CN111574749A - Method for preparing polyurea surface reinforced modified polypropylene expanded bead (EPP) product - Google Patents
Method for preparing polyurea surface reinforced modified polypropylene expanded bead (EPP) product Download PDFInfo
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- CN111574749A CN111574749A CN202010410635.4A CN202010410635A CN111574749A CN 111574749 A CN111574749 A CN 111574749A CN 202010410635 A CN202010410635 A CN 202010410635A CN 111574749 A CN111574749 A CN 111574749A
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- -1 polypropylene Polymers 0.000 title claims abstract description 51
- 229920002396 Polyurea Polymers 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000011324 bead Substances 0.000 title claims abstract description 20
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 14
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 41
- 239000011248 coating agent Substances 0.000 claims abstract description 38
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 26
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 17
- 229920000570 polyether Polymers 0.000 claims abstract description 17
- 229920000098 polyolefin Polymers 0.000 claims abstract description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012948 isocyanate Substances 0.000 claims abstract description 14
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- 150000002148 esters Chemical class 0.000 claims abstract description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000004073 vulcanization Methods 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000011976 maleic acid Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 claims description 4
- 150000003505 terpenes Chemical class 0.000 claims description 4
- 235000007586 terpenes Nutrition 0.000 claims description 4
- GQZXRLWUYONVCP-UHFFFAOYSA-N 3-[1-(dimethylamino)ethyl]phenol Chemical compound CN(C)C(C)C1=CC=CC(O)=C1 GQZXRLWUYONVCP-UHFFFAOYSA-N 0.000 claims description 3
- DLYLVPHSKJVGLG-UHFFFAOYSA-N 4-(cyclohexylmethyl)cyclohexane-1,1-diamine Chemical compound C1CC(N)(N)CCC1CC1CCCCC1 DLYLVPHSKJVGLG-UHFFFAOYSA-N 0.000 claims description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 3
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 claims description 3
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 claims description 3
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N Tetradecane Natural products CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- 229920001748 polybutylene Polymers 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 2
- FRXCPDXZCDMUGX-UHFFFAOYSA-N tridecane-1,1-diamine Chemical compound CCCCCCCCCCCCC(N)N FRXCPDXZCDMUGX-UHFFFAOYSA-N 0.000 claims description 2
- XJIAZXYLMDIWLU-UHFFFAOYSA-N undecane-1,1-diamine Chemical compound CCCCCCCCCCC(N)N XJIAZXYLMDIWLU-UHFFFAOYSA-N 0.000 claims description 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 claims 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims 2
- 239000004793 Polystyrene Substances 0.000 claims 1
- 229920001400 block copolymer Polymers 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 claims 1
- 229920002223 polystyrene Polymers 0.000 claims 1
- 229920000428 triblock copolymer Polymers 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 108010064470 polyaspartate Proteins 0.000 description 16
- 239000000463 material Substances 0.000 description 11
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004794 expanded polystyrene Substances 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000001680 brushing effect Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 229920000805 Polyaspartic acid Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- JMLPVHXESHXUSV-UHFFFAOYSA-N dodecane-1,1-diamine Chemical compound CCCCCCCCCCCC(N)N JMLPVHXESHXUSV-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- XGSHEASGZHYHBU-UHFFFAOYSA-N tetradecane-1,1-diamine Chemical compound CCCCCCCCCCCCCC(N)N XGSHEASGZHYHBU-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/365—Coating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6204—Polymers of olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/02—Polyureas
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/02—Polyamines
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a method for preparing a polyurea surface reinforced modified polypropylene expanded bead (EPP) product, which comprises the following steps: the polyurea coating capable of bonding EPP with high strength is prepared, and comprises a component A, 40-60 parts of isocyanate, 1-20 parts of hydroxyl-terminated polyolefin and 1-15 parts of polyether glycol; the component B comprises: 30-40 parts of maleic ester, 10-30 parts of long carbon chain diamine and 20-35 parts of alicyclic diamine; and the component C is as follows: 5-10 parts of tackifying resin, 10-15 parts of compatilizer and 10-15 parts of dispersing agent. According to the invention, the hydrocarbon chain segment, the tackifying resin and the compatilizer are introduced in the polyurea synthesis process, so that the compatibility and the interface bonding force are improved, the generation of cracks among EPP beads due to deformation of the product in use is avoided, the strength, the wear resistance, the tear resistance, the weather resistance and the like of the EPP product are enhanced by the coating, the surface pores generated in the molding process are covered, and the waterproof property of the EPP product is endowed.
Description
Technical Field
A method for preparing a polyurea surface reinforced modified polypropylene foaming bead (EPP) product belongs to the field of chemical film forming, and particularly relates to coating, film forming, reinforcing and modifying the surface of the EPP product.
Background
The polypropylene expanded bead (EPP) material has the excellent characteristics of light weight, shock resistance, shock absorption, corrosion resistance, heat insulation, sound insulation and the like, and compared with the traditional direct forming process, the EPP expanded bead has the greatest advantages of free forming property, uniform size and stable foaming multiplying power of the expanded bead, so that the EPP expanded bead is very suitable for molding and forming, and can produce products with complex geometric structures and high dimensional precision. The first bead expanded products to be industrially produced were expanded polystyrene beads (EPS), and then expanded polyethylene beads (EPE) and expanded polypropylene beads (EPP). Among them, EPP is superior to EPE in thermal stability, superior to EPS in impact resistance, has the advantages of rigidity and toughness, has excellent aging resistance and corrosion resistance, and is an environment-friendly material, so that EPP is widely applied to industries such as packaging, building, automobile and the like, and particularly the demand in the automobile industry is rapidly increased. In view of the rapid increase of EPP material application in various countries of the world, the research on the subsequent forming and processing products is also continuous.
Polyurea is an elastomeric substance formed by the reaction of isocyanate (referred to as component A) and amino compound (referred to as component B), wherein component A can be a monomer, a polymer, a derivative of isocyanate, a prepolymer, a semi-prepolymer and other compositions, but component B must be composed of an amino-terminated resin and an amino-terminated chain extender. Polyaspartate (PAE) polyurea coatings are low activity, slow-reacting aliphatic polyureas that occur after aromatic polyureas and conventional aliphatic polyureas. The PAE polyurea thoroughly overcomes the defects of the traditional polyurea which takes primary amine as raw material, has too fast reaction speed and poor adhesive force, greatly prolongs the gelling time, has excellent surface leveling property, wetting property and penetrating property, and has strong interface bonding strength. The PAE polyurea coating technology can be used for preparing a two-component coating which is cured within 1 hour, and compared with the traditional coating technology, the PAE polyurea material technology has obvious advantages: the film thickness range of the coating is large, and the content of solid components is high; secondly, the material body has higher impact resistance and wear resistance; the curing speed and the gel time are controllable; high strain and chemical resistance, can enhance the mechanical and corrosion resistance of the material, and is beneficial to the all-round protection of the material; the product has good flexibility, and no crack is generated when the product is folded; sixthly, the paint can be mechanically sprayed or brushed and is not easy to generate sagging phenomenon. These advantages can make the PAE polyurea coating have wider application range when the thickness of the coating is thinner, the time for meeting the use condition is shorter, and the PAE polyurea coating can be sprayed or brushed by common mechanical equipment and achieve better use effect. PAE is essentially aliphatic secondary amine, which is prepared by Michael addition reaction of dialkyl maleate and aliphatic primary diamine to convert primary amine into secondary amine and reduce the reactivity of hydrogen atom and isocyanic acid radical, because the reaction belongs to gradual addition polymerization reaction of hydrogen transfer and takes place by attacking carbonium ion of isocyanate by nucleophilic center of active hydride, and the reactivity of secondary amine is less than that of primary amine, thus reducing the whole reactivity and greatly reducing the reaction speed due to steric effect. Due to the specific structure of PAE, PAE has a characteristic reactivity when reacted with isocyanates. The amino group in the PAE structure is in steric encirclement of a sterically coronary structure [5], and the ester moiety in this structure acts as an inducer slowing the reaction rate with the isocyanate (NCO) component, resulting in longer gel times and performance stability. When X between two NH groups in the structural formula of the PAE is substituted by radicals of other structures, PAE series derivatives are generated, and PAE with different reaction activities and gel time can be obtained. Thus, by varying the X groups, the cure speed of the PAE polyurea material coating can be controlled. When the two components are subjected to crosslinking reaction and curing, the aliphatic polyurea with impact resistance, wear resistance, water resistance and good weather resistance can be obtained.
Although EPP is widely applied in various industries, a certain amount of gaps are remained between beads due to different factors in the forming process of EPP products, and particularly, the phenomenon of water seepage is often caused in the situation that the products are in contact with water or are soaked in water for a long time; in addition, the surface strength, abrasion resistance, tear resistance and the like of the EPP product are required to be further enhanced during the use process. Because polyolefin is a difficult-to-stick material, the polyolefin is mainly caused by the factors of lower surface energy, no functional group, regular structure, high crystallinity and the like. Therefore, without surface treatment, polyolefins are difficult to wet and bond by common coatings and adhesives. According to the invention, a large amount of hydrocarbon chain segments are introduced in the synthesis process of polyurea, the affinity of the coating and polyolefin is improved, the interface bonding force between the tackifying resin and the EPP is further improved by the compatibilizer, and the polyurea flexibility is improved to avoid cracks among EPP beads generated by deformation of the product in the using process, so that the strength, wear resistance, tear resistance, weather resistance and the like of the EPP product are enhanced by the coating, and surface pores generated in the forming process are covered, so that the EPP product is endowed with a waterproof characteristic.
Disclosure of Invention
The invention aims to provide a method for enhancing the surface performance of an EPP product through a polyurea coating, the EPP has performance superior to most foaming materials and is widely applied, and the polyurea coating can further improve the strength, the wear resistance, the weather resistance, the waterproofness, the tearing resistance and the like of the EPP product. Because polyolefin belongs to a difficult-to-adhere material and high peel strength of paint and adhesive is difficult to achieve, the adhesion and compatibility of EPP and polyurea need to be improved, the invention increases hydrocarbon chain segments similar to polyolefin by introducing hydroxyl-terminated polyolefin and long carbon chain diamine in the preparation process of polyaspartic acid ester polyurea, improves the affinity with EPP, further improves the interfacial adhesion with EPP by tackifying resin and compatilizer, solves the problems of difficult adhesion and low peel strength of EPP, finally improves the strength, wear resistance, weather resistance, waterproofness, tear resistance and other properties of EPP products, and expands more application ranges.
1. In order to achieve the purpose, the invention provides a method for preparing a polyurea surface reinforced modified polypropylene expanded bead (EPP) product, which comprises the following steps: a polyurea coating for preparing a high strength bondable EPP comprising: the component A comprises 40-60 parts of isocyanate, 1-20 parts of hydroxyl-terminated polyolefin, 1-15 parts of polyether glycol, 30-40 parts of maleic acid ester, 10-30 parts of long carbon chain diamine and 20-35 parts of alicyclic diamine; 5-10 parts of tackifying resin of the component C, 10-15 parts of compatilizer and 10-15 parts of dispersing agent, wherein the proportion of the ABC component is 1.2-2:1.3-2.2: 0.2-0.5.
2. The isocyanate in the component A comprises at least one of 2, 4-dimethyldecanediisocyanate, 2, 4-trimethyldecanediisocyanate and 2,4, 6-trimethyldecanediisocyanate monomer; the hydroxyl-terminated polyolefin comprises at least one of hydroxyl-terminated polybutadiene, hydroxyl-terminated polypropylene and hydroxyl-terminated polybutylene oligomer (with polymerization degree of 40-90); the polyether diol comprises at least one of butanediol polyether and hexanediol polyether; the mixing molar ratio of the isocyanate, the hydroxyl-terminated polyolefin and the polyether glycol is as follows: 4-6: 1-3: 0.5-2.5.
3. The component A is prepared by the following method: adding isocyanate into a reaction kettle, heating to 60-80 ℃, adding hydroxyl polyolefin and polyether glycol during stirring, and vacuumizing to-0.01-0.02 Mpa. And keeping the temperature and the pressure for 8-12 h to obtain the component A with excessive-NCO.
4. The maleic acid ester in the component B comprises at least one of dimethyl maleate, diethyl maleate and dipropyl maleate; the long-carbon chain diamine comprises at least one of decamethylene diamine, undecane diamine, dodecane diamine, tridecane diamine and tetradecane diamine; the alicyclic diamine comprises at least one of 3,3 dimethyl-4, 4-dicycloethylmethanediamine (DMDC), Isophoronediamine (IPDA), 4' -diaminodicyclohexylmethane (PACM); the mixed molar ratio of the maleic acid ester, the long carbon chain diamine and the alicyclic diamine is as follows: 3-4: 1-2: 1.5-2.5.
5. The component B is prepared by the following method: : adding the long-carbon-chain diamine and alicyclic diamine monomers into a reactor filled with nitrogen, heating to 60-100 ℃, adding maleic ester while stirring, keeping the reaction pressure of 0.1-0.5 MPa, controlling the adding speed of the maleic ester, and reacting for 4-16 h to obtain a component B resin;
6. the tackifying resin in the component C comprises at least one of terpene resin, special rosin, hydrogenated C5 petroleum resin and copolymerized petroleum resin; the compatilizer comprises at least one of SBS, SEBS and SIS; the dispersant comprises at least one of acetone, methyl ethyl ketone, ethyl acetate, trichloroethane, cyclohexane, toluene and solvent gasoline.
7. The component C is prepared by the following method: and adding the tackifying resin, the compatilizer and the dispersing agent into a closed container with stirring, and stirring at normal temperature until the tackifying resin, the compatilizer and the dispersing agent are dissolved to obtain the required component C.
8. The preparation method of the polyurea reinforced polypropylene expanded bead (EPP) product comprises the specific operation of fully mixing A, B and C components, spraying, brushing or rolling the mixture on the surface of the EPP product (cured for 24 hours at 40 ℃) to form a polyurea coating with the thickness of 0.2-1 mm, and then drying the product on a vulcanization bed at 90-100 ℃ for 2-5 minutes, so that the drying of the coating is accelerated, the bonding force between the coating and the EPP is enhanced, the construction process is simple and convenient, and the bonding force of the product is high.
Detailed Description
Example 1
(1) Preparing a component A: 50g of 2, 4-dimethyl decyl diisocyanate and 60g of 2,2, 4-trimethyl decyl diisocyanate are added into a reaction kettle, the temperature is raised to 70 ℃, stirring is started, 28g of hydroxyl polypropylene and 23.5g of hexanediol polyether are added during stirring, and the reaction kettle is vacuumized to-0.01 MPa. Keeping the temperature and the pressure for 8 hours to obtain the component A with excessive-NCO.
(2) Preparing a component B: adding 45g of decaalkanediamine and 58g of 3, 3-dimethyl-4, 4-dicycloethylmethanediamine (DMDC) into a reactor filled with nitrogen, heating to 80 ℃, adding 70g of dimethyl maleate while stirring, keeping the reaction pressure of 0.2MPa, controlling the adding speed of maleate, and reacting for 8h to obtain the component B.
(3) Preparing a component C: adding terpene resin 5g, hydrogenated C5 petroleum resin 7g, SEBS12g and SIS10g into a closed container with stirring, adding ethyl acetate 25g, and stirring at normal temperature until the mixture is dissolved to obtain the required component C.
(4) Firstly, EPP products are cured for 24 hours at 40 ℃, the size deformation of the products caused by the pressure difference between the inside and the outside of beads during molding is reduced, then the prepared three components of 150gA, 155gB and 34gC are mixed and sprayed on the surface of the EPP products through a high-speed mixer to form a polyurea coating with the thickness of 0.3mm, then the polyurea coating is dried for 4 minutes on a vulcanization bed at 90 ℃, the drying of the coating is accelerated, the bonding force between the coating and the EPP is enhanced, and then the products are naturally placed for 10 hours, so that the bonding force of the products is high, and the performance is excellent.
Example 2
(1) Preparing a component A: 355g of 2, 2-dimethyl decamethylene diisocyanate and 430g of 2,4, 6-trimethyl decamethylene diisocyanate are added into a reaction kettle, the temperature is increased to 80 ℃, stirring is started, 212g of hydroxyl polybutadiene and 248g of butanediol polyether are added during stirring, and the vacuum pumping is carried out until the pressure is-0.02 Mpa. Keeping the temperature and the pressure for 12 hours to obtain the component A with excessive-NCO.
(2) Preparing a component B: adding 305g of decanediamine and 411g of 3, 3-dimethyl-4, 4-dicycloethylmethanediamine (DMDC) into a reactor filled with nitrogen, heating to 70 ℃, adding 490g of dimethyl maleate while stirring, keeping the reaction pressure of 0.2MPa, controlling the adding speed of maleate, and reacting for 6h to obtain the component B.
(3) Preparing a component C: adding 36g of special rosin, 49g of copolymerized petroleum resin, SEBS78g and SBS70g into a stirring closed container, adding 175g of ethyl acetate, and stirring at normal temperature until the components are dissolved to obtain the required component C.
(4) Firstly, curing an EPP product at 40 ℃ for 24h, recovering the deformation generated by molding and cooling, then mixing and spraying the prepared 1000gA, 1150g B and 150gC components on the surface of the EPP product through a high-speed mixer to form a polyurea coating with the thickness of 0.5mm, then drying the polyurea coating on a vulcanization bed at 90 ℃ for 5 min to accelerate the drying of the coating and enhance the bonding force between the coating and the EPP, and then naturally standing for 10h to obtain the target product.
Example 3
(1) Preparing a component A: 1006g of 2, 2-dimethyl decamethylene diisocyanate is added into a reaction kettle, the temperature is raised to 75 ℃, stirring is started, 195g of hydroxyl-terminated polypropylene, 75g of hydroxyl-terminated polybutadiene and 208g of hexanediol polyether are added during stirring, and the vacuum pumping is carried out until the pressure is-0.01 MPa. Keeping the temperature and the pressure for 10 hours to obtain the component A with excessive-NCO.
(2) Preparing a component B: 377g of dodecanediamine and 535g of isophorone diamine (IPDA) are added into a reactor which is aerated with nitrogen, the temperature is raised to 80 ℃, 654g of diethyl maleate is added while stirring, the reaction pressure of 0.2MPa is kept, the adding speed of maleate is controlled, and the reaction is carried out for 7h, thus obtaining the component B.
(3) Preparing a component C: 100g of terpene resin and SEBS198g are added into a closed container with stirring, then 235g of ethyl acetate is added and stirred at normal temperature until the component C is dissolved, thus obtaining the required component C.
(4) Firstly, curing an EPP product (at 40 ℃ for 24h) to reduce the dimensional deformation generated by the change of the internal pressure of the EPP, then mixing the prepared 1360gA, 1400g B and 470gC components by a high-speed mixer, then brushing the mixture on the surface of the EPP product to form a 1mm polyurea coating, then drying the polyurea coating on a vulcanization bed at 95 ℃ for 5 minutes to accelerate the drying of the coating and enhance the bonding force between the coating and the EPP, and then naturally standing for 10h to obtain the target product.
Example 4
(1) Preparing a component A: adding 3.41kg of 2,2, 4-trimethyl decamethylene diisocyanate into a reaction kettle, heating to 78 ℃, stirring, adding 0.92kg of hydroxyl polybutadiene and 0.78kg of hexanediol polyether into the reaction kettle during stirring, and vacuumizing to-0.02 Mpa. Keeping the temperature and the pressure for 9 hours to obtain the component A with excessive-NCO.
(2) Preparing a component B: adding 1.35kg of tetradecanediamine and 1.74kg of 4,4' -diaminodicyclohexylmethane (PACM) into a reactor filled with nitrogen, heating to 80 ℃, adding 2.11kg of dipropyl maleate while stirring, keeping the reaction pressure of 0.2MPa, controlling the adding speed of maleate, and reacting for 7.5h to obtain the component B.
(3) Preparing a component C: adding 0.22kg of hydrogenated C5 petroleum resin and 0.31kg of SIS into a stirring closed container, adding 0.78kg of ethyl acetate, and stirring at normal temperature until the components are dissolved to obtain the required component C.
(4) Firstly, an EPP product is cured for 24 hours at 40 ℃, then the prepared three components of 5kgA, 5.2kg B and 0.6kgC are mixed by a high-speed mixer and then are coated on the surface of the EPP product in a rolling way to form a polyurea coating with the thickness of 0.8mm, then the polyurea coating is dried for 5 minutes on a vulcanization bed at 95 ℃, the drying of the coating is accelerated, the bonding force between the coating and the EPP is enhanced, and then the EPP product is naturally placed for 10 hours to obtain a target product.
The above examples illustrate the present invention in detail. It is to be understood that the above description is not intended to limit the present invention, and the present invention is not limited to the above examples, and that various changes, modifications, additions, deletions, and substitutions which may be made by those skilled in the art within the spirit of the present invention are also within the scope of the present invention.
Claims (8)
1. A method for preparing polyurea surface reinforced modified polypropylene expanded bead (EPP) products, which is characterized in that polyurea coatings capable of bonding EPP with high strength are prepared, and the method comprises the following steps: the component A comprises 40-60 parts of isocyanate, 1-20 parts of hydroxyl-terminated polyolefin, 1-15 parts of polyether glycol, 30-40 parts of maleic acid ester, 10-30 parts of long carbon chain diamine and 20-35 parts of alicyclic diamine; 5-10 parts of tackifying resin of the component C, 10-15 parts of compatilizer and 10-15 parts of dispersing agent, wherein the proportion of the ABC component is 1.2-2:1.3-2.2: 0.2-0.5.
2. The component A according to claim 1, characterized in that: the isocyanate comprises at least one of 2, 4-dimethyl decyl diisocyanate, 2, 4-trimethyl decyl diisocyanate and 2,4, 6-trimethyl decyl diisocyanate monomers; the hydroxyl-terminated polyolefin comprises at least one of hydroxyl-terminated polybutadiene, hydroxyl-terminated polypropylene and hydroxyl-terminated polybutylene oligomer (with polymerization degree of 40-90); the polyether diol comprises at least one of butanediol polyether and hexanediol polyether; the mixing molar ratio of the isocyanate, the hydroxyl-terminated polyolefin and the polyether glycol is as follows: 4-6: 1-3: 0.5-2.5.
3. The method of claim 1, wherein the component A is prepared by the following method: adding isocyanate into a reaction kettle, heating to 60-80 ℃, adding hydroxyl polyolefin and polyether glycol during stirring, and vacuumizing to-0.01-0.02 Mpa. And keeping the temperature and the pressure for 8-12 h to obtain the component A with excessive-NCO.
4. The component B according to claim 1, wherein: the maleate comprises at least one of dimethyl maleate, diethyl maleate and dipropyl maleate; the long-carbon chain diamine comprises at least one of decamethylene diamine, undecane diamine, dodecane diamine, tridecane diamine and tetradecane diamine; the alicyclic diamine comprises at least one of 3,3 dimethyl-4, 4-dicycloethylmethanediamine (DMDC), Isophoronediamine (IPDA), 4' -diaminodicyclohexylmethane (PACM); the mixed molar ratio of the maleic acid ester, the long carbon chain diamine and the alicyclic diamine is as follows: 3-4: 1-2: 1.5-2.5.
5. The process according to claim 1, wherein the component B is prepared by the following method: adding the long-carbon-chain diamine and alicyclic diamine monomers into a reactor filled with nitrogen, heating to 60-100 ℃, adding maleic ester while stirring, keeping the reaction pressure of 0.1-0.5 MPa, controlling the adding speed of the maleic ester, and reacting for 4-16 h to obtain the component B resin.
6. The component C according to claim 1, characterized in that: the tackifying resin comprises at least one of terpene resin, special rosin, hydrogenated C5 petroleum resin and copolymerized petroleum resin; the compatilizer comprises at least one of SBS (styrene-butadiene-styrene triblock copolymer), SEBS (linear triblock copolymer taking polystyrene as a terminal segment and taking ethylene-butylene copolymer obtained by hydrogenation of polybutadiene as a middle elastic block) and SIS (styrene-isoprene-styrene triblock copolymer); the dispersant comprises at least one of acetone, methyl ethyl ketone, ethyl acetate, trichloroethane, cyclohexane, toluene and solvent gasoline.
7. The method of claim 1, wherein the component C is prepared by the following method: and adding the tackifying resin, the compatilizer and the dispersing agent into a closed container with stirring, and stirring at normal temperature until the tackifying resin, the compatilizer and the dispersing agent are dissolved to obtain the required component C.
8. A preparation method of the polyurea reinforced polypropylene expanded bead (EPP) product as claimed in any one of claims 1 to 7, characterized in that the A, B and C three components are fully mixed, sprayed, brushed or rolled on the surface of the EPP product (cured for 24h at 40 ℃) to form a polyurea coating with 0.2 mm-1 mm, and then dried on a vulcanization bed at 90-100 ℃ for 2-5 minutes to accelerate the drying of the coating and enhance the bonding force between the coating and the EPP, the construction process is simple and convenient, and the bonding force between the product is high.
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