CN102219891B - Method for preparing poly-oxalate-1,4-butylene - Google Patents
Method for preparing poly-oxalate-1,4-butylene Download PDFInfo
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- CN102219891B CN102219891B CN2011101248547A CN201110124854A CN102219891B CN 102219891 B CN102219891 B CN 102219891B CN 2011101248547 A CN2011101248547 A CN 2011101248547A CN 201110124854 A CN201110124854 A CN 201110124854A CN 102219891 B CN102219891 B CN 102219891B
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Abstract
The invention relates to a method for preparing poly-oxalate-1,4-butylene, and belongs to the technical field of high polymer materials. The method comprises the following steps of: putting diethyl oxalate, 1,4-butanediol and a catalyst into a reactor, and reacting at the constant temperature of between 80 and 170 DEG C with stirring under the protection of N2 with the flow of between 0.06 and 0.16 m<3>/hour for 0.5 to 5 hours to obtain the poly-oxalate-1,4-butylene, wherein a ratio of the diethyl oxalate to the 1,4-butanediol is 1:1-1:3; and the catalyst is oxalic acid preferably, and the catalyst is 0.1 to 5.0 molar percent based on the diethyl oxalate. In the method, the diethyl oxalate and the 1,4-butanediol also can react at the constant temperature of between 110 and 180 DEG C under the vacuum degree of between 200 and 500 Pa under constant pressure for 3 to 8 hours in the presence of the catalyst to obtain the poly-oxalate-1,4-butylene with higher intrinsic viscosity. By the method, the reaction time is shortened, the vacuum degree of the reaction is reduced, the cost is low, and operation and aftertreatment are simple, so the method is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of oxalic acid-1 that gathers, (Poly (Butylene Oxalate), preparation method PBO) belongs to technical field of polymer materials to the 4-butanediol ester.
Background technology
Conventional plastic derives from non-renewable petroleum resources, and is difficult to degraded, causes white pollution.Therefore, the bio-degradable plastics of development non-petroleum base replaces conventional plastic, and is all significant to plastic industry Sustainable development and ecological environmental protection.
Aliphatic polyester has favorable biological degradability, is the research focus of bio-degradable plastics.The subject matter that present biodegradable aliphatic polyester exists is mechanical property and cost problem.Study more aliphatic polyester comprise POLYACTIC ACID (PLA), PHA (PHA), gather (6-caprolactone) (PCL), poly (propylene carbonate) (PPC), poly butylene succinate (PBS) and polytetramethylene glycol Succinic Acid/adipic acid ester (PBSA) etc.Wherein, the wetting ability of PLA and fragility are stronger; The process window of PHA is narrower, the machine-shaping cycle is long, toughness is relatively poor and production capacity is less; PCL is from petroleum resources, and the T of PCL
g(second-order transition temperature) and T
m(melt temperature) is low, and application is had certain limitation; The softening temperature of PPC is low, can not use separately; PBS depends on oil, to moisture-sensitive.Generally, the cost of above-mentioned aliphatic polyester is all higher, has also influenced their commercialization application.
Compare with above-mentioned aliphatic polyester; The melt temperature of gathering barkite is higher, and multiple melt temperature of gathering oxalic acid alkanol ester is more than 100 ℃, and melt temperature surpasses 100 ℃ few in number in the aliphatic polyester; The static better heat stability of therefore gathering barkite, process window is broad also.Gathering barkite can be synthetic by oxalate diester or oxalic acid and divalent alcohol, and its raw material oxalate diester or oxalic acid derive from the biomass renewable resources, and cost is lower.Oxalate diester like dimethyl oxalate and oxalic acid diethyl ester, has been realized the preparation of CO gas-phase catalytic coupling method in the industry now, reduced synthetic cost.CO gas-phase catalytic coupling method is a kind of chemical technology of green, has effectively utilized the by product CO of industry such as coking industry, Steel industry, has reduced carbon emission.Traditional compound method is that oxalic acid carries out esterification with corresponding alcohol.In the industrial making method of oxalic acid, also main raw material in the sodium formate method with CO; And carbohydrate oxidation method and Mierocrystalline cellulose alkali fusion are raw material with biomass, like starch, Mierocrystalline cellulose etc., wide material sources and renewable.In addition, CO
2Electrochemical reduction also can make oxalic acid, this method can reduce industrial by-products CO
2Discharging, reduce cost, relax Greenhouse effect.Therefore, gather the synthetic significant with the development low-carbon economy of barkite to relaxing Greenhouse effect.
Can be that raw material is produced with the wood chip in the oxalic acid industry, can be that the raw material oxidation makes with starch or glucose mother liquid also, therefore is the raw material in a kind of biomass source.Gather oxalic acid-1, the 4-butanediol ester is with oxalic acid diethyl ester and 1, and the 4-butyleneglycol is a raw material, and it is lower to have a cost, the reproducible advantage of wide material sources.Gather oxalic acid-1; The melt temperature of 4-butanediol ester is 103 ℃, is higher than 100 ℃, only be lower than melt temperature in the melt temperature in straight chain diprotic acid and straight dihydric alcohol copolyesters and be 155 ℃ gather the oxalic acid glycol ester; Has good static heat stability, temperature process window broad.Therefore gather oxalic acid-1, the 4-butanediol ester has the potentiality that become general-purpose plastics as a kind of biodegradable material.Can be used as the masterbatch of general-purpose plastics, also can be used as material of main part and thermoplastic starch, amphipathic compatilizer hydroxyl functional polyester carries out blend, the preparation starch-based degradable plastics.
Gather oxalic acid-1, the 4-butanediol ester can obtain through oxalic acid and butyleneglycol direct polymerization.There is following problem in oxalic acid: the thermostability of oxalic acid is relatively poor, begins to decompose at 150 ℃; Oxalic acid distils easily, in heating more than 170 ℃, can decarboxylation produce formic acid; Oxalic acid in the presence of terepthaloyl moietie 90 ℃ begin to decompose, its decomposition activation energy is 24kcal/mol, the decomposition of oxalic acid can make the reactant substantial proportion change; Oxalic acid contains crystal water usually, need carry out dry pre-treatment under the lesser temps, and cost is improved.
Gather oxalic acid-1, the 4-butanediol ester can also obtain through oxalate diester and butanediol ester exchange.Oxalic acid diethyl ester is a kind of conventional reagent, and cost is lower, can be with 1, and 4-butyleneglycol generation transesterification reaction obtains gathering oxalic acid-1, the 4-butanediol ester.Oxalic acid diethyl ester has following characteristics: boiling point is 185 ℃, and 163 ℃ of dimethyl oxalates that are than boiling point are higher, and thermostability is better, and the TR that makes reaction to select is wideer, and higher relatively temperature of reaction helps shortening the reaction times.Therefore, the inventor adopts oxalic acid diethyl ester and 1, and what the 4-butyleneglycol prepared high limiting viscosity ([η]) gathers oxalic acid-1,4-butanediol ester.
At US.Pat.Nos.4,186, among the 189A, oxalic acid diethyl ester and 1 are disclosed, the 4-butyleneglycol carries out transesterification reaction earlier under normal pressure, until the ethanol that obtains calculated amount, the polycondensation of reducing pressure again.The amount of substance ratio is 1: 1.15 a oxalic acid diethyl ester and 1, the 4-butyleneglycol, and metatitanic acid four (2-Ethylhexyl Alcohol) ester of adding 1% is a catalyzer, at nitrogen (N
2) protection is down respectively at 140 ℃ and 160 ℃ of isothermal reaction 2h, decompression phase is at 2～3mmHg pressure, and 160 ℃ are reacted 20h and 2h with 180 ℃ of difference constant temperature and pressures.The limiting viscosity of product is 0.95dL/g, T
mIt is 105 ℃.The method severe reaction conditions needs to use condition of high vacuum degree, under laboratory condition, realize with industrial all being difficult to, and cost is very high, and the reaction time reaches 26h, and cost is high.In addition, said method is not reported N
2The flow size.
At Finelli et al, European Polymer Journal in 38,1987 (2002), discloses with dimethyl oxalate and 1, and the 4-butyleneglycol is a raw material, and mass polymerization has been synthesized and gathered oxalic acid-1, the 4-butanediol ester.Reaction is catalyzer with the tetra-n-butyl titanate, at 150 ℃ of isothermal reaction 2h, is warming up to 160～170 ℃ of decompressions again and reacts constant until torque readings, gathers oxalic acid-1, the M of 4-butanediol ester
n(number average relative molecular mass) is 7600.Pressure and N when in addition, the document is not reported reaction total time, catalyzer add-on, decompression
2Concrete reaction conditions such as flow size.
Summary of the invention
To gathering oxalic acid-1 in the prior art; The defective of 4-butanediol ester cost height and long reaction time; The object of the present invention is to provide a kind of oxalic acid-1 that gathers, the preparation method of 4-butanediol ester, the said oxalic acid-1 that gathers; The 4-butanediol ester adopts and to derive from biomass, cost is lower and thermostability is higher oxalic acid diethyl ester and 1, and the 4-butyleneglycol carries out copolymerization and makes.
For realizing the object of the invention, the technical scheme of employing is following.
A kind of oxalic acid-1 that gathers, the preparation method of 4-butanediol ester, said preparing method's concrete steps are following:
With oxalic acid diethyl ester, 1,4-butyleneglycol and catalyzer place reactor drum, at N
2Protection is warming up to 80～170 ℃ down, and the complete fusion of reactant is carried out obtaining the oxalic acid-1 that gathers of the present invention behind constant temperature stirring reaction 0.5～5h, the 4-butanediol ester.Gained gathers oxalic acid-1, and the chemical structure of 4-butanediol ester is suc as formula shown in the I:
Wherein, said oxalic acid diethyl ester and 1, the amount of substance ratio of 4-butyleneglycol is 1: 1～1: 3, is preferably 1:1.1.
Said catalyzer is: the mixture of sodium methylate, sodium hydroxide, Pottasium Hydroxide, triethylamine, tetra-n-butyl titanate, Antimony Trioxide: 99.5Min, antimony trisulfide, germanium dioxide, zinc acetate, tosic acid, camphorsulfonic acid, oxalic acid, Succinic Acid, hexanodioic acid, sebacic acid, 1,4 cyclohexanedicarboxylic acid or terephthalic acid one of them or zinc acetate and antimony trisulfide; Be preferably oxalic acid.The amount of substance of catalyzer be oxalic acid diethyl ester amount of substance 0.1～5.0%, be preferably oxalic acid diethyl ester amount of substance 1.0%.
Said N
2Flow be 0.06～0.16m
3/ h is preferably 0.1m
3/ h.
The said constant temperature stirring reaction time is preferably 5h.
What prepare gathers oxalic acid-1, and the limiting viscosity of 4-butanediol ester is 0.04～0.44dL/g, and melt temperature is 50～180 ℃.Wherein, gather oxalic acid-1, the 1836 type Ubbelohde viscometers of capillary inner diameter 0.38mm are adopted in the limiting viscosity test of 4-butanediol ester, and solvent is a trichloromethane, measures with reference to standard GB/T 1632-93.
For the acquired character viscosity higher gather oxalic acid-1, the 4-butanediol ester can gather oxalic acid-1 with what prepare with preparation method provided by the present invention, the 4-butanediol ester adopts the vacuum final minification to gather the further optimization process of method method, the concrete grammar step is following:
To gather oxalic acid-1 with what preparation method provided by the present invention prepared; The 4-butanediol ester is that 110～180 ℃, vacuum tightness are under 200～500Pa condition in temperature, carries out constant temperature and pressure copolyreaction 3～8h; Obtain limiting viscosity higher gather oxalic acid-1,4-butanediol ester.
Wherein, said vacuum tightness is preferably 400Pa; The constant temperature and pressure copolyreaction reaction times is preferably 3h.
What prepare gathers oxalic acid-1, and the limiting viscosity of 4-butanediol ester is 0.05～0.45dL/g, and melt temperature is 50～180 ℃.Wherein, gather oxalic acid-1, the 1836 type Ubbelohde viscometers of capillary inner diameter 0.38mm are adopted in the limiting viscosity test of 4-butanediol ester, and solvent is a trichloromethane, measures with reference to standard GB/T 1632-93.
Beneficial effect
1. a kind of oxalic acid-1 that gathers provided by the present invention, the preparation method of 4-butanediol ester is through ratio, the N to the amount of substance of reactant
2The reaction times has been shortened in the optimization of reaction conditionss such as flow, temperature of reaction, catalyst type and consumption greatly, has reduced reaction vacuum tightness, is fit to suitability for industrialized production; What prepare gathers oxalic acid-1, and 4-butanediol ester limiting viscosity is higher, can be as the masterbatch of general-purpose plastics;
2. a kind of oxalic acid-1 that gathers provided by the present invention, the preparation method of 4-butanediol ester existing conventional polyester poly-unit capable of using carries out polymerization, and is simple to operate, carries out suitability for industrialized production easily;
3. a kind of oxalic acid-1 that gathers provided by the present invention; The catalyzer that the preparation method selected for use of 4-butanediol ester, especially oxalic acid, cost is low and aftertreatment is simple; Catalysis makes gathers oxalic acid-1, and the 4-butanediol ester has favorable biological degradability, higher limiting viscosity and fusing point.
Description of drawings
Fig. 1 prepares for embodiment 1 gathers oxalic acid-1, the crystallization curve in the DSC spectrogram of 4-butanediol ester.
Fig. 2 prepares for embodiment 1 gathers oxalic acid-1, the melting curve in the DSC spectrogram of 4-butanediol ester.
Fig. 3 prepares for embodiment 1 gathers oxalic acid-1, the infrared spectrum of 4-butanediol ester.
Fig. 4 prepares for embodiment 1 gathers oxalic acid-1, the 4-butanediol ester
1H NMR spectrogram.
Fig. 5 prepares for embodiment 1 gathers oxalic acid-1, the 4-butanediol ester
13C NMR spectrogram.
Embodiment
In order to prove absolutely the mode of characteristic of the present invention and embodiment of the present invention, provide embodiment below.
The product of following examples all pass through infrared spectrum,
1H NMR spectrogram with
13The test of C NMR spectrogram proves and gathers oxalic acid-1, the 4-butanediol ester.All products gather oxalic acid-1, and the 1836 type Ubbelohde viscometers of capillary inner diameter 0.38mm are all adopted in the limiting viscosity test of 4-butanediol ester, and solvent is a trichloromethane, measures with reference to standard GB/T 1632-93.
Take by weighing respectively 0.5mol oxalic acid diethyl ester (73.07g), 0.5mol 1, the sodium methylate of 4-butyleneglycol (45.06g) and 0.005mol adds in three mouthfuls of round-bottomed flasks of 500ml, feeds N
2, flow is 0.1m
3/ h, oil bath is heated control reaction temperature at 140 ℃, mechanical stirring, the complete fusion of reactant picks up counting when temperature of reaction rises to 140 ℃, isothermal reaction 5h, obtaining product is dark white solid, limiting viscosity is 0.04dL/g.
Fig. 1 gathers oxalic acid-1 for what present embodiment prepared, and the crystallization curve in the DSC spectrogram of 4-butanediol ester is 55.9 ℃ by the visible present embodiment product Tc of Fig. 1.
Fig. 2 gathers oxalic acid-1 for what present embodiment prepared, and the melting curve in the DSC spectrogram of 4-butanediol ester is higher by the visible present embodiment product melt temperature of Fig. 2, is 104.8 ℃.
Fig. 3 gathers oxalic acid-1, the infrared spectrum of 4-butanediol ester for what present embodiment prepared.Visible by Fig. 3,1740cm
-1Be the stretching vibration peak of ester carbonyl group, 1169cm
-1Be carbonyl C-O-C antisymmetric stretching vibration peak, 2964cm
-1Be CH
2The antisymmetric stretching vibration peak, 1464cm
-1And 778cm
-1Be CH
2Flexural vibration peak in the face.Said characteristic peak has reflected the ester group structure on the polyester macromolecule skeleton, proves that product that present embodiment prepares is for gathering oxalic acid-1, the 4-butanediol ester.
Fig. 4 gathers oxalic acid-1, the 4-butanediol ester for what present embodiment prepared
1H NMR spectrogram.Owing to gather oxalic acid-1, the molecular structure unit of 4-butanediol ester is a symplex structure, and is visible by Fig. 4,
1In the H NMR spectrogram, δ 7.285 is CDCl
3Solvent peak δ 1.899 (s, 4H, 2 * OCCH
2C
H 2C
H 2CH
2CO), δ 4.363 (s, 4H, 2 * OCC
H 2CH
2CH
2C
H 2CO), the product that said characteristic peak proof present embodiment prepares is for gathering oxalic acid-1, and other side reactions do not take place the 4-butanediol ester.
Fig. 5 gathers oxalic acid-1, the 4-butanediol ester for what present embodiment prepared
13C NMR spectrogram.Visible by Fig. 5, the triplet at δ 76.765, δ 77.019 and δ 77.273 places is solvent C DCl
3The peak, δ 4.851 places are the CH that does not link to each other with carbonyl
2The peak, promptly corresponding 1, two CH of intermediary in the 4-butyleneglycol structure
2δ 66.290 is the CH that links to each other with carbonyl
2The peak, promptly corresponding 1, two CH that link to each other with alcoholic extract hydroxyl group in the 4-butyleneglycol structure
2δ 157.630 is the peak of carbonyl carbon.Said characteristic peak shows that the product for preparing is for gathering oxalic acid-1, the 4-butanediol ester.
Embodiment 2
Take by weighing respectively 0.5mol oxalic acid diethyl ester, 0.5mol 1, the NaOH of 4-butyleneglycol and 0.005mol adds in three mouthfuls of round-bottomed flasks of 500ml, feeds N
2, flow is 0.1m
3/ h, oil bath is heated control reaction temperature at 140 ℃, mechanical stirring, the complete fusion of reactant picks up counting when temperature of reaction rises to 140 ℃, and isothermal reaction 5h obtains product for gathering oxalic acid-1, and the 4-butanediol ester is dark white solid, and limiting viscosity is 0.04dL/g.
Embodiment 3
Take by weighing respectively 0.5mol oxalic acid diethyl ester, 0.5mol 1, the KOH of 4-butyleneglycol and 0.005mol adds in three mouthfuls of round-bottomed flasks of 500ml, feeds N
2, flow is 0.1m
3/ h, oil bath is heated control reaction temperature at 140 ℃, mechanical stirring, the complete fusion of reactant picks up counting when temperature of reaction rises to 140 ℃, and isothermal reaction 5h obtains product for gathering oxalic acid-1, and the 4-butanediol ester is dark white solid, and limiting viscosity is 0.06dL/g.
Embodiment 4
Take by weighing respectively 0.5mol oxalic acid diethyl ester, 0.5mol 1, the triethylamine of 4-butyleneglycol and 0.005mol adds in three mouthfuls of round-bottomed flasks of 500ml, feeds N
2, flow is 0.1m
3/ h, oil bath is heated control reaction temperature at 140 ℃, mechanical stirring, the complete fusion of reactant picks up counting when temperature of reaction rises to 140 ℃, and isothermal reaction 5h obtains product for gathering oxalic acid-1, and the 4-butanediol ester is dark white solid, and limiting viscosity is 0.04dL/g.
Embodiment 5
Take by weighing respectively 0.5mol oxalic acid diethyl ester, 0.5mol 1, the tosic acid of 4-butyleneglycol and 0.005mol adds in three mouthfuls of round-bottomed flasks of 500ml, feeds N
2, flow is 0.1m
3/ h, oil bath is heated control reaction temperature at 140 ℃, mechanical stirring, the complete fusion of reactant picks up counting when temperature of reaction rises to 140 ℃, and isothermal reaction 5h obtains product for gathering oxalic acid-1, and the 4-butanediol ester is dark white solid, and limiting viscosity is 0.19dL/g.
Embodiment 6
Take by weighing respectively 0.5mol oxalic acid diethyl ester, 0.5mol 1, the camphorsulfonic acid of 4-butyleneglycol and 0.005mol adds in three mouthfuls of round-bottomed flasks of 500ml, feeds N
2, flow is 0.1m
3/ h, oil bath is heated control reaction temperature at 140 ℃, mechanical stirring, the complete fusion of reactant picks up counting when temperature of reaction rises to 140 ℃, and isothermal reaction 5h obtains product for gathering oxalic acid-1, and the 4-butanediol ester is dark white solid, and limiting viscosity is 0.21dL/g.
Embodiment 7
Take by weighing respectively 0.5mol oxalic acid diethyl ester, 0.5mol 1, the Succinic Acid of 4-butyleneglycol and 0.005mol adds in three mouthfuls of round-bottomed flasks of 500ml, feeds N
2, flow is 0.1m
3/ h, oil bath is heated control reaction temperature at 140 ℃, mechanical stirring, the complete fusion of reactant picks up counting when temperature of reaction rises to 140 ℃, and isothermal reaction 5h obtains product for gathering oxalic acid-1, and the 4-butanediol ester is dark white solid, and limiting viscosity is 0.36dL/g.
Embodiment 8
Take by weighing respectively 0.5mol oxalic acid diethyl ester, 0.5mol 1, the hexanodioic acid of 4-butyleneglycol and 0.005mol adds in three mouthfuls of round-bottomed flasks of 500ml, feeds N
2, flow is 0.1m
3/ h, oil bath is heated control reaction temperature at 140 ℃, mechanical stirring, the complete fusion of reactant picks up counting when temperature of reaction rises to 140 ℃, and isothermal reaction 5h obtains product for gathering oxalic acid-1, and the 4-butanediol ester is dark white solid, and limiting viscosity is 0.40dL/g.
Embodiment 9
Take by weighing respectively 0.5mol oxalic acid diethyl ester, 0.5mol 1, the sebacic acid of 4-butyleneglycol and 0.005mol adds in three mouthfuls of round-bottomed flasks of 500ml, feeds N
2, flow is 0.1m
3/ h, oil bath is heated control reaction temperature at 140 ℃, mechanical stirring, the complete fusion of reactant picks up counting when temperature of reaction rises to 140 ℃, and isothermal reaction 5h obtains product for gathering oxalic acid-1, and the 4-butanediol ester is dark white solid, and limiting viscosity is 0.39dL/g.
Embodiment 10
Take by weighing respectively 0.5mol oxalic acid diethyl ester, 0.5mol 1, the 1,4 cyclohexanedicarboxylic acid of 4-butyleneglycol and 0.005mol adds in three mouthfuls of round-bottomed flasks of 500ml, feeds N
2, flow is 0.1m
3/ h, oil bath is heated control reaction temperature at 140 ℃, mechanical stirring, the complete fusion of reactant picks up counting when temperature of reaction rises to 140 ℃, and isothermal reaction 5h obtains product for gathering oxalic acid-1, and the 4-butanediol ester is dark white solid, and limiting viscosity is 0.30dL/g.
Embodiment 11
Take by weighing respectively 0.5mol oxalic acid diethyl ester, 0.5mol 1, the terephthalic acid of 4-butyleneglycol and 0.005mol adds in three mouthfuls of round-bottomed flasks of 500ml, feeds N
2, flow is 0.1m
3/ h, oil bath is heated control reaction temperature at 140 ℃, mechanical stirring, the complete fusion of reactant picks up counting when temperature of reaction rises to 140 ℃, and isothermal reaction 5h obtains product for gathering oxalic acid-1, and the 4-butanediol ester is dark white solid, and limiting viscosity is 0.19dL/g.
Embodiment 12
Take by weighing respectively 0.5mol oxalic acid diethyl ester, 0.5mol 1, the Antimony Trioxide: 99.5Min of 4-butyleneglycol and 0.005mol adds in three mouthfuls of round-bottomed flasks of 500ml, feeds N
2, flow is 0.1m
3/ h, oil bath is heated control reaction temperature at 140 ℃, mechanical stirring, the complete fusion of reactant picks up counting when temperature of reaction rises to 140 ℃, and isothermal reaction 5h obtains product for gathering oxalic acid-1, and the 4-butanediol ester is dark white solid, and limiting viscosity is 0.04dL/g.
Embodiment 13
Take by weighing respectively 0.5mol oxalic acid diethyl ester, 0.5mol 1, the zinc acetate of 4-butyleneglycol and 0.005mol adds in three mouthfuls of round-bottomed flasks of 500ml, feeds N
2, flow is 0.1m
3/ h, oil bath is heated control reaction temperature at 140 ℃, mechanical stirring, the complete fusion of reactant picks up counting when temperature of reaction rises to 140 ℃, and isothermal reaction 5h obtains product for gathering oxalic acid-1, and the 4-butanediol ester is dark white solid, and limiting viscosity is 0.20dL/g.
Embodiment 14
Take by weighing respectively 0.5mol oxalic acid diethyl ester, 0.5mol 1, the tetra-n-butyl titanate of 4-butyleneglycol and 0.005mol adds in three mouthfuls of round-bottomed flasks of 500ml, feeds N
2, flow is 0.1m
3/ h, oil bath is heated control reaction temperature at 140 ℃, mechanical stirring, the complete fusion of reactant picks up counting when temperature of reaction rises to 140 ℃, and isothermal reaction 5h obtains product for gathering oxalic acid-1, and the 4-butanediol ester is dark white solid, and limiting viscosity is 0.20dL/g.
Embodiment 15
Take by weighing respectively 0.5mol oxalic acid diethyl ester, 0.5mol 1, the zinc acetate of 4-butyleneglycol, 0.0025mol and the antimony trisulfide of 0.0025mol add in three mouthfuls of round-bottomed flasks of 500ml, feed N
2, flow is 0.1m
3/ h, oil bath is heated control reaction temperature at 140 ℃, mechanical stirring, the complete fusion of reactant picks up counting when temperature of reaction rises to 140 ℃, and isothermal reaction 5h obtains product for gathering oxalic acid-1, and the 4-butanediol ester is dark white solid, and limiting viscosity is 0.31dL/g.
Embodiment 16
Take by weighing respectively 0.5mol oxalic acid diethyl ester, 0.5mol 1, the oxalic acid of 4-butyleneglycol and 0.0025mol adds in three mouthfuls of round-bottomed flasks of 500ml, feeds N
2, flow is 0.1m
3/ h, oil bath is heated control reaction temperature at 140 ℃, mechanical stirring, the complete fusion of reactant picks up counting when temperature of reaction rises to 140 ℃, and isothermal reaction 5h obtains product for gathering oxalic acid-1, and the 4-butanediol ester is dark white solid, and limiting viscosity is 0.20dL/g.
Embodiment 17
Take by weighing respectively 0.5mol oxalic acid diethyl ester, 0.5mol 1, the oxalic acid of 4-butyleneglycol and 0.025mol adds in three mouthfuls of round-bottomed flasks of 500ml, feeds N
2, flow is 0.1m
3/ h, oil bath is heated control reaction temperature at 140 ℃, mechanical stirring, the complete fusion of reactant picks up counting when temperature of reaction rises to 140 ℃, and isothermal reaction 5h obtains product for gathering oxalic acid-1, and the 4-butanediol ester is dark white solid, and limiting viscosity is 0.25dL/g.
Embodiment 18
Take by weighing respectively 0.5mol oxalic acid diethyl ester, 0.575mol 1, the oxalic acid of 4-butyleneglycol (51.82g) and 0.005mol adds in three mouthfuls of round-bottomed flasks of 500ml, feeds N
2, flow is 0.10m
3/ h, oil bath is heated control reaction temperature at 140 ℃, mechanical stirring, the complete fusion of reactant picks up counting when temperature of reaction rises to 140 ℃, and isothermal reaction 5h obtains product for gathering oxalic acid-1, and the 4-butanediol ester is dark white solid, and limiting viscosity is 0.44dL/g.
Embodiment 19
Take by weighing respectively 0.5mol oxalic acid diethyl ester, 0.55mol 1, the oxalic acid of 4-butyleneglycol (49.57g) and 0.005mol adds in three mouthfuls of round-bottomed flasks of 500ml, feeds N
2, flow is 0.1m
3/ h, the oil bath heating, mechanical stirring when temperature of reaction rises to 140 ℃ of complete fusions of reactant, picks up counting, and isothermal reaction 5h finishes transesterification reaction, obtains product of transesterification reaction for gathering oxalic acid-1, the 4-butanediol ester; Again temperature of reaction is reduced to 120 ℃ naturally, is evacuated to 400Pa, constant temperature and pressure continues reaction 3h, obtains product for gathering oxalic acid-1, and the 4-butanediol ester is dark white solid, and limiting viscosity is 0.35dL/g.
Embodiment 20
Take by weighing respectively 0.5mol oxalic acid diethyl ester, 0.55mol 1, the oxalic acid of 4-butyleneglycol and 0.005mol adds in three mouthfuls of round-bottomed flasks of 500ml, feeds N
2, flow is 0.1m
3/ h, the oil bath heating, mechanical stirring, temperature of reaction rise to 140 ℃ of complete fusions of reactant, pick up counting, and isothermal reaction 5h finishes transesterification reaction, obtains product of transesterification reaction for gathering oxalic acid-1, the 4-butanediol ester; Again temperature of reaction is risen to 180 ℃, be evacuated to 400Pa, constant temperature and pressure continues reaction 3h, obtains product for gathering oxalic acid-1, and the 4-butanediol ester is dark white solid, and limiting viscosity is 0.28dL/g.
Embodiment 21
Take by weighing respectively 0.5mol oxalic acid diethyl ester, 0.55mol 1, the oxalic acid of 4-butyleneglycol and 0.005mol adds in three mouthfuls of round-bottomed flasks of 500ml, feeds N
2, flow is 0.1m
3/ h, the oil bath heating, mechanical stirring, temperature of reaction rise to 140 ℃ of complete fusions of reactant, pick up counting, and isothermal reaction 5h finishes transesterification reaction, obtains product of transesterification reaction for gathering oxalic acid-1, and 4-butanediol ester, limiting viscosity are 0.44dL/g; Just temperature of reaction rises to 160 ℃ again, is evacuated to 400Pa, and constant temperature and pressure continues reaction 3h, obtains product for gathering oxalic acid-1, and the 4-butanediol ester is dark white solid, and limiting viscosity is 0.45dL/g.
Embodiment 22
Take by weighing respectively 0.5mol oxalic acid diethyl ester, 0.55mol 1, the oxalic acid of 4-butyleneglycol and 0.005mol adds in three mouthfuls of round-bottomed flasks of 500ml, feeds N
2, flow is 0.1m
3/ h, the oil bath heating, mechanical stirring, temperature of reaction rise to 140 ℃ of complete fusions of reactant, pick up counting, and isothermal reaction 5h finishes transesterification reaction, obtains product of transesterification reaction for gathering oxalic acid-1, and 4-butanediol ester, limiting viscosity are 0.44dL/g; Again temperature of reaction is risen to 160 ℃, be evacuated to 400Pa, constant temperature and pressure continues reaction 8h, obtains product for gathering oxalic acid-1, and the 4-butanediol ester is dark white solid, and limiting viscosity is 0.45dL/g.
The present invention includes but be not limited to above embodiment, every any replacement or local improvement of being equal to of under spirit of the present invention and principle, carrying out all will be regarded as within protection scope of the present invention.
Claims (9)
1. one kind is gathered oxalic acid-1, and the preparation method of 4-butanediol ester is characterized in that: said preparing method's concrete steps are following:
With oxalic acid diethyl ester, 1,4-butyleneglycol and catalyzer place reactor drum, at N
2Protection down is warming up to 80～170 ℃, carry out constant temperature stirring reaction 0.5～5h after, obtaining product gathers oxalic acid-1, the 4-butanediol ester;
Wherein, said oxalic acid diethyl ester and 1, the amount of substance ratio of 4-butyleneglycol is 1: 1～1: 3;
Said catalyzer is: sodium methylate, sodium hydroxide, Pottasium Hydroxide, triethylamine, tetra-n-butyl titanate, Antimony Trioxide: 99.5Min, antimony trisulfide, germanium dioxide, zinc acetate, tosic acid, camphorsulfonic acid, oxalic acid, Succinic Acid, hexanodioic acid, sebacic acid, 1; The mixture of 4-cyclohexane cyclohexanedimethanodibasic or terephthalic acid one of them or zinc acetate and antimony trisulfide, the amount of substance of catalyzer be oxalic acid diethyl ester amount of substance 0.1～5.0%;
Said N
2Flow be 0.06～0.16m
3/ h.
2. a kind of oxalic acid-1 that gathers according to claim 1, the preparation method of 4-butanediol ester is characterized in that: said oxalic acid diethyl ester and 1, the amount of substance ratio of 4-butyleneglycol is 1: 1.1.
3. a kind of oxalic acid-1 that gathers according to claim 1, the preparation method of 4-butanediol ester is characterized in that: catalyzer is an oxalic acid.
4. a kind of oxalic acid-1 that gathers according to claim 1, the preparation method of 4-butanediol ester is characterized in that: the amount of substance of catalyzer be oxalic acid diethyl ester amount of substance 1.0%.
5. a kind of oxalic acid-1 that gathers according to claim 1, the preparation method of 4-butanediol ester is characterized in that: N
2Flow be 0.1m
3/ h.
6. a kind of oxalic acid-1 that gathers according to claim 1, the preparation method of 4-butanediol ester is characterized in that: the constant temperature stirring reaction time is 5h.
7. according to one of them described a kind of oxalic acid-1 that gathers of claim 1～6, the preparation method of 4-butanediol ester is characterized in that:
Be that 110～180 ℃, vacuum tightness are under 200～500Pa condition further, carry out constant temperature and pressure copolyreaction 3～8h, obtain gathering oxalic acid-1, the 4-butanediol ester in temperature.
8. a kind of oxalic acid-1 that gathers according to claim 7, the preparation method of 4-butanediol ester is characterized in that: said vacuum tightness is 400Pa.
9. a kind of oxalic acid-1 that gathers according to claim 7, the preparation method of 4-butanediol ester is characterized in that: the constant temperature and pressure copolyreaction reaction times is 3h.
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| JP6519484B2 (en) * | 2013-12-24 | 2019-05-29 | 東洋製罐グループホールディングス株式会社 | Polyoxalate |
| CN104086756A (en) * | 2014-07-28 | 2014-10-08 | 营口康辉石化有限公司 | Production method of optical transparent film-level polyester |
| CN115785424A (en) * | 2022-07-04 | 2023-03-14 | 新倍斯(杭州)材料科技有限公司 | Hydrolysis-resistant composite titanium catalyst, preparation method and preparation method of high-molecular-weight oxalic acid-based polyester |
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| JP特开2010-77240A 2010.04.08 |
| L.Finelli,et al..Thermal properties of poly(butylene oxalate) copolymerized with azelaic acid.《European Polymer Journal》.2002,第38卷1987-1993. * |
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