CN104163913A - Preparation method of polybutylece aliphatic diacid terephthalate type copolyester - Google Patents
Preparation method of polybutylece aliphatic diacid terephthalate type copolyester Download PDFInfo
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- CN104163913A CN104163913A CN201410345165.2A CN201410345165A CN104163913A CN 104163913 A CN104163913 A CN 104163913A CN 201410345165 A CN201410345165 A CN 201410345165A CN 104163913 A CN104163913 A CN 104163913A
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Abstract
The invention discloses a preparation method of polybutylece aliphatic diacid terephthalate type copolyester (PBT type copolyester), and the PBT type copolyester is prepared from terephthalic acid and 1, 4-butanediol as raw materials by adding of an aliphatic diacid as a comonomer; the preparation method comprises the following two steps: (1) direct esterification reaction of the terephthalic acid, the 1, 4-butanediol and the aliphatic diacid in the role of a liquid titanium series catalyst; or first step esterification reaction of the aliphatic diacid and the 1, 4-butanediol in the role of the liquid titanium series catalyst, and second step esterification of the aliphatic diacid and the terephthalic acid and the 1, 4-butanediol; and (2) polymerization of obtained esterified products under the conditions of the pressure of 20Pa-200Pa, the temperature of 230 to 260 DEG C and the time of 1-4h. The method uses the hydrolysis resistant titanium series catalyst, and the prepared PBT type copolyester has the melting point of 170 to 220 DEG C, the intrinsic viscosity of 0.7-1.2dL / g and good use performances.
Description
Technical field
The invention belongs to the synthetic field of the polyester of one of macromolecular material, relate to a kind of poly terephthalic acid fat diacid butanediol ester type copolyesters preparation method of (being called for short PBT type copolyesters), particularly relate to a kind of preparation method who uses the synthetic poly terephthalic acid fat diacid butanediol ester type copolyesters of liquid condition titanium series catalyst of hydrolysis.
Background technology
Polybutylene terephthalate (be called for short PBT) have excellent machinery, electric, resistance to chemical attack, easy-formation and agent of low hygroscopicity can etc., be a kind of model engineering plastic of high comprehensive performance.PBT has good over-all properties, if still use separately, its heat-drawn wire is low, bad mechanical property, and goods easily produce anisotropy, warpage occurs, and notched Izod impact strength is not ideal enough etc., so PBT could apply mostly after modification.The method of modifying of PBT mainly comprises physically modified, chemical modification etc., and wherein one of chemical modification method is the means by copolymerization, and in PBT molecule, introducing new segment becomes PBT type copolyesters, has better properties or new function.In addition, PBT belongs to aromatic polyester, and biological degradability is poor, can not use as degradable material; When prepared by PBT, add aliphaticdicarboxylic acid to replace part pure terephthalic acid (being called for short PTA) and can synthesize PBT type copolyesters, aliphaticdicarboxylic acid has oxalic acid, succinic acid, pentanedioic acid, hexanodioic acid etc., and this class PBT type copolyesters has good mechanical property and biological degradability concurrently.
The synthetic route of PBT can be divided into ester-interchange method and direct esterification, and wherein direct esterification is for raw material with pure terephthalic acid's (be called for short PTA) and 1,4 – butyleneglycol (abbreviation BD).This technical process is short, and facility investment is lower, and energy consumption is also lower, but need properly settle 1,4 – Butanediol problem.Because reaction conditions is harsher, reaction medium is acid strong, and part 1,4 – Butanediol cyclisation generates tetrahydrofuran (THF) (being called for short THF), and quality product is had a negative impact.Ester-interchange method is that to take dimethyl terephthalate (DMT) (be called for short DMT) and BD be raw material, in this technique Exchange Ester Process, produces methyl alcohol, and the boiling point of methyl alcohol and THF are approaching, are difficult to separation.In recent years due to raw material DMT production and sales seldom, therefore, it is all direct esterification that large-scale PBT produces, the production of PBT type copolyesters can adopt ester-interchange method or direct esterification.
Esterification, polycondensation during PBT and copolyesters thereof are synthetic all need catalyzer, traditional catalyzer mainly contains: organic titanate, comprise tetrabutyl titanate, isopropyl titanate etc., and the salt of titanium and derivative thereof, as titanous oxalate, titanium hydroxide, titanium oxyoxalate etc.In PBT type copolyesters synthetic, catalizer variety and consumption have a great impact effect to preparation process and quality product; Good catalyzer itself is easy to use, be difficult for inactivation, can there is good catalytic activity to esterification and polymerization process, simultaneously to raw material 1, the amount of 4 – butyleneglycol side reactions generation tetrahydrofuran (THF)s (being called for short THF) is less, thereby further improves relative molecular weight and the quality product of PBT and copolyesters thereof.
In the preparation process of PBT type copolyesters, mostly adopt at present the titanate ester materials such as tetrabutyl titanate as catalyzer, because titanic acid ester exists the defect of facile hydrolysis, first the result of hydrolysis is to have reduced its catalytic activity, the usage quantity needing strengthens, cause in the finished product titanium content higher, PBT product performance decline, and as high in content of carboxyl end group, form and aspect b value rises; In actual use, need add catalyzer in batches, for example, before esterification, add major part, after esterification finishes, add partially catalyzed agent, use procedure is inconvenient; Prepared PBT type copolyesters product performance, as limiting viscosity is less than 0.7, do not reach actual service requirements.
Patent CN 102276806A discloses a kind of preparation method of polyterephthalic acid ethane diacid butanediol ester.It is reaction monomers that the method be take PTA or DMT, barkite, BD, first carry out esterification or ester-exchange reaction, prepare the two hydroxy butyl esters of terephthalic acid and oxalic acid hydroxy butyl ester and oligopolymer in pairs, subsequently, by the two hydroxy butyl esters of terephthalic acid and oxalic acid, hydroxy butyl ester and oligopolymer carry out the PBT type multipolymer that polyreaction obtains having biological degradability in pairs.In esterification or Exchange Ester Process, adopt acetate as catalyzer, in polymerization process, adopt one or more in Sb, Ti, Ge, Sn, Al compound.In specific embodiment, acetate adopts manganese acetate, adopts respectively a kind of and tetrabutyl titanate mixing in ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony glycol to use as catalyzer in polymerization process.Shortcoming is that antimony compounds is heavy metal, is unfavorable for environmental protection and cleaner production, and antimony compounds is solid in addition, inconvenient while being added continuously to reaction system; And mix the tetrabutyl titanate using, there is the defects such as facile hydrolysis, easy inactivation.
Existing a kind of PBT type copolyesters, as polybutylene terephthalate-Co-poly adipate succinic acid ester (being called for short PBAT) has openly been reported synthetic method and thermal decomposition behavior (plastics industry thereof by Yuan Renxu, Xu Yibin etc., 2012,40 12 phases of volume, 73～77), according to synthesizing respectively after benzene dicarboxylic acid butanediol and poly adipate succinic acid ester oligopolymer, synthetic PBAT under the effect of tetrabutyl titanate catalyzer.This process is carried out in 250ml glass flask, and synthetic product is only for performance analysis, and concrete preparation method is not clear and definite.
Patent CN101475690B discloses a kind of preparation method of biodegradable PBT type copolyesters.The method is division step, first with hexanodioic acid and BD, under catalyzer condition, synthesize poly adipate succinic acid ester prepolymer, re-use the synthetic PBT prepolymer of DMT and BD ester-interchange method, after finally above-mentioned two kinds of prepolymers being mixed, PBT type copolymer product is synthesized in polycondensation again.The catalyzer adopting is one or more in tetrabutyl titanate, isopropyl titanate, stannous octoate, Cobaltous diacetate or manganese acetate.In this inventive embodiment, adopt tetrabutyl titanate as catalyzer, this catalyzer is the easy inactivation of hydrolysis not, deposits defect in the use.
Tan Xiaoling has openly reported a kind of synthetic and characterizing method (polyester industrial of degradable PBST polyester, 2011,24 1 phases of volume, 10～14), adopting PTA, BD, succinic acid is raw material, with direct esterification, synthesized the copolyesters with degradability, the catalyzer of use is homemade organic titanium series catalysts TY-1, performance and the consumption of not mentioned detailed preparation process and Titanium series catalyst TY-1.
Therefore, select the Titanium series catalyst of hydrolysis, and suitable processing condition prepare the PBT type copolyesters with good use properties or biological degradability, there is vast potential for future development.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of preparation method for poly terephthalic acid fat diacid butanediol ester type copolyesters, using and overcome the following defect existing in prior art: the preparation of PBT type copolyesters at present adopts the titanate ester materials such as tetrabutyl titanate to use as catalyzer mostly, because titanic acid ester is easily hydrolyzed, the result of hydrolysis has reduced its catalytic activity, the usage quantity needing strengthens, cause in the finished product titanium content higher, PBT copolyesters product performance decline, as high in content of carboxyl end group, form and aspect b value rising end carboxyl-content, form and aspect b value is the performance index of polyester product, in actual use, need add catalyzer in batches, for example, before esterification, add major part, after esterification finishes, add partially catalyzed agent, use procedure is inconvenient, prepared PBT type copolyesters product performance, as limiting viscosity is less than 0.7, do not reach actual service requirements.
The preparation method of a kind of poly terephthalic acid fat diacid butanediol ester type copolyesters of the present invention, a kind of in the fat diacids such as oxalic acid, succinic acid, hexanodioic acid, pentanedioic acid of take is comonomer, with terephthalic acid, 1,4 – butyleneglycols, under liquid condition titanium series catalyst effect, are prepared poly terephthalic acid fat diacid butanediol ester type copolyesters.
Concrete steps are divided 2 stages:
(1) prepare the two hydroxy butyl esters of the two hydroxy butyl esters of terephthalic acid and fat diacid and oligopolymer: take terephthalic acid, fat diacid and Isosorbide-5-Nitrae butyleneglycol is raw material, adds after liquid condition titanium series catalyst, directly carries out esterification; Or take fat diacid and Isosorbide-5-Nitrae butyleneglycol is raw material, adds after liquid condition titanium series catalyst, carries out the first step esterification;
(2) again according to above-mentioned gained esterification products, add terephthalic acid, Isosorbide-5-Nitrae butyleneglycol and liquid condition titanium series catalyst, enter second step esterification; By the two hydroxy butyl esters of terephthalic acid and the two hydroxy butyl esters of fat diacid and oligopolymer.Carry out polyreaction: controlling reaction absolute pressure is 20Pa～200Pa, and temperature of reaction is 230～260 ℃, and the reaction times is 1～4h, prepares poly terephthalic acid fat diacid butanediol ester type copolyesters.
Fat diacid of the present invention is a kind of in oxalic acid, succinic acid, pentanedioic acid, hexanodioic acid etc.
The integral molar quantity and 1 of terephthalic acid and fat diacid in described step (1), the ratio of the molar weight of 4 butyleneglycols is 1:1.1～2.5, the molar weight of fat diacid account for terephthalic acid and fat diacid integral molar quantity 5～60%, the molar weight of fat diacid is 1:0.053～1.0 with the ratio of terephthalic acid molar weight.
In described step (1), when terephthalic acid, fat diacid and Isosorbide-5-Nitrae butyleneglycol directly carry out esterification, temperature of reaction is 160～230 ℃, and pressure is 0.1～0.3MPa (absolute pressure), and the reaction times is 3～5h.
In described step (1), when fat diacid and Isosorbide-5-Nitrae butyleneglycol carry out the first step esterification, the molar weight of fat diacid and Isosorbide-5-Nitrae butyleneglycol is 1:1.8～3.0, and temperature of reaction is 160～230 ℃, pressure is 0.1～0.3MPa (absolute pressure), and the reaction times is 1～3h; When obtained esterification products carries out second step esterification with terephthalic acid, Isosorbide-5-Nitrae butyleneglycol again, temperature of reaction is 160～230 ℃, and pressure is 0.1～0.3MPa (absolute pressure), and the reaction times is 1～3h.。
Liquid condition titanium series catalyst hydrolysis of the present invention, dissolve each other with BDO, liquid condition titanium series catalyst is the technology of Sinopec Tianjin Branch Company, in Chinese patent ZL201010266068.6, is described later in detail.
Also can adopt another kind of prior art, in the Chinese patent that is 2012104194168 at application number, be described later in detail, patent name is " for polybutylene terephthalate synthetic Titanium series catalyst preparation method and application ", its preparation method is summarized as follows: (A) titanium compound, glycerol, alkaline substance are reacted 0.1～12 hour under 0～100 ℃ of temperature condition in solvent, wherein titanium compound is Ti (OR)
4, R is the alkyl that is selected from 1～10 carbon atom; (B) in the reaction product of above-mentioned (A) step, the acetate that adds phosphorus compound and a kind of Na of being selected from, Li, Mg, Zn metallic element, under 50～200 ℃ of temperature condition, react 0.1～12 hour, remove small molecules, make the liquid catalyst of homogeneous, stable, hydrolysis.
Wherein the mol ratio of titanium compound and glycerol is 1:0.1～20, the mol ratio of titanium compound and alkaline substance is 1:0.05～5, the mol ratio of titanium compound and phosphorus compound is 1:0.1～10, the mol ratio of titanium compound and described metallic element is 1:0.02～10, and the mol ratio of titanium compound and solvent is 1:2～50.The micromolecular method in reaction system is removed in described separation, is a kind of method of routine, as common distillating method.
In described step (1), the consumption of liquid condition titanium series catalyst, when carrying out direct esterification reaction, the content meter with titanium atom quality in the total mass of terephthalic acid and fat diacid, Ti content is 50 * 10
-6～150 * 10
-6.
In described step (1), the consumption of liquid condition titanium series catalyst, when carrying out the first step esterification, the quality in titanium atom quality to fat diacid, Ti content is 50 * 10
-6～150 * 10
-6; While carrying out second step esterification, the quality in titanium atom quality to terephthalic acid, Ti content is 50 * 10
-6～150 * 10
-6;
The preparation-obtained polybutylene terephthalate type of the present invention copolyesters, fusing point is 170～220 ℃, limiting viscosity is 0.7～1.2dL/g.This copolyesters preparation method is simple, the mechanical property of product is good, have biological degradability, can be used for the manufacture of film, fiber and other plastic products.
In the present invention, the limiting viscosity of polyester, fusing point, form and aspect b value etc. are analytical test by the following method:
(1) limiting viscosity: take 0.125g left and right section sample, be dissolved in the mixed solvent of phenol/tetrachloroethane (mass ratio is 1:1), in 25 ± 0.5 ℃, NCY-2 type automatic viscosity measurer is measured.
(2) fusing point: the DSC131 differential scanning instrument producing with Setaram company is measured.Test condition: the section sample that takes 10mg left and right packs in DSC sample pool, at N
2protection under with 50 ℃/min, be warming up to 260 ℃, keep after 3min, then with 10 ℃/min cooling, record heats up and temperature lowering curve.
(3) form and aspect b value: measure with the full-automatic colour examining colour-difference-metre of TC-P II G.
Embodiment
The preparation of liquid condition titanium series catalyst (according to ZL201010266068.6 embodiment):
To being equipped with in the reactor of agitator, separating funnel and condenser, add 42.6g titanium isopropylate (0.15mol) and 3.1g tetraethoxy (0.015mol) and 100g dehydrated alcohol, mix.Toward the mixing solutions that slowly splashes into 63.3g monohydrate potassium (0.3mol) and 150g dehydrated alcohol in reactor, after dripping and finishing, room temperature to 100 ℃ reaction 1 hour.Separate out white depositions, continue to add 4.1g sodium-acetate (0.03mol) and 55.2g triethyl phosphate (0.3mol), at 50～200 ℃, react 0.5～3 hour, remove small molecules, become homogeneous liquid to system, make liquid condition titanium series catalyst A.
The preparation of liquid condition titanium series catalyst (being 2012104194168 patent working examples according to application number):
To being equipped with in the reactor of agitator, separating funnel and condenser, add 42.6g titanium isopropylate (0.15mol) and 6.9g glycerol (0.075mol) and 50g1,4-butyleneglycol (0.56mol), mixes.Toward the solution that slowly splashes into 3.0g sodium hydroxide (0.075mol) and 50g deionized water in reactor, after dripping and finishing, room temperature to 100 ℃ reaction 1 hour.Separate out white depositions, continue to add 16.1g tetra-hydration magnesium acetates (0.075mol) and 13.7g triethyl phosphate (0.075mol), 50 ℃ of beginnings, be warming up to gradually at 160 ℃ coreaction 3 hours, remove small molecules, become homogeneous liquid to system, obtain catalyst B.
By above-mentioned two kinds of Titanium series catalysts that method makes, be hydrolysis, dissolve each other with Isosorbide-5-Nitrae butyleneglycol, select wherein any one for the preparation of embodiment 1～8 PBT type copolyesters.
Embodiment 1
By 498g terephthalic acid (PTA) (3.0mol), 354g succinic acid (3.0mol), 1350g1,4-butyleneglycol (BD) (15.0mol) and catalyst A (content meter in the total mass based on terephthalic acid and succinic acid, the weight content of titanium atom is 50 * 10
-6), add reactor directly to carry out esterification, temperature of reaction is that 160 ℃, reaction pressure are under the condition of 0.1MPa (absolute pressure), reaction times is 5 hours, distillate reaches 95% when above of theoretical value, esterification finishes, and obtaining intermediate product is the two hydroxy butyl esters of terephthalic acid and the two hydroxy butyl esters of succinic acid and oligopolymer.Under the condition that is 100Pa in 230 ℃ of temperature of reaction, absolute pressure by gained intermediate product, carry out polyreaction, react 3 hours, prepare polybutylene terephthalate type copolyesters, afterwards multipolymer is extruded with bar shaped continuously from polymeric kettle bottom, through water cooling, pelletizing.
Prepared PBT copolyesters product is carried out to performance test, and analytical results is in Table 1.
Embodiment 2
By 498g PTA (3.0mol), 23.2g hexanodioic acid (0.159mol), 313g BD (3.48mol) and catalyst B, (content meter in the total mass based on terephthalic acid and hexanodioic acid, the weight content of titanium atom is 70 * 10
-6), add reactor directly to carry out esterification, temperature of reaction is that 180 ℃, reaction pressure are under the condition of 0.3MPa (absolute pressure), reaction times is 4.5 hours, distillate reaches 95% when above of theoretical value, esterification finishes, and obtaining intermediate product is the two hydroxy butyl esters of terephthalic acid and the two hydroxy butyl esters of hexanodioic acid and oligopolymer.Under the condition that is 200Pa in 240 ℃ of temperature of reaction, absolute pressure by gained intermediate product, carry out polyreaction, react 4 hours, prepare polybutylene terephthalate type copolyesters, afterwards multipolymer is extruded with bar shaped continuously from polymeric kettle bottom, through water cooling, pelletizing.
Prepared PBT copolyesters product is carried out to performance test, and analytical results is in Table 1.
Embodiment 3
By 498g PTA, ((content meter in the total mass based on terephthalic acid and pentanedioic acid, the mass content of titanium atom is 100 * 10 for 3.0mol, 119g pentanedioic acid (0.9mol), 562gBD (6.24mol) and catalyst A
-6), add reactor directly to carry out esterification, temperature of reaction is that 230 ℃, reaction pressure are under the condition of 0.1MPa (absolute pressure), reaction times is 3 hours, distillate reaches 95% when above of theoretical value, esterification finishes, and obtaining intermediate product is the two hydroxy butyl esters of terephthalic acid and the two hydroxy butyl esters of pentanedioic acid and oligopolymer.Under the condition that is 20Pa in 260 ℃ of temperature of reaction, absolute pressure by gained intermediate product, carry out polyreaction, react 1 hour, prepare polybutylene terephthalate type copolyesters, afterwards multipolymer is extruded with bar shaped continuously from polymeric kettle bottom, through water cooling, pelletizing.
Prepared PBT copolyesters product is carried out to performance test, and analytical results is in Table 1.
Embodiment 4
By 498g PTA (3.0mol), 189g oxalic acid (2.1mol), 918gBD (10.2mol) and catalyst B, (content meter in the total mass based on terephthalic acid and oxalic acid, the mass content of titanium atom is 150 * 10
-6), add reactor directly to carry out esterification, temperature of reaction is that 210 ℃, reaction pressure are under the condition of 0.2MPa (absolute pressure), reaction times is 3.5 hours, distillate reaches 95% when above of theoretical value, esterification finishes, and obtaining intermediate product is the two hydroxy butyl esters of terephthalic acid and the two hydroxy butyl esters of oxalic acid and oligopolymer.Under the condition that is 60Pa in 250 ℃ of temperature of reaction, absolute pressure by gained intermediate product, carry out polyreaction, react 2 hours, prepare polybutylene terephthalate type copolyesters, afterwards multipolymer is extruded with bar shaped continuously from polymeric kettle bottom, through water cooling, pelletizing.
Prepared PBT copolyesters product is carried out to performance test, and analytical results is in Table 1.
Embodiment 5
By 354g succinic acid (3.0mol), 486g BD (5.4mol) and catalyst A, (the quality meter based on succinic acid, the weight content of titanium atom is 50 * 10
-6), add reactor to carry out the first step esterification, temperature of reaction is that 160 ℃, reaction pressure are under the condition of 0.1MPa (absolute pressure), reacts 3 hours, distillate has reached the more than 95% of theoretical value; Now, to adding 498g PTA (3.0mol), 351gBD (9.6mol) and catalyst A in reactor, (the quality meter based on PTA, the weight content of titanium atom is 50 * 10 again
-6) carry out second step esterification, temperature of reaction is that 160 ℃, reaction pressure are under the condition of 0.1MPa (absolute pressure), react 3 hours, distillate has reached the more than 95% of theoretical value, esterification finishes, and obtaining intermediate product is the two hydroxy butyl esters of terephthalic acid and the two hydroxy butyl esters of fat diacid and oligopolymer.Under the condition that is 100Pa in 230 ℃ of temperature of reaction, absolute pressure by gained intermediate product, carry out polyreaction, react 4 hours, prepare polybutylene terephthalate type copolyesters, afterwards multipolymer is extruded with bar shaped continuously from polymeric kettle bottom, through water cooling, pelletizing.
Prepared PBT copolyesters product is carried out to performance test, and analytical results is in Table 1.
Embodiment 6
By 70.1g hexanodioic acid (0.48mol), 129.6g BD (1.44mol) and catalyst B, (the quality meter based on hexanodioic acid, the weight content of titanium atom is 150 * 10
-6), add reactor to carry out the first step esterification, temperature of reaction is that 230 ℃, reaction pressure are under the condition of 0.3MPa (absolute pressure), reacts 1 hour, distillate has reached the more than 95% of theoretical value; Now, to adding 498g PTA (3.0mol), 495gBD (5.5mol) and catalyst A in reactor, (the quality meter based on PTA, the weight content of titanium atom is 150 * 10 again
-6) carry out second step esterification, temperature of reaction is that 230 ℃, reaction pressure are under the condition of 0.3MPa (absolute pressure), react 1 hour, distillate has reached the more than 95% of theoretical value, esterification finishes, and obtaining intermediate product is the two hydroxy butyl esters of terephthalic acid and the two hydroxy butyl esters of fat diacid and oligopolymer.Under the condition that is 20Pa in 260 ℃ of temperature of reaction, absolute pressure by gained intermediate product, carry out polyreaction, react 1 hour, prepare polybutylene terephthalate type copolyesters, afterwards multipolymer is extruded with bar shaped continuously from polymeric kettle bottom, through water cooling, pelletizing.
Prepared PBT copolyesters product is carried out to performance test, and analytical results is in Table 1.
Embodiment 7
By 119g pentanedioic acid (0.9mol), 202g BD (2.25mol) and catalyst B, (the quality meter based on succinic acid, the weight content of titanium atom is 80 * 10
-6), add reactor to carry out the first step esterification, temperature of reaction is that 210 ℃, reaction pressure are under the condition of 0.2MPa (absolute pressure), reacts 2 hours, distillate has reached the more than 95% of theoretical value; Now, to adding 498g PTA (3.0mol), 500gBD (5.55mol) and catalyst B in reactor, (the quality meter based on PTA, the weight content of titanium atom is 80 * 10 again
-6) carry out second step esterification, temperature of reaction is that 210 ℃, reaction pressure are under the condition of 0.2MPa (absolute pressure), react 2.5 hours, distillate has reached the more than 95% of theoretical value, esterification finishes, and obtaining intermediate product is the two hydroxy butyl esters of terephthalic acid and the two hydroxy butyl esters of fat diacid and oligopolymer.Under the condition that is 50Pa in 245 ℃ of temperature of reaction, absolute pressure by gained intermediate product, carry out polyreaction, react 2.5 hours, prepare polybutylene terephthalate type copolyesters, afterwards multipolymer is extruded with bar shaped continuously from polymeric kettle bottom, through water cooling, pelletizing.
Prepared PBT copolyesters product is carried out to performance test, and analytical results is in Table 1.
Embodiment 8
By 189g oxalic acid (2.1mol), 378g BD (4.2mol) and catalyst A, (the quality meter based on succinic acid, the weight content of titanium atom is 90 * 10
-6), add reactor to carry out the first step esterification, temperature of reaction is that 180 ℃, reaction pressure are under the condition of 0.2MPa (absolute pressure), reacts 2 hours, distillate has reached the more than 95% of theoretical value; Now, to adding 498g PTA (3.0mol), 495gBD (5.49mol) and catalyst A in reactor, (the quality meter based on PTA, the weight content of titanium atom is 90 * 10 again
-6) carry out second step esterification, temperature of reaction is that 180 ℃, reaction pressure are under the condition of 0.2MPa (absolute pressure), react 2 hours, distillate has reached the more than 95% of theoretical value, esterification finishes, and obtaining intermediate product is the two hydroxy butyl esters of terephthalic acid and the two hydroxy butyl esters of fat diacid and oligopolymer.Under the condition that is 200Pa in 240 ℃ of temperature of reaction, absolute pressure by gained intermediate product, carry out polyreaction, react 3.5 hours, prepare polybutylene terephthalate type copolyesters, afterwards multipolymer is extruded with bar shaped continuously from polymeric kettle bottom, through water cooling, pelletizing.
Prepared PBT copolyesters product is carried out to performance test, and analytical results is in Table 1.
Comparative example 1
Adopt with the direct esterification described in embodiment 1 and prepare PBT type copolyesters, (content meter in the total mass based on terephthalic acid and succinic acid, the weight content of titanium atom is 150 * 10 as catalyzer to use tetrabutyl titanate (being called for short TBT)
-6).
Prepared PBT copolyesters product is carried out to performance test, and analytical results is in Table 1.
Comparative example 2
Adopt with the distribution esterification process described in embodiment 6 and prepare PBT type copolyesters, (amount of the polyester based on generating, the weight content of titanium atom is 150 * 10 as catalyzer to use TBT
-6).
Prepared PBT copolyesters product is carried out to performance test, and analytical results is in Table 1.
Table 1
Claims (9)
1. a preparation method for poly terephthalic acid fat diacid butanediol ester type copolyesters, is characterized in that comprising the following steps:
(1) prepare the two hydroxy butyl esters of terephthalic acid and the two hydroxy butyl esters of fat diacid and oligopolymer: with terephthalic acid, fat diacid and 1,4 – butyleneglycol, for raw material, add after liquid condition titanium series catalyst, directly carry out esterification; Or with fat diacid and 1,4 – butyleneglycol, for raw material, add after liquid condition titanium series catalyst, carry out the first step esterification, in gained esterification products, add again terephthalic acid, 1,4 – butyleneglycol and liquid condition titanium series catalyst, carry out second step esterification;
(2) the two hydroxy butyl esters of terephthalic acid and the two hydroxy butyl esters of fat diacid and oligopolymer are carried out to polyreaction: control reaction pressure is 20Pa～200Pa (absolute pressure), temperature of reaction is 230～260 ℃, reaction times is 1～4h, prepares poly terephthalic acid fat diacid butanediol ester type copolyesters.
2. in accordance with the method for claim 1, it is characterized in that the fat diacid described in step (1) is a kind of in oxalic acid, succinic acid, pentanedioic acid, hexanodioic acid etc.
3. in accordance with the method for claim 1, it is characterized in that in step (1), terephthalic acid is 1:1.1～2.5 with the ratio of the integral molar quantity of fat diacid and the molar weight of Isosorbide-5-Nitrae butyleneglycol; The molar weight of fat diacid account for terephthalic acid and fat diacid integral molar quantity 5～50%, the molar weight of fat diacid is 1:0.053～1.0 with the ratio of terephthalic acid molar weight.
4. in accordance with the method for claim 1, it is characterized in that in step (1) terephthalic acid, fat diacid and 1, when 4 – butyleneglycols directly carry out esterification, temperature of reaction is 160～230 ℃, and pressure is 0.1～0.3MPa (absolute pressure), and the reaction times is 3～5h.
5. in accordance with the method for claim 1, it is characterized in that in step (1), fat diacid and 1, when 4 – butyleneglycols carry out the first step esterification, the molar weight of fat diacid and 1,4 – butyleneglycol is 1:1.8～3.0, and temperature of reaction is 160～230 ℃, pressure is 0.1～0.3MPa (absolute pressure), and the reaction times is 1～3h; When obtained esterification products carries out second step esterification with terephthalic acid, 1,4 – butyleneglycol again, temperature of reaction is 160～230 ℃, and pressure is 0.1～0.3MPa (absolute pressure), and the reaction times is 1～3h.
6. method according to claim 1, is characterized in that, the consumption of described liquid condition titanium series catalyst, and while carrying out direct esterification reaction, the content meter with titanium atom quality in the total mass of terephthalic acid and fat diacid, Ti content is 50 * 10
-6～150 * 10
-6.
7. method according to claim 1, is characterized in that, the consumption of described liquid condition titanium series catalyst, and while carrying out the first step esterification, the quality in titanium atom quality to fat diacid, Ti content is 50 * 10
-6～150 * 10
-6; While carrying out second step esterification, the quality in titanium atom quality to terephthalic acid, Ti content is 50 * 10
-6～150 * 10
-6.
8. method according to claim 1, is characterized in that, described liquid condition titanium series catalyst hydrolysis, dissolves each other with 1,4 – butyleneglycol.
9. method according to claim 1, is characterized in that, the fusing point of the poly terephthalic acid fat diacid butanediol ester type copolyesters making is 170～220 ℃, and limiting viscosity is 0.7～1.2dL/g.
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| CN108034046A (en) * | 2017-11-23 | 2018-05-15 | 中国科学院理化技术研究所 | A kind of high efficiency polyester composite catalyst and its preparation method and application |
| CN111019101A (en) * | 2019-12-31 | 2020-04-17 | 绍兴惠群新材料科技有限公司 | Method for preparing PBT copolyester |
| CN112876659A (en) * | 2021-01-18 | 2021-06-01 | 山东瑞丰高分子材料股份有限公司 | Preparation method of boiling-resistant PBAT composite material |
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