CN101250258A - Method for producing bio-degradable copolyester by employing composite catalyst - Google Patents
Method for producing bio-degradable copolyester by employing composite catalyst Download PDFInfo
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- CN101250258A CN101250258A CNA2008100918997A CN200810091899A CN101250258A CN 101250258 A CN101250258 A CN 101250258A CN A2008100918997 A CNA2008100918997 A CN A2008100918997A CN 200810091899 A CN200810091899 A CN 200810091899A CN 101250258 A CN101250258 A CN 101250258A
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- Prior art keywords
- composite catalyst
- acid
- biodegradable copolyester
- contain
- butyleneglycol
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- 239000003054 catalyst Substances 0.000 title claims abstract description 115
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 26
- 238000005886 esterification reaction Methods 0.000 claims abstract description 25
- -1 phosphite esters compound Chemical class 0.000 claims abstract description 24
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000292 calcium oxide Substances 0.000 claims abstract description 14
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010936 titanium Substances 0.000 claims abstract description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 7
- 230000000737 periodic effect Effects 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 230000032050 esterification Effects 0.000 claims description 24
- 150000007942 carboxylates Chemical class 0.000 claims description 22
- 238000000967 suction filtration Methods 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 244000144992 flock Species 0.000 claims description 11
- 238000009775 high-speed stirring Methods 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- 238000009833 condensation Methods 0.000 claims description 10
- 230000005494 condensation Effects 0.000 claims description 10
- 229960001866 silicon dioxide Drugs 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- 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 claims description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000001384 succinic acid Substances 0.000 claims description 7
- LVFFZQQWIZURIO-UHFFFAOYSA-N 2-phenylbutanedioic acid Chemical compound OC(=O)CC(C(O)=O)C1=CC=CC=C1 LVFFZQQWIZURIO-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- DVQJZMHWNRXGSM-UHFFFAOYSA-N bis(2-methylpropyl) hydrogen phosphite Chemical compound CC(C)COP(O)OCC(C)C DVQJZMHWNRXGSM-UHFFFAOYSA-N 0.000 claims description 5
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 claims description 4
- REKYPYSUBKSCAT-UHFFFAOYSA-N 3-hydroxypentanoic acid Chemical compound CCC(O)CC(O)=O REKYPYSUBKSCAT-UHFFFAOYSA-N 0.000 claims description 4
- BVXOPEOQUQWRHQ-UHFFFAOYSA-N dibutyl phosphite Chemical compound CCCCOP([O-])OCCCC BVXOPEOQUQWRHQ-UHFFFAOYSA-N 0.000 claims description 4
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 claims description 3
- 229940006015 4-hydroxybutyric acid Drugs 0.000 claims description 3
- IWHLYPDWHHPVAA-UHFFFAOYSA-N 6-hydroxyhexanoic acid Chemical compound OCCCCCC(O)=O IWHLYPDWHHPVAA-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 5
- 230000035484 reaction time Effects 0.000 abstract description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 abstract 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 abstract 1
- 229960005137 succinic acid Drugs 0.000 abstract 1
- 150000003609 titanium compounds Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 40
- 239000000203 mixture Substances 0.000 description 11
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000005453 pelletization Methods 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 241000237502 Ostreidae Species 0.000 description 6
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 235000020636 oyster Nutrition 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229910052787 antimony Inorganic materials 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- LPHBARMWKLYWRA-UHFFFAOYSA-N thallium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tl+3].[Tl+3] LPHBARMWKLYWRA-UHFFFAOYSA-N 0.000 description 3
- 150000003608 titanium Chemical class 0.000 description 3
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 206010023126 Jaundice Diseases 0.000 description 1
- 229910004339 Ti-Si Inorganic materials 0.000 description 1
- 229910010978 Ti—Si Inorganic materials 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 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 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a process for producing biodegradable copolyester through adopting composite catalyst, which comprises the following steps: firstly conducting esterification reaction for dihydric alcohol which is major 1, 4-butanediol and dicarboxylic acid which is major butanedioic acid, secondly adding homogeneous liquid composite catalyst solution into esterified ester to conduct polycondensation reaction, and finally obtaining biodegradable copolyester, wherein the preparation of homogeneous liquid composite catalyst solution comprises preparing composite catalyst using titanium compounds whose general formula is Ti (OR)4, phosphite esters compound, silica dioxide, calcium oxide and at least one metallic oxide which is chosen from periodic table of elements IIIA, and preparing composite catalyst into homogeneous liquid composite catalyst solution. The process overcomes the weaknesses existing in the current biodegradable copolyester production, has the advantages of small amount of catalyst, short reaction time, excellent hue of biodegradable copolyester which is produced, much idler molecular weight and distribution, flow-ability and various physicochemical indexes.
Description
(1) technical field:
The present invention relates to a kind of production method of organic polymer, mainly relate to a kind of production method of biodegradable copolyester.
(2) background technology:
Because the extensive utilization of the macromolecular material that polyethylene, polyvinyl chloride, polypropylene and polystyrene etc. are traditional, depleted plastics film, bubble wrap thing and plastics bag are also more and more serious to the pollution of environment, have become one of environmental hazard.Fats or be a kind of fully biodegradable polymkeric substance with the copolyesters of a small amount of aromatic nucleus, it can be under the effect of bacterium or enzyme, and eventual degradation becomes materials such as carbonic acid gas and water, environmental sound.Copolyesters is generally thermoplastic resin, have nontoxic, fusing point is higher, good mechanical property, be convenient to advantages such as processing, therefore biodegradable copolyester is expected to replace traditional macromolecular materials such as polyethylene, polyvinyl chloride, polypropylene and polystyrene fully and enters the general-purpose plastics field, reduce the usage quantity of traditional macromolecular material such as polyethylene, polyvinyl chloride, polypropylene and polystyrene, alleviate traditional macromolecular material pollution on the environment.Simultaneously, because it has nontoxicity and excellent biological compatibility, also good prospects for application will be arranged in fields such as medical material and pharmaceutical carriers.At present, Japan and Germany put into production, but higher as the production cost of biodegradable copolyesters such as poly butylene succinate, and many mechanical properties still can not satisfy the actual needs of specific industry.Therefore, people begin it has been carried out a large amount of study on the modification.CN ZL 200410040914.7 and CN ZL200610012284.1 adopt by with different copolymer diacid such as hexanodioic acid and the pyrovinic acid, the phenylsuccinic acid, 2 that have side group, the copolymerization of polymerization single polymerization monomers such as 2-dimethyl succinic acid etc. and different copolymer glycol such as ethylene glycol, propylene glycol, hexylene glycol, finally obtain random linear copolyester, improved the part mechanical property, made copolyesters have certain actual application value.Polycondensation catalyst plays crucial effects in the production process of copolyesters, in copolyesters industry, use antimony-based catalysts at present in a large number, because antimony compounds itself has certain toxicity, coexist with hypertoxic arsenic again at occurring in nature, therefore the biodegradable copolyester material with antimony-based catalyst production has been subjected to certain restriction on use range.Titanium series catalyst is because it is active high, do not contain heavy metal, thereby is subjected to paying close attention to widely.AcordiS company and sachtleben company have developed novel Titanium series catalyst respectively, has very high catalytic activity and stability, but more complicated aspect catalyst treatment, and side reaction is more obvious in the polycondensation process, long reaction time causes copolyesters product form and aspect poor than antimony-based catalyst.And the C94 Ti-Si catalyst is the catalyzer that is used for various copolyesters polycondensations of AcordiS company exploitation, but poor with the copolyesters product stability of its production, mechanical performance index is undesirable and problems such as jaundice, muddiness, never used on a large scale.
(3) summary of the invention:
The object of the present invention is to provide that catalyst levels is few, reaction times weak point, product polymerization degree height, good physical and chemical properties, nontoxic a kind of method that adopts composite catalyst to produce biodegradable copolyester.
For achieving the above object, a kind of method that adopts composite catalyst to produce biodegradable copolyester of the present invention,
May further comprise the steps successively:
One, esterification:
With mol ratio is 1～1.5: 1: 0～0.01 with 1, the 4-butyleneglycol is main dibasic alcohol, stir based on the di-carboxylic acid of Succinic Acid and hydroxycarboxylic acid after, at esterification temperature is that 150～230 ℃, absolute pressure are under the condition of 0.07～0.11MPa, stirring reaction 2～6h obtains carboxylate;
Two, polycondensation:
The liquid complex catalyst solution of homogeneous phase is joined in the carboxylate, at condensation temperature is 200～290 ℃, stir under the condition of absolute pressure＜100Pa and carry out polycondensation, no longer increase as reaction end with the agitator motor electric current, obtain the biodegradable copolyester melt, the biodegradable copolyester melt obtains biodegradable copolyester after cooling;
Wherein: the preparation of the liquid complex catalyst solution of described homogeneous phase may further comprise the steps successively:
(a), with general formula be Ti (OR)
4Titanium compound and second alcohol and water thorough mixing, wherein R is C
1-C
4In a kind of alkyl, obtain white flocks, throw out at first passes through suction filtration, passes through toluene wash, final drying then;
(b), dried throw out is dissolved in the phosphite ester compound, add silicon-dioxide, calcium oxide then and be selected from least a metal oxide among the periodic table of elements IIIA, in temperature is 100～200 ℃ of following total reflux high-speed stirring 6-10h, must contain sedimentary mixing solutions;
(c), throw out at first passes through suction filtration, final drying, composite catalyst;
(d), composite catalyst is dissolved in 1, make the liquid complex catalyst solution of homogeneous phase in the 4-butyleneglycol;
Wherein: general formula is Ti (OR)
4Titanium compound, phosphite ester compound, silicon-dioxide, calcium oxide and the mol ratio that is selected from least a metal oxide consumption among the periodic table of elements IIIA be 1: 0.15～0.4: 0.5～0.3: 0.1～0.3: 0.05～0.3.
Its formula of is Ti (OR)
4Titanium compound be in metatitanic acid tetramethyl ester, tetraethyl titanate, metatitanic acid orthocarbonate and the tetra-n-butyl titanate one or more.
Wherein phosphite ester compound is one or more in triphenyl phosphite, dibutyl phosphite, the phosphorous acid diisobutyl ester.
Wherein be selected from least a metal oxide among the periodic table of elements IIIA and be in the oxide compound of aluminium, indium, thallium one or more.
Wherein with 1, the 4-butyleneglycol is also to contain C in the dibasic alcohol of leading
2-C
4Dibasic alcohol in one or more.
Wherein also to contain C in the di-carboxylic acid of Succinic Acid
2-C
10Di-carboxylic acid in one or more.
Wherein with 1, the 4-butyleneglycol is also to contain in ethylene glycol, the glycol ether one or more in the main dibasic alcohol.
Wherein also to contain in pyrovinic acid, phenylsuccinic acid, the hexanodioic acid one or more in the di-carboxylic acid of Succinic Acid.
Wherein hydroxycarboxylic acid is one or more in oxyacetic acid, 4 hydroxybutyric acid, 6 hydroxycaproic acid, L-lactic acid, 3-hydroxybutyric acid, the 3-hydroxypentanoic acid.
Wherein the addition of composite catalyst is 100～300ppm of dibasic alcohol, di-carboxylic acid and hydroxycarboxylic acid reaction gross weight.
Owing in the production method of above-mentioned biodegradable copolyester, adopted composite catalyst, it had both overcome the restricted defective of product use range that present antimony-based catalyst is produced, also overcome present Titanium series catalyst product hue difference, physicochemical property is undesirable, can not realize the defective of suitability for industrialized production.A kind of method that adopts composite catalyst to produce biodegradable copolyester of the present invention, it is few to have catalyst levels, reaction times is short, the biodegradable copolyester form and aspect of producing are good, molecular weight and distribution thereof, flowability and every physical and chemical index be the ideal advantage comparatively, can be used for hydrostomia, blown film and injection moulding, its quality product and production efficiency all are higher than currently available products.
(4) embodiment:
Below in conjunction with embodiment the present invention is described in further detail.
Embodiment 1
(1), the preparation of composite catalyst:
In beaker, add metatitanic acid tetramethyl ester 172g under the normal temperature, ethanol 50g, water 50g mix stirring, obtain white flocks; Throw out at first passes through suction filtration, passes through toluene wash, final drying then; Dried throw out being joined in the 50g dibutyl phosphite, add silicon-dioxide 6g, calcium oxide 12g, aluminium sesquioxide 6g simultaneously, is 105 ℃ of following total reflux high-speed stirring 6h in temperature, must contain sedimentary mixing solutions; Throw out at first passes through suction filtration, and last vacuum-drying 10h obtains composite catalyst.
(2), the preparation of the liquid complex catalyst solution of homogeneous phase:
100g is dissolved in 1 with composite catalyst, makes the liquid complex catalyst solution of 2000ml homogeneous phase in the 4-butyleneglycol;
(3), esterification:
Add 100Kg Succinic Acid, 22Kg hexanodioic acid, 3.3Kg ethylene glycol, 89.8Kg 1 in the reactor of 1000L, 4-butyleneglycol and 250g oxyacetic acid are after stirring, at esterification temperature is 150 ℃, absolute pressure is under the condition of 0.1MPa, and stirring reaction 2h forms carboxylate;
(4), polycondensation:
Carboxylate during the liquid complex catalyst solution 720ml of homogeneous phase that will contain the 36g composite catalyst adds, at condensation temperature is 235 ℃, absolute pressure is that constant temperature stirs and carries out polycondensation 2.3h under the condition of 71Pa, this moment, the agitator motor electric current no longer increased, and was reaction end, obtained biodegradable copolyester melt involved in the present invention, the biodegradable copolyester melt is through extruding, stretch, cooling, pelletizing obtains the biodegradable copolyester particle.
Embodiment 2
(1), the preparation of composite catalyst:
In beaker, add tetraethyl titanate 228g under the normal temperature, ethanol 50g, water 50g mix stirring, obtain white flocks; Throw out at first passes through suction filtration, passes through toluene wash, final drying then; Dried throw out being joined in the 62g phosphorous acid diisobutyl ester, add silicon-dioxide 6g, calcium oxide 10g, indium trioxide 28g simultaneously, is 170 ℃ of following total reflux high-speed stirring 7h in temperature, must contain sedimentary mixing solutions; Throw out at first passes through suction filtration, and last vacuum-drying 8h obtains composite catalyst.
(2), the preparation of the liquid complex catalyst solution of homogeneous phase:
150g is dissolved in 1 with composite catalyst, makes the liquid complex catalyst solution of 2800ml homogeneous phase in the 4-butyleneglycol;
(3), esterification:
Add 100Kg Succinic Acid, 30Kg phenylsuccinic acid, 6Kg glycol ether, 94Kg1 in the 1000L reactor, 4-butyleneglycol and 228g4-hydroxybutyric acid are after stirring, at esterification temperature is 180 ℃, absolute pressure is under the condition of 0.08MPa, and stirring reaction 3h forms carboxylate;
(4), polycondensation:
The liquid complex catalyst solution 515ml of homogeneous phase that will contain the 27.6g composite catalyst adds in the carboxylate, at condensation temperature is 290 ℃, absolute pressure is that constant temperature stirs and carries out polycondensation 3.1h under the condition of 82Pa, this moment, the agitator motor electric current no longer increased, and was reaction end, obtained biodegradable copolyester melt involved in the present invention, the biodegradable copolyester melt is through extruding, stretch, cooling, pelletizing obtains the biodegradable copolyester particle.
Embodiment 3
(1), the preparation of composite catalyst:
In beaker, add metatitanic acid orthocarbonate 284g under the normal temperature, ethanol 50g, water 50g mix stirring, obtain white flocks; Throw out at first passes through suction filtration, passes through toluene wash, final drying then; Dried throw out is joined in the mixture of 50g phosphorous acid diisobutyl ester and 10g triethyl-phosphite, add silica 1 2g, calcium oxide 11g, thallium trioxide 45g simultaneously, in temperature is 200 ℃ of following total reflux high-speed stirring 8h, must contain sedimentary mixing solutions; Throw out at first passes through suction filtration, and last vacuum-drying 9h obtains composite catalyst.
(2), the preparation of the liquid complex catalyst solution of homogeneous phase:
140g is dissolved in 1 with composite catalyst, makes the liquid complex catalyst solution of 2100ml homogeneous phase in the 4-butyleneglycol;
(3), esterification:
In the 1000L reactor, add 106Kg Succinic Acid, 13.3Kg pyrovinic acid, 6Kg glycol ether, 94Kg1,4-butyleneglycol and 132g6-hydroxycaproic acid, 90gL-lactic acid, after stirring, at esterification temperature is 210 ℃, absolute pressure is under the condition of 0.078MPa, stirring reaction 2.5h forms carboxylate;
(4), polycondensation:
The liquid complex catalyst solution 735ml of homogeneous phase that will contain the 49g composite catalyst adds in the carboxylate, at condensation temperature is 260 ℃, absolute pressure is that constant temperature stirs and carries out polycondensation 2.9h under the condition of 66Pa, this moment, the agitator motor electric current no longer increased, and was reaction end, obtained biodegradable copolyester melt involved in the present invention, the biodegradable copolyester melt is through extruding, stretch, cooling, pelletizing obtains the biodegradable copolyester particle.
Embodiment 4
(1), the preparation of composite catalyst:
In beaker, add tetra-n-butyl titanate 340g under the normal temperature, ethanol 50g, water 50g mix stirring, obtain white flocks; Throw out at first passes through suction filtration, passes through toluene wash, final drying then; Dried throw out being joined in the 62g triphenyl phosphite, add silica 1 2g, calcium oxide 10g, aluminium sesquioxide 5g simultaneously, is 140 ℃ of following total reflux high-speed stirring 9h in temperature, must contain sedimentary mixing solutions; Throw out at first passes through suction filtration, and last vacuum-drying 9h obtains composite catalyst.
(2), the preparation of the liquid complex catalyst solution of homogeneous phase:
135g is dissolved in 1 with composite catalyst, makes the liquid complex catalyst solution of 2700ml homogeneous phase in the 4-butyleneglycol;
(3), esterification:
In the 1000L reactor, add 106Kg Succinic Acid, 14.6Kg hexanodioic acid, 6Kg glycol ether, 94Kg1,4-butyleneglycol, 2Kg ethylene glycol, after stirring, be 190 ℃ at esterification temperature, absolute pressure is under the condition of 0.95MPa, stirring reaction 2.5h forms carboxylate;
(4), polycondensation:
The liquid complex catalyst solution 1020ml of homogeneous phase that will contain the 51g composite catalyst adds in the carboxylate, in temperature is 250 ℃, absolute pressure is that constant temperature stirs and carries out polycondensation 2.8h under the condition of 77Pa, this moment, the agitator motor electric current no longer increased, and was reaction end, obtained biodegradable copolyester melt involved in the present invention, the biodegradable copolyester melt is through extruding, stretch, cooling, pelletizing obtains the biodegradable copolyester particle.
Embodiment 5
(1), the preparation of composite catalyst:
In beaker, add tetra-n-butyl titanate 340g under the normal temperature, ethanol 50g, water 50g mix stirring, obtain white flocks; Throw out at first passes through suction filtration, passes through toluene wash, final drying then; Dried throw out being joined in the 62g triphenyl phosphite, add silicon-dioxide 6g, calcium oxide 15g, aluminium sesquioxide 8g simultaneously, is 170 ℃ of following total reflux high-speed stirring 5.5h in temperature, must contain sedimentary mixing solutions; Throw out at first passes through suction filtration, and last vacuum-drying 8h obtains composite catalyst.
(2), the preparation of the liquid complex catalyst solution of homogeneous phase:
120g is dissolved in 1 with composite catalyst, makes the liquid complex catalyst solution of 2400ml homogeneous phase in the 4-butyleneglycol;
(3), esterification:
In the 1000L reactor, add 106Kg Succinic Acid, 5Kg pyrovinic acid, 14.6Kg hexanodioic acid, 6Kg glycol ether, 94Kg1,4-butyleneglycol and 104g3-hydroxybutyric acid, 57g3-hydroxypentanoic acid, after stirring, at esterification temperature is 225 ℃, absolute pressure is under the condition of 0.1MPa, stirring reaction 3.5h forms carboxylate;
(4), polycondensation:
The liquid complex catalyst solution 1120ml of homogeneous phase that will contain the 56g composite catalyst adds in the carboxylate, at condensation temperature is 290 ℃, absolute pressure is that constant temperature stirs and carries out polycondensation 3.2h under the condition of 59Pa, this moment, the agitator motor electric current no longer increased, and was reaction end, obtained biodegradable copolyester melt involved in the present invention, the biodegradable copolyester melt is through extruding, stretch, cooling, pelletizing obtains the biodegradable copolyester particle.
Embodiment 6
(1), the preparation of composite catalyst:
In beaker, add tetra-n-butyl titanate 340g under the normal temperature, ethanol 50g, water 50g mix stirring, obtain white flocks; Throw out at first passes through suction filtration, passes through toluene wash, final drying then; Dried throw out being joined in the 62g phosphorous acid diisobutyl ester, add silicon-dioxide 6g, calcium oxide 10g, indium trioxide 28g simultaneously, is 170 ℃ of following total reflux high-speed stirring 10h in temperature, must contain sedimentary mixing solutions; Throw out at first passes through suction filtration, and last vacuum-drying 12h obtains composite catalyst.
(2), the preparation of the liquid complex catalyst solution of homogeneous phase:
160g is dissolved in 1 with composite catalyst, makes the liquid complex catalyst solution of 3000ml homogeneous phase in the 4-butyleneglycol;
(2), esterification:
Add 100Kg Succinic Acid, 22Kg hexanodioic acid, 3Kg ethylene glycol, 6Kg glycol ether, 94Kg1 in the 1000L reactor, the 4-butyleneglycol is after stirring, at esterification temperature is 180 ℃, absolute pressure is under the condition of 0.88MPa, and stirring reaction 2.7h forms carboxylate;
(3), polycondensation:
The liquid complex catalyst solution 1220ml of homogeneous phase that will contain the 65g composite catalyst adds in the carboxylate, at condensation temperature is 265 ℃, absolute pressure is that constant temperature stirs and carries out polycondensation 2.8h under the condition of 70Pa, this moment, the agitator motor electric current no longer increased, and was reaction end, obtained biodegradable copolyester melt involved in the present invention, the biodegradable copolyester melt is through extruding, stretch, cooling, pelletizing obtains the biodegradable copolyester particle.
Embodiment 7
(1), the preparation of composite catalyst:
In beaker, add tetraethyl titanate 200g, tetra-n-butyl titanate 44g, ethanol 50g, water 50g under the normal temperature and mix stirring, obtain white flocks; Throw out at first passes through suction filtration, passes through toluene wash, final drying then; Dried throw out being joined in the 48g triethyl-phosphite, add silica 1 1g, calcium oxide 10g, thallium trioxide 45g, aluminium sesquioxide 2g simultaneously, is 200 ℃ of following total reflux high-speed stirring 6h in temperature, must contain sedimentary mixing solutions; Throw out at first passes through suction filtration, and last vacuum-drying 9h obtains composite catalyst.
(2), the preparation of the liquid complex catalyst solution of homogeneous phase:
150g is dissolved in 1 with composite catalyst, makes the liquid complex catalyst solution of 2250ml homogeneous phase in the 4-butyleneglycol;
(3), esterification:
Add 100Kg Succinic Acid, 12Kg pyrovinic acid, 3Kg phenylsuccinic acid, 5Kg glycol ether, 97Kg1 in the 1000L reactor, the 4-butyleneglycol is after stirring, at esterification temperature is 230 ℃, absolute pressure is under the condition of 0.08MPa, and stirring reaction 3h forms carboxylate;
(4), polycondensation:
The liquid complex catalyst solution 495ml of homogeneous phase that will contain the 33g composite catalyst adds in the carboxylate, at condensation temperature is 255 ℃, absolute pressure is that constant temperature stirs and carries out polycondensation 2.5h under the condition of 70Pa, this moment, the agitator motor electric current no longer increased, and was reaction end, obtained biodegradable copolyester melt involved in the present invention, the biodegradable copolyester melt is through extruding, stretch, cooling, pelletizing obtains the biodegradable copolyester particle.
Embodiment 8
(1), the preparation of composite catalyst:
In beaker, add tetra-n-butyl titanate 340g under the normal temperature, ethanol 50g, water 50g mix stirring, obtain white flocks; Throw out at first passes through suction filtration, passes through toluene wash, final drying then; Dried throw out is joined in the mixture of 51g triethyl-phosphite and 13g dibutyl phosphite, add silicon-dioxide 6g, calcium oxide 12g, indium trioxide 27g, thallium trioxide 3g simultaneously, in temperature is 110 ℃ of following total reflux high-speed stirring 5.5h, must contain sedimentary mixing solutions; Throw out at first passes through suction filtration, and last vacuum-drying 8h obtains composite catalyst.
(2), the preparation of the liquid complex catalyst solution of homogeneous phase:
150g is dissolved in 1 with composite catalyst, makes the liquid complex catalyst solution of 3000ml homogeneous phase in the 4-butyleneglycol;
(3), esterification:
In the 1000L reactor, add 101Kg Succinic Acid, 20Kg hexanodioic acid, 3Kg ethylene glycol, 2Kg glycol ether, 88Kg1,4-butyleneglycol and 200g6-hydroxycaproic acid, 40g 4 hydroxybutyric acid, 160g L-lactic acid, after stirring, at esterification temperature is 150 ℃, absolute pressure is under the condition of 0.09MPa, stirring reaction 3h forms carboxylate;
(4), polycondensation:
The liquid complex catalyst solution 730ml of homogeneous phase that will contain the 36.5g composite catalyst adds carboxylate, at condensation temperature is 245 ℃, absolute pressure is that constant temperature stirs and carries out polycondensation 2.5h under the condition of 73Pa, this moment, the agitator motor electric current no longer increased, and was reaction end, obtained biodegradable copolyester melt involved in the present invention, the biodegradable copolyester melt is through extruding, stretch, cooling, pelletizing obtains the biodegradable copolyester particle.
Embodiment 9
(1), the preparation of composite catalyst:
In beaker, add metatitanic acid tetramethyl ester 172g under the normal temperature, ethanol 50g, water 50g mix stirring, obtain white flocks; Throw out at first passes through suction filtration, passes through toluene wash, final drying then; Dried throw out being joined in the 88g triphenyl phosphite, add silicon-dioxide 6g, calcium oxide 10g, aluminium sesquioxide 28g simultaneously, is 170 ℃ of following total reflux high-speed stirring 8h in temperature, must contain sedimentary mixing solutions; Throw out at first passes through suction filtration, and last vacuum-drying 7h obtains composite catalyst.
(2), the preparation of the liquid complex catalyst solution of homogeneous phase:
110g is dissolved in 1 with composite catalyst, makes the liquid complex catalyst solution of 2200ml homogeneous phase in the 4-butyleneglycol;
(2), esterification:
In the 1000L reactor, add 100Kg Succinic Acid, 10Kg pyrovinic acid, 2Kg phenylsuccinic acid, 3Kg ethylene glycol, 94Kg1,4-butyleneglycol, 14Kg ethylene glycol, after stirring, at esterification temperature is 170 ℃, absolute pressure is under the condition of 0.9MPa, stirring reaction 2.8h forms carboxylate;
(3), polycondensation:
The liquid complex catalyst solution 1080ml of homogeneous phase that will contain the 54g composite catalyst adds in the carboxylate, at condensation temperature is 275 ℃, absolute pressure is that constant temperature stirs and carries out polycondensation 2h under the condition of 69Pa, this moment, the agitator motor electric current no longer increased, and was reaction end, obtained biodegradable copolyester melt involved in the present invention, the biodegradable copolyester melt is through extruding, stretch, cooling, pelletizing obtains the biodegradable copolyester particle.
More than the reaction parameter and the product performance index comparison and detection of each embodiment and existing catalyzer the results are shown in following table 1 and table 2:
Table one
| Project | Tetrabutyl titanate | C-94 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Catalyst levels (ppm) | 3000 | 300 | 165 | 120 | 230 | 280 |
| Esterification time (h) | 3.4 | 3.2 | 2 | 3 | 2.5 | 2.5 |
| Polymerization time (h) | 3.1 | 3.5 | 2.3 | 3.1 | 2.9 | 2.8 |
| Apparent | Yellow, more transparent | Yellow, muddiness | Oyster white, translucent | Milk yellow is translucent | Oyster white, translucent | Oyster white, translucent |
| Weight-average molecular weight (gPC) | 65200 | 87100 | 185000 | 180100 | 189500 | 200300 |
| Molecular weight distribution | 2.258 | 1.837 | 1.821 | 1.825 | 1.824 | 1.815 |
| MFR(g/min) | 12.5 | 7.8 | 4.5 | 4.5 | 4 | 2 |
| Limiting viscosity (dL/g) | 0.564 | 0.662 | 0.695 | 0.690 | 0.685 | 0.720 |
| Tensile strength (MPa) | 30 | 35 | 38 | 38 | 37 | 42 |
| Flexural strength (MPa) | 22 | 30 | 32 | 35 | 34 | 38 |
| Elongation at break (%) | 170 | 240 | 260 | 300 | 270 | 480 |
| Shock strength (KJ/m 2) | 44 | 47 | 47 | 47 | 47 | 56 |
Table two
| Project | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 |
| Catalyst levels (ppm) | 250 | 290 | 150 | 170 | 240 |
| Esterification time (h) | 3.5 | 2.7 | 3 | 3 | 2.8 |
| Polymerization time (h) | 3.2 | 2.8 | 2.5 | 2.5 | 2 |
| Apparent | White, translucent | Oyster white, translucent | Oyster white, translucent | White, translucent | Oyster white, translucent |
| Weight-average molecular weight (gPC) | 186400 | 195600 | 184700 | 190500 | 188400 |
| Molecular weight distribution | 1.819 | 1.823 | 1.819 | 1.806 | 1.830 |
| MFR(g/min) | 3.6 | 3 | 4.4 | 3.9 | 4.1 |
| Limiting viscosity (dL/g) | 0.685 | 0.696 | 0.702 | 0.699 | 0.689 |
| Tensile strength (MPa) | 38 | 39 | 37 | 39 | 40 |
| Flexural strength (MPa) | 35 | 36 | 37 | 35 | 36 |
| Elongation at break (%) | 300 | 420 | 360 | 380 | 410 |
| Shock strength (KJ/m 2) | 48 | 51 | 50 | 51 | 48 |
By various reaction parameters and product performance index contrast in table 1 and the table 2 as seen, the biodegradable copolyester that a kind of method that adopts composite catalyst to produce biodegradable copolyester involved in the present invention is produced is compared with the biodegradable copolyester of existing other similar catalyst production, it is few to have catalyst levels, reaction times is short, the biodegradable copolyester form and aspect of producing are good, molecular weight and distribution thereof, mobile and every physical and chemical index is the ideal advantage comparatively, can be used for hydrostomia, its quality product of blown film and injection moulding and production efficiency all are higher than currently available products, have realized the suitability for industrialized production of biodegradable copolyester.
Claims (10)
1. method that adopts composite catalyst to produce biodegradable copolyester may further comprise the steps successively:
One, esterification:
With mol ratio is 1～1.5: 1: 0～0.01 with 1, the 4-butyleneglycol is main dibasic alcohol, stir based on the di-carboxylic acid of Succinic Acid and hydroxycarboxylic acid after, at esterification temperature is that 150～230 ℃, absolute pressure are under the condition of 0.07～0.11MPa, stirring reaction 2～6h obtains carboxylate;
Two, polycondensation:
The liquid complex catalyst solution of homogeneous phase is joined in the carboxylate, at condensation temperature is 200～290 ℃, stir under the condition of absolute pressure＜100Pa and carry out polycondensation, no longer increase as reaction end with the agitator motor electric current, obtain the biodegradable copolyester melt, the biodegradable copolyester melt obtains biodegradable copolyester after cooling;
Wherein: the preparation of the liquid complex catalyst solution of described homogeneous phase may further comprise the steps successively:
(a), with general formula be Ti (OR)
4Titanium compound and second alcohol and water thorough mixing, wherein R is C
1-C
4In a kind of alkyl, obtain white flocks, throw out at first passes through suction filtration, passes through toluene wash, final drying then;
(b), dried throw out is dissolved in the phosphite ester compound, add silicon-dioxide, calcium oxide then and be selected from least a metal oxide among the periodic table of elements IIIA, in temperature is 100～200 ℃ of following total reflux high-speed stirring 6-10h, must contain sedimentary mixing solutions;
(c), throw out at first passes through suction filtration, final drying, composite catalyst;
(d), composite catalyst is dissolved in 1, make the liquid complex catalyst solution of homogeneous phase in the 4-butyleneglycol;
Wherein: general formula is Ti (OR)
4Titanium compound, phosphite ester compound, silicon-dioxide, calcium oxide and the mol ratio that is selected from least a metal oxide consumption among the periodic table of elements IIIA be 1: 0.15～0.4: 0.5～0.3: 0.1～0.3: 0.05～0.3.
2. a kind of method that adopts composite catalyst to produce biodegradable copolyester according to claim 1, its formula of is Ti (OR)
4Titanium compound be in metatitanic acid tetramethyl ester, tetraethyl titanate, metatitanic acid orthocarbonate and the tetra-n-butyl titanate one or more.
3. a kind of method that adopts composite catalyst to produce biodegradable copolyester according to claim 1, wherein phosphite ester compound is one or more in triphenyl phosphite, dibutyl phosphite, the phosphorous acid diisobutyl ester.
4. a kind of method that adopts composite catalyst to produce biodegradable copolyester according to claim 1 wherein is selected from least a metal oxide among the periodic table of elements IIIA and is in the oxide compound of aluminium, indium, thallium one or more.
5. a kind of method that adopts composite catalyst to produce biodegradable copolyester according to claim 1, wherein with 1, the 4-butyleneglycol is also to contain C in the dibasic alcohol of leading
2-C
4Dibasic alcohol in one or more.
6. a kind of method that adopts composite catalyst to produce biodegradable copolyester according to claim 1 is wherein also to contain C in the di-carboxylic acid of Succinic Acid
2-C
10Di-carboxylic acid in one or more.
7. a kind of according to claim 1 or 5 method that adopts composite catalyst to produce biodegradable copolyester, wherein with 1, the 4-butyleneglycol is also to contain in ethylene glycol, the glycol ether one or more in the main dibasic alcohol.
8. according to claim 1 or 6 described a kind of methods that adopt composite catalyst to produce biodegradable copolyester, wherein also to contain in pyrovinic acid, phenylsuccinic acid, the hexanodioic acid one or more in the di-carboxylic acid of Succinic Acid.
9. a kind of method that adopts composite catalyst to produce biodegradable copolyester according to claim 1, wherein hydroxycarboxylic acid is one or more in oxyacetic acid, 4 hydroxybutyric acid, 6 hydroxycaproic acid, L-lactic acid, 3-hydroxybutyric acid, the 3-hydroxypentanoic acid.
10. a kind of method that adopts composite catalyst to produce biodegradable copolyester according to claim 1, wherein the addition of composite catalyst is 100～300ppm of dibasic alcohol, di-carboxylic acid and hydroxycarboxylic acid reaction gross weight.
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