 0.000 claims description 35
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 28
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000314 lubricant Substances 0.000 claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims description 9
- 230000003078 antioxidant effect Effects 0.000 claims description 9
- 239000004611 light stabiliser Substances 0.000 claims description 9
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 6
- 150000003077 polyols Chemical class 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000007731 hot pressing Methods 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 22
- 238000001035 drying Methods 0.000 description 18
- 238000005406 washing Methods 0.000 description 18
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 8
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 8
- 235000010215 titanium dioxide Nutrition 0.000 description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- UUGLSEIATNSHRI-UHFFFAOYSA-N 1,3,4,6-tetrakis(hydroxymethyl)-3a,6a-dihydroimidazo[4,5-d]imidazole-2,5-dione Chemical compound OCN1C(=O)N(CO)C2C1N(CO)C(=O)N2CO UUGLSEIATNSHRI-UHFFFAOYSA-N 0.000 description 5
- 229920004933 Terylene® Polymers 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920006124 polyolefin elastomer Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical group CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 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
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0021—Combinations of extrusion moulding with other shaping operations combined with joining, lining or laminating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
- B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
- B29C66/45—Joining of substantially the whole surface of the articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/08—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the cooling method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/028—Net structure, e.g. spaced apart filaments bonded at the crossing points
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
- B29L2007/002—Panels; Plates; Sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2009/00—Layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0276—Polyester fibres
- B32B2262/0284—Polyethylene terephthalate [PET] or polybutylene terephthalate [PBT]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
- B32B2307/7265—Non-permeable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of waterproof coiled materials, in particular to a high-strength TPO waterproof coiled material and a preparation method thereof, and the high-strength TPO waterproof coiled material comprises the following processes: step 1, preparing TPO coiled materials: co-extruding TPO, modified POE, tetrahydroxymethyl glycoluril, filler and auxiliary agent to obtain TPO coiled material; step 2, preparing TPO waterproof coiled materials: and (3) superposing polyester cloth and grid cloth on the surface of the TPO coiled material obtained in the step (1) to form a blank body with the structure of the polyester cloth, the TPO coiled material, the grid cloth and the TPO coiled material from top to bottom, and compounding to obtain the TPO waterproof coiled material. According to the invention, the POE-g-GMA reacts with ricinoleic acid to obtain polyhydroxy POE, gamma-aminopropyl triethoxy silane reacts with 4-carboxyl-1, 8-naphthalene dicarboxylic anhydride to obtain imide siloxane, and the modified POE obtained by the reaction of the polyhydroxy POE-g-GMA and the ricinoleic acid is blended with TPO, filler and the like, so that the prepared TPO coiled material has better heat resistance, water resistance and mechanical properties.
Description
Technical Field
The invention relates to the technical field of waterproof coiled materials, in particular to a high-strength TPO waterproof coiled material and a preparation method thereof.
Background
As a waterproof product with good flexibility and bending, the waterproof coiled material can resist rainwater in the indoor environment, building groundwater permeated by air and moisture in the indoor air, and has a vital application position for building waterproofing. As one of the types of waterproof coiled materials, the TPO waterproof coiled material is a thermoplastic polyolefin waterproof coiled material, is a polymer formed by copolymerizing ethylene and propylene, and has more excellent comprehensive characteristics. But the strength of the existing TPO waterproof coiled material still has a lifting space. Therefore, we propose a high-strength TPO waterproof coiled material and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a high-strength TPO waterproof coiled material and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: the high-strength TPO waterproof coiled material sequentially comprises the following structures from top to bottom: polyester cloth, TPO coiled material, grid cloth and TPO coiled material;
Further, the TPO coiled material comprises the following components in parts by mass: 70-85 parts of thermoplastic polyolefin TPO, 25-30 parts of polyolefin elastomer POE, 10-20 parts of filler and 2.1-5.0 parts of auxiliary agent;
Polyolefin elastomer POE: from the dow chemical company, inc.
Further, the terylene cloth is waterproof terylene non-woven fabric with the thickness of 0.8-1.2 mm and is sourced from water-proof materials limited company of river city, township Tu Hongtai.
Further, the mesh cloth is glass fiber mesh cloth, the specification is 80-100 g/m 2, and the mesh cloth is from Sichuan-voyage silk screen product company of Anpingxian.
The preparation method of the high-strength TPO waterproof coiled material comprises the following processes:
step 1, preparing TPO coiled materials: taking TPO, POE, filler and auxiliary agent for coextrusion to obtain TPO coiled material;
Step 2, preparing TPO waterproof coiled materials: and (3) superposing polyester cloth and grid cloth on the surface of the TPO coiled material obtained in the step (1) to form a blank body with the structure of the polyester cloth, the TPO coiled material, the grid cloth and the TPO coiled material from top to bottom, and compounding to obtain the TPO waterproof coiled material.
Further, the process conditions of the compounding are as follows: hot pressing: the temperature is 165-200 ℃, the pressure is 2-5 MPa, and the time is 1-15 min;
Cold pressing: the temperature is 4-6 ℃, the pressure is 1-2 MPa, and the time is 12-20 min.
Further, the TPO coiled material is prepared by the following process:
TPO, modified POE, tetrahydroxymethyl glycoluril, filler and auxiliary agent are mixed, and are blended and extruded by an extruder, wherein the process conditions of the blending and extrusion are as follows: 160-180 ℃ of the feeding section, 180-200 ℃ of the plasticizing section, 190-210 ℃ of the metering section, 180-200 ℃ of the die opening temperature and 40-50 r/min of the screw rotating speed to obtain the TPO coiled material.
Further, the TPO coiled material comprises the following components in parts by mass: 70 to 85 parts of thermoplastic polyolefin TPO, 15 to 30 parts of modified POE, 3.0 to 5.4 parts of tetrahydroxymethyl glycoluril, 10 to 20 parts of filler and 2.1 to 5.0 parts of auxiliary agent;
The thickness of the TPO coiled material is 1.2-2.0 mm;
Thermoplastic polyolefin TPO: CA10A, from the Industrial company Liande Barceier;
the filler is nano active calcium carbonate which is derived from Wuhan Xingzhong Chengcheng technology Co;
further, the auxiliary agent comprises 1 to 3 parts of titanium dioxide, 0.3 to 0.5 part of antioxidant, 0.3 to 0.5 part of light stabilizer and 0.5 to 1.0 part of lubricant.
Titanium white powder: DR-2589, from Jiangsu Panhua chemical science and technology Co., ltd;
The antioxidant is a mixture of antioxidant 1010 and antioxidant 168, and is derived from national medicine group chemical reagent company;
The light stabilizer is one or more of TINUVIN 770, TINUVIN7622 and TINUVIN 765, which are derived from Basiff corporation of Germany;
The lubricant is one or two of stearic acid and calcium stearate, and is derived from national pharmaceutical group chemical reagent company.
Further, the modified POE is prepared by the following process:
step 1.1 preparation of polyol:
taking POE-g-GMA, adding ricinoleic acid, mixing, and standing for 100-150 min in nitrogen atmosphere; placing the mixture into a rheometer, and reacting for 5 to 10 minutes at the temperature of 170 to 180 ℃ and the rotating speed of 50 to 100 r/min; washing and drying to obtain polyhydroxy POE;
Step 1.2. Preparation of imide siloxanes:
Mixing gamma-aminopropyl triethoxysilane and 4-carboxyl-1, 8-naphthalene dianhydride, heating to 80-85 ℃, and stirring for reacting for 15-20 min to obtain amic acid siloxane;
Adding sodium carbonate and acetic anhydride, mixing, stirring, heating to 100-105 ℃, and reacting for 60-75 min; cooling, washing and drying to obtain imide siloxane;
step 1.3. Preparation of modified POE:
Mixing polyhydroxy POE and imide siloxane, adding a catalyst, placing in a rheometer, and reacting for 12-20 min under the conditions of 170-180 ℃ and 50-100 r/min of rotating speed; washing and drying to obtain the modified POE.
In the step 1.1, the mass ratio of POE-g-GMA to ricinoleic acid is 100 (16-30);
POE-g-GMA: glycidyl methacrylate grafted ethylene-octene copolymer, SOG-02, GMA content of 2.0wt% was derived from the good compatibility Polymer (Shanghai) Co., ltd.
Further, in step 1.2, the 4-carboxyl-1, 8-naphthalene dicarboxylic anhydride is subjected to carboxyl protection treatment, and the specific process is as follows:
mixing 4-carboxyl-1, 8-naphthalene dicarboxylic anhydride and 1, 4-dioxane, adding isobutene and boron trifluoride diethyl etherate, and stirring at 20-25 ℃ for reaction for 150-200 min;
The proportion of the 4-carboxyl-1, 8-naphthalene dicarboxylic anhydride, the isobutene, the boron trifluoride diethyl etherate and the 1, 4-dioxane is 24g (5.6-6.1 g) (4.2-4.7 g) 100mL;
Before the modified POE is used, i.e. before the TPO coiled material is prepared in the step 1, the TPO coiled material is placed in a dichloromethane solution of 50% trifluoroacetic acid, and stirred and reacted for 60-75 min at the temperature of 45-50 ℃ so as to remove isobutene groups; and then washing and drying.
In the technical scheme, isobutene reacts with carboxyl in 4-carboxyl-1, 8-naphthalene dianhydride to form tertiary butyl ester, and the steric hindrance effect of the tertiary butyl ester has higher stability to alkali, so that the carboxyl can be prevented from reacting in the preparation process of the modified POE, the carboxyl in the 4-carboxyl-1, 8-naphthalene dianhydride structure can be reserved and removed before use, and the prepared modified POE is beneficial to playing a role in the subsequent process.
In the step 1.2, the molar ratio of the gamma-aminopropyl triethoxysilane to the 4-carboxyl-1, 8-naphthalene dianhydride to the sodium carbonate is 1:1 (0.15-0.17);
the ratio of sodium carbonate to acetic anhydride was 0.6g/100mL.
In step 1.3, the mass ratio of polyhydroxy POE to imide siloxane to catalyst p-toluenesulfonic acid is 10 (23-33) (0.02-0.04).
Compared with the prior art, the invention has the following beneficial effects:
In the technical scheme, calcium carbonate is selected as a filler to be mixed with TPO and POE, so that the shrinkage of the TPO coiled material can be reduced, and the stability of the TPO coiled material can be improved; has better toughening effect, can effectively improve the impact strength of TPO and promote the improvement of the mechanical properties of the TPO coiled material. The modified POE is prepared from POE-g-GMA serving as a raw material, and after being blended with TPO, the modified POE can effectively improve the heat resistance, the water resistance and the toughness of the prepared TPO coiled material and reduce the sensitivity of the TPO coiled material to notch strength; the compatibility of the filler in TPO is improved, and the processability of TPO coiled materials is improved; and the reaction activity is higher, which is beneficial to the subsequent process.
Mixing POE-g-GMA with ricinoleic acid, and carrying out hydrophilic electric effects, wherein epoxy groups in the POE-g-GMA react with carboxyl groups in the ricinoleic acid preferentially to form ester groups and hydroxyl groups, and the hydroxyl groups in the ricinoleic acid are cooperated to obtain an ethylene-octene copolymer POE grafted with polyhydroxy-ricinoleic acid, which is denoted as polyhydroxy POE; the ricinoleic acid introduces long-chain unsaturated alkyl into POE molecular chains to form a comb-shaped structure, molecular repulsive force appears between side chains of the ricinoleic acid, so that POE main chains are forced to straighten and present a bar-shaped conformation, the disorder degree of the molecules is reduced, the regularity of crystals is improved, the side chains of the ricinoleic acid can be used as crystallization nucleation points of TPO in TPO coiled materials while the processability of the ricinoleic acid is not influenced, the crystallization rate and the crystallinity are improved, crystallization is promoted, and the tensile strength and the impact strength of the manufactured TPO coiled materials are effectively improved.
And mixing gamma-aminopropyl triethoxysilane with 4-carboxyl-1, 8-naphthalene dianhydride after carboxyl protection to enable amino to react with anhydride to generate amic acid and imidize to obtain siloxane with imide groups, which is named as imide siloxane. The hydroxyl in the modified POE reacts with the siloxane bond in the imide siloxane to obtain polysiloxane modified POE with a branched structure, so that the toughness of the modified POE is improved, further toughening of TPO is realized, and the good rigidity-toughness balance of the TPO coiled material can be promoted. And the introduction of naphthalene and imide structures can extrude molecular chains, promote the ordering of molecular structures, and prevent the growth of crystals, thereby refining grains, improving the heat resistance and mechanical properties of TPO coiled materials, enabling the surfaces of the TPO coiled materials to tend to be roughened, combining the influence of groups and molecular structures, and improving the water resistance of the TPO coiled materials.
In the preparation of TPO coiled materials, the tetramethylol glycoluril can be used as a cross-linking agent, and the methylol of the TPO coiled materials reacts with carboxyl (derived from modified POE and lubricant) in a system to enable molecular chains to be cross-linked, so that a three-dimensional interpenetrating network structure is formed, and the comprehensive properties of the TPO coiled materials and the TPO waterproof coiled materials prepared from the TPO coiled materials, such as heat resistance, water resistance, mechanical properties and the like, are further improved.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clearly and completely described, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following embodiments:
Thermoplastic polyolefin TPO: CA10A, from the Industrial company Liande Barceier;
POE-g-GMA: glycidyl methacrylate grafted ethylene-octene copolymer, SOG-02, GMA content of 2.0wt%, from Shanghai polymers Co., ltd;
the filler is nano active calcium carbonate which is derived from Wuhan Xingzhong Chengcheng technology Co;
titanium white powder: DR-2589, from Jiangsu Panhua chemical science and technology Co., ltd;
The antioxidant is a mixture of antioxidant 1010 and antioxidant 168, and is derived from national medicine group chemical reagent company;
the light stabilizer is TINUVIN 770, which is derived from Basiff corporation of Germany;
The lubricant is a mixture of stearic acid and calcium stearate, and is derived from national pharmaceutical group chemical reagent company;
The terylene cloth is waterproof terylene non-woven fabric with the thickness of 1.0mm and is sourced from water-proof materials limited company of river city, township Tu Hongtai;
the mesh cloth is glass fiber mesh cloth with the specification of 100g/m 2 and is sourced from the Sichuan-voyage silk screen product company of Anpingxian;
polyolefin elastomer POE: from the dow chemical company, inc;
POE-g-MAH: DF610, from Shenyang four-dimensional plastics Co., ltd.
Example 1: the preparation method of the high-strength TPO waterproof coiled material comprises the following processes:
Step 1, preparing TPO coiled materials:
step 1.1 preparation of polyol:
Mixing POE-g-GMA with ricinoleic acid, and standing in nitrogen atmosphere for 100min; placing in a rheometer, and reacting for 10min at 170 ℃ and a rotating speed of 100 r/min; washing and drying to obtain polyhydroxy POE; the mass ratio of POE-g-GMA to ricinoleic acid is 100:16;
Step 1.2. Preparation of imide siloxanes:
Mixing gamma-aminopropyl triethoxysilane and 4-carboxyl-1, 8-naphthalene dianhydride, heating to 80 ℃, and stirring for reacting for 20min to obtain amic acid siloxane; adding sodium carbonate and acetic anhydride, mixing, stirring, heating to 100 ℃, and reacting for 75min; cooling, washing and drying to obtain imide siloxane; the molar ratio of the gamma-aminopropyl triethoxysilane to the 4-carboxyl-1, 8-naphthalene dicarboxylic anhydride to the sodium carbonate is 1:1:0.15; the ratio of sodium carbonate to acetic anhydride is 0.6g/100mL;
The specific process of the 4-carboxyl-1, 8-naphthalene dicarboxylic anhydride is as follows:
Mixing 4-carboxyl-1, 8-naphthalene dicarboxylic anhydride and 1, 4-dioxane, adding isobutene and boron trifluoride diethyl etherate, and stirring at 20deg.C for reacting for 200min; the ratio of 4-carboxyl-1, 8-naphthalene dicarboxylic anhydride, isobutene, boron trifluoride diethyl etherate and 1, 4-dioxane is 24g:5.6g:4.2g:100mL;
Before the modified POE is used, namely, before the TPO coiled material is prepared in the step 1.4, the modified POE is placed in a 50% methylene dichloride solution of trifluoroacetic acid, stirred and reacted for 75 minutes at the temperature of 45 ℃ for catalytic hydrolysis so as to remove isobutene groups; then washing and drying;
step 1.3. Preparation of modified POE:
Mixing polyhydroxy POE and imide siloxane, adding a catalyst, placing in a rheometer, and reacting for 20min at the temperature of 170 ℃ and the rotating speed of 100 r/min; washing and drying to obtain modified POE; the mass ratio of the polyhydroxy POE to the imide siloxane to the catalyst p-toluenesulfonic acid is 10:23:0.02;
step 1.4. Preparation of TPO coil:
TPO, modified POE, tetrahydroxymethyl glycoluril, filler and auxiliary agent are mixed, and are blended and extruded by an extruder, wherein the process conditions of the blending and extrusion are as follows: the feeding section is 170 ℃, the plasticizing section is 190 ℃, the metering section is 200 ℃, the die temperature is 190 ℃, the screw rotating speed is 40r/min, and the TPO coiled material with the thickness of 1.6mm is obtained; TPO coiled material comprises the following mass components: 85 parts of thermoplastic polyolefin TPO, 15 parts of modified POE, 3.0 parts of tetramethylol glycoluril, 10 parts of filler and 2.1 parts of auxiliary agent; the auxiliary agent comprises 1 part of titanium dioxide, 0.3 part of antioxidant, 0.3 part of light stabilizer and 0.5 part of lubricant;
step 2, preparing TPO waterproof coiled materials:
Stacking polyester cloth and grid cloth on the surface of the TPO coiled material obtained in the step 1 to form a blank body with the structure of the polyester cloth, the TPO coiled material, the grid cloth and the TPO coiled material from top to bottom, compounding, wherein the compounding process conditions are as follows: hot pressing: the temperature is 165 ℃, the pressure is 2MPa, and the time is 15min; cold pressing: the temperature is 4 ℃, the pressure is 2MPa, and the time is 20min, so that the TPO waterproof coiled material is obtained.
Example 2: the preparation method of the high-strength TPO waterproof coiled material comprises the following processes:
Step 1, preparing TPO coiled materials:
step 1.1 preparation of polyol:
Taking POE-g-GMA, adding ricinoleic acid, mixing, and standing for 100-150 min in nitrogen atmosphere; placing in a rheometer, and reacting for 8min at the temperature of 175 ℃ and the rotating speed of 75 r/min; washing and drying to obtain polyhydroxy POE; the mass ratio of POE-g-GMA to ricinoleic acid is 100:23;
Step 1.2. Preparation of imide siloxanes:
mixing gamma-aminopropyl triethoxysilane and 4-carboxyl-1, 8-naphthalene dianhydride, heating to 82 ℃, and stirring for reacting for 18min to obtain amic acid siloxane; adding sodium carbonate and acetic anhydride, mixing, stirring, heating to 102 ℃, and reacting for 68min; cooling, washing and drying to obtain imide siloxane; the molar ratio of the gamma-aminopropyl triethoxysilane to the 4-carboxyl-1, 8-naphthalene dicarboxylic anhydride to the sodium carbonate is 1:1:0.16; the ratio of sodium carbonate to acetic anhydride is 0.6g/100mL;
The specific process of the 4-carboxyl-1, 8-naphthalene dicarboxylic anhydride is as follows:
Mixing 4-carboxyl-1, 8-naphthalene dicarboxylic anhydride and 1, 4-dioxane, adding isobutene and boron trifluoride diethyl etherate, and stirring at 22 ℃ for reaction for 180min; the ratio of 4-carboxyl-1, 8-naphthalene dicarboxylic anhydride, isobutene, boron trifluoride diethyl etherate and 1, 4-dioxane is 24g:5.8g:4.5g:100mL;
Before the modified POE is used, namely before the TPO coiled material is prepared in the step 1.4, the modified POE is placed in a dichloromethane solution of 50% trifluoroacetic acid, stirred and reacted for 68 minutes at 48 ℃ for catalytic hydrolysis so as to remove isobutene groups; then washing and drying;
step 1.3. Preparation of modified POE:
Mixing polyhydroxy POE and imide siloxane, adding a catalyst, placing in a rheometer, and reacting for 16min at the temperature of 175 ℃ and the rotating speed of 75 r/min; washing and drying to obtain modified POE; the mass ratio of the polyhydroxy POE to the imide siloxane to the catalyst p-toluenesulfonic acid is 10:28:0.03;
step 1.4. Preparation of TPO coil:
TPO, modified POE, tetrahydroxymethyl glycoluril, filler and auxiliary agent are mixed, and are blended and extruded by an extruder, wherein the process conditions of the blending and extrusion are as follows: the feeding section is 170 ℃, the plasticizing section is 190 ℃, the metering section is 200 ℃, the die temperature is 190 ℃, and the screw rotation speed is 45r/min, so that the TPO coiled material with the thickness of 1.6mm is obtained; TPO coiled material comprises the following mass components: 78 parts of thermoplastic polyolefin TPO, 23 parts of modified POE, 4.2 parts of tetramethylol glycoluril, 15 parts of filler and 3.6 parts of auxiliary agent; the auxiliary agent comprises 2 parts of titanium dioxide, 0.4 part of antioxidant, 0.4 part of light stabilizer and 0.8 part of lubricant;
step 2, preparing TPO waterproof coiled materials:
Stacking polyester cloth and grid cloth on the surface of the TPO coiled material obtained in the step 1 to form a blank body with the structure of the polyester cloth, the TPO coiled material, the grid cloth and the TPO coiled material from top to bottom, compounding, wherein the compounding process conditions are as follows: hot pressing: the temperature is 190 ℃, the pressure is 3MPa, and the time is 8min; cold pressing: the temperature is 5 ℃, the pressure is 1.5MPa, and the time is 16min, so that the TPO waterproof coiled material is obtained.
Example 3: the preparation method of the high-strength TPO waterproof coiled material comprises the following processes:
Step 1, preparing TPO coiled materials:
step 1.1 preparation of polyol:
Mixing POE-g-GMA with ricinoleic acid, and standing in nitrogen atmosphere for 150min; placing in a rheometer, and reacting for 5min at 180 ℃ and a rotating speed of 50 r/min; washing and drying to obtain polyhydroxy POE; the mass ratio of POE-g-GMA to ricinoleic acid is 100:30;
Step 1.2. Preparation of imide siloxanes:
Mixing gamma-aminopropyl triethoxysilane and 4-carboxyl-1, 8-naphthalene dianhydride, heating to 85 ℃, and stirring for reaction for 15-min to obtain amic acid siloxane; adding sodium carbonate and acetic anhydride, mixing, stirring, heating to 105 ℃, and reacting for 60min; cooling, washing and drying to obtain imide siloxane; the molar ratio of the gamma-aminopropyl triethoxysilane to the 4-carboxyl-1, 8-naphthalene dicarboxylic anhydride to the sodium carbonate is 1:1:0.17; the ratio of sodium carbonate to acetic anhydride is 0.6g/100mL;
The specific process of the 4-carboxyl-1, 8-naphthalene dicarboxylic anhydride is as follows:
Mixing 4-carboxyl-1, 8-naphthalene dicarboxylic anhydride and 1, 4-dioxane, adding isobutene and boron trifluoride diethyl etherate, and stirring at 25 ℃ for reaction for 150min; the ratio of 4-carboxyl-1, 8-naphthalene dicarboxylic anhydride, isobutene, boron trifluoride diethyl etherate and 1, 4-dioxane is 24g:6.1g:4.7g:100mL;
before the modified POE is used, namely before the TPO coiled material is prepared in the step 1.4, the modified POE is placed in a dichloromethane solution of 50% trifluoroacetic acid, stirred and reacted for 60 minutes at the temperature of 50 ℃ for catalytic hydrolysis so as to remove isobutene groups; then washing and drying;
step 1.3. Preparation of modified POE:
Mixing polyhydroxy POE and imide siloxane, adding a catalyst, placing in a rheometer, and reacting for 12min at 180 ℃ and a rotating speed of 50 r/min; washing and drying to obtain modified POE; the mass ratio of the polyhydroxy POE to the imide siloxane to the catalyst p-toluenesulfonic acid is 10:33:0.04;
step 1.4. Preparation of TPO coil:
TPO, modified POE, tetrahydroxymethyl glycoluril, filler and auxiliary agent are mixed, and are blended and extruded by an extruder, wherein the process conditions of the blending and extrusion are as follows: the feeding section is 170 ℃, the plasticizing section is 190 ℃, the metering section is 200 ℃, the die temperature is 190 ℃, and the screw rotation speed is 50r/min, so that the TPO coiled material with the thickness of 1.6mm is obtained; TPO coiled material comprises the following mass components: 70 parts of thermoplastic polyolefin TPO, 30 parts of modified POE, 5.4 parts of tetramethylol glycoluril, 20 parts of filler and 5.0 parts of auxiliary agent; the auxiliary agent comprises 3 parts of titanium dioxide, 0.5 part of antioxidant, 0.5 part of light stabilizer and 1.0 part of lubricant;
step 2, preparing TPO waterproof coiled materials:
Stacking polyester cloth and grid cloth on the surface of the TPO coiled material obtained in the step 1 to form a blank body with the structure of the polyester cloth, the TPO coiled material, the grid cloth and the TPO coiled material from top to bottom, compounding, wherein the compounding process conditions are as follows: hot pressing: the temperature is 200 ℃, the pressure is 2MPa, and the time is 1min; cold pressing: the temperature is 6 ℃, the pressure is 1MPa, and the time is 20min, so that the TPO waterproof coiled material is obtained.
Comparative example 1: the preparation method of the high-strength TPO waterproof coiled material comprises the following processes:
Step 1, preparing TPO coiled materials:
step 1.1 preparation of polyol:
Mixing POE-g-GMA with ricinoleic acid, and standing in nitrogen atmosphere for 100min; placing in a rheometer, and reacting for 10min at 170 ℃ and a rotating speed of 100 r/min; washing and drying to obtain polyhydroxy POE; the mass ratio of POE-g-GMA to ricinoleic acid is 100:16;
step 1.2. Preparation of modified POE:
mixing polyhydroxy POE and gamma-aminopropyl triethoxysilane, adding a catalyst, placing in a rheometer, and reacting for 20min at the temperature of 170 ℃ and the rotating speed of 100 r/min; washing and drying to obtain modified POE; the mass ratio of the polyhydroxy POE to the imide siloxane to the catalyst p-toluenesulfonic acid is 10:23:0.02;
step 1.3 and step 2 are the same as step 1.4 and step 2 in example 1, and a TPO waterproof roll is obtained.
Comparative example 2: the preparation method of the high-strength TPO waterproof coiled material comprises the following processes:
Step 1, preparing TPO coiled materials:
TPO, POE-g-MAH, tetrahydroxymethyl glycoluril, filler and auxiliary agent are mixed, and the mixture is extruded by an extruder under the following process conditions: the feeding section is 170 ℃, the plasticizing section is 190 ℃, the metering section is 200 ℃, the die temperature is 190 ℃, the screw rotating speed is 40r/min, and the TPO coiled material with the thickness of 1.6mm is obtained; TPO coiled material comprises the following mass components: 85 parts of thermoplastic polyolefin TPO, 15 parts of POE-g-MAH, 3.0 parts of tetramethylol glycoluril, 10 parts of filler and 2.1 parts of auxiliary agent; the auxiliary agent comprises 1 part of titanium dioxide, 0.3 part of antioxidant, 0.3 part of light stabilizer and 0.5 part of lubricant;
Step 2 was the same as step 2 in example 1 to obtain a TPO waterproof roll.
Comparative example 3: the preparation method of the high-strength TPO waterproof coiled material comprises the following processes:
Step 1, preparing TPO coiled materials:
Mixing TPO, POE, filler and auxiliary agent, and blending and extruding by an extruder, wherein the technological conditions of blending and extruding are as follows: the feeding section is 170 ℃, the plasticizing section is 190 ℃, the metering section is 200 ℃, the die temperature is 190 ℃, the screw rotating speed is 40r/min, and the TPO coiled material with the thickness of 1.6mm is obtained; TPO coiled material comprises the following mass components: 85 parts of thermoplastic polyolefin TPO, 15 parts of POE, 10 parts of filler and 2.1 parts of auxiliary agent; the auxiliary agent comprises 1 part of titanium dioxide, 0.3 part of antioxidant, 0.3 part of light stabilizer and 0.5 part of lubricant;
Step 2 was the same as step 2 in example 1 to obtain a TPO waterproof roll.
Experiment: taking TPO waterproof coiled materials obtained in examples 1-3 and comparative examples 1-3, preparing samples, respectively detecting the performances of the samples and recording detection results:
Mechanical property test: the tensile property of a TPO coiled material sample is tested by taking GB/T328.9 as a reference standard, and the tensile rate is 200mm/min;
Impact resistance test: taking GB/T1843 as a reference standard, performing a cantilever beam notch impact test on a TPO coiled material sample, wherein the experimental temperature is-20 ℃;
And (3) water resistance test: immersing a TPO coiled material sample in hot water at 70 ℃ for 168 hours, taking out, wiping off water, recording and calculating the mass change rate of the sample before and after the experiment, and recording as the water absorption rate;
and after the water resistance test, carrying out mechanical property test on the sample again to obtain heat-resistant water aging performance data.
| Tensile Strength (MPa) | Notched impact strength (kJ/m 2) | Water absorption (%) | Tensile Strength after aging (MPa) | |
| Example 1 | 18.7 | 80.7 | 1.2 | 16.5 |
| Example 2 | 20.4 | 84.5 | 0.7 | 18.2 |
| Example 3 | 21.3 | 87.1 | 0.3 | 19.4 |
| Comparative example 1 | 15.2 | 74.8 | 2.4 | 12.1 |
| Comparative example 2 | 14.7 | 70.0 | 7.6 | 10.0 |
| Comparative example 3 | 12.8 | 62.7 | 4.7 | 8.9 |
From the data in the above table, the following conclusions can be clearly drawn:
The TPO coiled materials obtained in examples 1-3 are compared with the TPO coiled materials obtained in comparative examples 1-3, and the detection results show that the TPO coiled materials obtained in examples 1-3 are better in tensile strength, notch impact strength, water absorption and tensile strength data after aging compared with the comparative examples, which fully demonstrates that the invention realizes improvement of the comprehensive properties such as heat resistance, water resistance and mechanical properties of the TPO coiled materials and TPO waterproof coiled materials prepared by the TPO coiled materials.
Comparative example 1 replaces the imide siloxane with an equal mass of gamma-aminopropyl triethoxysilane as compared with example 1; comparative example 2 the modified POE was replaced with equal mass POE-g-MAH; the TPO coiled material in the comparative example 3 is prepared from thermoplastic polyolefin TPO, POE, filler and auxiliary agent; the TPO coiled materials obtained in comparative examples 1-3 have poor tensile strength, notch impact strength, water absorption and tensile strength data after aging, and the arrangement of POE modification technology and used components of the TPO coiled materials can promote the improvement of the comprehensive properties such as heat resistance, water resistance, mechanical properties and the like of the TPO coiled materials and the TPO waterproof coiled materials prepared by the TPO coiled materials.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation method of a high-strength TPO waterproof coiled material is characterized by comprising the following steps: the method comprises the following steps:
step 1, preparing TPO coiled materials: co-extruding TPO, modified POE, tetrahydroxymethyl glycoluril, filler and auxiliary agent to obtain TPO coiled material;
Step 2, preparing TPO waterproof coiled materials: stacking polyester cloth and grid cloth on the surface of the TPO coiled material obtained in the step 1 to form a blank body with the structure of the polyester cloth, the TPO coiled material, the grid cloth and the TPO coiled material from top to bottom in sequence; compounding to obtain TPO waterproof coiled materials;
the TPO coiled material comprises the following components in parts by mass: 70 to 85 parts of thermoplastic polyolefin TPO, 15 to 30 parts of modified POE, 3.0 to 5.4 parts of tetrahydroxymethyl glycoluril, 10 to 20 parts of filler and 2.1 to 5.0 parts of auxiliary agent;
The modified POE is prepared by the following process:
step 1.1 preparation of polyol:
Taking POE-g-GMA, adding ricinoleic acid, mixing, and standing for 100-150 min in nitrogen atmosphere; placing the mixture into a rheometer, and reacting for 5-10 min at the temperature of 170-180 ℃ and the rotating speed of 50-100r/min to obtain polyhydroxy POE;
Step 1.2. Preparation of imide siloxanes:
Mixing gamma-aminopropyl triethoxysilane and 4-carboxyl-1, 8-naphthalene dianhydride, heating to 80-85 ℃, and stirring for reacting for 15-20 min to obtain amic acid siloxane;
adding sodium carbonate and acetic anhydride, mixing, stirring, heating to 100-105 ℃, and reacting for 60-75min to obtain imide siloxane;
step 1.3. Preparation of modified POE:
mixing polyhydroxy POE and imide siloxane, adding a catalyst, placing in a rheometer, and reacting for 12-20 min at the temperature of 170-180 ℃ and the rotating speed of 50-100 r/min to obtain the modified POE.
2. The method for preparing the high-strength TPO waterproof coiled material according to claim 1, which is characterized in that: in the step 1.1, the mass ratio of POE-g-GMA to ricinoleic acid is 100 (16-30).
3. The method for preparing the high-strength TPO waterproof coiled material according to claim 1, which is characterized in that: in the step 1.2, 4-carboxyl-1, 8-naphthalene dicarboxylic anhydride is subjected to carboxyl protection treatment;
The molar ratio of the gamma-aminopropyl triethoxysilane to the 4-carboxyl-1, 8-naphthalene dicarboxylic anhydride to the sodium carbonate is 1:1 (0.15-0.17).
4. The method for preparing the high-strength TPO waterproof coiled material according to claim 1, which is characterized in that: in the step 1.3, the mass ratio of polyhydroxy POE, imide siloxane and catalyst p-toluenesulfonic acid is 10 (23-33) (0.02-0.04).
5. The method for preparing the high-strength TPO waterproof coiled material according to claim 1, which is characterized in that: the process conditions of the compounding are as follows: hot pressing: the temperature is 165-200 ℃, the pressure is 2-5 MPa, and the time is 1-15 min;
Cold pressing: the temperature is 4-6 ℃, the pressure is 1-2 MPa, and the time is 12-20 min.
6. The method for preparing the high-strength TPO waterproof coiled material according to claim 1, which is characterized in that: in the step 1, the technological conditions of co-extrusion are as follows: 160-180 ℃ of the feeding section, 180-200 ℃ of the plasticizing section, 190-210 ℃ of the metering section, 180-200 ℃ of the die opening temperature and 40-50 r/min of the screw rotating speed.
7. The method for preparing the high-strength TPO waterproof coiled material according to claim 1, which is characterized in that: the auxiliary agent comprises 1 to 3 parts of titanium dioxide, 0.3 to 0.5 part of antioxidant, 0.3 to 0.5 part of light stabilizer and 0.5 to 1.0 part of lubricant.
8. A high strength TPO waterproof roll manufactured by the manufacturing method according to any one of claims 1 to 7.
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