CN1117785C - Process for synthesizing aromatic aliphatic superbranched polyester - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 18
- 229920000728 polyester Polymers 0.000 title claims description 13
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 239000002253 acid Substances 0.000 claims abstract description 11
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 18
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004246 zinc acetate Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000013557 residual solvent Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000010189 synthetic method Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- DEVNRZWPTRSOBN-UHFFFAOYSA-N CCOC1=C(C=C(C=C1O)O)C#N Chemical compound CCOC1=C(C=C(C=C1O)O)C#N DEVNRZWPTRSOBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 238000005057 refrigeration Methods 0.000 claims description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 abstract description 44
- 238000005886 esterification reaction Methods 0.000 abstract description 13
- 229920000587 hyperbranched polymer Polymers 0.000 abstract description 13
- 239000000178 monomer Substances 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 8
- -1 3, 5-dihydroxybenzoic acid ester Chemical class 0.000 abstract description 7
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- 238000006068 polycondensation reaction Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 125000003118 aryl group Chemical group 0.000 abstract description 5
- 230000009477 glass transition Effects 0.000 abstract description 2
- 229920006150 hyperbranched polyester Polymers 0.000 abstract description 2
- LFHYUORJDCHLPQ-UHFFFAOYSA-N propyl 3,5-dihydroxybenzoate Chemical compound CCCOC(=O)C1=CC(O)=CC(O)=C1 LFHYUORJDCHLPQ-UHFFFAOYSA-N 0.000 abstract 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- UYEMGAFJOZZIFP-UHFFFAOYSA-N alpha-resorcylic acid Natural products OC(=O)C1=CC(O)=CC(O)=C1 UYEMGAFJOZZIFP-UHFFFAOYSA-N 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- 239000001117 sulphuric acid Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- 230000032050 esterification Effects 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 230000007704 transition Effects 0.000 description 7
- SIEILFNCEFEENQ-UHFFFAOYSA-N dibromo-acetic acid Natural products OC(=O)C(Br)Br SIEILFNCEFEENQ-UHFFFAOYSA-N 0.000 description 6
- QPRUZWIMJNNVCA-UHFFFAOYSA-N C(CC)(=O)OCCC.OC=1C(=C(C#N)C=C(C1)O)OCC Chemical compound C(CC)(=O)OCCC.OC=1C(=C(C#N)C=C(C1)O)OCC QPRUZWIMJNNVCA-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 241000723353 Chrysanthemum Species 0.000 description 2
- 235000007516 Chrysanthemum Nutrition 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000006254 rheological additive Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- LTMJJNPVAMLQGV-PWNYCUMCSA-N (-)-(2R,3R)-2,3-dihydroxybutanamide Chemical compound C[C@@H](O)[C@@H](O)C(N)=O LTMJJNPVAMLQGV-PWNYCUMCSA-N 0.000 description 1
- DXTLCLWOCYLDHL-UHFFFAOYSA-N 2-ethoxybenzonitrile Chemical compound CCOC1=CC=CC=C1C#N DXTLCLWOCYLDHL-UHFFFAOYSA-N 0.000 description 1
- QBTDQJMLMVEUTQ-UHFFFAOYSA-N 3,5-diacetyloxybenzoic acid Chemical compound CC(=O)OC1=CC(OC(C)=O)=CC(C(O)=O)=C1 QBTDQJMLMVEUTQ-UHFFFAOYSA-N 0.000 description 1
- 101100189378 Caenorhabditis elegans pat-3 gene Proteins 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- CJQQHFJSKUJCAC-UHFFFAOYSA-N ethyl 2-ethoxy-3,5-dihydroxybenzoate Chemical compound CCOC1=C(C=C(C=C1O)O)C(=O)OCC CJQQHFJSKUJCAC-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- UUKXEGBKCPJYRR-UHFFFAOYSA-N methyl 2-ethoxy-3,5-dihydroxybenzoate Chemical compound CCOC1=C(C=C(C=C1O)O)C(=O)OC UUKXEGBKCPJYRR-UHFFFAOYSA-N 0.000 description 1
- QAYQKAPOTVSWLS-UHFFFAOYSA-N methyl 2-ethoxybenzoate Chemical compound CCOC1=CC=CC=C1C(=O)OC QAYQKAPOTVSWLS-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for synthesizing aromatic adipose hyperbranched polyester, which comprises: firstly, 3, 5-dihydroxyhenzoic acid is used as a raw material, and under the catalysis condition of concentrated sulphuric acid, the 3, 5-dihydroxyhenzoic acid carries out an esterification reaction with propyl alcohol so as to prepare 3, 5-dihydroxybenzoic acid propyl ester; then, through a normal pressure solution of 3, 5-dihydroxybenzoic acid ester and 2-chloroethanol, 3, 5-dihydroxybenzoic acid propyl ester of aromatic monomers is synthesized by reacting. The aromatic monomers with an AB2 type structure carry out a polycondensation reaction to obtain an aromatic hyperbranched polymer. Compared with the prior art, the polymer of the present invention has the advantages of great reduction of glass transition temperature and less decomposition temperature change, and the processing performance of the polymer is enhanced.
Description
The present invention relates to a kind of synthetic method of aromatic aliphatic superbranched polyester, belong to the functional high molecule material technical field.
Since the nineties, based on AB
nThe multi-functional monomeric highly-branched polymers of type (n 〉=2) is paid close attention to because of its particular structure and special performances have caused widely.Highly-branched polymers is divided into two classes again: adopt multistep processes synthetic branch-shape polymer (Dentrimer) and the synthetic hyperbranched polymer (Hyperbranchedpolymer) that obtains of single stage method step by step.Two base polymers all show good solubility, low body and soltion viscosity and special thermal characteristics.The preparation of branch-shape polymer must be adopted the process of the synthetic and purifying of multistep, and cost height, cycle are long, thereby have limited its industrial application.The hyperbranched polymer similar to its performance only needs the one-step polymerization reaction can be met the polymeric articles of application requiring usually, and commercial exploitation has good prospects, and can be applied to numerous areas such as rheology modifier, tackiness agent, coating and medicament slow release material.
Many building-up reactionss all can be used for the preparation of hyperbranched polymer, as polycondensation, addition polymerization, ring-opening polymerization etc.Main hyperbranched polymer comprises hyper-branched polyester, polyethers, urethane, polyetherketone etc.Wherein polyester product is subjected to paying close attention to widely because of its reliable monomer source and easy synthetic method.The monomeric species of lard type hyper-branched polyester is few, and the thermostability of its polymeric articles is relatively poor, and second-order transition temperature is low, thereby can't be used as structured material.By contrast, the fragrant hyperbranched polymer has high glass transition and fusing point, poor processability, thereby limited its application.Therefore, fragrant hyperbranched polymer and monomeric modification are become the effective way that realizes this type material widespread use.
Prepare the U.S. Pat 3 that the technology of highly branched non-crosslinked polyester appears at 1972 the earliest with multistep and single stage method, 669, in 939, this invention has been introduced and has been adopted polyhydric monocarboxylic acid melt phase polycondensation to prepare the process of hyperbranched polymer and the application in paint field thereof.U.S. Pat 4,857,630 describe in detail and how to adopt single stage method to prepare hyperbranched poly phenylene compound, and find that the special construction of this polymkeric substance can reduce the viscosity of polystyrene melt effectively.U.S. Pat 788,070 is by having (HOOC) n
1-Ar-(O-CO-alkyl) n
2(n
1=1, n
2=2 or n
1=2, n
2=1) monomer of general formula has synthesized the fragrant hyper-branched polyester, and this product second-order transition temperature and decomposition temperature are respectively 190 ℃ and 435+5 ℃, and processing difficulties, mechanical property are not good.U.S. Pat 5225,522 has been introduced a kind of method of synthetic aromatic ester type hyperbranched polymer, and this is invented with (HOOC) n
1-Ar-(OH) n
2(n
1=1, n
2=2 or n
1=2, n
2=1) is raw material, the first step is carried out the esterification of raw material, second step adopted oxyethane that esterification products is carried out alkoxylate under condition of high voltage, and then adopt chromatographic column that product is separated, obtain required monomer, the 3rd step synthesized the hyperbranched polymer of aromatic ester type by monomeric melt phase polycondensation.The esterification of this method, alkylated reaction and product separation process complexity need to adopt high-tension apparatus, cost height, danger bigger, are difficult for realizing industrialization.
The objective of the invention is to propose a kind of synthetic method of aromatic aliphatic superbranched polyester,, and reduce production costs with the super preparation technology of simplification aromatic aliphatic type with the change polyester.
The synthetic method of the aromatic aliphatic superbranched polyester that the present invention proposes may further comprise the steps:
1. according to mol ratio 1: 10～50 ratio, with 3,5-resorcylic acid (hereinafter to be referred as DBA) and anhydrous C
1-3Alkanol mixes, in said mixture, drip the catalyzer vitriol oil, the dripping quantity of the vitriol oil and the mol ratio of DBA are 1: 3～4, under the reflux temperature of alkanol, reacted 24～48 hours, and got yellow transparent solution, steam and remove residual solvent, add 2～3 times to the water of residual solvent amount, refrigeration obtains 3,5-resorcylic acid ester (C after placing a few hours
1-3) the product precipitation, to filter, oven dry obtains a kind of white solid thing;
2. above-mentioned white solid thing and chloroethanol are mixed mutually according to the ratio of mol ratio 1: 1.0～2.5, add mass ratio with above-mentioned white solid thing and be 1: 0.8～1.2 anhydrous K
2CO
3And with the mass ratio of above-mentioned white solid thing be 1: 0.01 KI, add with above-mentioned white solid thing mol ratio be in 1: 15～25 the solvent (solvent can adopt propyl alcohol, dimethyl formamide (being abbreviated as DMF) or dioxane), in 90～95 ℃, N
2Reacted under the gas shiled condition 24～48 hours, and obtained 3,5-dihydroxy ethoxy benzonitrile acid esters (C
1-3) reaction mixture.Remove residual solvent, adding acid for adjusting pH value is 1～2, with ether residuum is extracted, and steams and removes ether; Then residuum is carried out alkali cleaning, washing, obtain 3,5-dihydroxy ethoxy benzonitrile acid esters (C
1-3) crude product, after recrystallizing methanol, obtain the white solid thing;
3. white solid thing and the zinc acetate with above-mentioned second step joins in the reactor, and the mass ratio of adding is 1: 0.03～0.05, logical N
2Gas shiled is heated to 175～195 ℃ with reaction system, reacts 1～3 hour, keeps temperature-resistant, is lower than in vacuum tightness to continue reaction 2～5 hours under the condition of 5mmHg, obtains the light yellow solid polymkeric substance, and productive rate is 85～96%, is product of the present invention.
The present invention is with 3, and the 5-resorcylic acid is a raw material, by the esterification of raw material and the alkoxylation of esterification products and chloroethanol, has synthesized a kind of new aromatic AB that contains aliphatic chain
2The type monomer:
Wherein, R is the alkyl that has 1～3 carbon atom.
Further, pass through AB
2The monomeric melt polycondensation reaction of type can obtain novel aromatic aliphatic superbranched polymkeric substance.Compare the second-order transition temperature T of institute's synthetic polymer with the similar fragrant hyperbranched polymer of fatty chain not
gSignificantly reduced, and decomposition temperature T
dChange little.Characteristics of the present invention are: at first adopt simple and easy to do normal pressure solution reaction to realize that the alkoxylation of DBA esterification products and product thereof separate, greatly simplified the operation of alkylated reaction, reduced synthetic and isolating cost; Secondly in fragrant hyperbranched poly ester structure, successfully introduce fatty segment, reduced the T of product
gObtained having the novel hyperbranched aromatic aliphatic type polyester of good mechanical processing characteristics.
At first, in order to prevent the reaction of carboxyl and chloroethanol, need carry out protection to carboxyl by esterification.Can adopt G
1-4The straight chain alkanol, as methyl alcohol, ethanol, propyl alcohol and butanols, preferentially select propyl alcohol, hydroxyl is protected.Esterification by methyl alcohol, ethanol, propyl alcohol and DBA obtains corresponding esterification products with high yield.The present invention's second step alkylated reaction is to realize that by the esterification products of the first step and the reaction of chloroethanol reaction is carried out in solution, and the yield of this reaction generally about 30%, also can further participate in reaction after the unreacted MONOMER RECOVERY.The solvent that this step reaction can be adopted has propyl alcohol, DMF and dioxane etc., wherein with propyl alcohol for most preferably.Propyl alcohol is the good solvent of reactant and product, can guarantee suitable reaction temperature under its reflux temperature, removes by the mode of rotary evaporation easily again after reaction simultaneously.The side reaction of transesterify it should be noted that if the esterification products of the first step when being methyl esters or ethyl ester, when selecting for use propyl alcohol to be solvent, can take place.The 3rd step was the AB that at high temperature carries out
2The monomeric melt polycondensation reaction of type synthesizes aromatic aliphatic superbranched polymkeric substance.Reaction is to carry out under catalyst for esterification reaction (as the zinc acetate) catalytic condition in routine, under the condition of molten monomer, the temperature of polyreaction is not had strict especially restriction.For the carrying out that guarantees to react, the reaction later stage needs system is vacuumized processing, and reaction can directly obtain product after finishing, and yield is more than 85%.
The polyreaction formula is as follows:
Wherein R is the alkyl that has 1-3 carbon atom.
With in the prior art with 3,5 diacetoxy phenylformic acid are that the similar fragrant hyperbranched polymer of not fatty segmental that raw material synthesizes is compared (its second-order transition temperature and decomposition temperature are respectively 190 ℃ and 435 ± 5 ℃), the second-order transition temperature of the aromatic aliphatic superbranched polymeric articles that the present invention is prepared is respectively 58 ℃ and 398 ℃, second-order transition temperature has reduced about 130 ℃, and decomposition temperature has only reduced by 30～40 ℃, changes little.This explanation changes the structure of polymkeric substance by introduce short fatty segment in polymkeric substance, can improve the processing characteristics of polymkeric substance effectively.Institute of the present invention synthetic polymkeric substance can be applied to process rheology modifier, blending compatilizer etc.Below by embodiment technology of the present invention is given to illustrate further.
Embodiment 1:
With 30g3,5-resorcylic acid (DBA) and the anhydrous propyl alcohol of 400ml join in the there-necked flask of 500ml, add zeolite, be heated to backflow, when 3, after 5-resorcylic acid solid all dissolves, drip the 15ml vitriol oil with dropping funnel, back flow reaction 24 hours gets yellow transparent solution.Steam to remove propyl alcohol with Rotary Evaporators, about 100ml heavy-gravity liquid, add 700ml water, placed refrigerating chamber 10 hours, have the crystal of a large amount of chrysanthemum shapes to separate out in the solution, suction filtration dry the 30.3g white solid, fusing point is 104～108 ℃, productive rate is 80.2%.H
1-NMR spectrogram result (ppm) is as follows: 0.9 (3H), and 1.75 (2H), 4.1 (2H), 6.8 (1H), 7.05 (2H), 9.5 (2H, OH).
With the above-mentioned white solid 3 of 10g, 5-resorcylic acid propyl ester, 150ml propyl alcohol, 7.4ml2-chloroethanol, 20gK
2CO
3And a spot of KI joins in the four-hole bottle.Heating, stirring, logical N
2Gas shiled, reaction is 24 hours under 92 ℃ of conditions.Rotary evaporation is removed propyl alcohol, obtains brown heavy-gravity liquid, the pH value is transferred to strongly-acid after adding water, has oily matter to generate in the liquid, use extracted with diethyl ether, except that ether gets brown xanchromatic viscous liquid.Gained liquid is again through alkali cleaning, and place the washing back, and residuum becomes light yellow waxy solid.Gained solid recrystallization in methyl alcohol obtains white solid 4.34g, is 3,5-dihydroxy ethoxy benzonitrile propyl propionate, and its fusing point is 91～94 ℃, productive rate is 30.0%.H
1-NMR spectrogram result (ppm) is as follows: 0.9 (3H), and 1.75 (2H), 4.1 (2H), 3.75 (4H), 4.0 (4H), 4.92 (2H, OH), 6.8 (1H), 7.05 (2H)
With 2g3,5-dihydroxy ethoxy benzonitrile propyl propionate and a spot of zinc acetate join in the polymerization reactor, logical N
2Gas shiled is heated to 175 ℃ with system, reacts 1.5 hours, keeps temperature-resistant, is lower than in vacuum tightness to continue reaction 3.5 hours under the condition of 2mmHg, finally obtains light yellow solid polymkeric substance 1.50g.Productive rate is 95.4%.Polymkeric substance proton magnetic spectrum figure belongs to CH at the 1.0ppm place
3The hydrogen atom peak obviously disappear, other each peak-to-peak position is similar to the monomer spectrogram, each peak relatively flat proves that polyreaction has removed propyl alcohol.The second-order transition temperature that is recorded polymkeric substance by differential scanning calorimeter (DSC) is 58 ℃, and the heat decomposition temperature that is recorded polymkeric substance by thermal gravimetric analyzer (TGA) is 398 ℃, and the intrinsic viscosity of polymkeric substance in DMF is η
LnhBe 0.40dL/g.
Embodiment 2:
With 30g3,5-resorcylic acid (DBA) and the anhydrous propyl alcohol of 400ml join in the there-necked flask of 500ml, add zeolite, be heated to backflow, when 3, after 5-resorcylic acid solid all dissolves, drip the 15ml vitriol oil with dropping funnel, back flow reaction 48 hours gets yellow transparent solution.Steam except that propyl alcohol with Rotary Evaporators, get about 100ml heavy-gravity liquid, add 700ml water, placed refrigerating chamber 10 hours, and had the crystal of a large amount of chrysanthemum shapes to separate out in the solution, suction filtration dry 30.7g white solid 3,5-resorcylic acid propyl ester, fusing point are 104～107 ℃, and productive rate is 81.3%.
With 10g3,5-resorcylic acid propyl ester, 150ml propyl alcohol, 7.4ml2-chloroethanol, 20gK
2CO
3And a spot of KI joins in the four-hole bottle.Heating, stirring, logical N
2Gas shiled, reaction is 24 hours under 92 ℃ of conditions.Rotary evaporation is removed propyl alcohol, obtains brown heavy-gravity liquid, the pH value is transferred to strongly-acid after adding water, has oily matter to generate in the liquid, use extracted with diethyl ether, except that ether gets brown xanchromatic viscous liquid.Gained liquid is again through alkali cleaning, and place the washing back, and residuum becomes light yellow waxy solid.Gained solid recrystallization in methyl alcohol obtains white solid 3,5-dihydroxy ethoxy benzonitrile propyl propionate 4.14g, and fusing point is 91～94 ℃, productive rate is 28.6%.
With 2g3,5-dihydroxy ethoxy benzonitrile propyl propionate and a spot of zinc acetate join in the polymerization reactor, logical N
2Gas shiled is heated to 175 ℃ with system, reacts 1.5 hours, keeps temperature-resistant, is lower than in vacuum tightness to continue reaction 3.5 hours under the condition of 2mmHg, finally obtains light yellow solid polymkeric substance 1.49g.Productive rate is 94.7%.
Embodiment 3:
Adopt the condition identical with embodiment 2 to synthesize 3,5-resorcylic acid propyl ester must white solid 3,5-resorcylic acid propyl ester 30.5g, and fusing point is 104～107 ℃, productive rate is 80.7%.
With 10g3,5-resorcylic acid propyl ester, 150ml propyl alcohol, 11.1ml2-chloroethanol, 20gK
2CO
3And a spot of KI joins in the four-hole bottle.Heating, stirring, logical N
2Gas shiled, reaction is 24 hours under 92 ℃ of conditions.Rotary evaporation is removed propyl alcohol, obtains brown heavy-gravity liquid, the pH value is transferred to strongly-acid after adding water, has oily matter to generate in the liquid, use extracted with diethyl ether, except that ether gets brown xanchromatic viscous liquid.Gained liquid is again through alkali cleaning, and place the washing back, and residuum becomes light yellow waxy solid through the long period.Gained solid recrystallization in methyl alcohol obtains white solid 4.2g, and fusing point is 91～94 ℃, and productive rate is 29.0%.
With 2g3,5-dihydroxy ethoxy benzonitrile propyl propionate and a spot of zinc acetate join in the polymerization reactor, logical N
2Gas shiled is heated to 175 ℃ with system, reacts 1.5 hours, keeps temperature-resistant, is lower than in vacuum tightness to continue reaction 3.5 hours under the condition of 2mmHg, finally obtains light yellow solid polymkeric substance 1.49g.Productive rate is 94.7%.
Embodiment 4:
Adopt the condition identical with embodiment 2 to synthesize 3,5-resorcylic acid propyl ester must white solid 30.5g, and fusing point is 104～107 ℃, and productive rate is 80.7%.
Adopt the condition identical with embodiment 3 to synthesize 3,5 dihydroxy ethoxy benzonitrile propyl propionate products, obtain white solid 4.1g, fusing point is 91～94 ℃, and productive rate is 28.3%
With 2g3,5-dihydroxy ethoxy benzonitrile propyl propionate and a spot of zinc acetate join in the polymerization reactor, logical N
2Gas shiled is heated to 190 ℃ with system, reacts 1.5 hours, keeps temperature-resistant, is lower than in vacuum tightness to continue reaction 3.5 hours under the condition of 2mmHg, finally obtains light yellow solid polymkeric substance 1.48g.Productive rate is 94.1%.
Embodiment 5:
Adopt the condition identical with embodiment 2 to synthesize 3,5-resorcylic acid propyl ester must white solid 30.5g, and fusing point is 104～107 ℃, and productive rate is 80.7%.
Adopt the condition identical with embodiment 3 to synthesize 3,5 dihydroxy ethoxy benzonitrile propyl propionate products, obtain white solid 4.1g, fusing point is 91～94 ℃, and productive rate is 28.3%
With 2g3,5-dihydroxy ethoxy benzonitrile propyl propionate and a spot of zinc acetate join in the polymerization reactor, logical N
2Gas shiled is heated to 190 ℃ with system, reacts 1.5 hours, keeps temperature-resistant, continues reaction 3.5 hours under the condition of vacuum tightness at 2～5mmHg, finally obtains light yellow solid polymkeric substance 1.39g.Productive rate is 88.4%.
Embodiment 6:
With the methyl alcohol substituted propanol, adopt method and the feed ratio identical to make 3, the 5-methyl dihydroxy benzoate with embodiment 1.Product is a white solid, and 168～170 ℃ of fusing points, productive rate are 80.3%.H
1-NMR spectrogram result (ppm) is as follows: 3.9 (3H), and 6.41 (1H), 6.9 (2H), 9.6 (2H, OH).
With the DMF substituted propanol, adopt method and the feed ratio identical to make 3,5-dihydroxy ethoxy-benzoic acid methyl ester product, productive rate 15% with embodiment 1.
Adopt method and the feed ratio identical with embodiment 4 to carry out 3, the melt polymerization of 5-dihydroxy ethoxy-benzoic acid methyl ester obtains light yellow polymer solids 1.45g, and productive rate is 87.7%.
Embodiment 7:
With the ethanol substituted propanol, adopt method and the feed ratio identical to make 3, the 5-methyl dihydroxy benzoate with embodiment 1.Product is a white solid, and 116～118 ℃ of fusing points, productive rate are 81.4%.H
1-NMR spectrogram result (ppm) is as follows: 1.15 (3H), and 4.12 (2H), 6.42 (1H), 6.91 (2H), 9.5 (2H, OH).
With the DMF substituted propanol, adopt method and the feed ratio identical to make 3,5-dihydroxy ethoxybenzoic acid ethyl ester product, productive rate 17% with embodiment 1.
Adopt method and the feed ratio identical with embodiment 4 to carry out 3, the melt polymerization of 5-dihydroxy ethoxy benzonitrile acetoacetic ester obtains light yellow polymer solids 1.4g, and productive rate is 86.5%.
Claims (1)
1, a kind of synthetic method of aromatic aliphatic superbranched polyester is characterized in that, this method may further comprise the steps:
(1) according to mol ratio be 1: 10～50 ratio, with 3, the 5-resorcylic acid is hereinafter to be referred as DBA and anhydrous C
1-3Alkanol mixes, in said mixture, drip the catalyzer vitriol oil, the dripping quantity of the vitriol oil and the mol ratio of DBA are 1: 3～4, under the reflux temperature of alkanol, reacted 24～48 hours, and got yellow transparent solution, steam and remove residual solvent, add 2～3 times to the water of residual solvent amount, refrigeration obtains 3,5-resorcylic acid ester C after placing a few hours
1-3The product precipitation is filtered, and oven dry obtains a kind of white solid thing;
(2) above-mentioned white solid thing and chloroethanol are mixed mutually according to the ratio of mol ratio 1: 1.0～2.5, add mass ratio with above-mentioned white solid thing and be 1: 0.8～1.2 anhydrous K
2CO
3And with the mass ratio of above-mentioned white solid thing be 1: 0.01 KI, add with above-mentioned white solid thing mol ratio be in 1: 15～25 the solvent, in 90～95 ℃, N
2Reacted under the gas shiled condition 24～48 hours, and obtained 3,5-dihydroxy ethoxy benzonitrile acid esters C
1-3Reaction mixture, remove residual solvent, adding acid for adjusting pH value is 1～2, with ether residuum is extracted, and steam to remove ether; Then residuum is carried out alkali cleaning, washing, obtain 3,5-dihydroxy ethoxy benzonitrile acid esters C
1-3Crude product, after recrystallizing methanol, obtain the white solid thing;
(3) white solid thing and the zinc acetate with above-mentioned second step joins in the reactor, and the mass ratio of adding is 1: 0.03～0.05, logical N
2Gas shiled is heated to 175～195 ℃ with reaction system, reacts 1～3 hour, keeps temperature-resistant, is lower than in vacuum tightness to continue reaction 2～5 hours under the condition of 5mmHg, obtains the light yellow solid polymkeric substance, is product of the present invention.
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