CN114933846A - Non-isocyanate polyurethane coating and preparation method and application thereof - Google Patents
Non-isocyanate polyurethane coating and preparation method and application thereof Download PDFInfo
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- CN114933846A CN114933846A CN202210509840.5A CN202210509840A CN114933846A CN 114933846 A CN114933846 A CN 114933846A CN 202210509840 A CN202210509840 A CN 202210509840A CN 114933846 A CN114933846 A CN 114933846A
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- 239000012948 isocyanate Substances 0.000 title claims abstract description 78
- 239000011527 polyurethane coating Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 90
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 76
- 238000000576 coating method Methods 0.000 claims abstract description 72
- 239000011248 coating agent Substances 0.000 claims abstract description 63
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 58
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 58
- 150000005676 cyclic carbonates Chemical class 0.000 claims abstract description 50
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 238000004140 cleaning Methods 0.000 claims abstract description 15
- 230000003373 anti-fouling effect Effects 0.000 claims abstract description 12
- 150000001412 amines Chemical class 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 239000004593 Epoxy Substances 0.000 claims description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 15
- 239000001569 carbon dioxide Substances 0.000 claims description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- PLDLPVSQYMQDBL-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethoxy)-2,2-bis(oxiran-2-ylmethoxymethyl)propoxy]methyl]oxirane Chemical compound C1OC1COCC(COCC1OC1)(COCC1OC1)COCC1CO1 PLDLPVSQYMQDBL-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 239000003973 paint Substances 0.000 claims description 3
- 229920000768 polyamine Polymers 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims 1
- 230000002209 hydrophobic effect Effects 0.000 abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052710 silicon Inorganic materials 0.000 abstract description 15
- 239000010703 silicon Substances 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 description 27
- 239000004814 polyurethane Substances 0.000 description 21
- 229920002635 polyurethane Polymers 0.000 description 21
- 238000012360 testing method Methods 0.000 description 13
- 230000003068 static effect Effects 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229920001296 polysiloxane Polymers 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- 239000002518 antifoaming agent Substances 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 6
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- DMKSVUSAATWOCU-HROMYWEYSA-N loteprednol etabonate Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)OCCl)(OC(=O)OCC)[C@@]1(C)C[C@@H]2O DMKSVUSAATWOCU-HROMYWEYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000005871 repellent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 229920002873 Polyethylenimine Polymers 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- QGMGHALXLXKCBD-UHFFFAOYSA-N 4-amino-n-(2-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1C(=O)NC1=CC=CC=C1N QGMGHALXLXKCBD-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 1
- 125000005586 carbonic acid group Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—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
- C08G18/61—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a non-isocyanate polyurethane coating and a preparation method and application thereof. The non-isocyanate polyurethane coating comprises the following components in parts by weight: 0.5-1.5 parts of single-end cyclic carbonate polydimethylsiloxane; 35-50 parts of pentaerythritol cyclic carbonate; 8-10 parts of an amine curing agent; 40-55 parts of a solvent. The non-isocyanate polyurethane coating only needs to be added with a small amount of organic silicon components, the production cost is low, and the formed coating has high transparency, excellent hydrophobic and oleophobic and antifouling self-cleaning properties and good mechanical properties.
Description
Technical Field
The invention relates to the technical field of non-isocyanate polyurethane, and particularly relates to a non-isocyanate polyurethane coating and a preparation method and application thereof.
Background
Polyurethanes, which are polymers containing urethane groups in the macromolecular backbone, are known as polyurethanes. Polyurethane has many excellent properties, so it has wide applications in the fields of buildings, electronics, airplanes, cruise ships, furniture, and the like. The conventional preparation of polyurethanes uses diisocyanates as one of the starting materials. The diisocyanate is synthesized by a toxic phosgene method, the preparation process is not environment-friendly, and the synthesized diisocyanate contains toxic-NCO functional groups and has great harm to human bodies. In addition, when a polyurethane is synthesized from a diisocyanate as a raw material, the reaction system cannot contain water because water causes a side reaction with — NCO of the diisocyanate to generate bubbles, which affects the performance of the polyurethane. Due to the defects of environmental pollution, high requirements on preparation process and the like of the traditional polyurethane, the research on the non-isocyanate polyurethane is more and more so as to replace the traditional polyurethane.
The raw materials of the non-isocyanate polyurethane do not contain toxic-NCO, and the preparation process of the raw materials needs to consume greenhouse gas carbon dioxide, so the non-isocyanate polyurethane is an environment-friendly material. The non-isocyanate polyurethane still has the excellent performance of polyurethane, so the non-isocyanate polyurethane is expected to replace the traditional polyurethane to be applied to the fields of coatings, adhesives, foams, sealants and the like.
The organic silicon is adopted to modify the non-isocyanate polyurethane pair, so that the non-isocyanate polyurethane has hydrophobic and oleophobic properties. The patent with publication number CN113336949A provides a hydrophobic and oleophobic non-isocyanate polyurethane coating, because one of the raw materials of the coating contains organosilicon molecular chains, the coating formed after the coating is cured has good hydrophobic and oleophobic properties. However, the synthesis of amino-organosilyl pentaerythritol cyclic carbonates requires the use of more silicone (polydimethylsiloxane) which is more costly, resulting in higher production costs for the coating. In addition, a larger amount of silicone results in a higher content of silicone molecular chains in the coating after the coating is cured, which leads to a decrease in the transparency of the coating.
Therefore, research and solution of the problems of high production cost and reduced coating transparency caused by high organosilicon content of hydrophobic and oleophobic non-isocyanate polyurethane are in urgent need.
Disclosure of Invention
The invention aims to overcome the problems of high production cost and reduced coating transparency caused by high organic silicon content of hydrophobic and oleophobic non-isocyanate polyurethane in the prior art, and provides a non-isocyanate polyurethane coating. The non-isocyanate polyurethane coating only needs to be added with a small amount of organic silicon components, the production cost is low, and the formed coating has high transparency, excellent hydrophobic and oleophobic and antifouling self-cleaning properties and good mechanical properties.
It is a further object of the present invention to provide a method for preparing the above non-isocyanate polyurethane coating.
It is a further object of the present invention to provide the use of the above non-isocyanate polyurethane coating for the preparation of an antifouling self-cleaning coating or an industrial paint.
The above object of the present invention is achieved by the following technical solutions:
a non-isocyanate polyurethane coating comprises the following components in parts by weight:
the pentaerythritol cyclic carbonate contains four cyclic carbonate groups.
In the non-isocyanate polyurethane coating of the present invention, the one-terminal cyclic carbonate polydimethylsiloxane is polydimethylsiloxane having one cyclic carbonate group at one terminal, and the cyclic carbonate group thereof can react with an amine curing agent to form a urethane bond. Pentaerythritol cyclic carbonate is a compound containing four cyclic carbonate groups that can undergo polymerization with amine-based curing agents to form multiple urethane linkages. The pentaerythritol cyclic carbonate and the single-end cyclic carbonate polydimethylsiloxane can also have a grafting reaction through an amine curing agent.
When the coating is cured, the single-end cyclic carbonate polydimethylsiloxane in the coating system is enriched on the surface of the coating due to the low surface energy of the polydimethylsiloxane, and the coating has only one reaction site, so that the reaction rate of grafting the single-end cyclic carbonate polydimethylsiloxane to the pentaerythritol cyclic carbonate is slow; the pentaerythritol cyclic carbonate is mainly distributed in the coating system and has four cyclic carbonate groups and more reaction sites, so that the reaction rate of the polymerization reaction of the pentaerythritol cyclic carbonate and the amine curing agent is higher. During curing, pentaerythritol cyclic carbonate is preferentially subjected to polymerization reaction with an amine curing agent and then is subjected to reaction with single-end cyclic carbonate polydimethylsiloxane (namely, the pentaerythritol cyclic carbonate and the single-end cyclic carbonate polydimethylsiloxane are subjected to grafting reaction through the amine curing agent), so that organic silicon molecular chains of the cured single-end cyclic carbonate polydimethylsiloxane are mainly enriched on the surface of the coating and have high density. In this case, even if the amount of the added silicone component (single-terminal cyclic carbonate polydimethylsiloxane) is small, the formed coating has excellent water-and-oil-repellent and antifouling self-cleaning properties, and the transparency of the coating is high due to the low content of the silicone molecular chain.
If the double-end cyclic carbonate polydimethylsiloxane is selected instead of the single-end cyclic carbonate polydimethylsiloxane, both ends of the double-end cyclic carbonate polydimethylsiloxane react with the amine curing agent during curing to be difficult to concentrate on the surface of the coating, the surface of the cured coating has few organic silicon molecular chains and low density, and the hydrophobic and oleophobic properties of the coating are poor; if pentaerythritol cyclic carbonate with two or three cyclic carbonic acid groups is selected, the film forming effect of the coating is poor due to few reaction sites, low crosslinking density and poor film forming effect, the organic silicon molecular chains on the surface of the formed coating are few, the density is low, the hydrophobic and oleophobic properties of the coating are poor, and the antifouling and self-cleaning properties are also poor.
The coating formed by the non-isocyanate polyurethane coating has a static contact angle to water of 102-103 degrees, a static contact angle to the dian methane of 54-70 degrees, a static contact angle to the hexadecane of 52-60 degrees and outstanding hydrophobic and oleophobic properties, is superior to most of the existing commercially available hydrophobic and oleophobic materials and has the same hydrophobic and oleophobic properties as the non-isocyanate polyurethane coating of patent CN 113336949A. The results show that the cured coating of the non-isocyanate polyurethane coating has excellent hydrophobic and oleophobic properties. The content of silicon element in the non-isocyanate polyurethane coating is about 0.5-3% of the mass of the coating, and the content of silicon element in the non-isocyanate polyurethane coating of patent CN113336949A is about 10-20% of the mass of the coating, so that the non-isocyanate polyurethane coating realizes excellent hydrophobic and oleophobic effects by obviously reducing the silicon content of the non-isocyanate polyurethane coating to be lower than that of the existing material.
In addition, the coating formed by the non-isocyanate polyurethane coating has good gloss, hardness, flexibility, impact resistance and chemical resistance.
The non-isocyanate polyurethane coating only needs to be added with a small amount of organic silicon components, the production cost is low, and the formed coating has high transparency, excellent hydrophobic and oleophobic properties, antifouling self-cleaning properties and good mechanical properties.
Preferably, the other terminal end of the one-terminal cyclic carbonate polydimethylsiloxane is a methoxy group.
Preferably, the number average molecular weight of the single-end cyclic carbonate polydimethylsiloxane is 2040-6040.
More preferably, the number average molecular weight of the single-end epoxy polydimethylsiloxane is 3040 to 5040.
Preferably, the single-terminal cyclic carbonate polydimethylsiloxane is obtained by reacting a single-terminal epoxy-based polydimethylsiloxane with carbon dioxide.
More preferably, the number average molecular weight of the single-end epoxy polydimethylsiloxane is 2000-6000.
More preferably, the number average molecular weight of the single-end epoxy polydimethylsiloxane is 3000-5000.
More preferably, the single-terminal epoxy polydimethylsiloxane has a structure shown as a formula (I):
wherein m is an integer of 25 to 90.
More preferably, the reaction comprises the steps of: and introducing carbon dioxide into the polymer, and reacting for 2-40 h at 60-180 ℃ and 0.5-4.0 Mpa to obtain the single-end cyclic carbonate polydimethylsiloxane. The yield of the single-end cyclic carbonate polydimethylsiloxane prepared under the condition is high and is close to 100 percent.
Further preferably, the reaction is carried out in a solvent system; the solvent is at least one of dimethylformamide, dimethyl sulfoxide or acetonitrile.
Further preferably, the reaction is also added with a catalyst; the catalyst is tetrabutylammonium bromide.
Specifically, the reaction process for obtaining the single-terminal cyclic carbonate polydimethylsiloxane by reacting the single-terminal epoxy group polydimethylsiloxane with carbon dioxide is as follows:
preferably, the pentaerythritol cyclic carbonate is obtained by reacting pentaerythritol glycidyl ether with carbon dioxide.
More preferably, the reaction comprises the steps of: introducing carbon dioxide into pentaerythritol glycidyl ether, and reacting for 2-40 h at 60-180 ℃ and 0.5-4.0 Mpa to obtain the pentaerythritol cyclic carbonate.
Further preferably, the reaction is carried out in a solvent system; the solvent is at least one of dimethylformamide, dimethyl sulfoxide or acetonitrile.
Further preferably, the reaction is also added with a catalyst; the catalyst is tetrabutylammonium bromide.
Specifically, the reaction process for obtaining pentaerythritol cyclic carbonate by reacting pentaerythritol glycidyl ether with a sufficient amount of carbon dioxide is as follows:
amine-based curing agents conventional in the art (non-isocyanate polyurethane) may be used in the present invention.
Preferably, the amine curing agent is at least one of a diamine curing agent or a polyamine curing agent.
More preferably, the diamine curing agent is at least one of ethylenediamine, butanediamine, hexanediamine, 1, 8-octanediamine, decanediamine, 1, 12-dodecanediamine, isophoronediamine, p-phenylenediamine, or polyetherdiamine.
More preferably, the polyamine curing agent is at least one of polyethyleneimine or tetraethylenepentamine.
Preferably, the solvent is at least one of 1-ethyl-2-pyrrolidone, dimethyl sulfoxide, dimethylformamide, 1-methyl-2-pyrrolidone or acetonitrile.
Preferably, the non-isocyanate polyurethane coating further comprises 0.5-2.0 parts of a defoaming agent.
The addition of the defoaming agent is beneficial to reducing the generation of bubbles during the curing of the coating, so that the cured coating is smoother and smoother.
Preferably, the antifoaming agent is at least one of BYK-R605, TEGO Airex 900 or TEGO Airex 962.
According to the preparation method of the non-isocyanate polyurethane coating, the components are mixed to obtain the non-isocyanate polyurethane coating.
Preferably, the mixing process is carried out at 10-30 ℃.
The application of the non-isocyanate polyurethane coating in preparing the antifouling self-cleaning coating or the industrial paint is also within the protection scope of the invention.
Compared with the prior art, the invention has the beneficial effects that:
the non-isocyanate polyurethane coating only needs to be added with a small amount of organic silicon components, the production cost is low, and the formed coating has high transparency, excellent hydrophobic and oleophobic and antifouling self-cleaning properties and good mechanical properties.
Drawings
FIG. 1 is an infrared spectrum of a single-ended cyclic carbonate polydimethylsiloxane prepared in example 1.
FIG. 2 is an infrared spectrum of pentaerythritol cyclic carbonate prepared in example 1.
FIG. 3 is a graph of the oil repellency writing test results for coatings formed from the non-isocyanate polyurethane coating of example 1.
FIG. 4 is a graph of the results of self-cleaning performance tests of coatings formed from the non-isocyanate polyurethane coating of example 1.
Detailed Description
In order to more clearly and completely describe the technical scheme of the invention, the invention is further described in detail by the specific embodiments, and it should be understood that the specific embodiments described herein are only used for explaining the invention, and are not used for limiting the invention, and various changes can be made within the scope defined by the claims of the invention.
Example 1
This example provides a single terminal cyclic carbonate polydimethylsiloxane, pentaerythritol cyclic carbonate, and a non-isocyanate polyurethane coating comprising both.
1. The single-end cyclic carbonate polydimethylsiloxane is prepared by the following steps:
adding single-terminal epoxy polydimethylsiloxane (with the number average molecular weight of 4000) into a high-pressure reaction kettle, adding an organic solvent (with the amount of 30% of the mass of the single-terminal epoxy polysiloxane), simultaneously adding a catalyst tetrabutylammonium bromide (with the amount of 1.0% of the mass of the single-terminal epoxy polydimethylsiloxane), introducing carbon dioxide to maintain the pressure at 4.0Mpa, reacting, controlling the reaction temperature at 120 ℃, and reacting for 10 hours to obtain the single-terminal cyclic carbonate polydimethylsiloxane # 1. The prepared single-end cyclic carbonate polydimethylsiloxane No. 1 is characterized by a Spectrum 2000 Fourier infrared spectrometer to obtain an infrared spectrogram, as shown in figure 1. As can be seen from FIG. 1, the characteristic peaks of the cyclic carbonate appear very clearly in the infrared spectrum, indicating that the synthesis of the single-end cyclic carbonate polydimethylsiloxane No. 1 is successful.
2. The pentaerythritol cyclic carbonate is prepared by the following steps:
adding pentaerythritol glycidyl ether into a high-pressure reaction kettle, adding an organic solvent (the dosage is 20%), simultaneously adding a catalyst tetrabutylammonium bromide (the dosage is 1%), introducing carbon dioxide to maintain the pressure at 2.0Mpa,and (3) carrying out reaction for 10h at the reaction temperature of 120 ℃ to obtain the pentaerythritol cyclic carbonate. The pentaerythritol cyclic carbonate obtained by the preparation is characterized by a Spectrum 2000 Fourier infrared spectrometer to obtain an infrared spectrogram, as shown in figure 2. As can be seen from FIG. 2, at 1795cm -1 Has a very obvious characteristic peak which is characteristic of the cyclic carbonate functional group and is at 912cm -1 The characteristic peak of epoxy at (a) completely disappeared, indicating that the epoxy group had been completely converted to a cyclic carbonate functional group.
3. The non-isocyanate polyurethane coating is prepared by the following steps: preparing the components according to the formula shown in the table 1, mixing at 25 ℃, and uniformly stirring to obtain the non-isocyanate polyurethane coating.
Table 1 non-isocyanate polyurethane coating formulation of example 1
| Serial number | Components | Weight fraction of |
| 1 | Single terminal cyclic carbonate polydimethylsiloxane 1# | 1 |
| 2 | Pentaerythritol cyclic carbonate | 39 |
| 3 | Polyethylene imine | 10 |
| 4 | Dimethylformamide (DMF) | 49.5 |
| 5 | Defoaming agent BYK-R605 | 0.5 |
| 6 | In total | 100 |
Example 2
This example provides a single terminal cyclic carbonate polydimethylsiloxane and a non-isocyanate polyurethane coating including the same.
1. The single-end cyclic carbonate polydimethylsiloxane is prepared by the following steps:
adding single-terminal epoxy polydimethylsiloxane (with the number average molecular weight of 3000) into a high-pressure reaction kettle, adding an organic solvent (with the amount of 40% of the mass of the single-terminal epoxy polysiloxane), simultaneously adding a catalyst tetrabutylammonium bromide (with the amount of 1.5% of the mass of the single-terminal epoxy polydimethylsiloxane), introducing carbon dioxide to maintain the pressure at 3.0Mpa, carrying out reaction, controlling the reaction temperature at 130 ℃, and reacting for 12 hours to obtain the single-terminal cyclic carbonate polydimethylsiloxane # 2. The infrared characterization of the single-ended cyclic carbonate polydimethylsiloxane # 2 showed that the spectrum was similar to that of the single-ended cyclic carbonate polydimethylsiloxane # 1 of example 1, indicating that the synthesis of the single-ended cyclic carbonate polydimethylsiloxane # 2 was successful.
2. The non-isocyanate polyurethane coating is prepared by the following steps: preparing the components according to the formula of the table 2, mixing at 25 ℃, and stirring uniformly to obtain the non-isocyanate polyurethane coating.
This example is a non-isocyanate polyurethane coating prepared according to the same procedure as example 1 and having the formulation shown in Table 2.
Table 2 non-isocyanate polyurethane coating formulations of example 2
| Serial number | Components | Weight fraction of |
| 1 | Single terminal cyclic carbonate polydimethylsiloxane 2# | 0.5 |
| 2 | Pentaerythritol cyclic carbonate | 50 |
| 3 | Polyethylene imine | 9 |
| 4 | 1-Ethyl-2-pyrrolidone (NEP) | 40 |
| 5 | Defoaming agent TEGO Airex 900 | 0.5 |
| 6 | In total | 100 |
Wherein, the pentaerythritol cyclic carbonate in table 2 is taken from the pentaerythritol cyclic carbonate prepared in example 1.
Example 3
This example provides a single terminal cyclic carbonate polydimethylsiloxane and a non-isocyanate polyurethane coating including the same.
1. The single-end cyclic carbonate polydimethylsiloxane is prepared by the following steps:
adding single-end epoxy polydimethylsiloxane (with the number average molecular weight of 5000) into a high-pressure reaction kettle, adding an organic solvent (with the amount of 10% of the mass of the single-end epoxy polysiloxane), simultaneously adding tetrabutylammonium bromide (with the amount of 1.5% of the mass of the single-end epoxy polydimethylsiloxane) serving as a catalyst, introducing carbon dioxide to maintain the pressure at 2.0Mpa, reacting, controlling the reaction temperature at 140 ℃, and reacting for 20 hours to obtain the single-end cyclic carbonate polydimethylsiloxane # 3. The infrared characterization of the single-end cyclic carbonate polydimethylsiloxane # 3 is carried out, and the obtained spectrogram is similar to that of the single-end cyclic carbonate polydimethylsiloxane # 1 in the example 1, which indicates that the synthesis of the single-end cyclic carbonate polydimethylsiloxane # 3 is successful.
2. The non-isocyanate polyurethane coating is prepared by the following steps: the components are prepared according to the formula of the table 3, mixed at 25 ℃ and stirred uniformly to obtain the non-isocyanate polyurethane coating.
Table 3 non-isocyanate polyurethane coating formulation of example 3
| Serial number | Components | Weight fraction of |
| 1 | Single terminal |
1.5 |
| 2 | Pentaerythritol cyclic carbonate | 35 |
| 3 | Dimethyl sulfoxide (DMSO) | 55 |
| 4 | Ethylene diamine | 8 |
| 5 | Defoaming agent TEGO Airex 962 | 0.5 |
| 6 | In total | 100 |
Wherein, the pentaerythritol cyclic carbonate in table 3 was taken from the pentaerythritol cyclic carbonate prepared in example 1.
Performance testing
1. Testing of coating Properties
The non-isocyanate polyurethane coatings of examples 1-3 were sprayed separately and cured at 120 ℃ for 2h to form coatings. In addition, a commercially available polyester Polyol (curing agent Duranate manufactured by Asahi Kasei K.K.) Arcol Polyol 3553 was also used TM HDI) prepared bicomponentPolyurethane coating and Dow epoxy D.E.R TM 331 were subjected to the same spray and cure treatments to produce coatings, designated comparative coating # 1 and comparative coating # 2, respectively.
The formed coating was subjected to a performance test to obtain corresponding test results, and the test standards and test results of the performance test are shown in table 4.
TABLE 4 Performance test results of the coatings
As can be seen from Table 4, the cured coating of the non-isocyanate polyurethane coating of the present invention has good gloss, impact strength, adhesion, flexibility and corrosion resistance; the static contact angle to water reaches 102-103 degrees, the static contact angle to the Dicrepresentative methane reaches 54-70 degrees, and the static contact angle to hexadecane reaches 52-60 degrees, which are far larger than the contact angles of the comparative coating 1# and the comparative coating 2 #. In addition, the static contact angle and the static contact angle to hexadecane of the coating with the performance after curing of the non-isocyanate polyurethane coating are equivalent to the static contact angle (78-115 ℃) to water, the static contact angle (40-82 ℃) to the dianiline and the static contact angle (40-78 ℃) to the hexadecane of the coating (examples 1-6 of patent CN 113336949A) formed after curing of the hydrophobic and oleophobic non-isocyanate polyurethane coating of patent CN 113336949A. The results show that the cured coating of the non-isocyanate polyurethane coating has excellent hydrophobic and oleophobic properties. The content of silicon element in the non-isocyanate polyurethane coating is about 0.5-3% of the mass of the coating, and the content of silicon element in the non-isocyanate polyurethane coating of patent CN113336949A is about 10-20% of the mass of the coating, so that the non-isocyanate polyurethane coating realizes excellent hydrophobic and oleophobic effects by obviously reducing the silicon content of the non-isocyanate polyurethane coating to be lower than that of the existing material.
2. Antifouling Property test
The coating of example 1, after curing, was tested for antifouling properties. The antifouling performance test comprises an oil-repellent handwriting test and a self-cleaning performance test.
The oil-repellent handwriting test method comprises the following steps: and (3) writing on the coating by using an oil marking pen, on one hand, observing whether the oil handwriting shrinks, and on the other hand, testing whether the oil handwriting can be wiped off by a common paper towel without leaving any trace.
The self-cleaning performance test method comprises the following steps: dust was scattered on the surface of the coating, water was dropped on the place where the dust was present, and if the dust was left with water and the dust was completely peeled off from the coating, the self-cleaning performance was evaluated to be excellent.
The results of the oil repellency test are shown in FIG. 3. As can be seen from FIG. 3, the ink marks on the coating shrink into discontinuous traces in the coating treatment area, and the traces can be easily wiped off by a common paper towel, which shows that the oil-repellent handwriting performance of the coating formed after the non-isocyanate polyurethane coating is cured is excellent.
The results of the self-cleaning performance test are shown in fig. 4. As can be seen from FIG. 4, the leftmost picture shows that dust is on the surface of the coating, the middle picture shows the dropping water test process, and the rightmost picture shows that the dust is completely removed from the surface of the coating along with the dropping water after the dropping water, which shows that the coating formed by curing the non-isocyanate polyurethane coating of the present invention has excellent self-cleaning performance.
3. Transparency test
The non-isocyanate polyurethane coatings of examples 1-3 were sprayed onto glass slides, cured to form coatings, and transparency tests were performed according to the following methods: the light transmittance of the coating was measured by an ultraviolet-visible spectrometer, while a glass slide which was not subjected to spray coating treatment was used as a blank. And measuring the light transmittance at the position with the wavelength of 500nm in three times at different positions of each coating, and calculating to obtain the light transmittance of each coating. The light transmittance of the coatings formed from the non-isocyanate polyurethane coatings of examples 1, 2 and 3 was 99%, 98.5% and 99%, respectively, indicating that the non-isocyanate polyurethane coatings of the present invention formed high transparency, which further demonstrates the low level of silicone molecular chains in the coatings.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The non-isocyanate polyurethane coating is characterized by comprising the following components in parts by weight:
the pentaerythritol cyclic carbonate contains four cyclic carbonate groups.
2. The non-isocyanate polyurethane coating of claim 1, wherein the single-terminal cyclic carbonate polydimethylsiloxane is obtained by reacting a single-terminal epoxy-based polydimethylsiloxane with carbon dioxide.
3. The non-isocyanate polyurethane coating of claim 2, wherein the reacting comprises the steps of: and introducing carbon dioxide into the single-end epoxy group polydimethylsiloxane, and reacting for 2-40 h at the temperature of 60-180 ℃ and under the pressure of 0.5-4.0 Mpa to obtain the single-end cyclic carbonate polydimethylsiloxane.
4. The non-isocyanate polyurethane coating of claim 1, wherein the pentaerythritol cyclic carbonate is obtained by reacting pentaerythritol glycidyl ether with carbon dioxide.
5. The non-isocyanate polyurethane coating of claim 4, wherein the reacting comprises the steps of: introducing carbon dioxide into pentaerythritol glycidyl ether, and reacting for 2-40 h at 60-180 ℃ and 0.5-4.0 Mpa to obtain the pentaerythritol cyclic carbonate.
6. The non-isocyanate polyurethane coating of claim 1, wherein the amine curing agent is at least one of a diamine curing agent or a polyamine curing agent.
7. The non-isocyanate polyurethane coating of claim 1, wherein the solvent is at least one of 1-ethyl-2-pyrrolidone, dimethyl sulfoxide, dimethylformamide, 1-methyl-2-pyrrolidone, or acetonitrile.
8. The non-isocyanate polyurethane coating of claim 1, further comprising 0.5 to 2.0 parts of a defoamer.
9. The method of preparing a non-isocyanate polyurethane coating of any one of claims 1 to 8, wherein the non-isocyanate polyurethane coating is prepared by mixing the components.
10. Use of the non-isocyanate polyurethane coating of any one of claims 1 to 8 for the preparation of an antifouling self-cleaning coating or an industrial paint.
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| CN116284798A (en) * | 2023-03-15 | 2023-06-23 | 山东共聚有机硅技术研究院有限公司 | Preparation method of polyurethane modified organosilicon tackifier and application of polyurethane modified organosilicon tackifier in silicone rubber |
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|---|---|---|---|---|
| CN101812175A (en) * | 2009-02-20 | 2010-08-25 | 任旭 | Nonisocyanate polyurethane synthesized by using carbon dioxide(CO2) as raw material |
| JP2016056307A (en) * | 2014-09-11 | 2016-04-21 | 大日精化工業株式会社 | Reactive polysiloxane compound, and coating material composition including the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812175A (en) * | 2009-02-20 | 2010-08-25 | 任旭 | Nonisocyanate polyurethane synthesized by using carbon dioxide(CO2) as raw material |
| JP2016056307A (en) * | 2014-09-11 | 2016-04-21 | 大日精化工業株式会社 | Reactive polysiloxane compound, and coating material composition including the same |
Non-Patent Citations (1)
| Title |
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| PROGRESS IN ORGANIC COATINGS: "Synthesis and properties of poly(dimethylsiloxane)-based non-isocyanate polyurethanes coatings with good anti-smudge properties", 《PROGRESS IN ORGANIC COATINGS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116284798A (en) * | 2023-03-15 | 2023-06-23 | 山东共聚有机硅技术研究院有限公司 | Preparation method of polyurethane modified organosilicon tackifier and application of polyurethane modified organosilicon tackifier in silicone rubber |
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