CN111138623B - Organic silicon modified polyether-polycarbonate waterborne polyurethane and preparation method thereof - Google Patents
Organic silicon modified polyether-polycarbonate waterborne polyurethane and preparation method thereof Download PDFInfo
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- CN111138623B CN111138623B CN202010026291.7A CN202010026291A CN111138623B CN 111138623 B CN111138623 B CN 111138623B CN 202010026291 A CN202010026291 A CN 202010026291A CN 111138623 B CN111138623 B CN 111138623B
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- modified polyether
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- waterborne polyurethane
- diisocyanate
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 78
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 78
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 51
- 239000004814 polyurethane Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 38
- 229910052710 silicon Inorganic materials 0.000 title claims description 37
- 239000010703 silicon Substances 0.000 title claims description 37
- 229920005862 polyol Polymers 0.000 claims abstract description 40
- 150000003077 polyols Chemical class 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000004593 Epoxy Substances 0.000 claims abstract description 28
- 239000004970 Chain extender Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 16
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 15
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 229920001451 polypropylene glycol Polymers 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 230000003472 neutralizing effect Effects 0.000 claims description 9
- 229920000768 polyamine Polymers 0.000 claims description 9
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical group OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 8
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 4
- 150000003384 small molecules Chemical class 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 6
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920006264 polyurethane film Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- -1 epoxide compound Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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- 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
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- 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
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4692—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing silicon
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明公开了一种有机硅改性聚醚‑聚碳酸酯水性聚氨酯的制备方法，包括：(1)将环氧化合物、二氧化碳、起始剂、催化剂A与含环氧基硅烷偶联剂混合，经反应制备得到有机硅改性聚醚‑聚碳酸酯多元醇；起始剂选自多羟基小分子或多羟基聚合物；(2)将步骤(1)制备的有机硅改性聚醚‑聚碳酸酯多元醇、二异氰酸酯、多羟基亲水扩链剂与催化剂B搅拌反应，制备得到末端带有NCO基团的聚氨酯预聚物，再依次经碱性中和剂反应及扩链反应制备得到有机硅改性聚醚‑聚碳酸酯水性聚氨酯。采用本方法制备的有机硅改性聚醚‑聚碳酸酯水性聚氨酯具有优异的拉伸强度、耐热性及耐水性。
The invention discloses a preparation method of organosilicon-modified polyether-polycarbonate water-based polyurethane, comprising: (1) mixing epoxy compound, carbon dioxide, initiator, catalyst A and epoxy-containing silane coupling agent , and the organosilicon-modified polyether-polycarbonate polyol is prepared through the reaction; the initiator is selected from polyhydroxy small molecules or polyhydroxy polymers; (2) the organosilicon-modified polyether-polyol prepared in step (1) is Polycarbonate polyol, diisocyanate, polyhydroxy hydrophilic chain extender and catalyst B are stirred and reacted to prepare a polyurethane prepolymer with an NCO group at the end, which is then prepared by an alkaline neutralizer reaction and a chain extension reaction in turn. The silicone-modified polyether-polycarbonate water-based polyurethane was obtained. The silicone-modified polyether-polycarbonate water-based polyurethane prepared by the method has excellent tensile strength, heat resistance and water resistance.
Description
Technical Field
The invention belongs to the technical field of waterborne polyurethane, and particularly relates to organic silicon modified polyether-polycarbonate waterborne polyurethane and a preparation method thereof.
Background
With the development and progress of society, petroleum resources are increasingly exhausted in large quantity, and the utilization of petrochemical resources can cause environmental pollution. Carbon dioxide is a rich and inexpensive carbon-resource, and the effective utilization of carbon dioxide is a breakthrough in the world today to get rid of the dependence on petroleum resources.
The polyols used in conventional waterborne polyurethanes are mainly polyester polyols and polyether polyols. The polyester polyurethane is poor in hydrolysis resistance, while the polyether polyurethane is poor in mechanical properties. Thus, polyether-polycarbonates resulting from the ring-opening copolymerization of carbon dioxide and propylene oxide have been produced.
Chinese patent document with application publication number CN 105566597A discloses carbon dioxide-based waterborne polyurethane, a preparation method and a coating, wherein the method comprises the steps of stirring and reacting carbon dioxide-based dihydric alcohol, polyester or polyether dihydric alcohol, diisocyanate and a carboxylic acid hydrophilic chain extender or an amine hydrophilic chain extender to obtain a polyurethane prepolymer with NCO at the tail end; then adding an alkaline or acidic neutralizing agent into the polyurethane prepolymer with NCO at the tail end and stirring to obtain a water-based polyurethane prepolymer; and finally, adding a polyamine chain extender into the waterborne polyurethane prepolymer to obtain the carbon dioxide-based waterborne polyurethane coating.
However, the carbon dioxide-based waterborne polyurethane coating prepared in the technical scheme has the defects of insufficient mechanical strength, poor water resistance and heat resistance and the like.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a preparation method of organic silicon modified polyether-polycarbonate waterborne polyurethane, and the prepared organic silicon modified polyether-polycarbonate waterborne polyurethane has excellent tensile strength, water resistance and heat resistance.
The specific technical scheme is as follows:
a preparation method of organic silicon modified polyether-polycarbonate waterborne polyurethane comprises the following steps:
(1) mixing an epoxy compound, carbon dioxide, an initiator, a catalyst A and an epoxy group-containing silane coupling agent, and reacting to prepare the organic silicon modified polyether-polycarbonate polyol;
the initiator is selected from polyhydroxy small molecules or polyhydroxy polymers;
(2) stirring and reacting the organic silicon modified polyether-polycarbonate polyol prepared in the step (1), diisocyanate, a polyhydroxy hydrophilic chain extender and a catalyst B to prepare a polyurethane prepolymer with an NCO group at the terminal;
(3) reacting the polyurethane prepolymer with the NCO group at the tail end prepared in the step (2) with an alkaline neutralizing agent to obtain a water-based polyurethane prepolymer;
(4) and (3) mixing the waterborne polyurethane prepolymer prepared in the step (3), water and a polyamine chain extender, and reacting to prepare the organic silicon modified polyether-polycarbonate waterborne polyurethane.
According to the invention, the epoxy silane coupling agent is added in the copolymerization reaction of the epoxy compound and carbon dioxide as a third reaction monomer, and the organosilicon modified polyether-polycarbonate polyol is obtained through copolymerization and is used as a soft segment to prepare the waterborne polyurethane, so that the water resistance, weather resistance and mechanical properties of the polyurethane film are improved.
In the step (1):
the epoxy compound is selected from the common classes, such as ethylene oxide or propylene oxide; preferably, the epoxide compound is selected from propylene oxide.
In step (1), the initiator simultaneously functions as a chain transfer agent and is selected from polyhydroxy small molecules or polyhydroxy polymers.
And the polyhydroxy small molecules such as propylene glycol and butanediol.
The polyhydroxy polymer is polyethylene glycol or polypropylene glycol.
Preferably, the initiator is selected from polypropylene glycol, and tests show that by using polypropylene glycol as the initiator and the chain transfer agent, on one hand, other chain segments can be introduced as little as possible, the chain segments of the product are more regular, and the molecular weight distribution is narrower; on the other hand, the properties are stable, the phase state is not influenced by the experiment temperature and pressure, and the experiment error is reduced.
More preferably, the number average molecular weight of the polypropylene glycol is 200 to 1000 g/mol. Tests show that the number average molecular weight of the organosilicon modified polyether-polycarbonate polyol prepared by using the polypropylene glycol with the number average molecular weight range as an initiator is moderate, and the mechanical property of the waterborne polyurethane film finally prepared by using the organosilicon modified polyether-polycarbonate polyol as a soft segment is better.
Preferably, the epoxy-containing silane coupling agent is selected from a commercially available silane coupling agent, KH 560.
Preferably:
the molar ratio of the epoxy compound, the initiator and the epoxy-containing silane coupling agent is 1:
(1-5)%: (5-15)%; the organic silicon content in the product organic silicon modified polyether-polycarbonate polyol can be regulated and controlled in a large range by adjusting the molar ratio of the epoxy compound to the epoxy-containing silane coupling agent; and the content of the organic silicon in the product organic silicon modified polyether-polycarbonate polyol can be regulated and controlled in a small range by adjusting the molar ratio of the epoxy compound to the initiator.
In the reactor, the pressure of the carbon dioxide is 2-5 MPa.
The catalyst A is selected from double metal cyanide complexes, such as zinc-cobalt double metal cyanide complexes;
the mass ratio of the epoxy compound to the catalyst A is 1: (0.01-0.1)%.
In the step (1), the ternary polymerization reaction is greatly influenced by the reaction temperature, preferably, the reaction temperature is 80-120 ℃, and tests show that when the reaction temperature is lower than 80 ℃, the organosilicon chain segment is basically not detected in the product. Further preferably, the reaction temperature is 100 ℃ and the reaction time is 5-24 h.
Further preferably:
the initiator is selected from polypropylene glycols having an average number average molecular weight of 400 g/mol;
the molar ratio of the epoxy compound, the initiator and the epoxy-containing silane coupling agent is 1: (1.19-4.26)%: 7.5 percent.
Tests show that the number average molecular weight of the prepared organic silicon modified polyether-polycarbonate polyol is 1500-4000 g/mol by using polypropylene glycol with the number average molecular weight of 400g/mol as an initiator; meanwhile, the molar ratio of an epoxy compound, an initiator and a silane coupling agent containing an epoxy group is 1: (1.19-4.26)%: and when 7.5 percent of the total organic silicon content is obtained, the content of organic silicon chain segments in the prepared organic silicon modified polyether-polycarbonate polyol is 3.6-5.4 percent.
In the step (2):
the diisocyanate is selected from at least one of 2, 4-toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and 1, 6-hexamethylene diisocyanate;
the polyhydroxy hydrophilic chain extender is selected from 2, 2-dimethylolpropionic acid and/or 2, 2-dimethylolbutyric acid;
the catalyst B is preferably dibutyltin dilaurate;
the molar ratio of the diisocyanate to the organosilicon modified polyether-polycarbonate polyol to the polyhydroxy hydrophilic chain extender is 1: (15-40)%: (20-40)%;
the mass ratio of the diisocyanate to the catalyst B is 1: (0.01-0.1)%;
the reaction temperature is 75-85 ℃, and the reaction time is 1.5-3 h.
In the step (3):
the alkaline neutralizing agent is selected from triethylamine, ammonia water or sodium hydroxide;
the molar ratio of the alkaline neutralizing agent to the polyhydroxy hydrophilic chain extender is 1: 0.8 to 1.1;
the reaction temperature is 30-45 ℃, and the reaction time is 20-40 min.
In the step (4):
the polyamine chain extender is selected from at least one of ethylenediamine, 1, 3-propanediamine and 1, 4-butanediamine;
the molar ratio of the polyamine chain extender to the diisocyanate is 1: 1.6 to 3.3;
the mass ratio of the waterborne polyurethane prepolymer to water is (25-60): 100, respectively;
the reaction temperature is 15-30 ℃, and the reaction time is 1-2 h.
The reaction formula of the whole preparation process is shown as the following formula:
further preferably:
in the step (1):
the molar ratio of the epoxy compound, the initiator and the epoxy-containing silane coupling agent is 1: (3.41-4.26)%: 7.5 percent;
in the step (2):
the molar ratio of the diisocyanate to the organosilicon modified polyether-polycarbonate polyol to the polyhydroxy hydrophilic chain extender is 1: (20-26)%: (22-26)%;
in the step (3):
the molar ratio of the alkaline neutralizing agent to the polyhydroxy hydrophilic chain extender is 1: 1;
in the step (4):
the molar ratio of the polyamine chain extender to the diisocyanate is 1: 1.83 to 1.91.
Tests show that the organic silicon modified polyether-polycarbonate waterborne polyurethane prepared by the process has better mechanical property.
Still more preferably:
in the step (1):
the molar ratio of the epoxy compound, the initiator and the epoxy-containing silane coupling agent is 1: 4.26%: 7.5 percent;
in the step (2):
the molar ratio of the diisocyanate to the organosilicon modified polyether-polycarbonate polyol to the polyhydroxy hydrophilic chain extender is 1: 25.9%: 22.7 percent;
in the step (3):
the molar ratio of the alkaline neutralizing agent to the polyhydroxy hydrophilic chain extender is 1: 1;
in the step (4):
the molar ratio of the polyamine chain extender to the diisocyanate is 1: 1.91.
tests show that the organosilicon modified polyether-polycarbonate waterborne polyurethane prepared by the process has excellent tensile strength, water resistance and heat resistance.
The invention also discloses the organosilicon modified polyether-polycarbonate waterborne polyurethane prepared by the method, and the structural general formula is as follows
In the formula:
R1is selected from
R2Is selected from-CH2CH2—、—CH2CH2CH2-or-CH2CH2CH2CH2—；
R3Is selected from
NH4Or Na;
R4is selected from
Wherein x is 1-15, y is 1-60, and z is 1-5.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of organic silicon modified polyether-polycarbonate waterborne polyurethane, which comprises the steps of adding an epoxy silane coupling agent as a third reaction monomer in a copolymerization reaction of an epoxy compound and carbon dioxide, copolymerizing to obtain organic silicon modified polyether-polycarbonate polyol, and using the organic silicon modified polyether-polycarbonate polyol as a soft segment to prepare the waterborne polyurethane, so that the water resistance, the heat resistance and the mechanical property of a polyurethane film are improved.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a silicone-modified polyether-polycarbonate polyol prepared in example 2;
FIG. 2 is an IR spectrum of the silicone-modified polyether-polycarbonate polyol prepared in example 2 and shows, for comparison, an IR spectrum of PPG-2000 versus the polyether-polycarbonate polyol prepared in comparative example 1;
FIG. 3 is a comparison graph of infrared spectra of waterborne polyurethanes prepared in example 2 and comparative examples 1-2, respectively;
FIG. 4 is a stress-strain curve of the organosilicon modified polyether-polycarbonate waterborne polyurethane prepared in examples 1-4 respectively;
FIG. 5 is a stress-strain curve of the aqueous polyurethane prepared in example 2 and comparative examples 1 to 2, respectively.
Detailed Description
To further clarify the objects, technical solutions and advantages of the present invention, the following detailed description of the present invention is provided with reference to specific examples, which should not be construed as limiting the scope of the present invention.
Example 1
Step 1: preparation of organosilicon modified polyether-polycarbonate polyols
Before the reaction started, a 100mL stainless steel autoclave was purged and dried under vacuum at 80 ℃ for 2h to remove the water from the autoclave. 34.08g (0.587mol) of propylene oxide, 10.4g (0.044mol) of KH560, 10.0g (0.025mol) of PPG-400 and 20mg of zinc-cobalt double metal cyanide complex were charged into a reaction vessel, which was charged with a small amount of CO2And the temperature is raised to 100 ℃ and then CO is adjusted2The pressure is 5MPa, and the reaction is carried out for 12 h. After the reaction is finished, cooling the reaction kettle in an ice-water bath, and slowly releasing the gas in the kettle at normal temperature. The crude product was dissolved with 20mL of dichloromethane and then precipitated in 150mL of n-hexane to give the organosilicon-modified polyether-polycarbonate polyol.
The number average molecular weight of the product was 1500g/mol, PDI was 1.7, carbonate content was 13.5 mol%, and silicone segment content was 3.6 mol%.
Step 2: preparation of organic silicon modified polyether-polycarbonate waterborne polyurethane
Adding 8.5g (0.0057mol) of the organic silicon modified polyether-polycarbonate polyol prepared in the step 1, 0.71g (0.005mol) of 2, 2-dimethylolpropionic acid and 0.001g of dibutyltin dilaurate catalyst into a 250mL four-neck flask, heating to 80 ℃, slowly dropwise adding 5g (0.022mol) of isophorone diisocyanate into the flask, reacting for 2h after dropwise adding, cooling to 40 ℃, adding 0.54g (0.005mol) of triethylamine, reacting for 0.5h, adding 10.8g of deionized water, cooling to 25 ℃, adding 25.2g (1.4mol) of deionized water and 0.69g (0.0115mol) of ethylenediamine, stirring for 1h at 600rpm, pouring into a tetrafluoroethylene mold, and curing for 48 h at 40 ℃ to obtain the organic silicon modified polyether-polycarbonate waterborne polyurethane, which is marked as WPU 1.
The tensile strength of the organosilicon-modified polyether-polycarbonate aqueous polyurethane prepared in this example was tested according to the method specified in GB/T1040.1-2006. The test data are listed in table 1 below.
Example 2
Step 1: preparation of organosilicon modified polyether-polycarbonate polyol
The preparation was carried out in the same manner as in step 1 of example 1 except that the amount of PPG-400 was changed to 8.1g (0.02mol) to obtain an organosilicon-modified polyether-polycarbonate polyol having a number average molecular weight of 2200g/mol, PDI of 2.0, a carbonate content of 17.1 mol% and an organosilicon segment content of 4.1 mol%.
Step 2: preparation of organic silicon modified polyether-polycarbonate waterborne polyurethane
Adding 10g (0.0045mol) of the organic silicon modified polyether-polycarbonate polyol prepared in the step 1, 0.79g (0.0056mol) of dimethylolpropionic acid and 0.001g of dibutyltin dilaurate catalyst into a 250mL four-neck flask, heating to 80 ℃, slowly dropwise adding 5g (0.022mol) of isophorone diisocyanate into the flask, reacting for 2h after dropwise adding, cooling to 40 ℃, adding 0.60g of triethylamine (0.0056mol), reacting for 0.5h, adding 12.0g of deionized water, cooling to 25 ℃, adding 27.9g of deionized water and 0.72g (0.012mol) of ethylenediamine, stirring for 1h at 600rpm, pouring into a tetrafluoroethylene mold, and curing for 48 h at 40 ℃ to obtain the organic silicon modified polyether-polycarbonate waterborne polyurethane, which is marked as WPU 2.
The tensile strength of the organosilicon-modified polyether-polycarbonate aqueous polyurethane prepared in this example was tested according to the method specified in GB/T1040.1-2006. The test data are listed in table 1 below. The water and heat resistance data for the products prepared in this example are set forth in Table 2 below.
Example 3
Step 1: preparation of organosilicon modified polyether-polycarbonate polyols
The preparation was carried out in the same manner as in step 1 of example 1 except that the amount of PPG-400 was changed to 5.9g (0.015mol) to obtain an organosilicon-modified polyether-polycarbonate polyol having a number average molecular weight of 3100g/mol, PDI of 2.2, a carbonate content of 21.9 mol% and a silicone segment content of 4.6 mol%.
Step 2: preparation of organic silicon modified polyether-polycarbonate waterborne polyurethane
Adding 12g (0.0039mol) of the organic silicon modified polyether-polycarbonate polyol prepared in the step 1, 0.89g (0.0063mol) of dimethylolpropionic acid and 0.001g of dibutyltin dilaurate catalyst into a 250mL four-neck flask, heating to 80 ℃, slowly dropwise adding 5g (0.022mol) of isophorone diisocyanate into the flask, reacting for 2h after dropwise adding, cooling to 40 ℃, adding 0.67g (0.0063mol) of triethylamine, reacting for 0.5h, adding 13.5g of deionized water, cooling to 25 ℃, adding 31.5g of deionized water and 0.72g (0.012mol) of ethylenediamine, stirring for 1h at 600rpm, pouring into a tetrafluoroethylene mold, and curing for 48 h at 40 ℃ to obtain the organic silicon modified polyether-polycarbonate waterborne polyurethane, which is marked as WPU 3.
The tensile strength of the organosilicon-modified polyether-polycarbonate aqueous polyurethane prepared in this example was tested according to the method specified in GB/T1040.1-2006. The test data are listed in table 1 below.
Example 4
Step 1: preparation of organosilicon modified polyether-polycarbonate polyols
The preparation method was the same as in step 1 of example 1, except that the mass of PPG-400 was changed to 2.7g (0.007mol), to obtain an organosilicon-modified polyether-polycarbonate polyol having a number average molecular weight of 3900 g/mol, PDI of 2.5, a carbonate content of 12.0 mol% and an organosilicon segment content of 5.4 mol%.
Step 2: preparation of organic silicon modified polyether-polycarbonate waterborne polyurethane
Adding 14g (0.0036mol) of the organic silicon modified polyether-polycarbonate polyol prepared in the step 1, 0.89g (0.0063mol) of dimethylolpropionic acid and 0.001g of dibutyltin dilaurate catalyst into a 250mL four-neck flask, heating to 80 ℃, slowly dropwise adding 5g (0.022mol) of isophorone diisocyanate into the flask, reacting for 2h after dropwise adding, cooling to 40 ℃, adding 0.67g (0.0063mol) of triethylamine, reacting for 0.5h, adding 13.5g of deionized water, cooling to 25 ℃, adding 31.5g of deionized water and 0.72g (0.012mol) of ethylenediamine, stirring for 1h at 600rpm, pouring into a tetrafluoroethylene mold, and curing for 48 h at 40 ℃ to obtain the organic silicon modified polyether-polycarbonate waterborne polyurethane, which is marked as WPU 4.
The tensile strength of the organosilicon-modified polyether-polycarbonate aqueous polyurethane prepared in this example was tested according to the method specified in GB/T1040.1-2006. The test data are listed in table 1 below.
Comparative example 1
Step 1: preparation of polyether-polycarbonate polyols
The preparation process was analogous to step 1 in the example, and compared with example 2, only the reactants were changed to 34.08g of propylene oxide and 8.1g of PPG-400 without adding KH560 to give a product of polyether-polycarbonate polyol having a number average molecular weight of 1900g/mol, PDI of 1.6 and a carbonate content of 14.9 mol%.
Step 2: preparation of polyether-polycarbonate waterborne polyurethane
Adding 10g of polyether-polycarbonate polyol prepared in the step 1, 0.79g of dimethylolpropionic acid and 0.001g of dibutyltin dilaurate catalyst into a 250mL four-neck flask, heating to 80 ℃, slowly dropwise adding 5g of isophorone diisocyanate into the flask, reacting for 2h after dropwise adding, cooling to 40 ℃, adding 0.60g of triethylamine, reacting for 0.5h, adding 11.9g of deionized water, cooling to 25 ℃, adding 27.9g of deionized water and 0.68g of ethylenediamine, stirring at 600rpm for 1h, pouring into a tetrafluoroethylene mold, and curing at 40 ℃ for 48 h to obtain polyether-polycarbonate waterborne polyurethane, which is marked as WPU-DB 1.
The polyether-polycarbonate aqueous polyurethane prepared in the present comparative example was tested for tensile strength according to the method specified in GB/T1040.1-2006. The test data are listed in table 1 below.
The water and heat resistance data for the product prepared in this comparative example are listed in table 2 below.
Comparative example 2
Adding 10g of PPG-2000, 0.79g of dimethylolpropionic acid and 0.001g of dibutyltin dilaurate catalyst into a 250mL four-neck flask, heating to 80 ℃, slowly dropwise adding 5g of isophorone diisocyanate into the flask, reacting for 2h after dropwise adding, cooling to 40 ℃, adding 0.60g of triethylamine, reacting for 0.5h, adding 12.0g of deionized water, cooling to 25 ℃, adding 27.9g of deionized water and 0.70g of ethylenediamine, stirring at 600rpm for 1h, pouring into a tetrafluoroethylene mold, and curing at 40 ℃ for 48 h to obtain the PPG waterborne polyurethane, WPTAU-DB 2.
The tensile strength of the aqueous polyurethane prepared in this comparative example was tested according to the method specified in GB/T1040.1-2006. The test data are listed in table 1 below. The water and heat resistance data for the product prepared in this comparative example are listed in table 2 below.
TABLE 1
TABLE 2
As can be seen from a comparison of the data in Table 2, the products prepared in the examples have better water resistance and heat resistance than the products prepared in comparative examples 1 to 2, respectively. The organosilicon modified polyether-polycarbonate waterborne polyurethane prepared by the method disclosed by the invention has better tensile strength, water resistance and heat resistance.
Claims (8)
1. A preparation method of organic silicon modified polyether-polycarbonate waterborne polyurethane is characterized by comprising the following steps:
(1) mixing an epoxy compound, carbon dioxide, an initiator, a catalyst A and an epoxy group-containing silane coupling agent, and reacting to prepare the organic silicon modified polyether-polycarbonate polyol;
the initiator is selected from polypropylene glycol with the number average molecular weight of 200-1000 g/mol;
in the reactor, the pressure of the carbon dioxide is 2-5 MPa;
the molar ratio of the epoxy compound, the initiator and the epoxy-containing silane coupling agent is 1: (3.41-4.26)%: 7.5 percent;
(2) stirring and reacting the organic silicon modified polyether-polycarbonate polyol prepared in the step (1), diisocyanate, a polyhydroxy hydrophilic chain extender and a catalyst B to prepare a polyurethane prepolymer with an NCO group at the terminal;
(3) reacting the polyurethane prepolymer with the NCO group at the tail end prepared in the step (2) with an alkaline neutralizing agent to obtain a water-based polyurethane prepolymer;
(4) and (3) mixing the waterborne polyurethane prepolymer prepared in the step (3), water and a polyamine chain extender, and reacting to prepare the organic silicon modified polyether-polycarbonate waterborne polyurethane.
2. The method for preparing the organosilicon modified polyether-polycarbonate waterborne polyurethane according to claim 1, wherein in the step (1):
the epoxy compound is selected from ethylene oxide or propylene oxide;
the epoxy-containing silane coupling agent is selected from KH 560.
3. The method for preparing the organosilicon modified polyether-polycarbonate waterborne polyurethane according to claim 1, wherein in the step (1):
the reaction is carried out at the temperature of 80-120 ℃ for 5-24 h;
the catalyst A is selected from double metal cyanide complexes;
the mass ratio of the epoxy compound to the catalyst A is 1: (0.01-0.1)%.
4. The preparation method of the organosilicon modified polyether-polycarbonate waterborne polyurethane as claimed in any one of claims 1 to 3, wherein in the step (1):
the initiator is selected from polypropylene glycol with the number average molecular weight of 400 g/mol;
the temperature of the reaction was 100 ℃.
5. The method for preparing the organosilicon modified polyether-polycarbonate waterborne polyurethane according to claim 1, wherein in the step (2):
the diisocyanate is selected from at least one of 2, 4-toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and 1, 6-hexamethylene diisocyanate;
the polyhydroxy hydrophilic chain extender is selected from 2, 2-dimethylolpropionic acid and/or 2, 2-dimethylolbutyric acid;
the catalyst B is selected from dibutyltin dilaurate;
the molar ratio of the diisocyanate to the organosilicon modified polyether-polycarbonate polyol to the polyhydroxy hydrophilic chain extender is 1: (15-40)%: (20-40)%;
the mass ratio of the diisocyanate to the catalyst B is 1: (0.01-0.1)%;
the reaction temperature is 75-85 ℃, and the reaction time is 1.5-3 h.
6. The method for preparing the organosilicon modified polyether-polycarbonate waterborne polyurethane according to claim 1, wherein in the step (3):
the alkaline neutralizing agent is selected from triethylamine, ammonia water or sodium hydroxide;
the molar ratio of the alkaline neutralizing agent to the polyhydroxy hydrophilic chain extender is 1: (0.8 to 1.1);
the reaction temperature is 30-45 ℃, and the reaction time is 20-40 min.
7. The method for preparing the organosilicon modified polyether-polycarbonate waterborne polyurethane according to claim 1, wherein in the step (4):
the polyamine chain extender is selected from at least one of ethylenediamine, 1, 3-propanediamine and 1, 4-butanediamine;
the molar ratio of the polyamine chain extender to the diisocyanate is 1: (1.6-3.3);
the mass ratio of the waterborne polyurethane prepolymer to water is (25-60): 100, respectively;
the reaction temperature is 15-30 ℃, and the reaction time is 1-2 h.
8. The organic silicon modified polyether-polycarbonate waterborne polyurethane prepared by the method of any one of claims 1-7.
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