CN101445592A - Biodegradable branched co-polyester and preparation method thereof - Google Patents
Biodegradable branched co-polyester and preparation method thereof Download PDFInfo
- Publication number
- CN101445592A CN101445592A CNA2008102465629A CN200810246562A CN101445592A CN 101445592 A CN101445592 A CN 101445592A CN A2008102465629 A CNA2008102465629 A CN A2008102465629A CN 200810246562 A CN200810246562 A CN 200810246562A CN 101445592 A CN101445592 A CN 101445592A
- Authority
- CN
- China
- Prior art keywords
- acid
- succinic acid
- butanediol
- polyester
- poly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000002253 acid Substances 0.000 claims abstract description 44
- -1 alkane diol Chemical class 0.000 claims abstract description 25
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000032050 esterification Effects 0.000 claims abstract description 18
- 238000005886 esterification reaction Methods 0.000 claims abstract description 18
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000004135 Bone phosphate Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 158
- 238000006243 chemical reaction Methods 0.000 claims description 91
- 238000003756 stirring Methods 0.000 claims description 81
- 229910052757 nitrogen Inorganic materials 0.000 claims description 79
- 239000001384 succinic acid Substances 0.000 claims description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 35
- RODWUXIZAKTQDY-UHFFFAOYSA-N [La].C(C)C(=O)C(=O)C Chemical compound [La].C(C)C(=O)C(=O)C RODWUXIZAKTQDY-UHFFFAOYSA-N 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 20
- 150000003384 small molecules Chemical class 0.000 claims description 17
- 229920001634 Copolyester Polymers 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 150000004703 alkoxides Chemical class 0.000 claims description 12
- DGXRZJSPDXZJFG-UHFFFAOYSA-N docosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCCCC(O)=O DGXRZJSPDXZJFG-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol Substances OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 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 9
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 claims description 8
- 239000000470 constituent Substances 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 6
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 150000007521 triprotic acids Chemical class 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- NGCDGPPKVSZGRR-UHFFFAOYSA-J 1,4,6,9-tetraoxa-5-stannaspiro[4.4]nonane-2,3,7,8-tetrone Chemical compound [Sn+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O NGCDGPPKVSZGRR-UHFFFAOYSA-J 0.000 claims description 2
- PXAPUVJKZMNUEA-UHFFFAOYSA-N [Hf].C(C)C(=O)C(=O)C Chemical compound [Hf].C(C)C(=O)C(=O)C PXAPUVJKZMNUEA-UHFFFAOYSA-N 0.000 claims description 2
- IWXHAHDGHQSYQZ-UHFFFAOYSA-N acetic acid;hafnium Chemical compound [Hf].CC(O)=O IWXHAHDGHQSYQZ-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- BNUDRLITYNMTPD-UHFFFAOYSA-N acetic acid;zirconium Chemical compound [Zr].CC(O)=O BNUDRLITYNMTPD-UHFFFAOYSA-N 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims description 2
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- AHBPBADERZDJKT-UHFFFAOYSA-N pentane-2,3-dione zirconium Chemical compound [Zr].C(C)C(=O)C(=O)C AHBPBADERZDJKT-UHFFFAOYSA-N 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
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 32
- 239000000463 material Substances 0.000 description 18
- 238000004821 distillation Methods 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 238000005303 weighing Methods 0.000 description 15
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 12
- 150000005690 diesters Chemical class 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 4
- 229940051250 hexylene glycol Drugs 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000004970 Chain extender Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920003232 aliphatic polyester Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical compound CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 description 2
- 229920002961 polybutylene succinate Polymers 0.000 description 2
- 239000004631 polybutylene succinate Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- JDRJCBXXDRYVJC-UHFFFAOYSA-N OP(O)O.N.N.N Chemical compound OP(O)O.N.N.N JDRJCBXXDRYVJC-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- LRGMAUZMDCZFIV-UHFFFAOYSA-N butanedioic acid butane-1,2,4-triol Chemical class OCC(CCO)O.C(CCC(=O)O)(=O)O LRGMAUZMDCZFIV-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- CDXVUROVRIFQMV-UHFFFAOYSA-N oxo(diphenoxy)phosphanium Chemical compound C=1C=CC=CC=1O[P+](=O)OC1=CC=CC=C1 CDXVUROVRIFQMV-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses biodegradable branched co-polyester and a preparation method thereof, and belongs to the polymeric chemical field. The preparation of branched co-polyester adopts a mature esterification and fasculation process route, butane diacid and butanediol which are used as main copolymerization units performs a copolymerization action with one or more than one of lateral group-containing aliphatic dibasic acid, C3, C5 to C8 alkane diacid, terephthalic acid or tribasic acid, or performs a copolymerization action with one or more than one of lateral group-containing dibasic alcohol, C2, C3, C5 to C10 alkane diol or aliphatic trivalent alcohol, so as to obtain random branched co-polyester finally. The intrinsic viscosity of prepared co-polyester ranges from 0.6 to 2.2dl/g, the melting point ranges from 70 to 115, the degree of crystallinity ranges from 20 to 70 percent, and the weight average molecular weight ranges from 5 to 300000. The co-polyester preparation method adopts efficient a blended catalyst, so that the polymerization time is reduced greatly, and the molecular weight and the performance of the products are increased. New performances are given to polyester through quoting third components containing lateral groupsor multi-functional groups, thereby extending the application range of polyester.
Description
Technical field
The invention belongs to copolyesters product and preparation method thereof technical field, particularly a kind of Biodegradable branched co-polyester and preparation method thereof.
Background technology
In recent years, along with the development of plastics industry and the enhancing of people's environmental consciousness, " white pollution " problem (as the waste plastic film, waste plastic packing bag etc. are to the pollution of environment) by conventional plastic causes just progressively gets more and more people's extensive concerning.How effectively to solve the use of plastic prod and the contradiction between the environmental disruption, what just show is more and more important.Therefore relevant various " environment-friendly materials " the especially research of biological degradation plastics and object of paying close attention to that application has become people.Particularly aliphatic polyester just more and more is subjected to people's favor as a kind of outstanding bio-degradable plastics.
Poly-succinic fourth diester (PBS) has mechanics and biodegradability preferably, therefore shows one's talent from biodegradable aliphatic polyester, and becomes the research focus of domestic and international researcher.Related products is commercialization.But the degree of crystallinity of PBS is higher, can reach 40%~60%, and is slower at the biodegradation rate of occurring in nature, and the Application Areas of shortcoming further limits PBS such as its molecular weight is low, and melt strength and melt viscosity are low.Compare with aromatic polyester, the aliphatic polyester greatest problem is a poor heat stability, side reactions such as decarboxylation, cyclisation and thermal destruction takes place easily, so be difficult to obtain the high-molecular weight product under comparatively high temps.For this reason, research and the application about polyester chain extender and catalyzer gets more and more people's extensive concerning.People are molecular weight (Zhao J.B, Li K.Y, the Yang W.T that chainextender improves PBS with the two hexanolactams (TBC) of paraphenylene terephthalamide, J Appl Polym Sci, 2007,106,590), the result shows the molecular weight that improves polyester to a certain extent that is introduced in of chainextender.But there is complex process in this method, to shortcoming such as environment is unfriendly, thereby its application is restricted.In addition, people again with a kind of with TiO
2And SiO
2Copolymerization mixed oxide compound high-activity polyester catalyst be incorporated into (Seidel U, Eckert T, Chem.Fibers Int, 1999,49,27) in the pet reaction.This catalyzer has high reaction activity and high, can reduce the reaction times of polyester, but its existence can make color articles problem such as turn to be yellow mutually, thereby influences the outward appearance of product.Generally speaking, the processing rheological of polymkeric substance is not only relevant with its molecular weight and the size that distributes thereof, but also relevant with the cladodification structure of polymkeric substance.Therefore, the research of relevant branched co-polyester just gets more and more people's extensive concerning.People are that the cladodification agent comes modification PBS with three methanol-based propane, thereby make cladodification PBS (Kim E.K, Bae J.S, J Appl Polym Sci, 2001,80,1388).The result shows that the introducing of cladodification agent can be at the rheological property that has to a certain degree improved PBS.But compare with pure PBS, the molecular weight of cladodification PBS and mechanical property are to a certain degree descending to some extent, thereby influence its range of application.
Summary of the invention
The purpose of this invention is to provide a kind of have an actual application value and competitive relatively Biodegradable branched co-polyester of price, and its preparation method.This copolyesters can overcome the defective on the pure PBS material property, as having higher relatively degree of crystallinity and crystallization velocity and lower melt strength and melt viscosity more slowly.
Another object of the present invention is at the defective that improves PBS and molecular weight of copolymer thereof via polycondensation, and a kind of composite catalyst system efficiently is provided.
Biodegradable branched co-polyester provided by the present invention, the component of its repeating unit constitute any a group in following three groups:
A. the acid constituents of (1) repeating unit: Succinic Acid;
(2) alkoxide component of repeating unit: butyleneglycol, the molar content that accounts for total alcohol is 75%~99.5%, all the other alkoxide components are aliphatic diol, the C that contains side group
2, C
3, C
5~C
10In alkanediol or the aliphatic tribasic alcohol one or more;
B. the acid constituents of (1) repeating unit: Succinic Acid, the molar content that accounts for total acid is 85%~99%, all the other acid constituentss are aliphatic dibasic acids, the C that contains side group
3, C
5~C
8In chain docosandioic acid, terephthalic acid or the triprotic acid one or more;
(2) alkoxide component of repeating unit: butyleneglycol;
C. the acid constituents of (1) repeating unit: Succinic Acid, the molar content that accounts for total acid is 85%~99%, all the other acid constituentss are aliphatic dibasic acids, the C that contains side group
3, C
5~C
8In chain docosandioic acid, terephthalic acid or the triprotic acid one or more;
(2) alkoxide component of repeating unit: butyleneglycol, the molar content that accounts for total alcohol is 75%~99.5%, all the other alkoxide components are aliphatic diol, the C that contains side group
2, C
3, C
5~C
10In alkanediol or the aliphatic tribasic alcohol one or more;
Wherein, the molar content ratio of alkoxide component and acid constituents is 1.1~1.4 among three groups of A, B and the C;
The intrinsic viscosity of the copolyesters that obtains is 0.6~2.2dl/g, 70~115 ℃ of fusing points, degree of crystallinity 20~70%, weight-average molecular weight is 5~300,000, tensile strength is 30~60MPa, elongation at break is 40~500%, and the biodegradability of described copolyesters is according to ASTMD5338 weightlessness 6~17% in a week.
Thermal properties such as the fusing point of Biodegradable branched co-polyester provided by the invention and degree of crystallinity are detected by differential scanning calorimeter, and intrinsic viscosity is to be solvent with the trichloromethane, utilize Ubbelohde viscosity number meter to detect down for 25 ℃ in temperature; The composition of branched co-polyester is to be solvent by deuterochloroform, characterizes the structure and the composition of branched co-polyester with the nuclear magnetic resonance spectrometer measured result; Molecular weight is to be solvent by chloroform, and polystyrene is a standard specimen, adopts the GPC method to measure.Tensile strength and elongation at break are tested according to the dumbbell shape sample of ASTM D638 regulation.The biodegradability of material adopts composting process to measure according to ASTM D5338.
Described copolyesters comprises poly-succinic acid-butanediol-common-Succinic Acid 1,2,4-trihydroxybutane ester; Poly-succinic acid-butanediol-altogether-Succinic Acid 1,2-hexylene glycol ester; Poly-succinic acid-butanediol-altogether-Succinic Acid 1, the 2-pentadiol ester; Poly-succinic acid-butanediol-altogether-Succinic Acid 1,2-decanediol ester; Poly-succinic acid-butanediol-altogether-the Succinic Acid hexylene glycol-altogether-Succinic Acid 1,2, the 3-glycerine ester; Poly-succinic acid-butanediol-altogether-the Succinic Acid hexylene glycol-altogether-Succinic Acid 1,2-hexylene glycol ester; Poly-succinic acid-butanediol-be total to-2,2-dimethyl succinic acid butanediol ester; Poly-succinic acid-butanediol-altogether-the pyrovinic acid butanediol ester; Poly-succinic acid-butanediol-altogether-the trimesic acid butanediol ester; Poly-succinic acid-butanediol-altogether-mutual-phenenyl two acid bromide two alcohol ester; Poly-succinic acid-butanediol-altogether-the terephthalic acid butyleneglycol-altogether-tetramethylene adipate; Poly-succinic acid-butanediol-altogether-the trimesic acid butyleneglycol-altogether-tetramethylene adipate; Poly-succinic acid-butanediol-altogether-Succinic Acid 1,2, the 3-glycerine ester; Poly-succinic, butyleneglycol, hexanodioic acid and 1,2, the copolyesters of 3-glycerol or poly-succinic, butyleneglycol, trimesic acid and 1,2, the copolyesters of 3-glycerol.
The described aliphatic diol of side group that contains is for having the C of alkyl branches (R)
2~C
10Alkanediol, wherein the carbon number of R is 1~12.
The described aliphatic dibasic acids of side group that contains is for having the C of alkyl branches (R)
3~C
8The chain docosandioic acid, wherein the carbon number of R is 1~12.
Described aliphatic tribasic alcohol is 1,2,4-trihydroxybutane or 1,2,3-glycerol.
Described triprotic acid is trimesic acid or benzene-1.
The preparation method of Biodegradable branched co-polyester provided by the present invention, finish according to following operation steps:
(1) prepolymer is synthetic
By acid and pure molar content and component in above-mentioned A, B or the C group, it is joined in the reactor with temperature-programmed mode temperature reaction system to 140~250 ℃, be warmed up to 180~240 ℃ with temperature-programmed mode behind the reaction 10min, keep this thermotonus 50~100min up to the system thickness, the prepolymer that obtains extremely no longer splashes 180~220 ℃ of following violent stirring.
(2) polycondensation of multipolymer
Esterification cools to 150~160 ℃ with system after finishing, and connects vacuum system, be evacuated to below the 0.5mmHg, reaction 5~10min does not participate in the small molecules of reaction and the water of remnants in the removal system, stop to vacuumize and feeding nitrogen, add composite catalyst 2 * 10
-4~50 * 10
-4G/g polyester, and stablizer 2 * 10
-4~50 * 10
-4The g/g polyester; Stir 10~30min and guarantee that catalyzer is dispersed in the reaction system, stop logical nitrogen, be evacuated to below the 0.5mmHg, and be rapidly heated to 200 ℃~240 ℃ of temperature of reaction, keep simultaneously stirring fast, isothermal reaction 30~100min promptly obtains product under vacuum state.
Described composite catalyst is one or more in tetrabutyl titanate, isopropyl titanate, titanium dioxide and silicon dioxide coprecipitate, antimonous oxide, zinc acetate, Cobaltous diacetate, lanthanum acetate, acetic acid zirconium, acetic acid hafnium, manganese acetate, zinc chloride, Lanthanum trichloride, zirconium chloride, hafnium chloride, methyl ethyl diketone lanthanum, methyl ethyl diketone zirconium, methyl ethyl diketone hafnium, inferior tin oxalate or the stannous octoate.Preferred tetrabutyl titanate and the mixture of methyl ethyl diketone lanthanum or the mixture of titanium dioxide and silicon dioxide coprecipitate and methyl ethyl diketone lanthanum, wherein the mol ratio of tetrabutyl titanate or titanium dioxide and silicon dioxide coprecipitate and methyl ethyl diketone lanthanum is 1: 1.
Described stablizer is one or more couplings in phosphoric acid, phosphorous acid, ortho phosphorous acid, tetra-sodium, ammonium phosphate, trimethyl phosphite 99, dimethyl phosphate, triphenylphosphate, diphenyl phosphate, triphenyl phosphite, phosphorous acid diphenyl ester, ammonium phosphite or the primary ammonium phosphate.
The new synthetic method of a kind of Biodegradable branched co-polyester provided by the invention, compare with the binary polyester, under the condition of same composition, the preparation technology and the catalyst system of the present invention's exploitation can shorten the course of processing and time greatly, the comonomer of side chain comonomer of Yin Ruing or trifunctional can be given the new performance of polyester and improve the processing characteristics of polyester simultaneously, has further expanded the Application Areas of Biodegradable branched co-polyester.
Embodiment
Provide embodiment below; but it is worthy of note that the present invention is not limited to these and implements example; the ordinary skill of this area to some nonessential change and adjustment that the present invention has done, still belongs to protection scope of the present invention according to the content of foregoing invention.
Embodiment 1
Present embodiment is preparation poly-succinic acid-butanediol-common-Succinic Acid 1,2,4-trihydroxybutane ester
Take by weighing Succinic Acid 0.40mol and butyleneglycol 0.4224mol respectively, and 1,2,4-trihydroxybutane 0.0176mol adds reactor, wherein connects stirring flatly, connects nitrogen protection flatly, and another mouth connects water trap and distillation column; Start stirring, reacting by heating system to 150 ℃; Be warmed up to 200 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 90min up to the system thickness, the prepolymer that obtains extremely no longer splashes 200 ℃ of following violent stirring.
Esterification cools to 155 ℃ with system after finishing, and removes water trap and prolong when continuing logical nitrogen, connect the vacuum pump interface, close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and the remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of tetrabutyl titanate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg, and be rapidly heated to 240 ℃, keep simultaneously stirring fast, isothermal reaction 60min promptly obtains product under vacuum state.
After testing, the mol ratio of succinic acid-butanediol ester and Succinic Acid 1,2,4 trihydroxybutane esters is 96.2/3.8 in the product.25 ℃ following that intrinsic viscosity is 0.90dl/g.Fusing point is 105 ℃, and degree of crystallinity is 43%.Weight-average molecular weight M
wBe 122000, tensile strength is 45MPa, and elongation at break is 36.8%, and the biodegradability of material is according to ASTMD5338 weightlessness 10% in a week.
Embodiment 2
Present embodiment is preparation poly-succinic acid-butanediol-common-Succinic Acid 1,2-hexylene glycol ester
Take by weighing Succinic Acid 0.40mol and butyleneglycol 0.396mol respectively, and 1,2-hexylene glycol 0.044mol adds reactor, wherein connects stirring flatly, connects nitrogen protection flatly, and another mouth connects water trap and distillation column; Start stirring, reacting by heating system to 150 ℃; Be warmed up to 180 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 90min up to the system thickness, the prepolymer that obtains extremely no longer splashes 200 ℃ of following violent stirring.
Esterification cools to 150 ℃ with system after finishing, and removes water trap and prolong when continuing logical nitrogen, connect the vacuum pump interface, close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and the remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of tetrabutyl titanate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg, and be rapidly heated to 200 ℃, keep simultaneously stirring fast, isothermal reaction 80min promptly obtains product under vacuum state.
After testing, succinic acid-butanediol ester and Succinic Acid 1 in the product, it is 90.4/9.6 that 2-hexylene glycol ester gets mol ratio.25 ℃ following that intrinsic viscosity is 0.74dl/g.Fusing point is 100 ℃, and degree of crystallinity is 32%.Weight-average molecular weight M
wBe 111000, tensile strength is 36MPa, and elongation at break is 210%, and the biodegradability of material is according to ASTMD5338 weightlessness 12% in a week.
Embodiment 3
Present embodiment is preparation poly-succinic acid-butanediol-common-Succinic Acid 1, the 2-pentadiol ester
Take by weighing Succinic Acid 0.40mol and 1 respectively, 2-pentanediol 0.066mol, and butyleneglycol 0.374mol add reactor, wherein connect stirring flatly, connect nitrogen protection flatly, and another mouth connects water trap and distillation column; Start stirring, reacting by heating system to 150 ℃; Be warmed up to 200 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 100min up to the system thickness, the prepolymer that obtains extremely no longer splashes 200 ℃ of following violent stirring.
Esterification cools to 150 ℃ with system after finishing, and removes water trap and prolong when continuing logical nitrogen, connect the vacuum pump interface, close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and the remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of tetrabutyl titanate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg, and be rapidly heated to 240 ℃, keep simultaneously stirring fast, isothermal reaction 90min promptly obtains product under vacuum state.
After testing, succinic acid-butanediol ester and Succinic Acid 1 in the product, the mol ratio of 2-pentadiol ester is 85.1/14.9.25 ℃ following that intrinsic viscosity is 0.70dl/g.Fusing point is 95 ℃, and degree of crystallinity is 30%.Weight-average molecular weight M
wBe 111000, the biodegradability of material is according to ASTMD5338 weightlessness 15% in a week.
Embodiment 4
Present embodiment is preparation poly-succinic acid-butanediol-common-Succinic Acid 1,2-decanediol ester
Take by weighing Succinic Acid 0.40mol and 1 respectively, 2-decanediol 0.10mol, and butyleneglycol 0.34mol add reactor, wherein connect stirring flatly, connect nitrogen protection flatly, and another mouth connects water trap and distillation column; Start stirring, reacting by heating system to 150 ℃; Be warmed up to 200 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 80min up to the system thickness, the prepolymer that obtains no longer splashes 200 ℃ of following violent stirring.
Esterification cools to 150 ℃ with system after finishing, and removes water trap and prolong when continuing logical nitrogen, connect the vacuum pump interface, close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and the remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of titanium silicon coprecipitate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg, and be rapidly heated to 240 ℃, keep simultaneously stirring fast, isothermal reaction 100min under vacuum state promptly obtains product.
After testing, Succinic Acid fourth diester and Succinic Acid 1 in the product, it is 78.4/21.6 that 2-decanediol ester gets mol ratio.25 ℃ following that intrinsic viscosity is 0.60dl/g.Fusing point is 80 ℃, and degree of crystallinity is 25%.Weight-average molecular weight M
wBe 102000, the biodegradability of material is according to ASTMD5338 weightlessness 15% in two weeks.
Embodiment 5
Present embodiment is preparation poly-succinic acid-butanediol-common-Succinic Acid hexylene glycol-common-Succinic Acid 1,2, the 3-glycerine ester
Take by weighing Succinic Acid 0.4mol and hexylene glycol 0.02mol respectively, 1,2,3-glycerol 0.02mol, and butyleneglycol 0.4mol add reactor, wherein connect stirring flatly, connect nitrogen protection flatly, and another mouth connects water trap and distillation column; Start stirring, reacting by heating system to 160 ℃; Be warmed up to 240 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 80min up to the system thickness, the prepolymer that obtains no longer splashes 200 ℃ of following violent stirring.
Esterification cools to 150 ℃ with system after finishing, and removes water trap and prolong when continuing logical nitrogen, connect the vacuum pump interface, close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and the remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of titanium silicon coprecipitate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg, and be rapidly heated to 240 ℃, keep simultaneously stirring fast, isothermal reaction 100min under vacuum state promptly obtains product.
After testing, succinic acid-butanediol ester, Succinic Acid hexylene glycol ester and Succinic Acid 1,2 in the product, the mol ratio of 3-glycerine ester is 91:4.5:4.5.25 ℃ following that intrinsic viscosity is 1.5dl/g.Fusing point is 102 ℃, and degree of crystallinity is 40%.Weight-average molecular weight Mw is 194000, and the biodegradability of material is according to ASTMD5338 weightlessness 8% in two weeks.
Embodiment 6
Present embodiment is preparation poly-succinic acid-butanediol-common-Succinic Acid hexylene glycol-common-Succinic Acid 1,2-hexylene glycol ester
Take by weighing Succinic Acid 0.4mol and hexylene glycol 0.02mol respectively, 1,2-hexylene glycol 0.02mol, and butyleneglycol 0.4mol add reactor, wherein connect stirring flatly, connect nitrogen protection flatly, and another mouth connects water trap and distillation column; Start stirring, reacting by heating system to 150 ℃; Be warmed up to 200 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 80min up to the system thickness, the prepolymer that obtains no longer splashes 200 ℃ of following violent stirring.
Esterification cools to 150 ℃ with system after finishing, and removes water trap and prolong when continuing logical nitrogen, connect the vacuum pump interface, close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and the remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of titanium silicon coprecipitate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg, and be rapidly heated to 240 ℃, keep simultaneously stirring fast, isothermal reaction 100min under vacuum state promptly obtains product.
After testing, succinic acid-butanediol ester, Succinic Acid hexylene glycol ester and Succinic Acid 1 in the product, the mol ratio of 2-hexylene glycol alcohol ester is 91:4.5:4.5.25 ℃ following that intrinsic viscosity is 1.4dl/g.Fusing point is 103 ℃, and degree of crystallinity is 40%.Weight-average molecular weight Mw is 183000, and the biodegradability of material is according to ASTMD5338 weightlessness 8% in two weeks.
Embodiment 7
Present embodiment is a preparation poly-succinic acid-butanediol-altogether-2,2-dimethyl succinic acid butanediol ester
Take by weighing Succinic Acid 0.35mol and 2 respectively, 2-dimethyl succinic acid 0.05mol, and butyleneglycol 0.44mol add reactor, wherein connect stirring flatly, connect nitrogen protection flatly, and another mouth connects water trap and distillation column; Start stirring, reacting by heating system to 150 ℃; Be warmed up to 180 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 90min up to the system thickness, the prepolymer that obtains no longer splashes 180 ℃ of following violent stirring.
Esterification cools to 150 ℃ with system after finishing, and removes water trap and prolong when continuing logical nitrogen, connect the vacuum pump interface, close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and the remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of titanium silicon coprecipitate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg, and be rapidly heated to 220 ℃, keep simultaneously stirring fast, isothermal reaction 100min under vacuum state promptly obtains product.
After testing, Succinic Acid fourth diester and 2 in the product, the mol ratio of 2-dimethyl succinic acid fourth diester is 88/12.Intrinsic viscosity under 25 ℃ is 0.90dl/g.Fusing point is 95 ℃, and degree of crystallinity is 34%.Weight-average molecular weight M
wBe 122000, the biodegradability of material is according to ASTMD5338 weightlessness 14% in two weeks.
Embodiment 8
Present embodiment is preparation poly-succinic acid-butanediol-common-pyrovinic acid butanediol ester
Take by weighing Succinic Acid 0.36mol and pyrovinic acid 0.04mol respectively, and butyleneglycol 0.44mol, add reactor, wherein connect stirring flatly, connect nitrogen protection flatly, another mouth connects water trap and distillation column; Start stirring, reacting by heating system to 150 ℃; Be warmed up to 180 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 90min up to the system thickness, the prepolymer that obtains no longer splashes 180 ℃ of following violent stirring.
Esterification cools to 150 ℃ with system after finishing, and removes water trap and prolong when continuing logical nitrogen, connect the vacuum pump interface, close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and the remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of titanium silicon coprecipitate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg, and be rapidly heated to 240 ℃, keep simultaneously stirring fast, isothermal reaction 100min under vacuum state promptly obtains product.
After testing, in the product Succinic Acid fourth diester and pyrovinic acid fourth diester to get mol ratio be 90.2/9.8.25 ℃ following that intrinsic viscosity is 0.92dl/g.Fusing point is 98 ℃, and degree of crystallinity is 36%.Weight-average molecular weight M
wBe 127000, the biodegradability of material is according to ASTMD5338 weightlessness 12% in two weeks.
Embodiment 9
Present embodiment is preparation poly-succinic acid-butanediol-common-trimesic acid butanediol ester
Take by weighing Succinic Acid 0.38mol and trimesic acid 0.02mol respectively, and butyleneglycol 0.44mol, add reactor, wherein connect stirring flatly, connect nitrogen protection flatly, another mouth connects water trap and distillation column; Start stirring, reacting by heating system to 150 ℃; Be warmed up to 200 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 80min up to the system thickness, the prepolymer that obtains no longer splashes 200 ℃ of following violent stirring.
Esterification cools to 150 ℃ with system after finishing, and removes water trap and prolong when continuing logical nitrogen, connect the vacuum pump interface, close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and the remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of titanium silicon coprecipitate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg, and be rapidly heated to 240 ℃, keep simultaneously stirring fast, isothermal reaction 100min under vacuum state promptly obtains product.
After testing, in the product succinic acid-butanediol ester and trimesic acid butanediol ester to get mol ratio be 95.3/4.7.25 ℃ following that intrinsic viscosity is 0.88dl/g.Fusing point is 106 ℃, and degree of crystallinity is 45%.Weight-average molecular weight M
wBe 119000, the biodegradability of material is according to ASTMD5338 weightlessness 7% in two weeks.
Embodiment 10
Present embodiment is preparation poly-succinic acid-butanediol-common-mutual-phenenyl two acid bromide two alcohol ester
Take by weighing Succinic Acid 0.36mol and terephthalic acid 0.04mol respectively, and butyleneglycol 0.44mol, add reactor, wherein connect stirring flatly, connect nitrogen protection flatly, another mouth connects water trap and distillation column; Start stirring, reacting by heating system to 150 ℃; Be warmed up to 220 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 80min up to the system thickness, the prepolymer that obtains no longer splashes 200 ℃ of following violent stirring.
Esterification cools to 150 ℃ with system after finishing, and removes water trap and prolong when continuing logical nitrogen, connect the vacuum pump interface, close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and the remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of titanium silicon coprecipitate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg, and be rapidly heated to 240 ℃, keep simultaneously stirring fast, isothermal reaction 100min under vacuum state promptly obtains product.
After testing, succinic acid-butanediol ester and mutual-phenenyl two acid bromide two alcohol ester's mol ratio is 90.4/9.6 in the product.Intrinsic viscosity under 25 ℃ is 0.89dl/g.Fusing point is 110 ℃, and degree of crystallinity is 46%.Weight-average molecular weight M
wBe 120000, the biodegradability of material is according to ASTMD5338 weightlessness 10% in two weeks.
Embodiment 11
Present embodiment is preparation poly-succinic acid-butanediol-common-terephthalic acid butyleneglycol-common-tetramethylene adipate
Take by weighing Succinic Acid 0.36mol and terephthalic acid 0.02mol respectively, hexanodioic acid 0.02mol and butyleneglycol 0.44mol add reactor, wherein connect stirring flatly, connect nitrogen protection flatly, and another mouth connects water trap and distillation column; Start stirring, reacting by heating system to 150 ℃; Be warmed up to 200 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 80min up to the system thickness, the prepolymer that obtains no longer splashes 200 ℃ of following violent stirring.
Esterification cools to 150 ℃ with system after finishing, and removes water trap and prolong when continuing logical nitrogen, connect the vacuum pump interface, close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and the remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of titanium silicon coprecipitate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg, and be rapidly heated to 240 ℃, keep simultaneously stirring fast, isothermal reaction 100min under vacuum state promptly obtains product.
After testing, the mol ratio of succinic acid-butanediol ester and mutual-phenenyl two acid bromide two alcohol ester and hexanodioic acid butyleneglycol is 90.5/4.7/4.8 in the product.Intrinsic viscosity under 25 ℃ is 0.86dl/g.Fusing point is 110 ℃, and degree of crystallinity is 46%.Weight-average molecular weight M
wBe 118000, the biodegradability of material is according to ASTMD5338 weightlessness 10% in two weeks.
Embodiment 12
Present embodiment is preparation poly-succinic acid-butanediol-common-trimesic acid butyleneglycol-common-tetramethylene adipate
Take by weighing Succinic Acid 0.36mol and trimesic acid 0.02mol respectively, hexanodioic acid 0.02mol and butyleneglycol 0.44mol add reactor, wherein connect stirring flatly, connect nitrogen protection flatly, and another mouth connects water trap and distillation column; Start stirring, reacting by heating system to 150 ℃; Be warmed up to 200 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 80min up to the system thickness, the prepolymer that obtains no longer splashes 200 ℃ of following violent stirring.
Esterification cools to 150 ℃ with system after finishing, and removes water trap and prolong when continuing logical nitrogen, connect the vacuum pump interface, close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and the remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of titanium silicon coprecipitate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg mmHg, and be rapidly heated to 240 ℃, keep simultaneously stirring fast, isothermal reaction 100min under vacuum state promptly obtains product.
After testing, the mol ratio of succinic acid-butanediol ester, trimesic acid butanediol ester and hexanodioic acid butyleneglycol is 91.0/4.6/4.4 in the product.Intrinsic viscosity under 25 ℃ is 0.88dl/g.Fusing point is 110 ℃, and degree of crystallinity is 46%.Weight-average molecular weight M
wBe 119000, the biodegradability of material is according to ASTMD5338 weightlessness 10% in two weeks.
Embodiment 13
Present embodiment is preparation poly-succinic acid-butanediol-common-Succinic Acid 1,2, the 3-glycerine ester
Take by weighing Succinic Acid 0.4mol and 1,2 respectively, 3-glycerol 0.0022mol, and butyleneglycol 0.4378mol add reactor, wherein connect stirring flatly, connect nitrogen protection flatly, and another mouth connects water trap and distillation column; Start stirring, reacting by heating system to 150 ℃; Be warmed up to 180 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 80min up to the system thickness, the prepolymer that obtains no longer splashes 180 ℃ of following violent stirring.
Esterification cools to 150 ℃ with system after finishing, and removes water trap and prolong when continuing logical nitrogen, connect the vacuum pump interface, close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and the remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of titanium silicon coprecipitate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg mmHg, and be rapidly heated to 240 ℃, keep simultaneously stirring fast, isothermal reaction 100min under vacuum state promptly obtains product.
After testing, succinic acid-butanediol ester and Succinic Acid 1,2 in the product, it is 99.6/0.4 that the 3-glycerine ester gets mol ratio.25 ℃ following that intrinsic viscosity is 2.2dl/g.Fusing point is 112 ℃, and degree of crystallinity is 49%.Weight-average molecular weight M
wBe 300000, the biodegradability of material is according to ASTMD5338 weightlessness 8% in two weeks.
Embodiment 14
Present embodiment is the atactic polyester of preparation (Succinic Acid, hexanodioic acid, butyleneglycol, 1,2,3-glycerol)
Take by weighing Succinic Acid 0.36mol and hexanodioic acid 0.04mol respectively, 1,2,3-glycerol 0.0022mol, and butyleneglycol 0.4378mol add reactor, wherein connect stirring flatly, connect nitrogen protection flatly, and another mouth connects water trap and distillation column; Start stirring, reacting by heating system to 150 ℃; Be warmed up to 200 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 80min up to the system thickness, the prepolymer that obtains no longer splashes 200 ℃ of following violent stirring.
Esterification cools to 150 ℃ with system after finishing, and removes water trap and prolong when continuing logical nitrogen, connect the vacuum pump interface, close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and the remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of titanium silicon coprecipitate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg mmHg, and be rapidly heated to 220 ℃, keep simultaneously stirring fast, isothermal reaction 100min under vacuum state promptly obtains product.
After testing, the intrinsic viscosity of 25 ℃ of following these atactic polyesters is 1.2dl/g.Fusing point is 103 ℃, and degree of crystallinity is 45%.Weight-average molecular weight Mw is 16000, and the biodegradability of material is according to ASTMD5338 weightlessness 7% in two weeks.
Embodiment 15
Present embodiment is the atactic polyester of preparation (Succinic Acid, trimesic acid, butyleneglycol, 1,2,3-glycerol)
Take by weighing Succinic Acid 0.38mol and trimesic acid 0.02mol respectively, 1,2,3-glycerol 0.0022mol, and butyleneglycol 0.4378mol add reactor, wherein connect stirring flatly, connect nitrogen protection flatly, and another mouth connects water trap and distillation column; Start stirring, reacting by heating system to 155 ℃; Be warmed up to 200 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 80min up to the system thickness, the prepolymer that obtains no longer splashes 200 ℃ of following violent stirring.
Esterification cools to 150 ℃ with system after finishing, and removes water trap and prolong when continuing logical nitrogen, connect the vacuum pump interface, close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and the remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of titanium silicon coprecipitate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg, and be rapidly heated to 240 ℃, keep simultaneously stirring fast, isothermal reaction 100min under vacuum state promptly obtains product.
The intrinsic viscosity of 25 ℃ of following these atactic polyesters is 1.8dl/g after testing.Fusing point is 103 ℃, and degree of crystallinity is 45%.Weight-average molecular weight Mw is 253000, and the biodegradability of material is according to ASTMD5338 weightlessness 6% in two weeks.
Reference
[1]Zhao?J.B,Li?K.Y,Yang?W.T,Chain?extension?of?polybutylene?adipate?and?polybutylenesuccinate?with?adipoyl-and?terephthaloyl-biscaprolactamate,J?Appl?Polym?Sci,2007,106,590.
[2]Seidel?U,Eckert?T,New,highly?active?PET?catalyst?commercially?available?on?productionscale,Chem.Fibers?Int,1999,49,27.
[3]Kim?E.K,Bae?J.S,Preparation?and?properties?of?branched?polybutylenesuccinate,J?ApplPolym?Sci,2001,80,1388.
Claims (9)
1, Biodegradable branched co-polyester, the component that it is characterized in that repeating unit constitutes any a group in following three groups:
A. the acid constituents of (1) repeating unit: Succinic Acid;
(2) alkoxide component of repeating unit: butyleneglycol, the molar content that accounts for total alcohol is 75%~99.5%, all the other alkoxide components are aliphatic diol, the C that contains side group
2, C
3, C
5~C
10In alkanediol or the aliphatic tribasic alcohol one or more;
B. the acid constituents of (1) repeating unit: Succinic Acid, the molar content that accounts for total acid is 85%~99%, all the other acid constituentss are aliphatic dibasic acids, the C that contains side group
3, C
5~C
8In chain docosandioic acid, terephthalic acid or the triprotic acid one or more;
(2) alkoxide component of repeating unit: butyleneglycol;
C. the acid constituents of (1) repeating unit: Succinic Acid, the molar content that accounts for total acid is 85%~99%, all the other acid constituentss are aliphatic dibasic acids, the C that contains side group
3, C
5~C
8In chain docosandioic acid, terephthalic acid or the triprotic acid one or more;
(2) alkoxide component of repeating unit: butyleneglycol, the molar content that accounts for total alcohol is 75%~99.5%, all the other alkoxide components are aliphatic diol, the C that contains side group
2, C
3, C
5~C
10In alkanediol or the aliphatic tribasic alcohol one or more;
Wherein, the molar content ratio of alkoxide component and acid constituents is 1.1~1.4 among three groups of A, B and the C;
The intrinsic viscosity of the copolyesters that obtains is 0.6~2.2dl/g, 70~115 ℃ of fusing points, degree of crystallinity 20~70%, weight-average molecular weight is 5~300,000, tensile strength is 30~60MPa, elongation at break is 40~500%, and the biodegradability of described copolyesters is according to ASTMD5338 weightlessness 6~17% in a week.
2, Biodegradable branched co-polyester according to claim 1 is characterized in that, described copolyesters comprises poly-succinic acid-butanediol-common-Succinic Acid 1,2,4 trihydroxybutane esters; Poly-succinic acid-butanediol-altogether-Succinic Acid 1,2-hexylene glycol ester; Poly-succinic acid-butanediol-altogether-Succinic Acid 1, the 2-pentadiol ester; Poly-succinic acid-butanediol-altogether-Succinic Acid 1,2-decanediol ester; Poly-succinic acid-butanediol-altogether-the Succinic Acid hexylene glycol-altogether-Succinic Acid 1,2, the 3-glycerine ester; Poly-succinic acid-butanediol-altogether-the Succinic Acid hexylene glycol-altogether-Succinic Acid 1,2-hexylene glycol ester; Poly-succinic acid-butanediol-be total to-2,2-dimethyl succinic acid butanediol ester; Poly-succinic acid-butanediol-altogether-the pyrovinic acid butanediol ester; Poly-succinic acid-butanediol-altogether-the trimesic acid butanediol ester; Poly-succinic acid-butanediol-altogether-mutual-phenenyl two acid bromide two alcohol ester; Poly-succinic acid-butanediol-altogether-the terephthalic acid butyleneglycol-altogether-tetramethylene adipate; Poly-succinic acid-butanediol-altogether-the trimesic acid butyleneglycol-altogether-tetramethylene adipate; Poly-succinic acid-butanediol-altogether-Succinic Acid 1,2, the 3-glycerine ester; Poly-succinic, butyleneglycol, hexanodioic acid and 1,2, the copolyesters of 3-glycerol or poly-succinic, butyleneglycol, trimesic acid and 1,2, the copolyesters of 3-glycerol.
3, Biodegradable branched co-polyester according to claim 1 is characterized in that, the described aliphatic diol of side group that contains is for having the C of alkyl branches (R)
2~C
10Alkanediol, wherein the carbon number of R is 1~12.
4, Biodegradable branched co-polyester according to claim 1 is characterized in that, the described aliphatic dibasic acids of side group that contains is for having the C of alkyl branches (R)
3~C
8The chain docosandioic acid, wherein the carbon number of R is 1~12.
5, Biodegradable branched co-polyester according to claim 1 is characterized in that, described aliphatic tribasic alcohol is 1,2,4-trihydroxybutane or 1,2,3-glycerol.
6, Biodegradable branched co-polyester according to claim 1 is characterized in that, described triprotic acid is trimesic acid or benzene-1.
7, a kind of preparation method of Biodegradable branched co-polyester is characterized in that, finishes according to following operation steps:
(1) prepolymer is synthetic
By acid and pure molar content and component in above-mentioned A, B or the C group, it is joined in the reactor with temperature-programmed mode temperature reaction system to 140~250 ℃, be warmed up to 180~240 ℃ with temperature-programmed mode behind the reaction 10min, keep this thermotonus 50~100min up to the system thickness, the prepolymer that obtains extremely no longer splashes 180~220 ℃ of following violent stirring.
(2) polycondensation of multipolymer
Esterification cools to 150~160 ℃ with system after finishing, and connects vacuum system, be evacuated to below the 0.5mmHg, reaction 5~10min does not participate in the small molecules of reaction and the water of remnants in the removal system, stop to vacuumize and feeding nitrogen, add composite catalyst 2 * 10
-4~50 * 10
-4G/g polyester, and stablizer 2 * 10
-4~50 * 10
-4The g/g polyester; Stir 10~30min and guarantee that catalyzer is dispersed in the reaction system, stop logical nitrogen, be evacuated to below the 0.5mmHg, and be rapidly heated to 200 ℃~240 ℃ of temperature of reaction, keep simultaneously stirring fast, isothermal reaction 30~100min promptly obtains product under vacuum state.
8, the method for preparing Biodegradable branched co-polyester according to claim 7, it is characterized in that described composite catalyst is one or more in tetrabutyl titanate, isopropyl titanate, titanium dioxide and silicon dioxide coprecipitate, antimonous oxide, zinc acetate, Cobaltous diacetate, lanthanum acetate, acetic acid zirconium, acetic acid hafnium, manganese acetate, zinc chloride, Lanthanum trichloride, zirconium chloride, hafnium chloride, methyl ethyl diketone lanthanum, methyl ethyl diketone zirconium, methyl ethyl diketone hafnium, inferior tin oxalate or the stannous octoate.
9, according to claim 7 or the 8 described methods that prepare Biodegradable branched co-polyester, it is characterized in that, described composite catalyst is the mixture of tetrabutyl titanate and methyl ethyl diketone lanthanum or the mixture of titanium dioxide and silicon dioxide coprecipitate and methyl ethyl diketone lanthanum, and wherein the mol ratio of tetrabutyl titanate or titanium dioxide and silicon dioxide coprecipitate and methyl ethyl diketone lanthanum is 1:1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2008102465629A CN101445592B (en) | 2008-12-25 | 2008-12-25 | Biodegradable branched co-polyester and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2008102465629A CN101445592B (en) | 2008-12-25 | 2008-12-25 | Biodegradable branched co-polyester and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101445592A true CN101445592A (en) | 2009-06-03 |
CN101445592B CN101445592B (en) | 2012-03-07 |
Family
ID=40741498
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2008102465629A Active CN101445592B (en) | 2008-12-25 | 2008-12-25 | Biodegradable branched co-polyester and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN101445592B (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102344556A (en) * | 2011-08-08 | 2012-02-08 | 北京旭阳化工技术研究院有限公司 | Biodegradable branched aromatic polyester-aliphatic polyester multi-block polymer |
CN102850533A (en) * | 2011-07-01 | 2013-01-02 | 上海杰事杰新材料(集团)股份有限公司 | Biodegradable polyester and its preparation method |
CN103788348A (en) * | 2013-12-27 | 2014-05-14 | 上海华谊(集团)公司 | Method for preparing modified poly(butylene succinate) (PBS) |
CN103842403A (en) * | 2011-09-02 | 2014-06-04 | 三星精密化学株式会社 | Production method for a biodegradable polyester copolymer resin |
CN107312165A (en) * | 2016-04-26 | 2017-11-03 | 中国科学院理化技术研究所 | Degradable thermoplastic polyester elastomer with side chain and preparation method thereof |
CN109897348A (en) * | 2018-12-19 | 2019-06-18 | 长春工业大学 | A kind of PBS composite material and preparation method of the toughener containing PBST |
CN111499849A (en) * | 2020-05-29 | 2020-08-07 | 陕西科技大学 | Polyhydroxy hydrophilic biodegradable material and preparation method and application thereof |
CN113881198A (en) * | 2021-10-22 | 2022-01-04 | 汉中聚智达远环能科技有限公司 | Biodegradable material with polar groups for adhesive tape production and preparation method thereof |
CN114133544B (en) * | 2021-12-13 | 2023-03-14 | 常州大学盱眙凹土研发中心 | Biodegradable hyperbranched modified PBS (Poly Butylene succinate) polyester and preparation method thereof |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100360581C (en) * | 2004-12-23 | 2008-01-09 | 中国石油化工股份有限公司 | Catalyst system and application in use for synthesizing degradable polyester |
CN1861660B (en) * | 2006-06-16 | 2010-07-28 | 清华大学 | Biologic degradable copolyester and preparation process thereof |
CN101597373A (en) * | 2008-06-06 | 2009-12-09 | 常利红 | The processing method of preparation aliphatic copolyester |
-
2008
- 2008-12-25 CN CN2008102465629A patent/CN101445592B/en active Active
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102850533B (en) * | 2011-07-01 | 2015-10-14 | 上海杰事杰新材料(集团)股份有限公司 | A kind of biodegradable polyesters and preparation method thereof |
CN102850533A (en) * | 2011-07-01 | 2013-01-02 | 上海杰事杰新材料(集团)股份有限公司 | Biodegradable polyester and its preparation method |
CN102344556A (en) * | 2011-08-08 | 2012-02-08 | 北京旭阳化工技术研究院有限公司 | Biodegradable branched aromatic polyester-aliphatic polyester multi-block polymer |
CN103842403B (en) * | 2011-09-02 | 2016-03-23 | 三星精密化学株式会社 | The preparation method of biodegradable polyethylene terephthalate copolymer resin |
CN103842403A (en) * | 2011-09-02 | 2014-06-04 | 三星精密化学株式会社 | Production method for a biodegradable polyester copolymer resin |
CN103788348B (en) * | 2013-12-27 | 2016-02-03 | 上海华谊(集团)公司 | Prepare the method for modified butanediol ester poly succinic acid |
CN103788348A (en) * | 2013-12-27 | 2014-05-14 | 上海华谊(集团)公司 | Method for preparing modified poly(butylene succinate) (PBS) |
CN107312165A (en) * | 2016-04-26 | 2017-11-03 | 中国科学院理化技术研究所 | Degradable thermoplastic polyester elastomer with side chain and preparation method thereof |
CN107312165B (en) * | 2016-04-26 | 2020-04-24 | 中国科学院理化技术研究所 | Degradable thermoplastic polyester elastomer with side chain and preparation method thereof |
CN109897348A (en) * | 2018-12-19 | 2019-06-18 | 长春工业大学 | A kind of PBS composite material and preparation method of the toughener containing PBST |
CN111499849A (en) * | 2020-05-29 | 2020-08-07 | 陕西科技大学 | Polyhydroxy hydrophilic biodegradable material and preparation method and application thereof |
CN113881198A (en) * | 2021-10-22 | 2022-01-04 | 汉中聚智达远环能科技有限公司 | Biodegradable material with polar groups for adhesive tape production and preparation method thereof |
CN113881198B (en) * | 2021-10-22 | 2024-03-01 | 汉中聚智达远环能科技有限公司 | Biodegradable material with polar groups for adhesive tape production and preparation method thereof |
CN114133544B (en) * | 2021-12-13 | 2023-03-14 | 常州大学盱眙凹土研发中心 | Biodegradable hyperbranched modified PBS (Poly Butylene succinate) polyester and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN101445592B (en) | 2012-03-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101445592B (en) | Biodegradable branched co-polyester and preparation method thereof | |
JP6034350B2 (en) | Polyester containing isosorbide | |
CN102336896B (en) | Preparation method of lightly-crosslinked aliphatic-aromatic copolyester | |
CN102344556B (en) | Biodegradable branched aromatic polyester-aliphatic polyester multi-block polymer | |
CN1861660B (en) | Biologic degradable copolyester and preparation process thereof | |
CN103025828B (en) | Blend of polylactic acid resin and copolyester resin, and molded product using same | |
CN103764714A (en) | Method for the preparation of (polybutylene-co-adipate terephthalate) through the in situ phosphorus containing titanium based catalyst | |
CN102050941B (en) | Macromolecular polymer and production method thereof | |
BR112016025409B1 (en) | composition, article, multilayer structure and method of improving gas barrier properties | |
CN102276808A (en) | Preparation method of polyterephthalic acid ethane diacid glycol copolyester | |
CN103946307A (en) | Polylactic acid resin and copolymer polyester resin blend, and molded product using same | |
KR101235016B1 (en) | Biodegradable Copolyester Resin with High Thermal Property and Process of Preparation thereof | |
CN101755010B (en) | Method for stabilizing polymers containing repeating lactic acid units, and stabilized polymers so made | |
JP3616522B2 (en) | Resin composition and method for producing the same | |
KR20120096165A (en) | Biodegradable copolyester resin made from biomass resources | |
TW201331259A (en) | Aliphatic-aromatic copolyetheresters | |
JP2024501278A (en) | Improved polyester compositions for extrusion blow molded containers | |
KR20150017797A (en) | Eco-friendly Copolyester Resin and Process of Preparing Same | |
TW201343378A (en) | Polyester hollow molded body and method for forming polyester hollow molded body | |
CN103665353B (en) | A kind of biodegradable copolyester and preparation method thereof | |
JP2013166874A (en) | Copolymerized polyester resin, and coating, coating agent, and adhesive using the same | |
JP2014025022A (en) | Method for producing copolymerized aromatic polyester | |
CN104356372A (en) | Cladodified fat-aromatic copolyester and synthesis method thereof | |
JPWO2013140947A1 (en) | Method for producing flame retardant polyester and flame retardant masterbatch | |
Sepehri et al. | Synthesis and characterization of copolymers of poly (ethylene terephthalate) and cyclohexane dimethanol in a semibatch reactor (including the process model) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |