CN102911349B - Caprolactone modified hyperbranched polyester and preparation method and application thereof - Google Patents
Caprolactone modified hyperbranched polyester and preparation method and application thereof Download PDFInfo
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- CN102911349B CN102911349B CN201210384314.7A CN201210384314A CN102911349B CN 102911349 B CN102911349 B CN 102911349B CN 201210384314 A CN201210384314 A CN 201210384314A CN 102911349 B CN102911349 B CN 102911349B
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- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229920006150 hyperbranched polyester Polymers 0.000 title abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 68
- 239000002904 solvent Substances 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 238000000576 coating method Methods 0.000 claims abstract description 43
- 238000010992 reflux Methods 0.000 claims abstract description 41
- 239000003377 acid catalyst Substances 0.000 claims abstract description 35
- -1 dihydroxytoluene alkyl carboxylic acid Chemical class 0.000 claims abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011248 coating agent Substances 0.000 claims abstract description 32
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 29
- 229930195729 fatty acid Natural products 0.000 claims abstract description 29
- 239000000194 fatty acid Substances 0.000 claims abstract description 29
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 229920002635 polyurethane Polymers 0.000 claims abstract description 10
- 239000004814 polyurethane Substances 0.000 claims abstract description 10
- 229920000728 polyester Polymers 0.000 claims description 129
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 68
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 66
- 230000004048 modification Effects 0.000 claims description 57
- 238000012986 modification Methods 0.000 claims description 57
- 239000011159 matrix material Substances 0.000 claims description 43
- 239000003054 catalyst Substances 0.000 claims description 35
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 24
- 150000002632 lipids Chemical class 0.000 claims description 19
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 17
- 239000005639 Lauric acid Substances 0.000 claims description 15
- 238000004821 distillation Methods 0.000 claims description 11
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 11
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 10
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 claims description 8
- 229920001610 polycaprolactone Polymers 0.000 claims description 8
- 239000004632 polycaprolactone Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 5
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 5
- 239000005642 Oleic acid Substances 0.000 claims description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- UVHLUYZMNUCVJN-UHFFFAOYSA-N 3-methyloctane-4,4-diol Chemical compound CCCCC(O)(O)C(C)CC UVHLUYZMNUCVJN-UHFFFAOYSA-N 0.000 claims description 4
- 102100024133 Coiled-coil domain-containing protein 50 Human genes 0.000 claims description 4
- 101000910772 Homo sapiens Coiled-coil domain-containing protein 50 Proteins 0.000 claims description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 239000013638 trimer Substances 0.000 claims description 4
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 claims description 3
- 229940059574 pentaerithrityl Drugs 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 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
- 230000035484 reaction time Effects 0.000 claims description 2
- 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 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 12
- 239000011347 resin Substances 0.000 abstract description 12
- 238000004132 cross linking Methods 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 239000012974 tin catalyst Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 36
- 239000007787 solid Substances 0.000 description 25
- 239000004645 polyester resin Substances 0.000 description 23
- 229910052739 hydrogen Inorganic materials 0.000 description 21
- 239000001257 hydrogen Substances 0.000 description 21
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 20
- 239000003921 oil Substances 0.000 description 17
- 229920000587 hyperbranched polymer Polymers 0.000 description 15
- 230000009286 beneficial effect Effects 0.000 description 11
- 150000002148 esters Chemical class 0.000 description 11
- 239000000178 monomer Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 150000002576 ketones Chemical class 0.000 description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 10
- 229920002554 vinyl polymer Polymers 0.000 description 10
- 230000002378 acidificating effect Effects 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 9
- 238000009835 boiling Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 239000013530 defoamer Substances 0.000 description 9
- 230000001681 protective effect Effects 0.000 description 9
- 239000005028 tinplate Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000012916 structural analysis Methods 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920001634 Copolyester Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- JUMYIBMBTDDLNG-OJERSXHUSA-N hydron;methyl (2r)-2-phenyl-2-[(2r)-piperidin-2-yl]acetate;chloride Chemical compound Cl.C([C@@H]1[C@H](C(=O)OC)C=2C=CC=CC=2)CCCN1 JUMYIBMBTDDLNG-OJERSXHUSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229940099204 ritalin Drugs 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses caprolactone modified hyperbranched polyester, and a preparation method and an application thereof. The preparation method includes mixing polyatomic alcohol with dihydroxytoluene alkyl carboxylic acid by mole part, adding acid catalysts and reflux solvents to react under N2 protection at 140-230 DEG C so as to obtain hyperbranched polyester; adding fatty acid into the hyperbranched polyester serving as the substrate, adding the acid catalysts and the reflux solvents to carry out reflux reaction under N2 protection at 140-240 DEG C until the acid value is lower than 15mgKOH/g so as to obtain the fatty acid modified hyperbranched polyester; and finally adding caprolactone and organic tin catalysts into the fatty acid modified hyperbranched polyester to react under N2 protection at 130-230 DEG C, and removing the organic solvents to obtain the caprolactone modified hyperbranched polyester. The caprolactone modified hyperbranched polyester has no defect of overhigh viscosity as the conventional hyperbranched resin, and good-performance coating films can be obtained after the caprolactone modified hyperbranched polyester is in crosslinking with the polyurethane curing agents. The preparation method can be used for preparing high-solid-content and solvent-free coatings.
Description
Technical field
The present invention relates to a kind of hyper-branched polyester, particularly relate to a kind of caprolactone modification hyper-branched polyester and preparation method thereof and application; Belong to organic high molecular compound field.
Background technology
Hyperbranched polymer has highly branched molecular structure and gives its good performance, comprise: (1) low viscosity: hyperbranched polymer has highly branched, compact three-dimensional globosity, molecular chain is easy entanglement not, compare with the linear polymer of suitable molecular weight, hyperbranched polymer has lower melting or soltion viscosity.(2) high resolution: compare with the linear polymer of same equimolecular quantity, the solubleness of hyperbranched polymer in solvent increases, and can greatly reduce the consumption of solvent, reduces costs and reduces discharge; (3) numerous active end group functional group: hyperbranched polymer is by " core " and repeating unit step reaction and prepare, and periphery can leave a lot of active function groups.Above performance makes hyperbranched polymer in fields such as coating, ink, catalyzer, drug delivery, linking agents, obtain application widely, is particularly suitable for doing high solid and solventless coatings.Hyperbranched polymer comprises polyester, polyethers, polymeric amide, urethane, polyacrylic ester etc., and hyper-branched polyester is the hyperbranched polymer the most widely of studying at present, and its synthetic method comprises: polycondensation, polyaddition reaction, ring-opening polymerization etc.Because hyperbranched polymer itself is the very large or even solid of viscosity at normal temperatures, be mixed with solution or solids content is low, or soltion viscosity is high, is unfavorable for very much the application in coating.Need carry out terminal groups modification to reduce its viscosity to hyperbranched polymer, improve performance.These current hyperbranched polymer modifications are mainly made the plant oil modified hyperbranched resin of raw material, self-drying type of Synolac or make UV cold coating.As United States Patent (USP) WO 03/070844(application number: WO2003US04883) described dimethylol propionic acid and caprolactone reaction forms hyperbranched copolyesters, but such resin still has larger viscosity and the hardness of filming is not high.Chinese invention patent application CN 101583650A(application number: 200780049865.5) disclose and utilized polycarboxylic acid and derivative and polyol reaction synthesis of super branched polyester, under synthetic like this hyper-branched polyester normal temperature, be high sticky or even solid, can only add a large amount of solvents to use.European patent WO 03/093343A1(application number: WO2003EP04121) described the superbrnaching end-hydroxy polyester of high functionality, be applied to there is good visual performance in coating, but they only can limitedly carry high solid.In addition, described hyper-branched polyester lacks the consistency good with nonpolar, non-proton solvent.European patent WO 2004/020503A1(application number: WO2003EP08088) described a kind of method of being prepared hyper-branched polyester by di-carboxylic acid and the polyether glycol at least with three hydroxyls, these polyester are applicable in coating.Same, its described hyper-branched polyester only can limitedly improve coating solid part and not have good solvent compatibility.
Summary of the invention
The object of the invention is to overcome the shortcoming of prior art, the caprolactone modification Hyperbranched Polyester Resin that a kind of viscosity is low is provided.
Another object of the present invention is to provide the preparation method of caprolactone modification Hyperbranched Polyester Resin.
The present invention also has an object to be to provide the coating that contains this caprolactone modification Hyperbranched Polyester Resin.
The object of the invention is achieved through the following technical solutions:
A preparation method for caprolactone modification hyper-branched polyester, comprises the steps:
(1), by molfraction, 1 part of polyvalent alcohol and 2 ~ 4 parts of dihydroxymethyl alkyl carboxylic acids are mixed, and add the reflux solvent of dihydroxymethyl alkyl carboxylic acid weight 0.1% ~ 1% acid catalyst and 8% ~ 15% in 140 ~ 230 ℃ of N
2under protection, react to acid number lower than 20mgKOH/g; Continue to add 4 ~ 8 parts of dihydroxymethyl alkyl carboxylic acids, and add 0.1% ~ 1% acid catalyst of dihydroxymethyl alkyl carboxylic acid weight and 8% ~ 15% reflux solvent, in 140 ~ 230 ℃ of N
2under protection, react to acid number and obtain matrix hyper-branched polyester lower than 20mgKOH/g;
(2), by molfraction, in the matrix hyper-branched polyester of preparing in step (1), add 2 ~ 4 parts of lipid acid, and add 0.1% ~ 1% acid catalyst of fatty acid wt and 8% ~ 15% reflux solvent, at N
2protect lower 140 ~ 240 ℃ of back flow reaction to acid number to obtain fatty acid modified hyper-branched polyester lower than 15mgKOH/g;
(3) in the fatty acid modified hyper-branched polyester of preparing in step (2), add caprolactone and organotin catalysts, in 130 ~ 230 ℃ at N
2the lower reaction 1 ~ 10h of protection, then distillation removes organic solvent and obtains caprolactone modification hyper-branched polyester; The consumption of described organotin catalysts is 0.01% ~ 0.1% of caprolactone weight; The mol ratio of polyvalent alcohol and caprolactone is 1:6 ~ 10;
Described polyvalent alcohol is one or more in ethyl butyl propanediol, neopentyl glycol, BDO, Ymer N120, TriMethylolPropane(TMP), tetramethylolmethane, ditrimethylolpropane, polycaprolactone dibasic alcohol, polycaprolactone tetravalent alcohol;
Described dihydroxymethyl alkyl carboxylic acid is dimethylol propionic acid and/or dimethylolpropionic acid;
Described acid catalyst is one or more in tosic acid, the vitriol oil and Hypophosporous Acid, 50;
Described lipid acid is one or more in lauric acid, sad, capric acid, palmitinic acid, oleic acid, stearic acid, eicosanoic acid;
Described organotin catalysts is dibutyl tin laurate or stannous octoate;
Described reflux solvent is dimethylbenzene or toluene.
For further realizing preparation method's object, the consumption of described organotin catalysts is preferably 0.05% ~ 0.08% of caprolactone weight.
In step (1), the temperature of two reactions is preferably all 140 ~ 180 ℃.
Temperature of reaction in step (2) is preferably 180 ~ 200 ℃.
Temperature of reaction in step (3) is preferably 160 ~ 190 ℃.
Reaction times in step (3) is preferably 1 ~ 2h.
Second object of the present invention, a kind of caprolactone modification hyper-branched polyester, it is prepared by aforesaid method, and the degree of branching of this hyper-branched polyester is 0.4 ~ 0.6, and under normal temperature, viscosity is 2000 ~ 15000cp.
The 3rd object of the present invention, provides a kind of coating, and this coating contains described caprolactone modification hyper-branched polyester and polyurethane curing agent; The amount of substance of the NCO group in polyurethane curing agent is 1.0～1.8 times of amount of substance of described caprolactone modification hyper-branched polyester OH group; Described polyurethane curing agent is one or more in toluene diisocyanate trimer, tolylene diisocyanate/TriMethylolPropane(TMP) affixture and hexamethylene diisocyanate trimer.
In the present invention, part material is described as follows:
Ymer N120 molecular weight is 300-3000, and structural formula is:
Wherein n is number of repeat unit, and its value is 5-50;
Polycaprolactone dibasic alcohol molecular weight is 200-2000, and structural formula is:
Wherein m and n are number of repeat unit, and its value is 1-30;
Polycaprolactone tetravalent alcohol molecular weight is 1000-4000, and structural formula is:
Wherein m, n, h, k are number of repeat unit, and its value is 1-20;
First the present invention utilizes polyvalent alcohol and AB
2matrix hyper-branched polyester is made in the reaction of type monomer dihydroxymethyl alkyl carboxylic acid, thereby then utilizes longer chain fatty acid and its generation esterification to introduce chain alkyl chain, and then has increased the kindliness of molecule, greatly reduces the viscosity of hyper-branched polyester.Unreacted hydroxyl again with caprolactone generation ring-opening reaction, so not only can extend to periphery by being hidden in intramolecular hydroxyl, increased the activity of hydroxyl, being beneficial to follow-up and polyurethane curing agent is cross-linked, and can make between remaining great amount of hydroxy group, to separate in molecule, reduce hydrogen bond action, further reduced again viscosity.
With respect to prior art, tool of the present invention has the following advantages and beneficial effect:
(1) viscosity is low: under synthetic Hyperbranched Polyester Resin normal temperature, viscosity is at 2000 ~ 15000mPas;
(2) hydroxyl reaction is active large: in lipid acid end-blocking part of hydroxyl, fall the low viscous while, utilize caprolactone the hydroxyl that is hidden in hyper-branched polyester inside can be extended to periphery, guaranteed the activity of hydroxyl;
(3) solvability is good: synthetic Hyperbranched Polyester Resin is easy to be dissolved in conventional aromatic hydrocarbons, ester class and ketones solvent, and the height that is easy to prepare solid content to 80% ~ 100% is admittedly containing coating;
(3) film performance is good: Hyperbranched Polyester Resin easily and polyurethane curing agent crosslinking curing film forming, film there is glossiness high (>90 °), the feature of snappiness good (<2mm), shock-resistance high (50cm), strong adhesion (1 grade).
Accompanying drawing explanation
Fig. 1-1st, embodiment 1 mesostroma hyper-branched polyester HBP-1-0(a), lauric acid modified ultra-branching polyester HBP-1-1(b) and lauric acid, caprolactone modification hyper-branched polyester HBP-1-2(c) infrared spectrum;
Fig. 1-2 is embodiment 1 mesostroma hyper-branched polyester HBP-1-0
1h NMR spectrogram;
Fig. 1-3rd, in embodiment 1 with matrix hyper-branched polyester HBP-1-0(a) and lauric acid, caprolactone modification hyper-branched polyester HBP-1-2(b) structural representation;
Fig. 2 is embodiment 2 mesostroma hyper-branched polyester HBP-2-0(a) and lauric acid, caprolactone modification hyper-branched polyester HBP-2-2(b) structural representation;
Fig. 3 is embodiment 3 matrix hyper-branched polyester HBP-3-0(a) and oleic acid, caprolactone modification hyper-branched polyester HBP-3-2(b) structural representation.
Fig. 4 is embodiment 4 matrix hyper-branched polyester HBP-4-0(a) and sad, caprolactone modification hyper-branched polyester HBP-4-2(b) structural representation;
Fig. 5 is embodiment 5 matrix hyper-branched polyester HBP-5-0(a) and stearic acid, caprolactone modification hyper-branched polyester HBP-5-2(b) structural representation;
Fig. 6 is the matrix hyper-branched polyester HBP-6-0(a of embodiment 6) and eicosanoic acid, caprolactone modification hyper-branched polyester HBP-6-2(b) structural representation;
Fig. 7 is embodiment 7 matrix hyper-branched polyester HBP-7-0(a) and lauric acid, caprolactone modification hyper-branched polyester HBP-7-2(b) structural representation;
Fig. 8 is embodiment 8 matrix hyper-branched polyester HBP-8-0(a) and palmitinic acid, caprolactone modification hyper-branched polyester HBP-8-2(b) structural representation;
Fig. 9 is embodiment 9 matrix hyper-branched polyester HBP-9-0(a) and capric acid, caprolactone modification hyper-branched polyester HBP-9-2(b) structural representation.
Embodiment
For better understanding the present invention, below in conjunction with drawings and Examples, the present invention will be further described, but embodiments of the present invention are not limited to this.The relevant method for testing performance relating in embodiment is below as follows:
Adopt the U.S. PERKIN ELMER spectrum of company 2000 Fourier infrared spectrographs to carry out hyper-branched polyester structural analysis; Adopt the degree of branching of Brooker,Switzerland AVANCE III400 nuclear magnetic resonance analyser detection hyper-branched polyester, with deuterated sulfoxide (DMSO-d
6) make solvent.
The degree of branching is to investigate the very important index of hyperbranched polymer structure, according to
1the relative peak area of H NMR is calculated their degree of branching.The degree of branching of hyperbranched polymer mainly contains two kinds of phraseologies:
Wherein, D, L, T represent respectively branching unit methyl, linear unit methyl, terminal units methyl;
On shodex KF-805 gel chromatograph (GPC), carry out the molecular weight of polymkeric substance and the mensuration of distribution thereof, take polystyrene as standard, tetrahydrofuran (THF) is solvent;
Adopt U.S. BROOKFIELD viscometer at 25 ℃, to measure hyperbranched polymer viscosity;
Press GB/T 12008.5-89 and measure polymkeric substance acid number;
Film performance is according to gloss, pencil hardness, snappiness, shock-resistance and the sticking power of GB/T 9754-2007, GB/T 6739-2006, GB/T 1731-1993, GB/T 20624.2-2006 and GB/T 9286-1998 difference testing coating, pencil is the advanced drawing pencil that Shanghai China Pencil Factory No.1 produces, and instrument is Tianjin Jing Ke material-testing machine factory and produces.
Embodiment 1
1, raw material is prepared
Polyvalent alcohol: ethyl butyl propanediol 16g(0.1mol); Dihydroxymethyl alkyl carboxylic acid: dimethylol propionic acid 80.4g(0.6mol); Lipid acid: lauric acid 40g(0.2mol); Caprolactone: 68.4g(0.6mol); An acidic catalyst: tosic acid 0.4g; Organotin catalysts: dibutyl tin laurate 0.05g; Reflux solvent: dimethylbenzene 11g.
2, preparation
(a) agitator, thermometer, water cooling phlegma water trap, N are being housed
2in the four-hole boiling flask of entrance, add 16g ethyl butyl propanediol, 26.8g dihydroxymethyl alkyl carboxylic acid (dimethylol propionic acid), 0.1g acid catalyst tosic acid and 2.5g reflux solvent dimethylbenzene, at 140 ℃ of N
2the lower reaction of protection is not until have water to distillate, be then gradually raised to 180 ℃ react to acid number lower than 20mgKOH/g(, by GB/T 12008.5-89, measure polymkeric substance acid number); Continue to add 53.6g dihydroxymethyl alkyl carboxylic acid, 0.2g acid catalyst tosic acid and 5g reflux solvent dimethylbenzene, at 140 ℃ of N
2the lower reaction of protection is not until have water to distillate, and is then gradually raised to 180 ℃ and reacts to acid number and obtain matrix hyper-branched polyester (HBP-1-0) lower than 20mgKOH/g.
Fig. 1-1(a) be gained matrix hyper-branched polyester (HBP-1-0) Infrared Characterization spectrogram, 3451.6cm
-1near the very strong absorption peak that occurs be-charateristic avsorption band of OH because the hydroxyl of HBP is all positioned at the end of chain, easily form in molecule and intermolecular hydrogen bonding, make 3451.6cm
-1near there is strong wide absorption peak again.At 2957.7cm
-1and 2874.9cm
-1the absorption peak at place is-CH
3,-CH
2-stretching vibration peak, at 1737.4cm
-1absorption peak be the charateristic avsorption band of ester carbonyl group, and the charateristic avsorption band (1690cm of raw material carboxyl
-1) do not occur, this shows that esterification has occurred really for hydroxyl and carboxyl, has generated hyperbranched polymer.
In Fig. 1-2, curve a is gained matrix hyper-branched polyester (HBP-1-0)
1h NMR spectrogram, the ownership of its nuclear magnetic resonance peak (δ, ppm) is as follows: 0.773-0.927(-C
h 3, H9) 0.994-1.221 (C
h 3, H2+H5+H7), 2.506(DMSO-d
6), 3.319-3.681 (C
h 2oH, H3), 3.758-3.956(-C
h 2oCO-, H8), 3.978-4.338 (C
h 2oCO-, H6), 4.656[(-O
h)
t, H1], 4.965[(-O
h)
l, H4].
As shown in curve b in Fig. 1-2, terminal units methyl (TERMINAL-C
h 3), linear unit methyl (LINEAR-C
h 3), branching unit methyl (DENTRITIC-C
h 3) in proton resonance peak respectively 1.021,1.077,1.172ppm place.
(b) in the matrix hyper-branched polyester of preparing in step (a), add lauric acid, residue tosic acid 0.1g and dimethylbenzene 3.5g at N
2protect lower 180 ℃ of back flow reaction to acid number to obtain fatty acid modified hyper-branched polyester (HBP-1-1) lower than 15mgKOH/g.
Fig. 1-1(b) be fatty acid modified hyper-branched polyester (HBP-1-1) infrared spectrum, at 3430.5cm
-1near the absorption peak that occurs be-charateristic avsorption band of OH that part of hydroxyl that lauric acid modified ultra-branching polyester is all also residual, has also showed characteristic peak in this position, but the intensity at peak and width are obvious little a lot.At 722.4cm
-1place's absorption peak is the charateristic avsorption band of chain alkyl.More than illustrate that hyper-branched polyester has passed through lauric acid modification really;
(c) in the fatty acid modified hyper-branched polyester of preparing in step (b), add caprolactone 68.4g(0.6mol), organotin catalysts dibutyl tin laurate 0.05g, in 190 ℃ of N
2under protective atmosphere, react 2h, then distillation removes organic solvent and obtains caprolactone modification hyper-branched polyester (HBP-1-2).
Fig. 1-1(c) be caprolactone modification hyper-branched polyester (HBP-1-2) infrared spectrum, at 3430.5cm
-1near the absorption peak that occurs be-charateristic avsorption band of OH to compare Fig. 1-1(b) through after the further modification of caprolactone, the absorption peak of this position more a little less than, this is to be not easy to form hydrogen bond because the introducing hydroxyl of caprolactone is spaced.
According to above-mentioned collection of illustrative plates, the structural formula of the present embodiment matrix hyper-branched polyester (HBP-1-0) is as Fig. 1-3(a) as shown in, the structural formula of caprolactone modification hyper-branched polyester is as Fig. 1-3(b) as shown in.
3, performance test:
After tested, under gained caprolactone modification hyper-branched polyester (HBP-1-2) normal temperature, viscosity is 10000cp; Molecular weight: 2000; The degree of branching: DB
frechet0.55, DB
frey0.55.Solubility property: as vinyl acetic monomer, N-BUTYL ACETATE, aromatic hydrocarbons is as toluene, dimethylbenzene with ester class, ketone as acetone, butanone can be miscible.Caprolactone modification hyper-branched polyester (HBP-1-2) is a kind of from essence or Synolac, and conventional Synolac is made into 70% solid content conventionally, and under normal temperature, viscosity is 10
5the mPas order of magnitude.Chain-like structure than conventional Synolac, under the cause normal temperature of caprolactone modification hyper-branched polyester (HBP-1-2) due to great amount of hydroxy group formation hydrogen bond itself, be solid-state, consume after modification and between part hydrogen bond and molecule, have benefited from three-dimensional globosity and be not easy again chain entanglement, thereby viscosity meeting is little a lot, this is also the advantage of Hyperbranched Polyester Resin maximum.The resin viscosity that can see 100% solid content in this example only has 10000mPas, and this is very beneficial for making highly filled even solventless coatings.
4, coating and performance
(1) preparation of coating: get the above-mentioned product of 50g (HBP-1-2), then add 0.5g BYK333 flow agent, 0.5gAC270 defoamer, 51g Bayer L75 polyurethane curing agent, after 20g vinyl acetic monomer is uniformly dispersed, on tinplate sheet and plank, film respectively.
(2) measure film performance: 92 ° of glossiness, pencil hardness F, shock-resistance 50cm, snappiness 1mm, adhesion 1 grade.
1, raw material is prepared
Polyvalent alcohol: neopentyl glycol 10.4g(0.1mol); Dihydroxymethyl alkyl carboxylic acid: dimethylol propionic acid 80.4g(0.6mol); Lipid acid: lauric acid 40g(0.2mol); Caprolactone: 68.4g(0.6mol); An acidic catalyst: vitriol oil 0.7g; Organotin catalysts: dibutyl tin laurate 0.05g; Reflux solvent: toluene 15g
2, preparation
(a) agitator, thermometer, water cooling phlegma water trap, N are being housed
2in the four-hole boiling flask of entrance, add 10.4g neopentyl glycol, 26.8g dihydroxymethyl alkyl carboxylic acid, the 0.15g acid catalyst vitriol oil and 3g toluene, at 140 ℃ of N
2protect lower reaction until do not have water to distillate, being then gradually raised to 180 ℃ reacts to acid number lower than 20mgKOH/g; Continue to add 53.6g dihydroxymethyl alkyl carboxylic acid, the 0.3g acid catalyst vitriol oil and 6g reflux solvent, at 140 ℃ of N
2the lower reaction of protection is not until have water to distillate, and is then gradually raised to 180 ℃ and reacts to acid number and obtain matrix hyper-branched polyester lower than 20mgKOH/g.Concrete infrared and
1h NMR analyzes similar to Example 1, no longer lists here, and the structural formula of matrix hyper-branched polyester (HBP-2-0) as shown in Figure 2 (a) shows.
(b) in the matrix hyper-branched polyester of preparing in step (a), add lauric acid 40g(0.2mol), residue acid catalyst vitriol oil 0.25g and reflux solvent toluene 9g be at N
2protect lower 180 ℃ of back flow reaction to acid number to obtain fatty acid modified hyper-branched polyester (HBP-2-1) lower than 15mgKOH/g;
(c) in the fatty acid modified hyper-branched polyester of preparing in step (b), add caprolactone 68.4g(0.6mol), organotin catalysts dibutyl tin laurate 0.05g, in 190 ℃ of N
2under protective atmosphere, react 2h, then distillation removes organic solvent and obtains caprolactone modification hyper-branched polyester (HBP-2-2), and its structural formula is as shown in Fig. 2 (b).
3, performance
Under HBP-2-2 product normal temperature, viscosity is 12500cp; Molecular weight: 2000 degrees of branching: D
bFrechet0.46, D
bFrey0.39; Solvability: as vinyl acetic monomer, N-BUTYL ACETATE, aromatic hydrocarbons is as toluene, dimethylbenzene with ester class, ketone as acetone, butanone can be miscible.Hyperbranched Polyester Resin is a kind of from essence or Synolac, and conventional Synolac is made into 70% solid content conventionally, and under normal temperature, viscosity is 10
5the mPas order of magnitude.Chain-like structure than conventional Synolac, under the cause normal temperature of matrix hyper-branched polyester due to great amount of hydroxy group formation hydrogen bond itself, be solid-state, consume after modification and between part hydrogen bond and molecule, have benefited from three-dimensional globosity and be not easy again chain entanglement, thereby viscosity meeting is little a lot, this is also the advantage of Hyperbranched Polyester Resin maximum.The resin viscosity that can see 100% solid content in this example only has 12500mPas, and this is very beneficial for us and makes highly filled even solventless coatings.
4, coating and performance
(1) preparation of coating: get the above-mentioned product HBP-2-2 of 50g, then add 0.5g BYK333 flow agent, 0.5gDefom5300 defoamer, 60g Bayer IL1451 solidifying agent, after 6g N-BUTYL ACETATE is uniformly dispersed, on tinplate sheet and plank, film respectively.
(2) measure film performance: 91 ° of glossiness, pencil hardness F, shock-resistance 50cm, snappiness 1mm, adhesion 1 grade.
1, raw material is prepared
Polyvalent alcohol: YmerN120 (molecular weight 1000) 70g(0.07mol); Dihydroxymethyl alkyl carboxylic acid: dimethylolpropionic acid 62.16g(0.42mol); Lipid acid: oleic acid 56.4g(0.2mol); Caprolactone: 47.88g(0.42mol); An acidic catalyst: Hypophosporous Acid, 50 0.4g; Organotin catalysts: dibutyl tin laurate 0.035g; Reflux solvent: dimethylbenzene 15g.
2, preparation
(a) agitator, thermometer, water cooling phlegma water trap, N are being housed
2in the four-hole boiling flask of entrance, add 70g polyvalent alcohol Ymer N120,20.72g dimethylolpropionic acid, 0.1 acid catalyst Hypophosporous Acid, 50 and 3g dimethylbenzene, at 140 ℃ of N
2protect lower reaction until do not have water to distillate, being then gradually raised to 180 ℃ reacts to acid number lower than 20mgKOH/g; Continue to add 41.44g dimethylolpropionic acid, 0.2g Hypophosporous Acid, 50 and 6g reflux solvent dimethylbenzene, at 140 ℃ of N
2the lower reaction of protection is not until have water to distillate, then being gradually raised to 180 ℃ reacts to acid number and obtains matrix hyper-branched polyester (HBP-3-0) lower than 20mgKOH/g, its general structural formula is as shown in Fig. 3 (a), and concrete structural analysis, collection of illustrative plates are similar to Example 1, no longer list;
(b) in the matrix hyper-branched polyester of preparing in step (a), add oleic acid 56.4g, residue acid catalyst 0.1g phosphorus v acid and reflux solvent dimethylbenzene 6g at N
2protect lower 180 ℃ of back flow reaction to acid number to obtain fatty acid modified hyper-branched polyester (HBP-3-1) lower than 15mgKOH/g;
(c) in the fatty acid modified hyper-branched polyester of preparing in step (b), add caprolactone 47.88g, organotin catalysts dibutyl tin laurate 0.035g, in 170 ℃ of N
2under protective atmosphere, react 2h, then distillation removes organic solvent and obtains caprolactone modification hyper-branched polyester (HBP-3-2), and its general structural formula as shown in Figure 3 (b).
3, performance
Under product (HBP-3-2) normal temperature, viscosity is 2000cp; Molecular weight 3500; The degree of branching: DB
frechet0.6, DB
frey0.53; Solvability: as vinyl acetic monomer, N-BUTYL ACETATE, aromatic hydrocarbons is as toluene, dimethylbenzene with ester class, ketone as acetone, butanone can be miscible.Hyperbranched Polyester Resin is a kind of from essence or Synolac, and conventional Synolac is made into 70% solid content conventionally, and under normal temperature, viscosity is 10
5the mPas order of magnitude.Chain-like structure than conventional Synolac, under the cause normal temperature of matrix hyper-branched polyester due to great amount of hydroxy group formation hydrogen bond itself, be solid-state, consume after modification and between part hydrogen bond and molecule, have benefited from three-dimensional globosity and be not easy again chain entanglement, thereby viscosity meeting is little a lot, this is also the advantage of Hyperbranched Polyester Resin maximum.The resin viscosity that can see 100% solid content in this example only has 2000mPas, and this is very beneficial for us and makes highly filled even solventless coatings.
4, coating and performance
(1) preparation of coating: get the above-mentioned product of 50g (HBP-3-2), then add 0.5g BYK323 flow agent, 0.5gDefom5300 defoamer after 53g Bayer IL1451 solidifying agent is uniformly dispersed, is filmed respectively on tinplate sheet and plank.
(2) measure film performance: 89 ° of glossiness, pencil hardness 4B, shock-resistance 50cm, snappiness 1mm, 3 grades of sticking power.
1, raw material is prepared
Polyvalent alcohol: TriMethylolPropane(TMP) 8.71g(0.065mol); Dihydroxymethyl alkyl carboxylic acid: dimethylolpropionic acid 86.58g(0.585mol); Lipid acid: sad 56.16g(0.39mol); Caprolactone: 44.46g(0.39mol); An acidic catalyst: Hypophosporous Acid, 50 0.55g; Organotin catalysts: sub-stannous octoate 0.03g; Reflux solvent: toluene 21g
2, preparation
(a) agitator, thermometer, water cooling phlegma water trap, N are being housed
2in the four-hole boiling flask of entrance, add 8.71g polyvalent alcohol, 28.86g dihydroxymethyl alkyl carboxylic acid, 0.15g acid catalyst Hypophosporous Acid, 50 and 4g toluene, at 140 ℃ of N
2protect lower reaction until do not have water to distillate, being then gradually raised to 180 ℃ reacts to acid number lower than 20mgKOH/g; Continue to add residue dihydroxymethyl alkyl carboxylic acid, 0.3g acid catalyst Hypophosporous Acid, 50 and 8g reflux solvent toluene, at 140 ℃ of N
2the lower reaction of protection is not until have water to distillate, and is then gradually raised to 180 ℃ and reacts to acid number and obtain matrix hyper-branched polyester (HBP-4-0) lower than 20mgKOH/g.As shown in Figure 4 (a), concrete structural analysis, collection of illustrative plates are similar to Example 1, no longer list for its general structural formula;
(b) in the matrix hyper-branched polyester of preparing in step (a), add the sad 56.16g of lipid acid, residue acid catalyst Hypophosporous Acid, 50 0.1g and reflux solvent toluene 10g at N
2protect lower 190 ℃ of back flow reaction to acid number to obtain fatty acid modified hyper-branched polyester (HBP-4-1) lower than 15mgKOH/g;
(c) in the fatty acid modified hyper-branched polyester of preparing in step (b), add caprolactone 44.46g, the sub-stannous octoate 0.03g of organotin catalysts, in 180 ℃ of N
2under protective atmosphere, react 2h, then distillation removes organic solvent and obtains caprolactone modification hyper-branched polyester (HBP-4-2), and its general structural formula as shown in Figure 4 (b).
3, performance
Under product (HBP-4-2) normal temperature, viscosity is 7000cp; The degree of branching: DB
frechet0.49, DB
frey0.43; Molecular weight: 2600; Solvability: as vinyl acetic monomer, N-BUTYL ACETATE, aromatic hydrocarbons is as toluene, dimethylbenzene with ester class, ketone as acetone, butanone can be miscible.Hyperbranched Polyester Resin is a kind of from essence or Synolac, and conventional Synolac is made into 70% solid content conventionally, and under normal temperature, viscosity is 10
5the mPas order of magnitude.Chain-like structure than conventional Synolac, under the cause normal temperature of matrix hyper-branched polyester due to great amount of hydroxy group formation hydrogen bond itself, be solid-state, consume after modification and between part hydrogen bond and molecule, have benefited from three-dimensional globosity and be not easy again chain entanglement, thereby viscosity meeting is little a lot, this is also the advantage of Hyperbranched Polyester Resin maximum.The resin viscosity that can see 100% solid content in this example only has 7000mPas, and this is very beneficial for us and makes highly filled even solventless coatings.
4, coating and performance
(1) preparation of coating: get the above-mentioned product of 50g (HBP-4-2), then add 0.5g BYK323 flow agent, 0.5gBYK141 defoamer, 40g Bayer L75 solidifying agent after 10g dimethylbenzene is uniformly dispersed, is filmed respectively on tinplate sheet and plank.
(2) film performance: 93 ° of glossiness, pencil hardness F, shock-resistance 50cm, snappiness 1mm, adhesion 1 grade.
1, raw material is prepared
Polyvalent alcohol: the polycaprolactone dibasic alcohol 70g(0.07mol that molecular weight is 1000); Dihydroxymethyl alkyl carboxylic acid: dimethylol propionic acid 56.28g(0.42mol); Lipid acid: stearic acid 39.83g(0.14mol); Caprolactone: 47.88g(0.42mol); An acidic catalyst: vitriol oil 0.44g; Organotin catalysts: sub-stannous octoate 0.03g; Reflux solvent: dimethylbenzene 15g
2, preparation
(a) agitator, thermometer, water cooling phlegma water trap, N are being housed
2in the four-hole boiling flask of entrance, add polyvalent alcohol, 18.76g dihydroxymethyl alkyl carboxylic acid, the 0.11g acid catalyst vitriol oil and 3g reflux solvent dimethylbenzene, at 140 ℃ of N
2protect lower reaction until do not have water to distillate, being then gradually raised to 180 ℃ reacts to acid number lower than 20mgKOH/g; Continue to add residue dihydroxymethyl alkyl carboxylic acid, the 0.22g acid catalyst vitriol oil and 6g reflux solvent dimethylbenzene, at 140 ℃ of N
2the lower reaction of protection is not until have water to distillate, then being gradually raised to 180 ℃ reacts to acid number and obtains matrix hyper-branched polyester (HBP-5-0) lower than 20mgKOH/g, its general structural formula is as shown in Fig. 5 (a), and concrete structural analysis, collection of illustrative plates are similar to Example 1, no longer list;
(b) in the matrix hyper-branched polyester of preparing in step (a), add lipid acid stearic acid 39.83g, residue acid catalyst vitriol oil 0.11g and reflux solvent dimethylbenzene 6g at N
2protect lower 180 ℃ of back flow reaction to acid number to obtain fatty acid modified hyper-branched polyester (HBP-5-1) lower than 15mgKOH/g;
(c) in the fatty acid modified hyper-branched polyester of preparing in step (b), add caprolactone, organotin catalysts, in 160 ℃ of N
2under protective atmosphere, react 1h, then distillation removes organic solvent and obtains caprolactone modification hyper-branched polyester (HBP-5-2), and its general structural formula is as shown in Fig. 5 (b).
3, performance
Under product (HBP-5-2) normal temperature, viscosity is 4600cp; The degree of branching: DB
frechet0.53, DB
frey0.46; Molecular weight 3500; Solvability: as vinyl acetic monomer, N-BUTYL ACETATE, aromatic hydrocarbons is as toluene, dimethylbenzene with ester class, ketone as acetone, butanone can be miscible.Hyperbranched Polyester Resin is a kind of from essence or Synolac, and conventional Synolac is made into 70% solid content conventionally, and under normal temperature, viscosity is 10
5the mPas order of magnitude.Chain-like structure than conventional Synolac, under the cause normal temperature of matrix hyper-branched polyester due to great amount of hydroxy group formation hydrogen bond itself, be solid-state, consume after modification and between part hydrogen bond and molecule, have benefited from three-dimensional globosity and be not easy again chain entanglement, thereby viscosity meeting is little a lot, this is also the advantage of Hyperbranched Polyester Resin maximum.The resin viscosity that can see 100% solid content in this example only has 4600mPas, and this is very beneficial for us and makes highly filled even solventless coatings.
4, coating and performance
(1) preparation of coating: get the above-mentioned product of 50g (HBP-5-2), then add 0.5g BYK358N flow agent, 0.5gDefom5300 defoamer, 65g Bayer IL1451 solidifying agent, after 5g acetone is uniformly dispersed, on tinplate sheet and plank, film respectively.
(2) film performance: 91 ° of glossiness, pencil hardness 3B, shock-resistance 50cm, snappiness 1mm, 2 grades of sticking power.
Embodiment 6
1, raw material is prepared
Polyvalent alcohol: tetramethylolmethane 6.8g(0.05mol); Dihydroxymethyl alkyl carboxylic acid: dimethylolpropionic acid 88.8g(0.6mol); Lipid acid: eicosanoic acid 156.26g(0.5mol); Caprolactone: 34.2g(0.3mol); An acidic catalyst: tosic acid 0.9g; Organotin catalysts: sub-stannous octoate 0.02g; Reflux solvent: dimethylbenzene 25g.
2, preparation
(a) agitator, thermometer, water cooling phlegma water trap, N are being housed
2in the four-hole boiling flask of entrance, add polyvalent alcohol, 29.6g dihydroxymethyl alkyl carboxylic acid, 0.15g acid catalyst and 4g dimethylbenzene, at 140 ℃ of N
2protect lower reaction until do not have water to distillate, being then gradually raised to 180 ℃ reacts to acid number lower than 20mgKOH/g; Continue to add residue dihydroxymethyl alkyl carboxylic acid, 0.3g acid catalyst and 8g reflux solvent, at 140 ℃ of N
2the lower reaction of protection is not until have water to distillate, then being gradually raised to 180 ℃ reacts to acid number and obtains matrix hyper-branched polyester (HBP-6-0) lower than 20mgKOH/g, as shown in Figure 6 (a), concrete structural analysis, collection of illustrative plates are similar to Example 1, no longer list for its general structural formula;
(b) in the matrix hyper-branched polyester of preparing in step (a), add lipid acid, residue acid catalyst and reflux solvent at N
2protect lower 200 ℃ of back flow reaction to acid number to obtain fatty acid modified hyper-branched polyester (HBP-6-1) lower than 15mgKOH/g;
(c) in the fatty acid modified hyper-branched polyester of preparing in step (b), add caprolactone, organotin catalysts, in 170 ℃ of N
2under protective atmosphere, react 1h, then distillation removes organic solvent and obtains caprolactone modification hyper-branched polyester (HBP-6-2), and its general structural formula as shown in Figure 6 (b).
3, performance
Under product (HBP-6-2) normal temperature, viscosity is 4000cp; The degree of branching: DB
frechet0.47, DB
frey0.41; Molecular weight: 5300; Solvability: as vinyl acetic monomer, N-BUTYL ACETATE, aromatic hydrocarbons is as toluene, dimethylbenzene with ester class, ketone as acetone, butanone can be miscible.Hyperbranched Polyester Resin is a kind of from essence or Synolac, and conventional Synolac is made into 70% solid content conventionally, and under normal temperature, viscosity is 10
5the mPas order of magnitude.Chain-like structure than conventional Synolac, under the cause normal temperature of matrix hyper-branched polyester due to great amount of hydroxy group formation hydrogen bond itself, be solid-state, consume after modification and between part hydrogen bond and molecule, have benefited from three-dimensional globosity and be not easy again chain entanglement, thereby viscosity meeting is little a lot, this is also the advantage of Hyperbranched Polyester Resin maximum.The resin viscosity that can see 100% solid content in this example only has 4000mPas, and this is very beneficial for us and makes highly filled even solventless coatings.
4, coating and performance
(1) preparation of coating: get the above-mentioned product of 50g (HBP-6-2), then add 0.4g BYK323 flow agent, 0.4gBYK141 defoamer, 30g Bayer N3390 solidifying agent after 10g pimelinketone is uniformly dispersed, is filmed respectively on tinplate sheet and plank.
(2) measure film performance: 91 ° of glossiness, pencil hardness B, shock-resistance 50cm, snappiness 1mm, 2 grades of sticking power.
1, raw material is prepared
Polyvalent alcohol: the polycaprolactone tetravalent alcohol 40g(0.04mol that molecular weight is 1000); Dihydroxymethyl alkyl acid: dimethylol propionic acid 64.32g(0.48mol); Lipid acid: lauric acid 80g(0.4mol); Caprolactone: 27.36g(0.24mol); An acidic catalyst: tosic acid 0.5g; Organotin catalysts: sub-stannous octoate 0.016g; Reflux solvent: toluene 15g.
2, preparation
(a) agitator, thermometer, water cooling phlegma water trap, N are being housed
2in the four-hole boiling flask of entrance, add polyvalent alcohol, 21.44g dihydroxymethyl alkyl carboxylic acid, 0.1g acid catalyst tosic acid and 3g reflux solvent toluene, at 140 ℃ of N
2protect lower reaction until do not have water to distillate, being then gradually raised to 180 ℃ reacts to acid number lower than 20mgKOH/g; Continue to add residue dihydroxymethyl alkyl carboxylic acid, 0.2g acid catalyst tosic acid and 6g reflux solvent toluene, at 140 ℃ of N
2the lower reaction of protection is not until have water to distillate, then being gradually raised to 180 ℃ reacts to acid number and obtains matrix hyper-branched polyester (HBP-7-0) lower than 20mgKOH/g, as shown in Figure 7 (a), concrete structural analysis, collection of illustrative plates are similar to Example 1, no longer list for its general structural formula;
(b) in the matrix hyper-branched polyester of preparing in step (a), add lipid acid lauric acid 80g, 0.2g residue acid catalyst tosic acid and reflux solvent toluene 6g at N
2protect lower 180 ℃ of back flow reaction to acid number to obtain fatty acid modified hyper-branched polyester (HBP-7-1) lower than 15mgKOH/g;
(c) in the fatty acid modified hyper-branched polyester of preparing in step (b), add caprolactone, organotin catalysts, in 160 ℃ of N
2under protective atmosphere, react 1h, then distillation removes organic solvent and obtains caprolactone modification hyper-branched polyester (HBP-7-2), and its general structural formula as shown in Figure 7 (b) shows.
3, performance
Under product (HBP-7-2) normal temperature, viscosity is 2500cp; The degree of branching: DB
frechet0.47, D
bFrey0.41; Molecular weight: 6000; Solvability: as vinyl acetic monomer, N-BUTYL ACETATE, aromatic hydrocarbons is as toluene, dimethylbenzene with ester class, ketone as acetone, butanone can be miscible.Hyperbranched Polyester Resin is a kind of from essence or Synolac, and conventional Synolac is made into 70% solid content conventionally, and under normal temperature, viscosity is 10
5the mPas order of magnitude.Chain-like structure than conventional Synolac, under the cause normal temperature of matrix hyper-branched polyester due to great amount of hydroxy group formation hydrogen bond itself, be solid-state, consume after modification and between part hydrogen bond and molecule, have benefited from three-dimensional globosity and be not easy again chain entanglement, thereby viscosity meeting is little a lot, this is also the advantage of Hyperbranched Polyester Resin maximum.The resin viscosity that can see 100% solid content in this example only has 2500mPas, and this is very beneficial for us and makes highly filled even solventless coatings.
4, coating and performance
(1) preparation of coating: get the above-mentioned product of 50g (HBP-7-2), then add 0.5g BYK358N flow agent, 0.5gAC270 defoamer, 20g Bayer N3390 solidifying agent after 5g butanone is uniformly dispersed, is filmed respectively on tinplate sheet and plank.
(2) measure film performance: 91 ° of glossiness, pencil hardness 4B, shock-resistance 50cm, snappiness 1mm, 2 grades of sticking power.
1, raw material is prepared
Polyvalent alcohol: BDO 9g(0.1mol); Dihydroxymethyl alkyl acid: dimethylol propionic acid 80.4g(0.6mol); Lipid acid: palmitinic acid 51.2g(0.2mol); Caprolactone: 68.4g(0.6mol); An acidic catalyst: vitriol oil 0.45g; Organotin catalysts: sub-stannous octoate 0.05g; Reflux solvent: dimethylbenzene 15g.
2, preparation
(a) agitator, thermometer, water cooling phlegma water trap, N are being housed
2in the four-hole boiling flask of entrance, add polyvalent alcohol, 26.8g dihydroxymethyl alkyl carboxylic acid, the 0.1g acid catalyst vitriol oil and 3g reflux solvent dimethylbenzene, at 140 ℃ of N
2protect lower reaction until do not have water to distillate, being then gradually raised to 180 ℃ reacts to acid number lower than 20mgKOH/g; Continue to add residue dihydroxymethyl alkyl carboxylic acid, the 0.2g acid catalyst vitriol oil and 6g reflux solvent dimethylbenzene, at 140 ℃ of N
2the lower reaction of protection is not until have water to distillate, then being gradually raised to 180 ℃ reacts to acid number and obtains matrix hyper-branched polyester (HBP-8-0) lower than 20mgKOH/g, its general structural formula is as shown in Fig. 3 (a), and concrete structural analysis, collection of illustrative plates are similar to Example 1, no longer list;
(b) in the matrix hyper-branched polyester of preparing in step (a), add lipid acid, the residue 0.15g acid catalyst vitriol oil and 6g reflux solvent dimethylbenzene at N
2protect lower 180 ℃ of back flow reaction to acid number to obtain fatty acid modified hyper-branched polyester (HBP-8-1) lower than 15mgKOH/g;
(c) in the fatty acid modified hyper-branched polyester of preparing in step (b), add caprolactone, organotin catalysts, in 190 ℃ of N
2under protective atmosphere, react 2h, then distillation removes organic solvent and obtains caprolactone modification hyper-branched polyester (HBP-8-2), and its general structural formula as shown in Figure 8 (b) shows.
3, performance
Viscosity 12500cp under product (HBP-8-2) normal temperature; The degree of branching: DB
frechet0.47, DB
frey0.41; Molecular weight: 1900; Solvability: as vinyl acetic monomer, N-BUTYL ACETATE, aromatic hydrocarbons is as toluene, dimethylbenzene with ester class, ketone as acetone, butanone can be miscible.Hyperbranched Polyester Resin is a kind of from essence or Synolac, and conventional Synolac is made into 70% solid content conventionally, and under normal temperature, viscosity is 10
5the mPas order of magnitude.Chain-like structure than conventional Synolac, under the cause normal temperature of matrix hyper-branched polyester due to great amount of hydroxy group formation hydrogen bond itself, be solid-state, consume after modification and between part hydrogen bond and molecule, have benefited from three-dimensional globosity and be not easy again chain entanglement, thereby viscosity meeting is little a lot, this is also the advantage of Hyperbranched Polyester Resin maximum.The resin viscosity that can see 100% solid content in this example only has 12500mPas, and this is very beneficial for us and makes highly filled even solventless coatings.
4, coating and performance
(1) preparation of coating: get the above-mentioned product of 50g (HBP-8-2), then add 0.5g BYK323 flow agent, 0.5gDefom5300 defoamer, 60g Bayer IL1451 solidifying agent, after 10g trimethylbenzene is uniformly dispersed, on tinplate sheet and plank, film respectively.
(2) measure film performance: 91 ° of glossiness, pencil hardness 2B, shock-resistance 50cm, snappiness 1mm, 2 grades of sticking power.
1, raw material is prepared
Polyvalent alcohol: ditrimethylolpropane 12.5g(0.05mol); Dihydroxymethyl alkyl carboxylic acid: dimethylol propionic acid 80.4g(0.6mol); Lipid acid: capric acid 86g(0.5mol); Caprolactone: 34.2g(0.3mol); An acidic catalyst: vitriol oil 0.89g; Organotin catalysts: sub-stannous octoate 0.025g; Reflux solvent: dimethylbenzene 22g.
2, preparation
(a) agitator, thermometer, water cooling phlegma water trap, N are being housed
2in the four-hole boiling flask of entrance, add polyvalent alcohol, 26.8g dihydroxymethyl alkyl carboxylic acid, the 0.15g acid catalyst vitriol oil and 4g dimethylbenzene, at 140 ℃ of N
2protect lower reaction until do not have water to distillate, being then gradually raised to 180 ℃ reacts to acid number lower than 20mgKOH/g; Continue to add residue dihydroxymethyl alkyl carboxylic acid, the 0.3g acid catalyst vitriol oil and 8g reflux solvent dimethylbenzene, at 140 ℃ of N
2the lower reaction of protection is not until have water to distillate, then being gradually raised to 180 ℃ reacts to acid number and obtains matrix hyper-branched polyester (HBP-9-0) lower than 20mgKOH/g, its general structural formula is as shown in Fig. 9 (a), and concrete structural analysis, collection of illustrative plates are similar to Example 1, no longer list;
(b) in the matrix hyper-branched polyester of preparing in step (a), add capric acid 86g, the residue 0.44g acid catalyst vitriol oil and 10g reflux solvent dimethylbenzene at N
2protect lower 180 ℃ of back flow reaction to acid number to obtain fatty acid modified hyper-branched polyester (HBP-9-1) lower than 15mgKOH/g;
(c) in the fatty acid modified hyper-branched polyester of preparing in step (b), add caprolactone, organotin catalysts, in 170 ℃ of N
2under protective atmosphere, react 1.5h, then distillation removes organic solvent and obtains caprolactone modification hyper-branched polyester (HBP-9-2), and its general structural formula as shown in Figure 9 (b).
3, performance
Under product (HBP-9-2) normal temperature, viscosity is 5500cp; The degree of branching: D
bFrechet0.44, D
bFrey0.38; Molecular weight: 4000; Solvability: as vinyl acetic monomer, N-BUTYL ACETATE, aromatic hydrocarbons is as toluene, dimethylbenzene with ester class, ketone as acetone, butanone can be miscible.Hyperbranched Polyester Resin is a kind of from essence or Synolac, and conventional Synolac is made into 70% solid content conventionally, and under normal temperature, viscosity is 10
5the mPas order of magnitude.Chain-like structure than conventional Synolac, under the cause normal temperature of matrix hyper-branched polyester due to great amount of hydroxy group formation hydrogen bond itself, be solid-state, consume after modification and between part hydrogen bond and molecule, have benefited from three-dimensional globosity and be not easy again chain entanglement, thereby viscosity meeting is little a lot, this is also the advantage of Hyperbranched Polyester Resin maximum.The resin viscosity that can see 100% solid content in this example only has 5500mPas, and this is very beneficial for us and makes highly filled even solventless coatings.
4, coating and performance
(1) preparation of coating: get the above-mentioned product of 50g (HBP-9-2), then add 0.5g BYK358N flow agent, 0.5gAC270 defoamer, 30g Bayer L75 solidifying agent after 10g ritalin is uniformly dispersed, is filmed respectively on tinplate sheet and plank.
(2) film performance: 91 ° of glossiness, pencil hardness 2B, shock-resistance 50cm, snappiness 1mm, 2 grades of sticking power.
Claims (8)
1. a preparation method for caprolactone modification hyper-branched polyester, is characterized in that comprising the steps:
(1), by molfraction, 1 part of polyvalent alcohol and 2～4 parts of dihydroxymethyl alkyl carboxylic acids are mixed, and add the reflux solvent of dihydroxymethyl alkyl carboxylic acid weight 0.1%～1% acid catalyst and 8%～15% in 140～230 ℃ of N
2under protection, react to acid number lower than 20mgKOH/g; Continue to add 4～8 parts of dihydroxymethyl alkyl carboxylic acids, and add 0.1%～1% acid catalyst of dihydroxymethyl alkyl carboxylic acid weight and 8%～15% reflux solvent, in 140～230 ℃ of N
2under protection, react to acid number and obtain matrix hyper-branched polyester lower than 20mgKOH/g;
(2), by molfraction, in the matrix hyper-branched polyester of preparing in step (1), add 2～4 parts of lipid acid, and add 0.1%～1% acid catalyst of fatty acid wt and 8%～15% reflux solvent, at N
2protect lower 140～240 ℃ of back flow reaction to acid number to obtain fatty acid modified hyper-branched polyester lower than 15mgKOH/g;
(3) in the fatty acid modified hyper-branched polyester of preparing in step (2), add caprolactone and organotin catalysts, in 130～230 ℃ at N
2the lower reaction 1～10h of protection, then distillation removes organic solvent and obtains caprolactone modification hyper-branched polyester; The consumption of described organotin catalysts is 0.01%～0.1% of caprolactone weight; The mol ratio of polyvalent alcohol and caprolactone is 1:6～10;
Described polyvalent alcohol is one or more in ethyl butyl propanediol, neopentyl glycol, BDO, Ymer N120, TriMethylolPropane(TMP), tetramethylolmethane, ditrimethylolpropane, polycaprolactone dibasic alcohol, polycaprolactone tetravalent alcohol;
Described dihydroxymethyl alkyl carboxylic acid is dimethylol propionic acid and/or dimethylolpropionic acid;
Described acid catalyst is one or more in tosic acid, the vitriol oil and Hypophosporous Acid, 50;
Described lipid acid is one or more in lauric acid, sad, capric acid, palmitinic acid, oleic acid, stearic acid and eicosanoic acid;
Described organotin catalysts is dibutyl tin laurate or stannous octoate;
Described reflux solvent is dimethylbenzene or toluene.
2. the preparation method of caprolactone modification hyper-branched polyester according to claim 1, is characterized in that: the consumption of described organotin catalysts is 0.05%～0.08% of caprolactone weight.
3. the preparation method of caprolactone modification hyper-branched polyester according to claim 1, is characterized in that: in step (1), the temperature of two reactions is all 140～180 ℃.
4. the preparation method of caprolactone modification hyper-branched polyester according to claim 1, is characterized in that: the temperature of reaction in step (2) is 180～200 ℃.
5. the preparation method of caprolactone modification hyper-branched polyester according to claim 1, is characterized in that: the temperature of reaction in step (3) is 160～190 ℃.
6. the preparation method of caprolactone modification hyper-branched polyester according to claim 1, is characterized in that: the reaction times in step (3) is 1～2h.
7. a caprolactone modification hyper-branched polyester, is characterized in that: it is prepared by method described in claim 1-6 any one, and the degree of branching of this hyper-branched polyester is 0.4～0.6, and under normal temperature, viscosity is 2000～15000cp.
8. a coating, is characterized in that: this coating contains caprolactone modification hyper-branched polyester claimed in claim 7 and polyurethane curing agent; The amount of substance of the NCO group in polyurethane curing agent is 1.0～1.8 times of amount of substance of described caprolactone modification hyper-branched polyester OH group; Described polyurethane curing agent is one or more in toluene diisocyanate trimer, tolylene diisocyanate/TriMethylolPropane(TMP) affixture and hexamethylene diisocyanate trimer.
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| CN113736075B (en) * | 2021-08-31 | 2022-06-24 | 深圳大学 | Preparation method of polylactone |
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| CN115677997A (en) * | 2022-11-02 | 2023-02-03 | 华南理工大学 | Low-viscosity UV (ultraviolet) photocuring hyperbranched polyester acrylate resin as well as preparation method and application thereof |
| CN116655374A (en) * | 2023-06-28 | 2023-08-29 | 深圳新致美精密齿研有限公司 | High solid-phase zirconia ceramic slurry and preparation method and application thereof |
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