CN106065060A - A kind of high-performance water-based polyurethane resin and preparation method thereof - Google Patents
A kind of high-performance water-based polyurethane resin and preparation method thereof Download PDFInfo
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- CN106065060A CN106065060A CN201610421719.1A CN201610421719A CN106065060A CN 106065060 A CN106065060 A CN 106065060A CN 201610421719 A CN201610421719 A CN 201610421719A CN 106065060 A CN106065060 A CN 106065060A
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- Prior art keywords
- polyurethane resin
- based polyurethane
- performance water
- water
- method preparing
- Prior art date
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 46
- 239000004645 polyester resin Substances 0.000 claims abstract description 27
- 229920001225 polyester resin Polymers 0.000 claims abstract description 27
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 18
- 239000008158 vegetable oil Substances 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 7
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 57
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 40
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 229920002635 polyurethane Polymers 0.000 claims description 20
- 239000004814 polyurethane Substances 0.000 claims description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 239000003240 coconut oil Substances 0.000 claims description 13
- 235000019864 coconut oil Nutrition 0.000 claims description 13
- 239000012948 isocyanate Substances 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- 235000019260 propionic acid Nutrition 0.000 claims description 8
- 239000003784 tall oil Substances 0.000 claims description 8
- 239000004359 castor oil Substances 0.000 claims description 7
- 235000019438 castor oil Nutrition 0.000 claims description 7
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000001988 toxicity Effects 0.000 abstract description 3
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 125000001931 aliphatic group Chemical group 0.000 abstract description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract description 2
- 239000000356 contaminant Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229930014626 natural product Natural products 0.000 abstract description 2
- 239000010773 plant oil Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 15
- 238000009413 insulation Methods 0.000 description 14
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 8
- FKXJWELJXMKBDI-UHFFFAOYSA-K [butyl-di(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(OC(=O)CCCCCCCCCCC)OC(=O)CCCCCCCCCCC FKXJWELJXMKBDI-UHFFFAOYSA-K 0.000 description 8
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 238000004448 titration Methods 0.000 description 7
- DDKIXUQHRSUCMN-UHFFFAOYSA-N n-butylbutan-1-amine;propan-2-one Chemical compound CC(C)=O.CCCCNCCCC DDKIXUQHRSUCMN-UHFFFAOYSA-N 0.000 description 6
- 150000004672 propanoic acids Chemical class 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 5
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- LZZKQVPDNSVEAX-UHFFFAOYSA-N C(CCC)[Sn].C(C=CC1=CC=CC=C1)(=O)O Chemical compound C(CCC)[Sn].C(C=CC1=CC=CC=C1)(=O)O LZZKQVPDNSVEAX-UHFFFAOYSA-N 0.000 description 1
- QNHMNEOAXKWUKU-UHFFFAOYSA-N CCCCNCCCC.N=C=O Chemical group CCCCNCCCC.N=C=O QNHMNEOAXKWUKU-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000013035 waterborne resin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
-
- 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
-
- 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
- C08G18/36—Hydroxylated esters of higher fatty 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
Landscapes
- 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
The invention discloses a kind of high-performance water-based polyurethane resin and preparation method thereof.The present invention prepares the method for high-performance water-based polyurethane resin with polyester resin, vegetable oil and diisocyanate as raw material, and raw material is cheap and easy to get, and the technological process of production is simply controlled, be easy to prepare on a large scale.And high-performance water-based polyurethane resin prepared by the inventive method both make use of the good physical and chemical performance of vegetable oil, make use of again vegetable oil to be that natural products, source be wide and the advantage of low cost, and do not have volatile organic contaminant during using.Additionally, high-performance water-based polyurethane resin of the present invention is directly introduced into the carbon carbon unsaturated double-bond in plant oil structure and long aliphatic chain in polyurethane resin structure and is made by adjusting the ratio of polyester resin and vegetable oil in raw material waterborne polyurethane resin of the present invention to have excellent resistance to water, alcohol resistance, wearability and a glossiness, and the advantage that it also has that toxicity is little, environmental protection, bin stability are high and easy to use.
Description
Technical field
The present invention relates to technical field of polymer materials, be specifically related to a kind of high-performance water-based polyurethane resin and preparation thereof
Method.
Background technology
Polyurethane is the abbreviation of polyurethanes, is commonly defined as on the main chain of macromolecular chain containing the amino repeating
The macromolecular compound of formic acid esters bond structure unit, is formed with hydroxy compounds polymer by isocyanates under normal circumstances.Its
Can be divided into solvent borne polyurethane and the big class of aqueous polyurethane two, wherein solvent borne polyurethane contains substantial amounts of organic solvent, not only
To environment, harm greatly also can be produced to health.With constantly improving and environmental protection consciousness of regulation
Enhancing, substituting organic solvent using water becomes the emphasis of research as the aqueous polyurethane of decentralized medium and is increasingly subject to pay attention to.
Compared to solvent borne polyurethane, aqueous polyurethane have the advantage that (1) using water as decentralized medium, process is without making
With organic solvent, therefore environmentally safe, and smell is little, nonflammable；(2) without poisonous isocyanato, more
Add safe and reliable；(3) and the binding ability of water is strong, there is good poisture-penetrability；(4) aqueous polyurethane system viscosity and polyurethane
Molecular resin amount is unrelated, and lower with the solvent type polyurethane resin solution phase specific viscosity of identical solid content, it is easier to processing；
(5) can mix with multiple water-base resins, to improve performance or to reduce cost.
Chinese patent application CN 105348487A discloses the preparation side of a kind of castor oil acidic group UV curable water-borne resin
Method, it utilizes the hydroxyl of castor oil acid self to react with isocyanates to obtain polyurethane structural, and the free carboxyl of the other end is used
Neutralize and be emulsified into aqueous, connect pentaerythritol triacrylate with hexamethylene diisocyanate trimer for core again and introduce double
Key, polyethylene glycol is soft section, and final synthesis dumbbell structure resin, the resin system being obtained has aqueous, photocuring, bio-based
Multiple good characteristics.
But, aqueous polyurethane is generally of following shortcoming: low-molecular-weight, glossiness, soft, resistance to ag(e)ing difference, resistance to
Aqueous difference, solid content are low, it is impossible to meet the demand of society, it is therefore desirable to develop a kind of have excellent resistance to water, alcohol resistance,
Wearability and the waterborne polyurethane resin of glossiness.
Content of the invention
Present invention seek to address that the problems of the prior art, a kind of high-performance water-based polyurethane resin and preparation side thereof are provided
Method.To this end, the present inventor's discovery after repeatedly testing, the water that polyester resin, vegetable oil are obtained with di-isocyanate reaction
Property polyurethane resin not only there is excellent resistance to water, alcohol resistance, wearability, also have that glossiness height, environmental protection, toxicity is little, storage
Deposit the high advantage of stability.
Therefore, it is an object of the invention to provide a kind of method preparing high-performance water-based polyurethane resin, it include with
Lower step:
(1) it is placed in polyester resin, dihydromethyl propionic acid and vegetable oil in reactor, be warming up to 105～110 DEG C, vacuum
Processed 1～3 hour；
(2) add acetone, make the system in reactor become solution, and cool to 55～65 DEG C；
(3) drip diisocyanate drip in 1～3 hour to finish, then reaction 0.5～1.5 hour；
(4) add catalyst and proceed reaction；
(5) nertralizer is added to be neutralized；
(6) water is added to carry out emulsion dispersion；
(7) make acetone abjection in system, obtain high-performance water-based polyurethane resin,
Wherein the polyester resin in step (1) and the weight ratio of vegetable oil are (1～10): 1.
Preferably, prepare in the method for high-performance water-based polyurethane resin in the present invention, polyester tree used in step (1)
The weight average molecular weight of fat is 1800～3500 and hydroxyl value is 45～65mgKOH/g.
It is highly preferred that prepare in the method for high-performance water-based polyurethane resin in the present invention, polyester used in step (1)
Resin be weight average molecular weight be 2000 and hydroxyl value be the polyester resin of 56mgKOH/g, weight average molecular weight is 3000 and hydroxyl value is
The polyester resin of 56mgKOH/g or weight average molecular weight are 2000 and hydroxyl value is 56mgKOH/g polyester resin and weight average molecular weight
It is 3000 and the mixture of polyester resin that hydroxyl value is 56mgKOH/g.
Most preferably, prepare in the method for high-performance water-based polyurethane resin in the present invention, polyester used in step (1)
Resin is that the polyester resin that weight is 2000 than the weight average molecular weight for 1:1 and hydroxyl value is 56mgKOH/g is with weight average molecular weight
3000 and the mixture of polyester resin that hydroxyl value is 56mgKOH/g.
Preferably, prepare in the method for high-performance water-based polyurethane resin in the present invention, the polyester resin in step (1) with
The weight ratio of vegetable oil is (5～10): 1.
Preferably, prepare in the method for high-performance water-based polyurethane resin in the present invention, vegetable oil used in step (1)
For one or more in coconut oil, tall oil, soybean oil, dehydrated castor oil.
It is highly preferred that prepare in the method for high-performance water-based polyurethane resin in the present invention, plant used in step (1)
Oil is the mixture of coconut oil and dehydrated castor oil；Coconut oil and the mixture of tall oil；Soya-bean oil, coconut oil and dehydrated castor oil
Mixture；Or the mixture of soya-bean oil, coconut oil, dehydrated castor oil and tall oil.
Most preferably, prepare in the method for high-performance water-based polyurethane resin in the present invention, plant used in step (1)
Oil for weight than the mixture of coconut oil and tall oil for 1:1.
Preferably, prepare in the method for high-performance water-based polyurethane resin in the present invention, two isocyanides used in step (3)
Acid esters be toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, hexamethylene diisocyanate, in IPDI one
Plant or multiple.
It is highly preferred that prepare in the method for high-performance water-based polyurethane resin in the present invention, used two different in step (3)
Cyanate is IPDI.
Preferably, prepare in the present invention in the method for high-performance water-based polyurethane resin, step (4) adds catalyst simultaneously
Proceed the content that the extent of reaction of reaction is NCO in reaction system and reach theoretical value or slightly below theoretical value.
Preferably, prepare in the method for high-performance water-based polyurethane resin in the present invention, catalyst used in step (4)
For the conventional catalyst for preparing aqueous polyurethane.
Preferably, prepare in the method for high-performance water-based polyurethane resin in the present invention, catalyst used in step (4)
For organic tin catalyst, such as dibutyl tin laurate, laurate butyl tin, stannous octoate etc..
It is highly preferred that prepare in the method for high-performance water-based polyurethane resin in the present invention, catalysis used in step (4)
Agent is weight than the mixture of dibutyl tin laurate and laurate butyl tin for 1:1.
Preferably, prepare in the present invention in the method for high-performance water-based polyurethane resin, step (5) adds nertralizer enter
The detailed process that row neutralizes, for the temperature of reaction system is dropped to 35～45 DEG C, is subsequently adding nertralizer, and reaction 0.2～0.5 is little
When.
Preferably, prepare in the method for high-performance water-based polyurethane resin in the present invention, nertralizer used in step (5)
For the conventional nertralizer for preparing aqueous polyurethane, such as NaOH, potassium hydroxide, sodium acid carbonate, triethylamine etc..
Preferably, prepare in the present invention in the method for high-performance water-based polyurethane resin, step (6) adds water carry out breast
Changing scattered detailed process is under agitation, adds water simultaneously to disperse 0.3～1 hour.
It is highly preferred that prepare in the method for high-performance water-based polyurethane resin in the present invention, the stir speed (S.S.) in step (6)
It is 300 revs/min～800 revs/min.
Preferably, prepare in the method for high-performance water-based polyurethane resin in the present invention, step makes acetone in system in (7)
Abjection is to carry out under vacuo.
It is highly preferred that prepare in the method for high-performance water-based polyurethane resin in the present invention, step (7) makes in system third
Ketone abjection is to carry out under-0.05MPa～-0.1MPa.
Additionally, the present invention also aims to provide a kind of high-performance water-based polyurethane tree being obtained by said method
Fat.
The high-performance water-based polyurethane resin of the present invention has excellent with polyester resin, vegetable oil and diisocyanate for raw material
Different hardness, glossiness, resistance to water, alcohol resistance and wearability, thus aqueous polyurethane of the present invention can be widely used for coating, gluing
The fields such as agent, leather finish, fabric coating.
Compared with prior art, the present invention prepares the method for high-performance water-based polyurethane resin with polyester resin, vegetable oil
Being raw material with diisocyanate, raw material is cheap and easy to get, and the technological process of production is simply controlled, be easy to prepare on a large scale.And the present invention
High-performance water-based polyurethane resin prepared by method both make use of the good physical and chemical performance of vegetable oil, make use of again vegetable oil
The advantage of wide for natural products, source in low cost, and do not have volatile organic contaminant during using.In addition, this
Carbon carbon unsaturated double-bond in plant oil structure and long aliphatic chain are directly introduced into poly-ammonia by bright high-performance water-based polyurethane resin
In ester resin structure and waterborne polyurethane resin of the present invention is made to have by adjusting the ratio of polyester resin and vegetable oil in raw material
Have excellent resistance to water, alcohol resistance, wearability and a glossiness, and it also has that toxicity is little, environmental protection, bin stability is high and makes
Use convenient advantage.
Detailed description of the invention
In order to make objects and advantages of the present invention more short and sweet, the present invention will be explained by specific examples below
Bright, but the present invention is only limitted to absolutely not these embodiments.Following example are only the present invention more preferably embodiment, and are only used for explaining
State the present invention, it is impossible to be interpreted as limiting the scope of the present invention.It should be pointed out that, all essence in the present invention and principle it
Interior done any modification, equivalent and improvement etc., should be included within the scope of the present invention.Therefore, the present invention
The protection domain of patent should be as the criterion with claims.
Preparation embodiment
Preparation embodiment 1
By 500 grams of polyester resin (weight average molecular weight is 2000, and hydroxyl value is 56mgKOH/g, be purchased from space field, Qingdao chemical industry),
13.31 grams of dihydromethyl propionic acids and 150 grams of coconut oil add to reactor, heat to 105 DEG C, then under-0.07MPa
Vacuum dehydration 2 hours；It is subsequently added 200 grams of acetone, make system in reactor become solution, and cool to 60 DEG C；Afterwards at 2 hours
Interior dropping 174 grams of toluene di-isocyanate(TDI)s, then insulation reaction 1 hour at 60 DEG C；It is subsequently added 0.2 gram of laurate dibutyl
Tin and 0.2 gram of laurate butyl tin, be further continued for carrying out insulation reaction at 60 DEG C, and took a sample every 20 minutes, then lead to
Cross the isocyanate group content in di-n-butylamine-acetone titration analytical reactions system, the NCO in reaction system
When content reaches theoretical value 5.62%, the temperature in reaction system is down to 40 DEG C, adds 18 grams of nertralizer triethylamines to be neutralized
React 20 minutes；Add 800 grams of water afterwards under the stir speed (S.S.) of 400 revs/min, and continue to stir 0.5 hour；Subsequently 40
DEG C and-0.1MPa under vacuumize, by reaction system acetone abjection, obtain high-performance water-based polyurethane resin.
Preparation embodiment 2
By 500 grams of polyester resin (weight average molecular weight is 2000, and hydroxyl value is 56mgKOH/g, be purchased from space field, Qingdao chemical industry),
13.31 grams of dihydromethyl propionic acids and 50 grams of coconut oil add to reactor, heat to 105 DEG C, then under-0.07MPa
Vacuum dehydration 2 hours；It is subsequently added 200 grams of acetone, make system in reactor become solution, and cool to 60 DEG C；Afterwards at 2 hours
Interior dropping 174 grams of toluene di-isocyanate(TDI)s, then insulation reaction 1 hour at 60 DEG C；It is subsequently added 0.2 gram of laurate dibutyl
Tin and 0.2 gram of laurate butyl tin, be further continued for carrying out insulation reaction at 60 DEG C, and took a sample every 20 minutes, then lead to
Cross the isocyanate group content in di-n-butylamine-acetone titration analytical reactions system, the NCO in reaction system
When content reaches theoretical value 5.62%, the temperature in reaction system is down to 40 DEG C, adds 18 grams of nertralizer triethylamines to be neutralized
React 20 minutes；Add 800 grams of water afterwards under the stir speed (S.S.) of 400 revs/min, and continue to stir 0.5 hour；Subsequently 40
DEG C and-0.1MPa under vacuumize, by reaction system acetone abjection, obtain high-performance water-based polyurethane resin.
Preparation embodiment 3
By 500 grams of polyester resin (weight average molecular weight is 2000, and hydroxyl value is 56mgKOH/g, be purchased from space field, Qingdao chemical industry),
13.31 grams of dihydromethyl propionic acids, 60 grams of coconut oil add to reactor, heat to 110 DEG C, then true under-0.08MPa
Empty dehydration 2.5 hours；It is subsequently added 200 grams of acetone, make system in reactor become solution, and cool to 60 DEG C；Afterwards at 3 hours
Interior dropping 174 grams of toluene di-isocyanate(TDI)s, then insulation reaction 1 hour at 60 DEG C；It is subsequently added 0.2 gram of laurate dibutyl
Tin and 0.2 gram of laurate butyl tin, be further continued for carrying out insulation reaction at 60 DEG C, and took a sample every 20 minutes, then lead to
Cross the isocyanate group content in di-n-butylamine-acetone titration analytical reactions system, the NCO in reaction system
When content reaches theoretical value 5.62%, the temperature in reaction system is down to 40 DEG C, adds 18 grams of nertralizer triethylamines to be neutralized
React 20 minutes；Add 800 grams of water afterwards under the stir speed (S.S.) of 500 revs/min, and continue to stir 0.5 hour；Subsequently 40
DEG C and-0.09MPa under vacuumize, by reaction system acetone abjection, obtain high-performance water-based polyurethane resin.
Preparation embodiment 4
By 500 grams of polyester resin (weight average molecular weight is 2000, and hydroxyl value is 56mgKOH/g, be purchased from space field, Qingdao chemical industry),
13.31 grams of dihydromethyl propionic acids, 30 grams of coconut oil and 30 grams of tall oils add to reactor, heat to 110 DEG C, then
Vacuum dehydration 2.5 hours under-0.08MPa；It is subsequently added 200 grams of acetone, make system in reactor become solution, and cool to 60
℃；174 grams of toluene di-isocyanate(TDI)s, then insulation reaction 1 hour at 60 DEG C is dripped afterwards in 3 hours；It is subsequently added 0.2
Gram dibutyl tin laurate and 0.2 gram of laurate butyl tin, be further continued for carrying out insulation reaction at 60 DEG C, and took every 20 minutes
Sample, then by the isocyanate group content in di-n-butylamine-acetone titration analytical reactions system, in reaction system
Isocyanate group content the temperature in reaction system is down to 40 DEG C when reaching theoretical value 5.62%, add 18 grams of nertralizers three
Ethamine is neutralized reaction 20 minutes；Add 800 grams of water afterwards under the stir speed (S.S.) of 500 revs/min, and continue to stir 0.5
Hour；Vacuumize under 40 DEG C and-0.09MPa subsequently, by the acetone abjection in reaction system, obtain high-performance water-based polyurethane
Resin.
Preparation embodiment 5
By 500 grams of polyester resin (weight average molecular weight is 3000, and hydroxyl value is 56mgKOH/g, be purchased from space field, Qingdao chemical industry),
13.31 grams of dihydromethyl propionic acids, 30 grams of coconut oil and 30 grams of tall oils add to reactor, heat to 110 DEG C, then
Vacuum dehydration 2.5 hours under-0.08MPa；It is subsequently added 200 grams of acetone, make system in reactor become solution, and cool to 60
℃；174 grams of toluene di-isocyanate(TDI)s, then insulation reaction 1 hour at 60 DEG C is dripped afterwards in 3 hours；It is subsequently added 0.2
Gram dibutyl tin laurate and 0.2 gram of laurate butyl tin, be further continued for carrying out insulation reaction at 60 DEG C, and took every 20 minutes
Sample, then by the isocyanate group content in di-n-butylamine-acetone titration analytical reactions system, in reaction system
Isocyanate group content the temperature in reaction system is down to 40 DEG C when reaching theoretical value 5.62%, add 18 grams of nertralizers three
Ethamine is neutralized reaction 20 minutes；Add 800 grams of water afterwards under the stir speed (S.S.) of 500 revs/min, and continue to stir 0.5
Hour；Vacuumize under 40 DEG C and-0.09MPa subsequently, by the acetone abjection in reaction system, obtain high-performance water-based polyurethane
Resin.
Preparation embodiment 6
By 250 grams of polyester resin (weight average molecular weight is 2000, and hydroxyl value is 56mgKOH/g, be purchased from space field, Qingdao chemical industry),
250 grams of polyester resin (weight average molecular weight is 3000, and hydroxyl value is 56mgKOH/g, is purchased from space field, Qingdao chemical industry), 13.31 grams of dihydroxies
Methylpropanoic acid, 30 grams of coconut oil and 30 grams of tall oils add to reactor, heat to 110 DEG C, then under-0.08MPa
Vacuum dehydration 2.5 hours；It is subsequently added 200 grams of acetone, make system in reactor become solution, and cool to 60 DEG C；Little 3 afterwards
When interior dropping 222 grams of IPDIs, then insulation reaction 1 hour at 60 DEG C；It is subsequently added 0.2 gram of laurate
Dibutyl tin and 0.2 gram of laurate butyl tin, be further continued for carrying out insulation reaction at 60 DEG C, and took a sample every 20 minutes,
Then by the isocyanate group content in di-n-butylamine-acetone titration analytical reactions system, the isocyanide in reaction system
When perester radical content reaches theoretical value 5.62%, the temperature in reaction system is down to 40 DEG C, adds 18 grams of nertralizer triethylamines to enter
Row neutralizes reaction 20 minutes；Add 800 grams of water afterwards under the stir speed (S.S.) of 500 revs/min, and continue to stir 0.5 hour；With
After vacuumize under 40 DEG C and-0.1MPa, by the acetone abjection in reaction system, obtain high-performance water-based polyurethane resin.
Comparative example
By 500 grams of polyester resin (weight average molecular weight is 2000, and hydroxyl value is 56mgKOH/g, be purchased from space field, Qingdao chemical industry),
13.31 grams of dihydromethyl propionic acids add to reactor, heat to 105 DEG C, and then under-0.07MPa, vacuum dehydration 2 is little
When；It is subsequently added 200 grams of acetone, make system in reactor become solution, and cool to 60 DEG C；Drip 174 grams in 2 hours afterwards
Toluene di-isocyanate(TDI), then insulation reaction 1 hour at 60 DEG C；It is subsequently added 0.2 gram of dibutyl tin laurate and 0.2 gram month
Cinnamic acid butyl tin, is further continued for carrying out insulation reaction at 60 DEG C, and took a sample every 20 minutes, then by di-n-butylamine-
Isocyanate group content in acetone titration analytical reactions system, the isocyanate group content in reaction system reaches theoretical
When being worth 5.62%, the temperature in reaction system is down to 40 DEG C, adds 18 grams of nertralizer triethylamines to be neutralized reaction 20 minutes；
Add 800 grams of water afterwards under the stir speed (S.S.) of 400 revs/min, and continue to stir 0.5 hour；Subsequently at 40 DEG C and-0.1MPa
Under vacuumize, by reaction system acetone abjection, obtain high-performance water-based polyurethane resin.
Testing example
By preparation embodiment 1 to 5 gained high-performance water-based polyurethane resin emulsion with reference to GB/T 1727-92 coat
It on tinplate, is placed in 60 DEG C of baking ovens baking film forming and is dried 24 hours, it is thus achieved that high-performance water-based polyurethane film, and it is entered
The following test of row:
Pencil hardness: carry out according to the regulation of GB/T6739-2006；
Wearability: carry out according to the regulation of GB/T 23988-2009；
Glossiness: carry out according to the regulation of GB/T 1743-1979
Resistance to water: carry out according to the regulation of GB/T 9274-88；And survey with reference to the regulation according to GB/T 6753 3-1986
Try the bin stability of high-performance water-based polyurethane of the present invention.
Above-mentioned test result is shown in table 1 below.
Table 1 high-performance water-based polyurethane of the present invention and the test result of comparative example
Test result from table 1 understands, high-performance water-based polyurethane resin prepared by the inventive method is implemented with contrast
It is higher that example waterborne polyurethane resin compares hardness, and wearability is more preferable, glossiness is higher, and resistance to water is more excellent, and bin stability is more preferable,
Particularly prepare the high-performance water-based polyurethane resin prepared by embodiment 6, solve standard aqueous polyurethane resin resistance to water
Difference, hardness is not high, glossiness is bad, the problem that wears no resistance.
Claims (10)
1. the method preparing high-performance water-based polyurethane resin, it is characterised in that comprise the following steps:
(1) it is placed in polyester resin, dihydromethyl propionic acid and vegetable oil in reactor, be warming up to 105～110 DEG C, vacuum dehydration
Process 1～3 hour；
(2) add acetone, make the system in reactor become solution, and cool to 55～65 DEG C；
(3) drip diisocyanate drip in 1～3 hour to finish, then reaction 0.5～1.5 hour；
(4) add catalyst and proceed reaction；
(5) nertralizer is added to be neutralized；
(6) water is added to carry out emulsion dispersion；
(7) make acetone abjection in system, obtain high-performance water-based polyurethane resin,
Wherein the polyester resin in step (1) and the weight ratio of vegetable oil are (1～10): 1.
2. the method preparing high-performance water-based polyurethane resin according to claim 1, it is characterised in that in step (1)
The weight average molecular weight of polyester resin used is 1800～3500 and hydroxyl value is 45～65mgKOH/g.
3. the method preparing high-performance water-based polyurethane resin according to claim 1, it is characterised in that in step (1)
Vegetable oil used is coconut oil, tall oil, soybean oil, one or more in dehydrated castor oil.
4. the method preparing high-performance water-based polyurethane resin according to claim 1, it is characterised in that in step (1)
The weight of polyester resin and vegetable oil than being (5～10): 1.
5. the method preparing high-performance water-based polyurethane resin according to claim 1, it is characterised in that in step (3)
Diisocyanate used is that toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone two are different
One or more in cyanate.
6. the method preparing high-performance water-based polyurethane resin according to claim 1, it is characterised in that in step (4)
Catalyst used is for for preparing the conventional catalyst of aqueous polyurethane.
7. the method preparing high-performance water-based polyurethane resin according to claim 1, it is characterised in that in step (5)
Nertralizer used is for for preparing the conventional nertralizer of aqueous polyurethane.
8. the method preparing high-performance water-based polyurethane resin according to claim 1, it is characterised in that in step (5)
Add the detailed process that nertralizer is neutralized for the temperature of reaction system is dropped to 35～45 DEG C, be subsequently adding nertralizer, instead
Answer 0.2～0.5 hour.
9. the method preparing high-performance water-based polyurethane resin according to claim 1, it is characterised in that in step (6)
The detailed process adding water to carry out emulsion dispersion is under agitation, adds water simultaneously to disperse 0.3～1 hour.
10. the height being obtained by the method preparing high-performance water-based polyurethane resin any one of claim 1 to 9
Performance waterborne polyurethane resin.
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| CN112175564A (en) * | 2020-10-29 | 2021-01-05 | 江苏东邦科技有限公司 | High-wear-resistance environment-friendly adhesive for bonding seat leather |
| CN112280316A (en) * | 2020-10-29 | 2021-01-29 | 江苏东邦科技有限公司 | Environment-friendly resin composite material for textiles |
| CN114133520A (en) * | 2021-08-26 | 2022-03-04 | 南京杰腾新材料科技有限公司 | Waterborne polyurethane resin and preparation method thereof |
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