CN108587548A - A kind of Silante terminated modified polycarbonate polyurethane adhesive resin and its preparation method and application - Google Patents
A kind of Silante terminated modified polycarbonate polyurethane adhesive resin and its preparation method and application Download PDFInfo
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- CN108587548A CN108587548A CN201810446770.7A CN201810446770A CN108587548A CN 108587548 A CN108587548 A CN 108587548A CN 201810446770 A CN201810446770 A CN 201810446770A CN 108587548 A CN108587548 A CN 108587548A
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- polycarbonate
- silane
- polyurethane adhesive
- adhesive resin
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 49
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 48
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 46
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 46
- 239000004840 adhesive resin Substances 0.000 title claims abstract description 30
- 229920006223 adhesive resin Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 23
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 34
- 229910000077 silane Inorganic materials 0.000 claims description 34
- 239000000853 adhesive Substances 0.000 claims description 18
- 230000001070 adhesive effect Effects 0.000 claims description 18
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 11
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- -1 ethylene, propylene, butylene, pentylene, hexylene Chemical group 0.000 claims description 6
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 5
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 5
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000005809 transesterification reaction Methods 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005292 vacuum distillation Methods 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- 150000004650 carbonic acid diesters Chemical class 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- 229940035437 1,3-propanediol Drugs 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 2
- 125000004956 cyclohexylene group Chemical group 0.000 claims description 2
- 125000004980 cyclopropylene group Chemical group 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims 1
- 239000007822 coupling agent Substances 0.000 claims 1
- 125000002524 organometallic group Chemical group 0.000 claims 1
- 239000003292 glue Substances 0.000 abstract description 4
- 239000012948 isocyanate Substances 0.000 abstract description 4
- 150000002513 isocyanates Chemical class 0.000 abstract description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 16
- 229920000570 polyether Polymers 0.000 description 16
- 229920005749 polyurethane resin Polymers 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- 150000003141 primary amines Chemical class 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 6
- 229940057499 anhydrous zinc acetate Drugs 0.000 description 5
- 239000000565 sealant Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 4
- 229920002396 Polyurea Polymers 0.000 description 3
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 description 3
- 238000005576 amination reaction Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 239000004432 silane-modified polyurethane Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241001295727 Amsonia tabernaemontana Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 229920013701 VORANOL™ Polymers 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 1
- 239000004839 Moisture curing adhesive Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000007098 aminolysis reaction Methods 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229940120638 avastin Drugs 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000013008 moisture curing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004588 polyurethane sealant Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- VNTDZUDTQCZFKN-UHFFFAOYSA-L zinc 2,2-dimethyloctanoate Chemical compound [Zn++].CCCCCCC(C)(C)C([O-])=O.CCCCCCC(C)(C)C([O-])=O VNTDZUDTQCZFKN-UHFFFAOYSA-L 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
-
- 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
- C08G18/44—Polycarbonates
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a kind of Silante terminated modified polycarbonate polyurethane adhesive resins and its preparation method and application.The process for preparing resins is to carry out end capping reaction in the presence of a catalyst by specific polycarbonate resin and primaryamino-silane coupling agent, and Silante terminated modified polycarbonate polyurethane adhesive resin is prepared.Preparation process of the present invention is simple, pollution-free, prepares polyurethane without using traditional isocyanates, technique is more environmentally-friendly；The prices of raw materials are cheap to be easy to get, and cost can be reduced compared with traditional silicane-modified polyurethane product；The resin modulus height of preparation, intensity are big, are suitable for the preparation of windshield glue.
Description
Technical Field
The invention relates to a silane modified resin, in particular to a silane end-capped modified polycarbonate polyurethane adhesive resin and application thereof in an automobile windshield adhesive formula.
Background
The Polyurethane (PU) has good bonding force to a base material, and has the advantages of wear resistance, high mechanical strength, good vibration absorption performance and the like, and the single-component moisture-cured PU windshield adhesive is sensitive to moisture and high in curing speed, and keeps excellent elasticity after being cured, so that the single-component PU resin has wide application in the field of automobile windshield adhesives. However, when the polyurethane adhesive is used as a single-component moisture curing adhesive, the polyurethane adhesive has free isocyanate groups, so that bubbles are easily generated in the curing process, and the bonding performance is influenced; free isocyanate groups can also be harmful to the environment; more importantly, the adhesion of polyurethane to glass substrates is not outstanding, so that the single-component moisture-curing PU windshield adhesive needs to be subjected to priming treatment of the substrates when in use, which not only makes the sizing process extremely inconvenient, but also increases the sizing cost.
Silane terminated modified polyurethane (SPUR) is a new type of polyurethane material. Compared with the traditional polyurethane materials, the SPUR blocked functional group is changed from-NCO group to hydrolysable methyl (ethyl) siloxane group, so that the SPUR resin does not contain free isocyanate group, thereby avoiding the adverse factors of foaming and the like during curing and being more environment-friendly. More importantly, the active group of SPUR is methyl (ethyl) siloxane, and the bonding capability to the glass substrate is very outstanding. Therefore, the proposal of using silane-terminated modified polyurethane sealant as primer-free automobile windshield adhesive is the main trend at present. However, in the current market, the main chain of the silane modified sealant is basically a polyether structure, and the mechanical property of the sealant can not meet the requirement of the automobile windshield adhesive. Therefore, in order to meet the performance requirements of the automotive windshield adhesive, the backbone structure of the resin needs to be adjusted.
Polycarbonate is a high molecular polymer containing carbonate groups in its molecular chain, and has excellent mechanical properties, hydrolysis resistance, heat resistance, oxidation resistance, wear resistance and flame retardancy. Compared with the traditional polyether polyurethane resin, the polyurethane resin with the polycarbonate as the main chain has obviously improved mechanical property, heat resistance and the like. Therefore, the silane modified polyurethane resin which takes the polycarbonate as the main chain and has siloxane end capping at two ends has excellent mechanical property and excellent bonding capacity to base materials such as glass and the like, and is suitable for preparing the automobile windshield adhesive.
At present, polycarbonate polyurethane chain segment structure is mainly formed by adopting polycarbonate polyol as a raw material and carrying out polymerization reaction with-NCO group. The method has the advantages of simple process and the disadvantages that the raw material for preparing the isocyanate is the highly toxic phosgene, which seriously harms the health of people and has great threat to the environment. And the isocyanate and the polyol react with moisture in the surrounding environment to generate carbon dioxide, so that cells are generated in the material, and the mechanical property of the polyurethane material is reduced. Recently, carbonate amination has gradually entered the public line of sight. The method takes carbonic acid diester and primary amine as raw materials to synthesize the carbamate structure, and compared with the traditional method, the method does not use free NCO and is a more environment-friendly method for synthesizing the carbamate structure.
By comprehensively considering the factors, the modified polyurethane resin with the polycarbonate structure as the main chain and the siloxane end caps at two ends needs to be obtained. Meanwhile, the synthesis method which does not use isocyanate raw materials, is environment-friendly and has simple and convenient process is provided.
Patent CN101993521A discloses a method for preparing silane modified polyurethane resin, which comprises silane modified polycarbonate polyurethane resin. The method is to react isocyanate silane with polycarbonate prepolymer with-OH terminal group to prepare the silane end-capped modified polycarbonate type polyurethane resin. The method has simple process, but the raw materials, especially the isocyanate silane, are expensive, so that the cost of the resin is higher, and the method is not suitable for industrial popularization; and the preparation process of the isocyanate silane is also a phosgene method, which causes certain environmental hazard.
Patent CN101712757A discloses a method for modifying polyether alcohol with silane, which comprises capping macromolecular polyether with carbonate monomer, and then carrying out carbonate aminolysis reaction with aminosilane to prepare silane modified polyurethane resin. The method does not use free NCO, and is more environment-friendly. However, the main chain is of a polyether structure, so that the mechanical strength is low, and the adhesive cannot be applied to the adhesion of the automobile windshield.
Patent CN 107698756A discloses a preparation method of a silane modified polyurea adhesive, which comprises reacting carbonate monomer with diamine to synthesize polyurea resin by carbonate amination method, and then reacting with amino silane to prepare the silane modified polyurea adhesive. The resin prepared by the method has high modulus, but the resin has high viscosity, is brittle and has low elongation at break due to the existence of excessive carbamido groups on a molecular chain.
Disclosure of Invention
The invention aims to provide a silane end-capped modified polycarbonate polyurethane adhesive resin, a preparation method and application thereof, and solves the problems that the traditional silane modified resin is low in mechanical property and cannot be applied to the bonding of automobile windshields by using new raw materials and a synthesis method. Meanwhile, the new synthesis method is more environment-friendly, and the preparation cost of the resin is reduced.
In order to achieve the purpose, the invention adopts the following technical scheme:
a silane end-capped modified polycarbonate polyurethane adhesive resin is obtained by reacting the following raw materials: based on the weight of the resin,
(a) the polycarbonate resin has a glass transition temperature of less than 30 ℃ and is used in an amount of 50-95 wt%, preferably 70-90 wt%;
(b) 4-45 wt%, preferably 9-29 wt% of a silane coupling agent with primary amino groups;
(c) the amount of the catalyst is not particularly limited as long as the catalyst can effectively catalyze the chemical reaction of the raw materials (a) and (b), and the higher the amount of the catalyst is, the higher the cost is, the more preferable the amount of the catalyst is, the amount of the catalyst is 0.1 to 10 wt%, and the more preferable the amount of the catalyst is 0.2 to 1 wt%;
component (a) of the present invention is one or more polycarbonate resins of formula (1)
Wherein:
n is an integer of 5 to 100,
R1or R2Identical or independently of one another is C1-C10, substituted or unsubstituted aliphatic or aromatic linear or branched hydrocarbon radicals, preferably selected from methyl, ethyl, propyl, phenyl, benzyl;
R3selected from C2-C10 alkylene, preferably from ethylene, propylene, butylene, pentylene, hexylene; c3-10 cycloalkylene, preferably one or more selected from cyclopropylene, cyclohexylene;
the polycarbonate resin of formula (1) of the present invention is prepared from a C3-C10 carbonic acid diester, preferably dimethyl carbonate, diethyl carbonate or diphenyl carbonate; and C2-C10 diol, preferably selected from 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol and 1, 6-hexanediol, through transesterification, wherein the mechanism and method of transesterification are reported in the literature, such as: LP Wang, GY Wang, F Wang, Synthesis of Polycarbonate Diol Catalyzed by Metal-organic framework Based on Zn2+ and textual Acid [ J ]. Advanced Materials Research,2013: 634-638.
The general formula of the primary amino silane coupling agent of the component (b) is shown as the formula (2):
(R4O)3-xR5xSiR6NH2(2)
wherein,
x is 0 or 1;
R4or R5Selected, identically or independently of one another, from C1-C10 alkyl, preferably C1-C4 alkyl;
r6 is selected from C1-C10 alkylene, preferably C3-C5 alkylene;
more preferably, x is 0 and R4is-CH3or-C2H5，R6is-CH2CH2CH2-, namely: 3-aminopropyltrimethoxysilane (KH540) and 3-aminopropyltriethoxysilane (KH 550).
The component (c) of the present invention is one or more alkali metal alkoxides, and/or one or more organic metals, and is represented by the general formula (3):
Y(OR7)m(3)
wherein,
y is a metal element, preferably selected from K, Na and Zn;
R7is C1-C3 straight chain alkyl, or C1-C3 acyl;
m is matched with the valence state of the metal element Y.
The invention also provides a method for preparing the silane end-capped modified polycarbonate polyurethane adhesive resin, which comprises the following steps:
according to the proportion,
(1) preparation of polycarbonate resin of component (a)
(2) Adding a component (a) polycarbonate resin, a component (b) silane coupling agent with primary amino and a component (c) into a reaction kettle, and stirring for reaction within a certain temperature range;
(3) after the reaction in the step (1) is finished, preferably carrying out vacuum rectification to remove low-boiling-point fractions, thus obtaining the silane-terminated modified polyurethane adhesive resin.
The molar ratio of the polycarbonate resin to the silane coupling agent with primary amino groups in the step (2) is 1: 1.5-3, preferably 1: 1.9-2.1.
The certain temperature range in the step (2) is 50-150 ℃, preferably 70-120 ℃, and more preferably 80-100 ℃.
The temperature range of the vacuum rectification in the step (3) is 30-80 ℃, and preferably 50-70 ℃; the vacuum degree of the vacuum distillation is in the range of 0.1 to 10kPa, preferably 0.1 to 1 kPa.
The invention has the positive effects that: the invention adopts an environment-friendly carbonate amination method, takes polycarbonate with low Tg as a main raw material, reacts with aminosilane, and the prepared resin is liquid at room temperature and has good interface flow wetting capacity. The resin synthesis process is simple and environment-friendly, and the raw materials are cheap and easy to obtain. Meanwhile, the polycarbonate structure of the main chain and siloxane groups at two ends achieve the effects of high resin strength, good toughness, strong bonding force with a glass substrate and the like, and are particularly suitable for preparing the automobile windshield adhesive.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention are shown in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
The resin testing method comprises the following steps:
1. the viscosity test is carried out at 25 ℃ using a Brookfield (model RV) rotary viscometer to determine the viscosity in accordance with DIN 53019.
2. The hydroxyl number content was tested by titration according to GB/T12008.3-2009.
3. Testing of primary amine number content was done by titration according to ASTM D2074-2007.
4. Determination of molecular weight distribution: gel Permeation Chromatography (GPC) was used for the test, THF was mobile phase, instrument type: agilent 1260.
II, raw material sources are as follows:
1. polycarbonate resin 1-1 was prepared by transesterification of dimethyl carbonate (available from Qingdao Xinrui chemical Co., Ltd.) and 1, 6-hexanediol (available from Langshan) in the presence of DMC catalyst (available from Huai' an Bade). The feeding molar ratio of the dimethyl carbonate to the 1, 6-hexanediol is 1.1: 1, 1, 6-hexanediol is added into dimethyl carbonate in a dropwise manner, the reaction temperature is 150 ℃, and the addition amount of a bimetallic catalyst DMC is 150 ppm. The end point of the reaction was determined by measuring the hydroxyl value content, with a hydroxyl value content of less than 0.5mgKOH/g being regarded as the end of the reaction. After the reaction is finished, distilling under reduced pressure to extract small molecular substances, and obtaining the polycarbonate resin. The product was characterized by GPC and had a number average molecular weight of 2000 and a molecular weight distribution of 1.25.
Polycarbonate resin 1-2, dimethyl carbonate and 1, 6-hexanediol are fed in a molar ratio of 1.04: 1, the rest preparation processes are the same as polycarbonate resin 1-1, and the product is characterized by GPC, the number average molecular weight is 4000, and the molecular weight distribution is 1.26.
1-3 parts of polycarbonate resin, wherein the feeding molar ratio of dimethyl carbonate to 1, 6-hexanediol is 1.02: 1, the addition amount of a bimetallic catalyst DMC is 200ppm, the rest preparation process is the same as that of polycarbonate resin 1-1, and the product is characterized by GPC, the number average molecular weight is 8000, and the molecular weight distribution is 1.30.
2. Polycarbonate resin 2, self-made; diethyl carbonate (from an avastin reagent) and 1, 5-pentanediol (from Hubei Jusheng technology) are used as raw materials, and ester exchange reaction is carried out under the DMC catalyst (from Huai' anbade). Feeding molar ratio of diethyl carbonate to 1, 5-pentanediol is 1.1: 1, 1, 5-pentanediol is added into diethyl carbonate in a dropwise manner, the reaction temperature is 150 ℃, and the addition amount of a bimetallic catalyst DMC is 150 ppm. The end point of the reaction was determined by measuring the hydroxyl value content, with a hydroxyl value content of less than 0.5mgKOH/g being regarded as the end of the reaction. After the reaction is finished, distilling under reduced pressure to extract small molecular substances, and obtaining the polycarbonate resin. The product was characterized by GPC and had a number average molecular weight of 4000 and a molecular weight distribution of 1.22.
3. Polycarbonate resin 3, self-made; diphenyl carbonate (from Mitsubishi, Japan) and 1, 4-cyclohexanediol (from Cinchanda chemical industry, Lianyunggang) were used as raw materials to carry out transesterification reaction under DMC catalyst (from Huaian Bade). The feeding molar ratio of the diphenyl carbonate to the 1, 4-cyclohexanediol is 1.1: the 1, 1, 4-cyclohexanediol is added into diphenyl carbonate in a dropwise manner, the reaction temperature is 160 ℃, and the addition amount of a bimetallic catalyst DMC is 200 ppm. The end point of the reaction was determined by measuring the hydroxyl value content, with a hydroxyl value content of less than 0.5mgKOH/g being regarded as the end of the reaction. After the reaction is finished, distilling under reduced pressure to extract small molecular substances, and obtaining the polycarbonate resin. The product was characterized by GPC, and had a number average molecular weight of 4000 and a molecular weight distribution of 1.30.
4. 3-aminopropyltrimethoxysilane, available from mezzanine, product designation: a-1110;
5. 3-aminopropyltriethoxysilane, available from mai chart, product designation: a-1100;
6. anhydrous zinc acetate, purchased from national medicine, CAS: 557-34-6;
7. sodium ethoxide, CP, purchased from national medicine, CAS: 141-52-6;
8. 3-isocyanatopropyltrimethoxysilane, available from the meiji diagram, product designation: A-Link 35;
9. MDI-100, available from Wawa Chemicals, product designation:MDI-100；
10. zinc iso-octoate, from advanced chemistry, product brand: BICAT 3228;
11. polyether polyol having a molecular weight of 4000 and a functionality of 2, available from eastern bluestar under the trade designation: DL-4000D
12. Polyether polyol, molecular weight 8000, functionality 2, available from dow chemical, trade name: VORANOL 8000LM
13. Polyether polyol, molecular weight 2000, functionality 2, available from eastern bluestar, trade name: DL-2000D
14. Polyether polyol, molecular weight 5000, functionality 3, available from wawa chemical, trade name: f3135
Example 1:
the silane end-capped modified polycarbonate polyurethane adhesive resin is prepared by adding 500g of polycarbonate 1-1(250mmol) with the number average molecular weight of 2000 and 89.6g of silane coupling agent A-1110(500mmol) into a 2L three-neck flask, stirring to 70 ℃ while heating, then adding 1g of anhydrous zinc acetate catalyst, and reacting at 70 ℃ until the primary amine value content of the system is lower than 0.1%. And then cooling the system to 30 ℃, distilling the product under reduced pressure for 1h under the vacuum degree of 0.1kPa, and removing the small molecular alcohol and water in the system to obtain the silane end-capped modified polycarbonate polyurethane adhesive resin SPCU1 with the viscosity of 7000 cP.
Example 2:
the silane end-capped modified polycarbonate polyurethane adhesive resin is prepared by adding 500g of polycarbonate 1-2(125mmol) with the number average molecular weight of 4000 and 44.8g of silane coupling agent A-1110(250mmol) into a 2L three-neck flask, stirring to 90 ℃ while heating, then adding 1g of anhydrous zinc acetate catalyst, and reacting at 90 ℃ until the primary amine value content of the system is lower than 0.1%. And then cooling the system to 50 ℃, distilling the product under reduced pressure for 1h under the vacuum degree of 1kPa, and removing the small molecular alcohol and water in the system to obtain the silane end-capped modified polycarbonate polyurethane adhesive resin SPCU2 with the viscosity of 21000 cP.
Example 3:
the silane end-capped modified polycarbonate polyurethane adhesive resin is prepared by adding 500g of polycarbonate 1-3(62.5mmol) with the number average molecular weight of 8000 and 23.3g of silane coupling agent A-1110(130mmol) into a 2L three-neck flask, heating while stirring to 120 ℃, then adding 1g of anhydrous zinc acetate catalyst, and keeping the temperature at 120 ℃ for reaction until the primary amine value content of the system is lower than 0.1%. And then cooling the system to 70 ℃, distilling the product under reduced pressure for 3h under the vacuum degree of 10kPa, and removing the small molecular alcohol and water in the system to obtain the silane end-capped modified polycarbonate polyurethane adhesive resin SPCU3 with the viscosity of 50000 cP.
Example 4:
the silane end-capped modified polycarbonate polyurethane adhesive resin is prepared by adding 500g of polycarbonate 1-2(125mmol) with the number average molecular weight of 4000 and 77.35g of silane coupling agent A-1100(350mmol) into a 2L three-neck flask, stirring to 90 ℃ while heating, then adding 2.0g of sodium ethoxide catalyst, and reacting at 90 ℃ until the primary amine value content of the system is lower than 0.1%. And then cooling the system to 50 ℃, distilling the product under reduced pressure for 2h under the vacuum degree of 1kPa, and removing the small molecular alcohol and water in the system to obtain the silane end-capped modified polycarbonate polyurethane adhesive resin SPCU4 with the viscosity of 25000 cP.
Example 5:
the silane end-capped modified polycarbonate polyurethane adhesive resin is prepared by adding 500g of polycarbonate 2(125mmol) with the number average molecular weight of 4000 and 55.25g of silane coupling agent A-1100(250mmol) into a 2L three-neck flask, stirring to 80 ℃ while heating, then adding 1.5g of sodium ethoxide catalyst, and reacting at 80 ℃ until the primary amine value content of the system is lower than 0.1%. And then cooling the system to 50 ℃, distilling the product under reduced pressure for 1h under the vacuum degree of 0.1kPa, and removing small molecular alcohol and water in the system to obtain the silane end-capped modified polycarbonate polyurethane adhesive resin SPCU5 with the viscosity of 25000 cP.
Example 6:
the silane end-capped modified polycarbonate polyurethane adhesive resin is prepared by adding 500g of polycarbonate 3(125mmol) with the number average molecular weight of 4000 and 44.8g of silane coupling agent A-1110(250mmol) into a 2L three-neck flask, stirring to 80 ℃ while heating, then adding 1g of anhydrous zinc acetate catalyst, and reacting at 80 ℃ until the primary amine value content of the system is lower than 0.1%. And then cooling the system to 50 ℃, distilling the product under reduced pressure for 1h under the vacuum degree of 0.1kPa, and removing small molecular alcohol and water in the system to obtain the silane end-capped modified polycarbonate polyurethane adhesive resin SPCU6 with the viscosity of 30000 cP.
Comparative example 1:
the preparation of the high modulus polyurethane resin comprises the steps of adding 280g of polyether diol DL-2000D (140mmol) with the number average molecular weight of 2000 and 200g of polyether triol F3135(40mmol) with the number average molecular weight of 5000 into a 2L three-neck flask, dropwise adding 87.5g of MDI-100(350mmol) after uniform mixing, heating to 70 ℃ while stirring, adding 0.1g of BICAT3228 catalyst, and reacting at 70 ℃ until the NCO content of a system is 2.2%, thus obtaining the high modulus polyurethane resin PU with the viscosity of 60000 cP.
Comparative example 2:
adding 500g of polyether glycol DL-4000D (125mmol) with the number average molecular weight of 4000 and 51.25g of A-Link35 silane coupling agent (250mmol) into a 2L three-neck flask, heating to 70 ℃ while stirring, adding 0.1g of BICAT3228 catalyst, and reacting at 70 ℃ until the NCO content of the system is lower than 0.05 percent to obtain the silane end-capped modified polyether polyurethane adhesive resin SPUR1 with the viscosity of 2000 cP.
Comparative example 3:
the preparation of the silane end-capped modified polyether polyurethane adhesive resin comprises the steps of adding 500g of polyether glycol VORANOL 8000LM (62.5mmol) with the number average molecular weight of 8000 and 25.63g of A-Link35 silane coupling agent (125mmol) into a 2L three-neck flask, heating to 70 ℃ while stirring, adding 0.1g of BICAT3228 catalyst, and reacting at 70 ℃ until the NCO content of a system is lower than 0.05 percent to obtain the silane end-capped modified polyether polyurethane adhesive resin SPUR2 with the viscosity of 5000 cP.
The application performance of the resin prepared in the embodiment of the invention and the comparative example in the adhesive is compared according to the following formula:
TABLE 1
| Components | Weight/% of | Origin of origin |
| SPCU/PU/SPUR | 45 | Self-made |
| Diisononyl phthalate (DINP) | 20 | Meifu |
| Carbon black | 23 | Cambot M570 |
| Ground calcium carbonate | 10 | Lida ultramicro LD-1000C |
| Silane A-171 | 0.6 | Mai chart |
| Silane A-187 | 1.2 | Mai chart |
| Organotin compounds | 0.2 | TIB |
And (3) mixing the formula for 1h in a vacuum environment by using a three-dimensional high-speed mixer at room temperature to obtain the corresponding sealant. Firstly, testing the surface drying time of the sealant according to the national standard; then preparing each test sample strip according to the national standard requirement, placing for 14 days in the environment of 23 ℃ and 50% relative humidity, and carrying out related tests on the sample strips according to the corresponding national standard and standard after the sample is completely cured. When the bonding strength of the sealant and the glass substrate is tested and a sample is prepared, the glass substrate is wiped clean only by acetone and is not treated by a primer. And then carrying out thermal oxygen aging for 300h at the temperature of 90 ℃, and then testing the performance of the alloy. The test criteria are as follows: shear strength (GB/T7124-1986), open time (GB/T13477), tensile strength (GB/T528-2009), 100% tensile modulus (GB/T528-2009), elongation at break (GB/T528-2009), Shore hardness A (GB-T2411-2008), and the test results are as follows:
TABLE 2
As can be seen from Table 2, the traditional PU adhesive has poor adhesion to glass substrates without brushing a base coat, has low shear strength and can not meet the industrial standard; the existing SPUR product has poor mechanical property and cannot be directly applied to the bonding of the automobile windshield rubber. Compared with the two types of the sealing glue, the silane end-capped modified polycarbonate polyurethane sealing glue SPCU has strong mechanical property, excellent bonding force to a glass substrate, excellent aging resistance and capability of meeting the application requirements of the automobile windshield glue. Therefore, the silane end-capped modified polycarbonate polyurethane adhesive resin prepared by taking the specific polycarbonate as the raw material and using the carbonate ammonolysis method not only meets the national requirement on 'clean production process' and reduces the raw material cost of the product, but also has obvious advantages in application of the bottomless coating automobile windshield adhesive compared with the traditional PU resin and the traditional SPUR resin, and each property can successfully meet the requirement of the adhesion of the automobile windshield.
Claims (10)
1. A silane end-capped modified polycarbonate polyurethane adhesive resin is characterized by being obtained by reacting the following raw materials: based on the weight of the resin,
(a) the polycarbonate resin has a glass transition temperature of less than 30 ℃ and is used in an amount of 50-95 wt%, preferably 70-90 wt%;
(b) 4-45 wt%, preferably 9-29 wt% of a silane coupling agent with primary amino groups;
(c) the catalyst is used in an amount of 0.1 to 10 wt%, preferably 0.2 to 1 wt%.
2. The silane-terminated, modified polycarbonate polyurethane adhesive resin of claim 1, wherein component (a) is one or more polycarbonate resins of formula (1)
Wherein:
n is an integer of 5 to 100,
R1or R2A substituted or unsubstituted aliphatic or aromatic linear or branched hydrocarbon radical, identical or independent of one another, of C1 to C10, preferably selected from the group consisting of methyl, ethyl, propyl, phenyl, benzyl;
R3selected from C2-C10 alkylene, preferably from ethylene, propylene, butylene, pentylene, hexylene; c3-10 cycloalkylene, preferably one or more selected from cyclopropylene and cyclohexylene.
3. The resin of claim 1 or 2, wherein the primary aminosilane coupling agent has the general formula of formula (2):
(R4O)3-xR5xSiR6NH2(2)
wherein,
x is 0 or 1;
R4or R5Selected, identically or independently of one another, from C1-C10 alkyl, preferably C1-C4 alkyl;
r6 is selected from C1-C10 alkylene, preferably C3-C5 alkylene;
more preferably, x is 0 and R4is-CH3or-C2H5，R6is-CH2CH2CH2-, namely: 3-aminopropyltrimethoxysilane (KH540) and 3-aminopropyltriethoxysilane (KH 550).
4. A resin according to any of claims 1 to 3 wherein the catalyst is one or more alkali metal alkoxides, and/or one or more organometallics, of the general formula (3):
Y(OR7)m(3)
wherein,
y is a metal element, preferably selected from K, Na and Zn;
R7is C1-C3 straight chain alkyl, or C1-C3 acyl;
m is matched with the valence state of the metal element Y.
5. A process for preparing the resin of any one of claims 1-4, comprising the steps of: according to the proportion,
(1) preparing a polycarbonate resin of component (a);
(2) adding a component (a) polycarbonate resin, a component (b) silane coupling agent with primary amino and a component (c) into a reaction kettle, and stirring for reaction;
(3) and (3) after the reaction in the step (2) is finished, removing low-boiling-point fractions to prepare the silane end-capped modified polycarbonate polyurethane adhesive resin.
6. The method of claim 5, wherein the component (a), the polycarbonate resin, is prepared from a C3-C10 carbonic acid diester, preferably selected from dimethyl carbonate, diethyl carbonate, or diphenyl carbonate; and a C2-C10 diol, preferably selected from 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol or 1, 6-hexanediol, by transesterification.
7. The method according to claim 5, wherein the molar ratio of the polycarbonate resin to the silane coupling agent having a primary amino group in the step (2) is 1:1.5 to 3, preferably 1:1.9 to 2.1.
8. The process according to any one of claims 5 to 7, wherein the reaction temperature in step (2) is in the range of 50 to 150 ℃, preferably 70 to 120 ℃, more preferably 80 to 100 ℃.
9. The method according to claim 5, characterized in that, in the step (3), the low boiling fraction is removed by vacuum distillation, and the temperature of the vacuum distillation is 30-80 ℃, preferably 50-70 ℃; the vacuum degree of the vacuum distillation is in the range of 0.1 to 10kPa, preferably 0.1 to 1 kPa.
10. Use of the silane end-capped modified polycarbonate polyurethane adhesive resin of any one of claims 1-4 or the silane end-capped modified polycarbonate polyurethane adhesive resin prepared by the method of preparation of any one of claims 5-9 in an automotive windshield adhesive.
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