CN117070178A - Reactive polyurethane adhesive for bonding special-shaped furniture and preparation method thereof - Google Patents
Reactive polyurethane adhesive for bonding special-shaped furniture and preparation method thereof Download PDFInfo
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- CN117070178A CN117070178A CN202311032575.7A CN202311032575A CN117070178A CN 117070178 A CN117070178 A CN 117070178A CN 202311032575 A CN202311032575 A CN 202311032575A CN 117070178 A CN117070178 A CN 117070178A
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- CN
- China
- Prior art keywords
- polyurethane adhesive
- bonding
- polyester polyol
- reactive polyurethane
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 59
- 239000004814 polyurethane Substances 0.000 title claims abstract description 59
- 239000000853 adhesive Substances 0.000 title claims abstract description 49
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 58
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 50
- 229920000570 polyether Polymers 0.000 claims abstract description 50
- 229920005862 polyol Polymers 0.000 claims abstract description 44
- 150000003077 polyols Chemical class 0.000 claims abstract description 44
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 26
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 25
- 239000012948 isocyanate Substances 0.000 claims abstract description 20
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 14
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000004970 Chain extender Substances 0.000 claims description 8
- 239000007822 coupling agent Substances 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 8
- 239000002318 adhesion promoter Substances 0.000 claims description 7
- 239000000872 buffer Substances 0.000 claims description 7
- 229920001971 elastomer Polymers 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229920002397 thermoplastic olefin Polymers 0.000 claims description 6
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 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 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000000806 elastomer Substances 0.000 claims description 4
- 239000003623 enhancer Substances 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 239000005060 rubber Substances 0.000 claims description 4
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 claims description 3
- YRTNMMLRBJMGJJ-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;hexanedioic acid Chemical compound OCC(C)(C)CO.OC(=O)CCCCC(O)=O YRTNMMLRBJMGJJ-UHFFFAOYSA-N 0.000 claims description 3
- XYOVHOQHZFTBKD-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;hexanedioic acid;2-(2-hydroxyethoxy)ethanol Chemical compound OCC(C)(C)CO.OCCOCCO.OC(=O)CCCCC(O)=O XYOVHOQHZFTBKD-UHFFFAOYSA-N 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-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
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group 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 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
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000378 calcium silicate Substances 0.000 claims description 3
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 229910052570 clay Inorganic materials 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 150000003505 terpenes Chemical class 0.000 claims description 3
- 235000007586 terpenes Nutrition 0.000 claims description 3
- 239000004408 titanium dioxide Substances 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
- 239000004711 α-olefin Substances 0.000 claims description 3
- 229920002334 Spandex Polymers 0.000 claims description 2
- 229920005586 poly(adipic acid) Polymers 0.000 claims description 2
- 238000012827 research and development Methods 0.000 claims description 2
- 239000004759 spandex Substances 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims 4
- 229920006465 Styrenic thermoplastic elastomer Polymers 0.000 claims 2
- 239000004831 Hot glue Substances 0.000 abstract description 9
- 238000013008 moisture curing Methods 0.000 abstract description 3
- 238000006757 chemical reactions by type Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000006172 buffering agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000012744 reinforcing agent Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920010499 Hytrel® 3078 Polymers 0.000 description 1
- 229920011462 Hytrel® 4068 Polymers 0.000 description 1
- 229920009336 Hytrel® G4074 Polymers 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920006344 thermoplastic copolyester Polymers 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- 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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- 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
Abstract
The invention discloses a reactive polyurethane adhesive for bonding special-shaped furniture and a preparation method thereof, wherein the polyurethane adhesive comprises the following raw materials: a first polyether polyol, a first polyester polyol, a thermoplastic elastomer, a tackifying resin, isocyanate and an auxiliary agent; wherein the acid value of the modified polyester polyol is 5-7 or 2-3; the modified polyether polyol contains secondary hydroxyl groups. The adhesive belongs to a single-component moisture curing reaction type polyurethane hot melt adhesive with heat resistance reaching 100 ℃ and difficult skinning, and simultaneously has higher adhesiveness and initial adhesiveness.
Description
Technical Field
The invention relates to the technical field of polyurethane adhesives, in particular to a reactive polyurethane adhesive for bonding special-shaped furniture and a preparation method thereof.
Background
The modern furniture is made of two large modules, namely solid wood furniture and plate type furniture. The plate-type furniture is favored in modern furniture by replacing solid wood plates slowly due to the advantages of convenience of the artificial plates, low cost and the like. Among them, the special-shaped furniture is especially popular in the recent years, and more furniture companies adopt the application. The special-shaped plate furniture technology mainly comprises two types of thermoplastic systems such as EVA, polyolefin and the like. The processing technology is also from manual to semi-automatic, and then to the current full-automatic.
EVA or polyolefin systems are used as special-shaped furniture bonding in the market at present, and polyurethane systems are not used for the application at present. The EVA and the polyolefin hot melt adhesive are thermoplastic systems, are melted into liquid by heating, and are solidified into solid by wetting a base material to achieve the effect of bonding strength, but because of the reversibility of the system, the hot melt adhesive products of the EVA and the polyolefin systems can crack at high temperature, and the problems of insufficient bonding strength, poor solvent resistance and water resistance and the like are solved.
Disclosure of Invention
In order to overcome the defects of the prior art, one of the purposes of the invention is to provide a reactive polyurethane adhesive for bonding special-shaped furniture, which belongs to a single-component moisture-curing reactive polyurethane hot melt adhesive with heat resistance up to 100 ℃ and difficult skinning, and has higher adhesiveness and initial adhesiveness; the second object of the invention is to provide a preparation method of the reactive polyurethane adhesive for bonding special-shaped furniture, which comprises the steps of pre-polymerizing to obtain a stable polyol system, using stronger resin to achieve initial adhesion and protecting the prepolymer of polyurethane, adding an antioxidant, a stabilizer, a reinforcing agent and the like to increase the stability and compatibility of the system, and greatly improving the initial adhesion of polyurethane hot melt adhesive.
One of the purposes of the invention is realized by adopting the following technical scheme:
the reactive polyurethane adhesive for bonding the special-shaped furniture comprises the following raw materials in parts by weight: 5-15 parts of first polyether polyol, 5-15 parts of first polyester polyol, 5-15 parts of thermoplastic elastomer, 5-15 parts of tackifying resin, 5-15 parts of isocyanate, 0-10 parts of modified polyether polyol, 0-20 parts of modified polyester polyol and 5-15 parts of auxiliary agent; wherein the acid value of the modified polyester polyol is 5-7 or 2-3; the modified polyether polyol contains secondary hydroxyl groups.
Further, the modified polyether polyol is polyether triol and/or polyether tetrol, the hydroxyl value is 33-37mgKOH/g, and the number average molecular weight is 200-4000.
Further, the first polyester polyol is one or more than two of poly (1, 6-hexanediol) glycol adipate, poly (adipic acid) -aromatic acid-diethylene glycol-ethylene glycol ester glycol, poly (adipic acid-neopentyl glycol) glycol ester glycol and poly (adipic acid-diethylene glycol-neopentyl glycol) glycol ester glycol, the number average molecular weight is 2000-6000, and the acid value of the modified polyether polyol is 0.01-0.05 mg KOH/g.
Further, the modified polyester polyol is a polyester polyol with an acid value of 4 to 10, which is purchased from Kunler Polymer (Shanghai) Inc., model 6161H, or an aromatic polyester polyol with model 2402, which is purchased from Spanish (Nanj) chemical technology development Co., ltd.
Further, the thermoplastic elastomer is one or a combination of more than two of thermoplastic polyurethane elastomer (TPU), amorphous alpha-olefin copolymer (APAO), polyester thermoplastic elastomer (TPEE), thermoplastic Polyolefin (TPO), styrene thermoplastic elastomer (TPES), rubber and ethylene/vinyl acetate (EVA).
Further, the isocyanate is 4,4 '-diphenylmethane diisocyanate or 2,4' -diphenylmethane diisocyanate; the tackifying resin comprises one or more of rosin resin, phenolic resin, terpene resin and petroleum resin.
Further, the auxiliary agent comprises one or a combination of more than two of a catalyst, an antioxidant, an enhancer, an adhesion promoter, a coupling agent, a buffering agent, a chain extender and a filler.
Further, the catalyst is an organotin catalyst; the coupling agent is a silane coupling agent; the buffer is phosphate; the chain extender is 1, 4-butanediol; the filler comprises one or more than two of carbon black, titanium dioxide, calcium carbonate, talcum powder, clay, calcium silicate or barium sulfate; the antioxidant is antioxidant 168 and/or antioxidant 1010; the adhesion promoter is basf FL3740 which effectively spreads the substrate.
The second purpose of the invention is realized by adopting the following technical scheme:
the preparation method of the reactive polyurethane adhesive for bonding the special-shaped furniture comprises the following steps of:
1) Dehydrating the modified polyester polyol and/or the modified polyether polyol, adding a part of isocyanate, stirring, heating, and reacting to obtain a prepolymer;
2) Adding a thermoplastic elastomer, tackifying resin, first polyether polyol and first polyester polyol into the prepolymer, and mixing;
3) Adding the rest isocyanate again to stir; and finally adding an auxiliary agent, mixing, and discharging to obtain the reactive polyurethane adhesive for bonding the special-shaped furniture.
Further, in step 1), the dehydration conditions include the following parameters: the temperature is 90-100 ℃, the pressure is minus 0.1-minus 0.09MPa, and the time is 1-2 h; the stirring rotating speed is 300-700 r/min; the heating temperature is 80-100 ℃, and the reaction temperature is 1-2 h.
Compared with the prior art, the invention has the beneficial effects that:
(1) The reactive polyurethane adhesive provided by the invention comprises the following raw materials: a first polyether polyol, a first polyester polyol, a thermoplastic elastomer, a tackifying resin, isocyanate and an auxiliary agent; wherein the modified polyether polyol and the modified polyester polyol are selected and added, and the acid value of the modified polyester polyol is 5-7 or 2-3; the secondary hydroxyl contained in the modified polyether polyol increases the reactivity and chain extension effect of isocyanate, thereby achieving the purposes of increasing the initial viscosity and the final strength of the polymer chain segment of the final polyurethane adhesive. The addition of thermoplastic elastomers can improve the bulk quick-drying properties of the polyurethane after it has been cured. The first polyester polyol can improve the strength and hardness of the molecular weight of the polyurethane adhesive, and the modified polyester polyol or the modified polyether polyol can be matched with the flexibility and wettability of the chain segment, so that the strength at high temperature and low temperature can be considered.
(2) When the polyurethane adhesive contains modified polyester polyol or modified polyether polyol, the stability of the system is poor, and the viscosity is unstable. The invention solves the technical problems by using the first polyester polyol with moderate acid value, wherein the modified polyester polyol is obtained from Kunler polymer (Shanghai) limited company, the model 6161H of which the acid value is 4-10 or obtained from Spanish (Nanjing) chemical technology research and development limited company, the model 2402 of which the aromatic polyester polyol can obviously improve the stability of the polyurethane adhesive and the viscosity stability performance.
(3) When the polyurethane adhesive of the present invention contains a modified polyester polyol or a modified polyether polyol, the stability of the polyurethane system is deteriorated, so that an additional antioxidant is required to stabilize the aging performance of the system, and a phosphate is required to be added as a buffer to improve the stability of the system.
(4) Because modified polyester polyol or modified polyether polyol is added to cause the stability of polyurethane to be poor, the preparation method of the polyurethane adhesive comprises the steps of firstly, pre-reacting the modified polyether polyol or modified polyester polyol with a higher acid value to prepare a prepolymer, so that the stability of a polyurethane system can be improved, and 2) adding components with higher initial viscosity such as thermoplastic elastomer, tackifying resin, first polyether polyol and first polyester polyol into the prepolymer to protect the polyurethane prepolymer; adding the rest isocyanate again to stir; finally, adding the auxiliary agent can greatly improve the initial viscosity of the polyurethane hot melt adhesive, and discharging after mixing to obtain the reactive polyurethane adhesive for bonding the special-shaped furniture.
(5) In the preparation method of the polyurethane adhesive, the thermoplastic substance is treated, and the thermoplastic substance is required to be melted at high temperature, so that the problems of secondary decomposition and instability of modified polyol are solved by pre-melting treatment and then temperature reduction.
Detailed Description
The present invention will be further described with reference to the following specific embodiments, and it should be noted that, on the premise of no conflict, new embodiments may be formed by any combination of the embodiments or technical features described below.
The reactive polyurethane adhesive for bonding the special-shaped furniture comprises the following raw materials in parts by weight: 5-15 parts of first polyether polyol, 5-15 parts of first polyester polyol, 5-15 parts of thermoplastic elastomer, 5-15 parts of tackifying resin, 5-15 parts of isocyanate, 0-10 parts of modified polyether polyol, 0-20 parts of modified polyester polyol and 5-15 parts of auxiliary agent; wherein the acid value of the modified polyester polyol is 5-7 or 2-3; the modified polyether polyol contains secondary hydroxyl groups.
Further, the modified polyether polyol is polyether triol and/or polyether tetrol, the hydroxyl value is 33-37mgKOH/g, and the number average molecular weight is 200-4000; polyether triols having a molecular weight of 3000 and a hydroxyl value of about 33 to 37mgKOH/g are preferably used. For example, GEP-330N of Shanghai high bridge petrochemical industry or polyether of the same type, the secondary hydroxyl contained in the modified polyether polyol can increase the reactivity and chain extension effect of isocyanate, thereby achieving the purposes of increasing the initial viscosity and the final strength of the polymer chain segment of the final polyurethane adhesive.
Further, the first polyester polyol may be a pre-synthesized polyester polyol, and the number average molecular weight of the combination of the reaction products, namely, the poly (1, 6-hexanediol) glycol adipate, the poly (adipic acid-aromatic acid-diethylene glycol-ethylene glycol) glycol, the poly (adipic acid-neopentyl glycol) glycol and the poly (adipic acid-diethylene glycol-neopentyl glycol) glycol is 2000-6000; preferably, carboxylate modified polyester polyol is used, and compared with modified polyether polyol, the first polyester polyol can greatly increase the molecular weight strength and hardness of the polyurethane adhesive, and the first polyester polyol and the polyester polyol are matched to achieve both the flexibility and wettability of the chain segment, so that the strength at high temperature and low temperature can be achieved. The number average molecular weight of the first polyester polyol is 2000-6000, and the acid value of the modified polyether polyol is 0.01-0.05 mg KOH/g.
Further, the modified polyester polyol or modified polyether polyol, which is a polyester polyol having an acid value of 4 to 10 obtained from Kunler Polymer (Shanghai) Inc., model 6161H or an aromatic polyester polyol having a model 2402 obtained from Spanish (Nanjing) chemical research and development Co., ltd, is preferably used because it deteriorates the stability of the system and causes unstable viscosity after addition, etc. The two modified polyester polyols can obviously improve the stability and the viscosity stability.
Further, the thermoplastic elastomer can improve the quick-drying performance of the body after the hot melt adhesive is solidified. The thermoplastic elastomer is one or more than two of thermoplastic polyurethane elastomer (TPU), amorphous alpha-olefin copolymer (APAO), polyester thermoplastic elastomer (TPEE), thermoplastic Polyolefin (TPO), styrene thermoplastic elastomer (TPES), rubber and ethylene/vinyl acetate (EVA). For example, duPont Hytrel 5566,Hytrel G4074,Hytrel 4068,Hytrel 3078 in the United states and the like or TPEE, TPC and TPO. Rubber systems are preferred as elastomers to increase adhesion and flexibility, particularly to enhance adhesion at temperatures below 10 degrees C, such as Korotten SEBS G1650MU, or 1726, or EVA which provides corresponding flexibility and initial adhesion.
Further, the isocyanate is 4,4 '-diphenylmethane diisocyanate or 2,4' -diphenylmethane diisocyanate; the tackifying resin comprises one or more of rosin resin, phenolic resin, terpene resin and petroleum resin.
Further, the auxiliary agent comprises one or a combination of more than two of a catalyst, an antioxidant, an enhancer, an adhesion promoter, a coupling agent, a buffering agent, a chain extender and a filler.
Further, the catalyst is an organotin catalyst; the coupling agent is a silane coupling agent; the buffer is phosphate; the chain extender is 1, 4-butanediol; the filler comprises one or more than two of carbon black, titanium dioxide, calcium carbonate, talcum powder, clay, calcium silicate or barium sulfate; the antioxidant is antioxidant 168 and/or antioxidant 1010, and can stabilize the ageing resistance of the polyurethane system; the adhesion promoter is basf FL3740 which effectively spreads the substrate.
The preparation method of the reactive polyurethane adhesive for bonding the special-shaped furniture comprises the steps of preparing an auxiliary agent, wherein the auxiliary agent comprises a catalyst, an antioxidant, an enhancer, an adhesion promoter, a coupling agent, a buffering agent, a chain extender and a filler; the method comprises the following steps:
1) Dehydrating the modified polyester polyol and/or the modified polyether polyol, adding a part of isocyanate, stirring, heating, and reacting to obtain a prepolymer;
2) Adding a thermoplastic elastomer, tackifying resin, first polyether polyol and first polyester polyol into the prepolymer; adding antioxidant and filler, and mixing;
3) Adding the rest isocyanate again to stir; and finally adding a catalyst, a chain extender, a coupling agent and a buffer, mixing, and discharging to obtain the reactive polyurethane adhesive for bonding the special-shaped furniture.
Further, in step 1), the dehydration conditions include the following parameters: the temperature is 90-100 ℃, the pressure is minus 0.1-minus 0.09MPa, and the time is 1-2 h; the stirring rotating speed is 300-700 r/min; the heating temperature is 80-100 ℃, and the reaction temperature is 1-2 h.
Examples 1 to 7
The formulations of the polyurethane adhesives of examples 1 to 7 are shown in Table 1.
Wherein the modified polyether polyol comprises: 1. polyether polyol with the model of GEP-330N and the hydroxyl value of 33-37, the acid value of 0.03mg KOH/g, the pH value of 5.8 and the viscosity of 750-950cps are purchased from Shanghai high-bridge petrochemical company; 2. polyether polyol with model of GEP-551C, which is purchased from Shanghai high-bridge petrochemical company, has hydroxyl value of 54-58, acid value of 0.03mg KOH/g, pH (6.7) and viscosity (25 ℃) of 400-600cps;
the modified polyester polyol includes: 1. purchased from Kunler Polymer (Shanghai)Polyester polyol of model 6163H, acid value of 5-7, hydroxyl value of 27-34, viscosity of 3500cps; 2. purchased from spandex (Nanjing)Aromatic polyester polyol with the model of PS2402 is developed by chemical technology. The acid value is 2-3mg KOH/g, the hydroxyl value is 250, and the viscosity is 8000cps.
Wherein the first polyether polyol is a Wanhua polyether difunctional polyol, the first polyester polyol is a winning polyester polyol 7360, the tackifying resin is a carbon nine resin, the isocyanate is MDI, the reinforcing agent is calcium carbonate, the buffering agent is phosphoric acid, and the antioxidant is an antioxidant 1010.
Table 1 formulations of polyurethane adhesives of examples 1 to 7
The preparation method of the polyurethane adhesive of examples 1-6 comprises the following steps: the polyurethane adhesive is prepared by mixing all the components in the formula of table 1.
The preparation method of the polyurethane adhesive of the embodiment 7 comprises the following steps:
1) Adding the modified polyester polyol into a reaction kettle, dehydrating for 1.5 hours at the temperature of 95 ℃ and the pressure of-0.095 MPa, adding 50% of isocyanate, stirring at the rotating speed of 500r/min, and reacting for 1-2 hours at the temperature of 90 ℃ to obtain a polyurethane prepolymer so as to stabilize the system in advance. Adding a thermoplastic elastomer, tackifying resin, first polyester polyol and first polyether polyol to protect polyurethane prepolymer, adding an antioxidant, a reinforcing agent and a buffer, stirring uniformly, adding the rest isocyanate again, and stirring for 1.5h; discharging, and carrying out nitrogen protection or vacuum sealing packaging to obtain the polyurethane adhesive.
Comparative example 1
Comparative example 1 is a polyurethane adhesive, and the specific formulation comprises the following raw materials in percentage by weight:
45% of EVA, 25% of carbon nine resin, 25% of calcium carbonate and 5% of wax.
Performance testing
The polyurethane adhesives of examples 1 to 7 and comparative example 1 were tested, wherein the test criteria are:
1. and (3) tensile force test: the wood tensile test was carried out in accordance with DIN 52188-1979 and the peel force test after 1 minute and 24 hours of coating the samples was carried out at a speed of 200m/min and a width of 1inch width.
2. Foot line dryness: and (5) testing whether the plate is stuck or not by overlapping the finished products.
3. Heat resistance test: and placing the finished product in an oven for testing the temperature programming, and testing the glue opening temperature at 5 ℃ per hour.
4. Skinning time: the apparatus was run to test the skinning condition of the glue per hour and the viscosity test on the next day. The test results are specifically shown in Table 2.
TABLE 2 Performance test results of polyurethane adhesives of each group
As can be seen from Table 2, the polyurethane adhesive of example 1 was not added with the modified polyether polyol or modified polyester polyol, so that the adhesion and the initial adhesion were the worst. While examples 2 to 6 are respectively added with modified polyester polyol or modified polyether polyol, so that the performances of bonding strength, initial adhesion and the like are obviously improved, wherein examples 5 to 6 are best in effect, the viscosity change and skinning speed can be effectively controlled, meanwhile, the initial adhesion and the final strength are obviously improved, and the adhesive is prepared by adopting a specific prepolymer preparation method in example 7, so that the effect is more obvious compared with the conventional method of directly mixing all the components. Compared with comparative example 1 which adopts EVA as the main raw material, the adhesive has better adhesiveness and initial adhesion.
In summary, the embodiment 7 can prepare the one-component moisture curing reactive polyurethane hot melt adhesive with super initial adhesion, heat resistance reaching 100 ℃ and difficult skinning, and the prepared polyurethane hot melt adhesive has higher adhesion and initial adhesion.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention are intended to be within the scope of the present invention as claimed.
Claims (10)
1. The reactive polyurethane adhesive for bonding the special-shaped furniture is characterized by comprising the following raw materials in parts by weight: 5-15 parts of first polyether polyol, 5-15 parts of first polyester polyol, 5-15 parts of thermoplastic elastomer, 5-15 parts of tackifying resin, 5-15 parts of isocyanate, 0-10 parts of modified polyether polyol, 0-20 parts of modified polyester polyol and 5-15 parts of auxiliary agent; wherein the acid value of the modified polyester polyol is 5-7 or 2-3; the modified polyether polyol contains secondary hydroxyl groups.
2. The reactive polyurethane adhesive for bonding special-shaped furniture according to claim 1, wherein the modified polyether polyol is polyether triol and/or polyether tetraol, has a hydroxyl value of 33-37mgKOH/g, a number average molecular weight of 200-4000 and an acid value of 0.01-0.05 mgKOH/g.
3. The reactive polyurethane adhesive for bonding profiled furniture as claimed in claim 1, wherein the first polyester polyol is one or a combination of two or more of poly (1, 6-hexanediol) diol, poly (adipic acid) -aromatic acid-diethylene glycol-ethylene glycol) diol, poly (adipic acid-neopentyl glycol) diol and poly (adipic acid-diethylene glycol-neopentyl glycol) diol, and has a number average molecular weight of 2000 to 6000.
4. The reactive polyurethane adhesive for bonding special-shaped furniture according to claim 1, wherein the modified polyester polyol is a polyester polyol having an acid value of 4 to 10, which is purchased from kunler polymer (Shanghai) limited, model 6161H, or an aromatic polyester polyol having a model 2402, which is purchased from spandex (Nanj) chemical research and development limited.
5. The reactive polyurethane adhesive for bonding profiled furniture of claim 1, wherein the thermoplastic elastomer is one or more of thermoplastic polyurethane elastomer, amorphous alpha-olefin copolymer, polyester thermoplastic elastomer, thermoplastic polyolefin, styrenic thermoplastic elastomer, rubber and ethylene/vinyl acetate.
6. The reactive polyurethane adhesive for profiled furniture bonding as claimed in claim 1, wherein the isocyanate is 4,4 'diphenylmethane diisocyanate or 2,4' diphenylmethane diisocyanate; the tackifying resin comprises one or more of rosin resin, phenolic resin, terpene resin and petroleum resin.
7. The reactive polyurethane adhesive for bonding profiled furniture of claim 1, wherein the auxiliary agent comprises one or a combination of more than two of a catalyst, an antioxidant, an enhancer, an adhesion promoter, a coupling agent, a buffer, a chain extender and a filler.
8. The reactive polyurethane adhesive for bonding profiled furniture of claim 7, wherein the catalyst is an organotin catalyst; the coupling agent is a silane coupling agent; the buffer is phosphate; the chain extender is 1, 4-butanediol; the filler comprises one or more than two of carbon black, titanium dioxide, calcium carbonate, talcum powder, clay, calcium silicate or barium sulfate; the antioxidant is antioxidant 168 and/or antioxidant 1010; the adhesion promoter is basf FL3740.
9. The method for preparing the reactive polyurethane adhesive for bonding special-shaped furniture according to any one of claims 1 to 8, which is characterized by comprising the following steps:
1) Dehydrating the modified polyester polyol and/or the modified polyether polyol, adding a part of isocyanate, stirring, heating, and reacting to obtain a prepolymer;
2) Adding a thermoplastic elastomer, tackifying resin, first polyether polyol and first polyester polyol into the prepolymer, and mixing;
3) Adding the rest isocyanate again to stir; and finally adding an auxiliary agent, mixing, and discharging to obtain the reactive polyurethane adhesive for bonding the special-shaped furniture.
10. The method for preparing a reactive polyurethane adhesive for bonding profiled furniture according to claim 9, wherein in step 1), the dehydration conditions include the following parameters: the temperature is 90-100 ℃, the pressure is minus 0.1-minus 0.09MPa, and the time is 1-2 h; the stirring rotating speed is 300-700 r/min; the heating temperature is 80-100 ℃, and the reaction temperature is 1-2 h.
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