CN105131261A - Synthesis method of biomass-derived hydroxyl telechelic polyester - Google Patents
Synthesis method of biomass-derived hydroxyl telechelic polyester Download PDFInfo
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- CN105131261A CN105131261A CN201510617545.1A CN201510617545A CN105131261A CN 105131261 A CN105131261 A CN 105131261A CN 201510617545 A CN201510617545 A CN 201510617545A CN 105131261 A CN105131261 A CN 105131261A
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- 229920000728 polyester Polymers 0.000 title claims abstract description 51
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 41
- 239000002028 Biomass Substances 0.000 title claims abstract description 29
- 238000001308 synthesis method Methods 0.000 title abstract 2
- 239000002253 acid Substances 0.000 claims abstract description 65
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000005886 esterification reaction Methods 0.000 claims abstract description 31
- 230000032050 esterification Effects 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 102
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 37
- 238000006068 polycondensation reaction Methods 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 17
- 238000010189 synthetic method Methods 0.000 claims description 15
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 10
- 235000011150 stannous chloride Nutrition 0.000 claims description 10
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 8
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 7
- 150000001263 acyl chlorides Chemical class 0.000 claims description 7
- 235000014655 lactic acid Nutrition 0.000 claims description 7
- 239000004310 lactic acid Substances 0.000 claims description 7
- 150000007520 diprotic acids Chemical class 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- -1 methylene-succinic acid acyl chlorides Chemical class 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 3
- 239000001639 calcium acetate Substances 0.000 claims description 3
- 235000011092 calcium acetate Nutrition 0.000 claims description 3
- 229960005147 calcium acetate Drugs 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 claims description 3
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000012643 polycondensation polymerization Methods 0.000 abstract 3
- 238000009833 condensation Methods 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 34
- 238000009835 boiling Methods 0.000 description 12
- 238000010792 warming Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 208000005156 Dehydration Diseases 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920004935 Trevira® Polymers 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- FMOKRXOFRDXQDW-UHFFFAOYSA-N dioctyl benzene-1,2-dicarboxylate 2-methylidenebutanedioic acid Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C(C(=C)CC(=O)O)(=O)O FMOKRXOFRDXQDW-UHFFFAOYSA-N 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a synthesis method of biomass-derived hydroxyl telechelic polyester. The method comprises the steps: performing esterification reaction on acid and alcohol, then performing multi-segment condensation polymerization to finally obtain a polyester product, wherein in the condensation process, esterification reaction is performed firstly, and then acid and alcohol are alternately added to perform condensation polymerization. The molar ratio of alcohol to acid in the whole process is 0.9-1.5. Raw materials used in the invention are biomass-derived, can be regenerated for esterification and multi-segment condensation polymerization, and finally, the polyester product with a controllable acid value and hydroxyl value can be finally obtained.
Description
Technical field
The invention belongs to polyester synthesis field, be specifically related to a kind of synthetic method of hydroxyl telechelic polyester of biomass source.
Background technology
Polyester is the polymkeric substance general name obtained by polyvalent alcohol and polyprotonic acid polycondensation, high molecular weight polyesters is a class excellent performance, broad-spectrum engineering plastics, and such as terephthalic acid (PTA) and ethylene glycol (EG) produce polyethylene terephthalate (PET) through polycondensation.Low molecular weight hydroxy-terminated polyester can be used for PAUR coating, PAUR is the resin that preparation coating uses the earliest, diprotic acid used has hexanodioic acid, phthalic anhydride, m-phthalic acid, terephthalic acid etc., polyvalent alcohol mainly adopts TriMethylolPropane(TMP), neopentyl glycol, diethylene glycol, 1,3 butylene glycol etc.The major part used in the synthesis of present polyester for the non-renewable resource such as oil, coal and the alcohol obtained and acid, also has some patent parts to employ the product of biomass source, the non-renewable chemical of Some substitute.Main raw material of the present invention is chemical that is reproducible, biomass source.Methylene-succinic acid can be obtained by fermenting process, and it is by hydrogenation process, and also can obtain saturated diprotic acid pyrovinic acid, pyrovinic acid esterification back end hydrogenation, also can obtain methyl isophthalic acid, 4-butyleneglycol.Ethylene glycol also can be obtained through special reaction process by raw materials such as glycerine, sugar alcohol and Mierocrystalline celluloses.Adopt the raw material of biomass source, the dependence to petroleum chemicals can be reduced, reduce the discharge of carbonic acid gas, belong to clean, the cutting edge technology of environmental protection.。
Summary of the invention
For present utilization of resources situation, the Nonrenewable energy resources such as oil, coal face exhausted problem, the present invention proposes the synthetic method using the diprotic acid of biomass source or polyprotonic acid, dibasic alcohol or polyvalent alcohol to prepare hydroxyl telechelic polyester material, prepare a kind of hydroxyl value and the controlled polyester of acid number, its main raw material used is the renewable product of biomass source.
The synthetic method of the hydroxyl telechelic polyester of a kind of biomass source of the present invention, be first carry out esterification by acid and alcohol, then carry out multistage polycondensation, in polycondensation process, first carry out esterification, alternately add again acid and alcohol carry out polycondensation, finally obtain polyester product; Whole reaction molar ratio of alcohol to acid is 0.9-1.5.
Further, described acid is biomass source, reproducible diprotic acid or polyprotonic acid and acyl chlorides product, anhydride product or dimethyl ester; Described alcohol is biomass source, reproducible dibasic alcohol or polyvalent alcohol.
Further, described acid is methylene-succinic acid, methylene-succinic acid acyl chlorides, itaconic anhydride, dimethyl itaconate, lactic acid or pyrovinic acid.
Further, described alcohol is 1,3-PD, glycerol, ethylene glycol or methyl isophthalic acid, 4-butyleneglycol.
Further, the quality of material added in described esterification is the 60-95% of material total mass, and molar ratio of alcohol to acid is 0.8-1.3; In described polycondensation, remaining alcohol and acid are divided into 1-10 part, 10-30min of being separated by alternately joins in system.
Further, described esterification reaction temperature is 100-200 DEG C, and pressure is 0-0.13MPa, and the reaction times is 4-10h.
Further, described polycondensation temperature is 150-240 DEG C, and pressure is 0-0.13MPa, and the reaction times is 4-6h.
Further, described esterification and polycondensation process use or do not use catalyzer, and described catalyzer is zinc acetate, calcium acetate, cobalt chloride, tin protochloride or tetrabutyl titanate, and catalyst levels is the 0-5% of material total mass.
Further, the number-average molecular weight of described polyester product is 300-5000, and molecular weight distribution is 1-5, and hydroxyl value is 2-200mgKOH/g, and acid number is 0-80mgKOH/g.
Compared with prior art, advantage of the present invention and positively effect are: raw material used in the present invention is reproducible chemical, obtained by the after chemical reactions such as agricultural waste material, starch and glucose and biological respinse, instead of non-renewable chemical, production process is pollution-free, is the developing direction of following chemical field; Adopt esterification and multistage polycondensation, realize the control of hydroxyl value and acid number.
Embodiment
In order to better implement the present invention, by following examples, the present invention will be further described but be not limited to these embodiments, according to content of the present invention nonessential improvement and adjustment more made for the present invention, still belongs to scope.
The invention discloses a kind of synthetic method of hydroxyl telechelic polyester of biomass source, the raw material of use is all biomass source, renewable, environmental protection.The present invention adopts multistage polycondensation in building-up process, by adding alcohol and acid repeatedly, respectively, hydroxyl and carboxyl are reacted when replacing excessive, instead of hydroxyl being excessive state, and reacting balance is carried out always, reaching acid number and hydroxyl value control.Meanwhile, alcohol and acid alternately add, and the concentration of reactive group can be made to maintain certain level, realize the control of forward and inverse reaction, to obtain the polyester of certain hydroxyl value and acid number.
A kind of synthetic method of hydroxyl telechelic polyester of biomass source, first carry out esterification by acid and alcohol, carry out multistage polycondensation again, first pre-reaction is carried out in polycondensation process, after the reaction of most of reactive group, more alternately add acid and alcohol carries out polycondensation, both ratios in reaction process are adjusted, make polycondensation more complete, the final polyester product obtaining anticipation; Whole reaction acid-alcohol ratio is 0.9-1.5.
The inventory that described esterification reaction process adds is the 60-95% of total mass, and molar ratio of alcohol to acid is 0.8-1.3, and esterification reaction temperature is 100-200 DEG C, and pressure is 0-0.13MPa (absolute pressure), and the reaction times is 4-10h.
The alcohol added in described polycondensation process and acid can be divided into 1-10 part, namely acid and alcohol alternately add 1-10 time respectively, and 10-30min of being separated by alternately joins in system, and polycondensation temperature is 150-240 DEG C, pressure is 0-0.13MPa (absolute pressure), and the reaction times is 4-6h.
Described esterification and polycondensation process use or do not use catalyzer, and described catalyzer is zinc acetate, calcium acetate, cobalt chloride, tin protochloride or tetrabutyl titanate, and catalyst levels is the 0.1-5% of material total mass.
Described acid is biomass source, reproducible diprotic acid or polyprotonic acid and corresponding acyl chlorides product, anhydride product or dimethyl ester, as methylene-succinic acid, methylene-succinic acid acyl chlorides, itaconic anhydride, dimethyl itaconate, lactic acid or pyrovinic acid etc., can composite use or be used alone.
Described alcohol is biomass source, reproducible dibasic alcohol or polyvalent alcohol, and as 1,3-PD, glycerol, ethylene glycol, methyl isophthalic acid, 4-butyleneglycol etc., can composite use or be used alone.
The number-average molecular weight of described polyester product is 300-5000, and molecular weight distribution is 1-5, and hydroxyl value is 2-200mgKOH/g, and acid number is 0-80mgKOH/g.Polyester product prepared by present method can realize the controllability of hydroxyl value and acid number, reasonably arranges production according to different product requirements.Due to reaction process, especially the reactive group ratio of later stage polycondensation process controls, and the molecular weight distribution of polyester is narrower, has active influence to its application performance of lifting.In reaction process, especially in polycondensation process, the operational condition such as acid-alcohol ratio, feed postition, temperature of reaction has larger impact to product performance.When using acid anhydrides to replace carboxylic acid, because its activity is higher, acid number is relatively low.
High molecular weight polyesters can be used as excellent performance, broad-spectrum engineering plastics, also can be made into trevira and polyester film; Lower molecular weight gathers hydroxyl telechelic polyester can film forming common with isocyanates solidifying agent, the coating that processability is excellent; Unsaturated polyester can under the effect of initiator independent film forming, be widely used in coating.
Embodiment 1
In the 250ml four-hole boiling flask that agitator, thermometer are housed, add methylene-succinic acid 65 grams, ethylene glycol 32 grams, tin protochloride 0.1 gram, in the oil bath pan of 100 DEG C, carry out esterification 6 hours.Remove agitator, access vacuum system, control vacuum tightness is 0.1MPa, be warming up to 180 DEG C and carry out polycondensation 3 hours, add 6 grams of methylene-succinic acids, after half an hour, add 3 grams of ethylene glycol again, reaction half an hour after cooling discharge, the polyester hydroxyl value obtained is 82.1mgKOH/g, and acid number is 25mgKOH/g.
Embodiment 2
In the 250ml four-hole boiling flask that agitator, thermometer are housed, add pyrovinic acid 66 grams, 1,3-PD 38 grams, tin protochloride 0.1 gram, in the oil bath pan of 200 DEG C, carry out esterification 6 hours.Remove agitator, connect vacuum system, control vacuum tightness is 0.1MPa, be warming up to 240 DEG C and carry out polycondensation 3 hours, add 6 grams of pyrovinic acids, after half an hour, add 3 gram 1 again, ammediol, reaction half an hour after cooling discharge, the polyester hydroxyl value obtained is 75.2mgKOH/g, and acid number is 12mgKOH/g.
Embodiment 3
In the 250ml four-hole boiling flask that agitator, thermometer are housed, add methylene-succinic acid 65 grams, glycerol 47 grams, tin protochloride 0.1 gram, in the oil bath pan of 100 DEG C, carry out esterification 6 hours.Remove agitator, connect vacuum system, control vacuum tightness is 0.1MPa, be warming up to 150 DEG C and carry out polycondensation 3 hours, add 6 grams of methylene-succinic acids, after half an hour, add 3 grams of ethylene glycol again, reaction half an hour after cooling discharge, the polyester hydroxyl value obtained is 80mgKOH/g, and acid number is 13mgKOH/g.
Embodiment 4
In the 250ml four-hole boiling flask that agitator, thermometer are housed, add methylene-succinic acid 65 grams, lactic acid 10 grams, ethylene glycol 36 grams, tin protochloride 0.1 gram, in the oil bath pan of 150 DEG C, carry out esterification 6 hours.Remove agitator, connect vacuum system, control vacuum tightness is 0.1MPa, is warming up to 180 DEG C and carries out polycondensation 3 hours, add 6 grams of methylene-succinic acids, 3 grams of ethylene glycol are added again after half an hour, add 3 grams of methylene-succinic acids after half an hour, after half an hour, add 1.5 grams of ethylene glycol again, reaction half an hour after cooling discharge, the polyester hydroxyl value obtained is 18mgKOH/g, and acid number is 0.2mgKOH/g.
Embodiment 5
In the 250ml four-hole boiling flask that agitator, thermometer are housed, add methylene-succinic acid 65 grams, lactic acid 10 grams, ethylene glycol 36 grams, tin protochloride 0.1 gram, in the oil bath pan of 150 DEG C, carry out esterification 6 hours.Remove agitator, connect vacuum system, control vacuum tightness is 0.01MPa, is warming up to 180 DEG C and carries out polycondensation 3 hours, add 6 grams of methylene-succinic acids, 3 grams of ethylene glycol are added again after half an hour, add 3 grams of methylene-succinic acids after half an hour, after half an hour, add 1.5 grams of ethylene glycol again, reaction half an hour after cooling discharge, the polyester hydroxyl value obtained is 35.3mgKOH/g, and acid number is 78.2mgKOH/g.
Embodiment 6
In the 250ml four-hole boiling flask that thermometer is housed, add methylene-succinic acid 65 grams, lactic acid 10 grams, ethylene glycol 36 grams, tin protochloride 0.1 gram, connects vacuum system, and control vacuum tightness is 0.1MPa, in the oil bath pan of 150 DEG C, carry out esterification 6 hours.Be warming up to 180 DEG C and carry out polycondensation 3 hours, add 6 grams of methylene-succinic acids, 3 grams of ethylene glycol are added again after half an hour, 3 grams of methylene-succinic acids are added after half an hour, 1.5 grams of ethylene glycol are added again after half an hour, reaction half an hour after cooling discharge, the polyester hydroxyl value obtained is 25.3mgKOH/g, and acid number is 8.2mgKOH/g.
Embodiment 7
In the 250ml four-hole boiling flask that agitator, thermometer are housed, add methylene-succinic acid 65 grams, lactic acid 10 grams, ethylene glycol 40 grams, tetrabutyl titanate 0.15 gram, in the oil bath pan of 150 DEG C, carry out esterification 6 hours.Remove agitator, connect vacuum system, control vacuum tightness is 0.01MPa, is warming up to 180 DEG C and carries out polycondensation 3 hours, add 6 grams of methylene-succinic acids, 3 grams of ethylene glycol are added again after half an hour, add 3 grams of methylene-succinic acids after half an hour, after half an hour, add 1.5 grams of ethylene glycol again, reaction half an hour after cooling discharge, the polyester hydroxyl value obtained is 185.3mgKOH/g, and acid number is 8.2mgKOH/g.
Embodiment 8
In the 250ml four-hole boiling flask that agitator, thermometer are housed, add methylene-succinic acid dioctyl phthalate 79 grams, ethylene glycol 31 grams, tetrabutyl titanate 0.15 gram, in the oil bath pan of 150 DEG C, carry out esterification 6 hours.Remove agitator, connect vacuum system, control vacuum tightness is 0.01MPa, is warming up to 180 DEG C and carries out polycondensation 3 hours, add 6 grams of methylene-succinic acids, 3 grams of ethylene glycol are added again after half an hour, add 3 grams of methylene-succinic acids after half an hour, after half an hour, add 1.5 grams of ethylene glycol again, reaction half an hour after cooling discharge, the polyester hydroxyl value obtained is 82.3mgKOH/g, and acid number is 6.2mgKOH/g.
Embodiment 9
In the 250ml four-hole boiling flask that agitator, thermometer are housed, add clothing health acyl chlorides 83.5 grams, ethylene glycol 31 grams, tetrabutyl titanate 0.15 gram, in the oil bath pan of 150 DEG C, carry out esterification 6 hours.Remove agitator, connect vacuum system, control vacuum tightness is 0.01MPa, be warming up to 180 DEG C and carry out polycondensation 3 hours, add 6 grams of methylene-succinic acids, after half an hour, add 3 grams of ethylene glycol again, after half an hour, add 3 grams of methylene-succinic acids, 1.5 grams of ethylene glycol are added again after half an hour, reaction was lowered the temperature after half an hour, repeatedly got polyester layer, 150 DEG C of high temperature dehydrations after washing, the polyester hydroxyl value obtained is 52.1mgKOH/g, and acid number is 21.2mgKOH/g.
Embodiment 10
In the 250ml four-hole boiling flask that agitator, thermometer are housed, add clothing health acyl chlorides 83.5 grams, ethylene glycol 31 grams, tetrabutyl titanate 0.15 gram, in the oil bath pan of 150 DEG C, carry out esterification 6 hours.Remove agitator, connect vacuum system, control vacuum tightness is 0.01MPa, be warming up to 180 DEG C and carry out polycondensation 3 hours, add 8.5 grams of clothing health acyl chlorides, after half an hour, add 3 grams of ethylene glycol again, after half an hour, add 8.5 grams of clothing health acyl chlorides, 1.5 grams of ethylene glycol are added again after half an hour, reaction was lowered the temperature after half an hour, repeatedly got polyester layer, 150 DEG C of high temperature dehydrations after washing, the polyester hydroxyl value obtained is 32.7mgKOH/g, and acid number is 26.9mgKOH/g.
Embodiment 11
In the 250ml four-hole boiling flask that agitator, thermometer are housed, add itaconic anhydride 56 grams, ethylene glycol 31 grams, tetrabutyl titanate 0.15 gram, in the oil bath pan of 150 DEG C, carry out esterification 6 hours.Remove agitator, connect vacuum system, control vacuum tightness is 0.01MPa, be warming up to 180 DEG C and carry out polycondensation 3 hours, add 5.6 grams of itaconic anhydrides, 3 grams of ethylene glycol are added again after half an hour, add 5.6 grams of itaconic anhydrides after half an hour, after half an hour, add 1.5 grams of ethylene glycol again, after half an hour, add 5.6 grams of itaconic anhydrides, 1.5 grams of ethylene glycol are added again after half an hour, reaction was lowered the temperature after half an hour, repeatedly got polyester layer, 150 DEG C of high temperature dehydrations after washing, the polyester hydroxyl value obtained is 20.1mgKOH/g, and acid number is 3.0mgKOH/g.
Embodiment 12
In the 250ml four-hole boiling flask that agitator, thermometer are housed, add pyrovinic acid 66 grams, 1,3-PD 38 grams, tin protochloride 0.1 gram, in the oil bath pan of 200 DEG C, carry out esterification 6 hours.Remove agitator, connect vacuum system, control vacuum tightness is 0.1MPa, be warming up to 240 DEG C and carry out polycondensation 3 hours, add 3 grams of pyrovinic acids, after half an hour, add 1.5 gram 1 again, ammediol, add 3 grams of pyrovinic acids after half an hour, after half an hour, add 1.5 grams of 1,3-PDs again, so repeatedly, altogether add 1.5 gram 1,3 propylene glycol 10 times, 3 grams of pyrovinic acids 10 times.After adding last glycerol, reaction half an hour after cooling discharge, the polyester hydroxyl value obtained is 65.3mgKOH/g, and acid number is 10.8mgKOH/g.
Above embodiment is only several in the several preferred implementation of the present invention, it should be pointed out that and the invention is not restricted to above-described embodiment; For the person of ordinary skill of the art, still the technical scheme described in previous embodiment can be modified, or equivalent replacement is carried out to wherein portion of techniques feature; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the spirit and scope of the present invention's technical scheme required for protection.
Claims (9)
1. a synthetic method for the hydroxyl telechelic polyester of biomass source, is characterized in that, is first to carry out esterification by acid and alcohol, carry out multistage polycondensation again, in polycondensation process, first carry out esterification, more alternately add acid and alcohol carry out polycondensation, finally obtain polyester product; Whole reaction molar ratio of alcohol to acid is 0.9-1.5.
2. the synthetic method of the hydroxyl telechelic polyester of a root a kind of biomass source according to claim 1, is characterized in that, described acid is biomass source, reproducible diprotic acid or polyprotonic acid and acyl chlorides product, anhydride product or dimethyl ester; Described alcohol is biomass source, reproducible dibasic alcohol or polyvalent alcohol.
3. the synthetic method of the hydroxyl telechelic polyester of a kind of biomass source according to claim 2, is characterized in that, described acid is methylene-succinic acid, methylene-succinic acid acyl chlorides, itaconic anhydride, dimethyl itaconate, lactic acid or pyrovinic acid.
4. the synthetic method of the hydroxyl telechelic polyester of a kind of biomass source according to claim 1, is characterized in that, described alcohol is 1,3-PD, glycerol, ethylene glycol or methyl isophthalic acid, 4-butyleneglycol.
5. the synthetic method of the hydroxyl telechelic polyester of a kind of biomass source according to claim 1, is characterized in that, the quality of material added in described esterification is the 60-95% of material total mass, and molar ratio of alcohol to acid is 0.8-1.3; In described polycondensation, remaining alcohol and acid are divided into 1-10 part, 10-30min of being separated by alternately joins in system.
6. the synthetic method of the hydroxyl telechelic polyester of a kind of biomass source according to claim 1, is characterized in that, described esterification reaction temperature is 100-200 DEG C, and pressure is 0-0.13MPa, and the reaction times is 4-10h.
7. the synthetic method of the hydroxyl telechelic polyester of a kind of biomass source according to claim 1, is characterized in that, described polycondensation temperature is 150-240 DEG C, and pressure is 0-0.13MPa, and the reaction times is 4-6h.
8. the synthetic method of the hydroxyl telechelic polyester of a kind of biomass source according to claim 1, it is characterized in that, described esterification and polycondensation process use or do not use catalyzer, described catalyzer is zinc acetate, calcium acetate, cobalt chloride, tin protochloride or tetrabutyl titanate, and catalyst levels is the 0-5% of material total mass.
9. the synthetic method of the hydroxyl telechelic polyester of a kind of biomass source according to claim 1, is characterized in that, the number-average molecular weight of described polyester product is 300-5000, and molecular weight distribution is 1-5, and hydroxyl value is 2-200mgKOH/g, and acid number is 0-80mgKOH/g.
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