CN109553776A - A kind of polyester block copolymer and the preparation method and application thereof - Google Patents

A kind of polyester block copolymer and the preparation method and application thereof Download PDF

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Publication number
CN109553776A
CN109553776A CN201710889156.3A CN201710889156A CN109553776A CN 109553776 A CN109553776 A CN 109553776A CN 201710889156 A CN201710889156 A CN 201710889156A CN 109553776 A CN109553776 A CN 109553776A
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block copolymer
reaction
dihydric alcohol
acid
polyester block
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CN109553776B (en
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崔晓文
汪永斌
庞小琳
姚君
黄华
胥保礼
戴伍国
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Nantong Xingchen Synthetic Materials Co Ltd
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Nantong Xingchen Synthetic Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/10—Applications used for bottles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/12—Applications used for fibers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention discloses a kind of polyester block copolymers, which is characterized in that shown in its structure such as following formula (I)；The present invention discloses a kind of preparation methods of polyester block copolymer.The method that the present invention passes through copolymerization, siliceous unit is polymerize into polyester molecule chain, obtained copolymer has excellent resistance to low temperature and lower surface tension, improve the not low temperature resistant feature of polyester resin, expanded its fiber, film, blow molding and engineering plastics field application space.An‑Bt (I)。

Description

A kind of polyester block copolymer and the preparation method and application thereof
Technical field
The invention belongs to high molecular synthetic material technical fields, and in particular to one kind has cold resistance and hydrophobic polyester Block copolymer and preparation method thereof.
Background technique
With the development of society, the progress of science and technology, demand of the mankind to material are growing, the life of high molecular synthetic material It produces and application has also obtained quick development.Wherein, engineering plastics are also to expand year by year in the application of every field.Polyester material Material refers mainly to PBT as one of five large-engineering plastics, and Chinese polybutylene terephthalate is semicrystalline thermoplastic Property resin, because having many advantages, such as high-modulus, high intensity, high resiliency and heat resistance, be mainly used in electronic apparatus, automobile, illumination, The fields such as machinery, spinning, communication, film and instrument and meter.PET, Chinese polyethylene terephthalate, due to its compared with Good mechanical property, high temperature resistance and scraping and wiping resistance performance, then be widely used in the fields such as spinning, film, blow molding.Our usual institutes The terylene said is exactly the silk spun using PET material.PTT, Chinese polypropylene terephthalate, as polyester family Nova, have excellent resilience and dyeability, new selection is provided for spinning industry.PCT, Chinese are poly- to benzene two Acid cyclohexyl alkane dimethyl ester and PEN, Chinese polyethylene naphthalate is due to its higher temperature tolerance and mechanical property Can, it is used for the fields such as machinery, electronics and the automobile in hot environment.
Above-mentioned these polyester materials being previously mentioned, mechanical property is all very excellent, but all more crisp, and toughness is insufficient, especially It is at low temperature, substantially without any toughness, to belong to and touch i.e. disconnected situation.The application of this disadvantage limitation polyester.I State is vast in territory, and the temperature difference of north and south different geographical is very big, and especially in winter, still the sun is shining in Hainan Island, warm wind is breezy, temperature Degree is more than 20 DEG C；Heilungkiang is then other scene, and shrewd wind, arctic weather, minimum temperature can be down to -40 DEG C. The clothes warming as resisting cold, polyester fiber, PBT fiber and ptt fiber can not play a role in such a case, use it The clothes made is estimated to be broken at a touch, this significantly limits the application of PET, PBT and PTT.For another example PET and PBT film, Especially biaxially oriented film is easy to attend to become fragile and Decrepitation Phenomena in the environment of -40 DEG C, for the equipment and device of its application Part brings security risk.In field of household appliances, since freezing chamber works in -20 DEG C of environment throughout the year, PBT injection grade material by Also application is limited in its brittleness.Therefore, as can finding a kind of substance of general character, the tough of these above-mentioned materials can be improved Property, especially low-temperature flexibility can obviously widen its application field, have very important realistic meaning.
Second aspect, polyester are to slough the high molecular polymer that hydrone obtains, ester bond by condensation by diacid and glycol Presence, then impart the certain polarity of polyester material.Polarity is higher, the easier moisture absorption, the other small molecules of easier absorption Or granule foreign, polarity is lower, then more be not easy the moisture absorption, more be not easy to adsorb other small molecules or granule foreign.Currently, PET Fiber, PBT fiber and ptt fiber are widely used on the various clothes of the mankind, and fluffy fibre structure can be protected preferably Warm, clothes can be done more rich, be worn more comfortable.In East China, annual winter is always cloudy and drizzly for days on end, the clothing that people are worn Take the hygroscopicity due to polyester fiber, also can be not as good as warm in the past, cotton-wadded quilt is also again but also not warm up not only, and one to becoming a fine day, become it is urgent not And to outdoor of taking allow the sun to dry.Film made by PET and PBT resin is transported for convenience, is generally always rolled, But due to the polarity of PET and PBT molecule, the film rolled is always difficult to be unfolded.Recent years, as automobile lamp escutcheon Material, exempt from spraying and exempt from the development of priming paint PBT material also quickly, however, to ensure that higher flatness and mirror surface requirement, mold The finish on surface is very high, the shortcomings that PBT material also encounters more difficult demoulding.Higher polarity also brings polyester material Material applies upper defect, how to reduce the polarity of polyester, the comfort for improving the convenience of its application and using, and also has very heavy The realistic meaning wanted.
The resistance to low temperature of polyester material how is improved simultaneously and reduces molecular polarity, expands its application field, mesh Before yet there are no announcement.Patent CN100551053C proposes the caking property for solving mylar, by one of mylar Anti-adhesive silicone liquid is coated on face, and the method for anti-mucus coating of stable and uniform on mylar meets electronic application The anti-sticking requirement in field.Patent CN105538853A discloses a kind of method of coextrusion, in upper epidermis or following table layer material Middle addition silicone additives carry out co-extrusion and obtain low polar film.Patent CN103042780B provides a kind of co-extrusion Method squeezes out polyester and thermoplastic elastomer (TPE) jointly, forms composite membrane, low temperature resistant to achieve the effect that.Patent CN104136534A discloses a kind of poly- (alkylene carbonates) resin combination of lower temperature resistance, by introducing epoxide Be copolymerized and is prepared for low temperature resistant resin material, but the introducing of epoxide, the polarity that resin is effectively reduced is failed to, This is not referred in the patent.Patent CN102382307A discloses a kind of preparation method for preparing dihydroxy aryl siloxanes, The compatibility for being copolymerized post-consumer polymer to improve polycarbonate and its, mainly by forming poly- carbonic acid with phosgene reaction in the solution Ester copolymer, but do not use polyester art shown in this article and fiber and film applications.United States Patent (USP) US5132392A By introduce containing end be polyether segment polysilane, the copolyesters of formation shows preferable hydrophilicity, but the change It closes object and the hydrophobic performance for improving resistance to low temperature and material is not provided.United States Patent (USP) US4927895A is by introducing special gather The resulting copolyesters of siloxanes improves the hydrolytic resistance of material, and used polysilane end group is alkyl epoxy group, passes through Epoxy reacts to form copolymer with the carboxyl end group of polyester or terminal hydroxy group, which does not also refer to resistance to low temperature and hydrophobicity The improvement of energy.United States Patent (USP) US4894427A provides a kind of polyester copolymer containing polysilane, is mainly contained by end Polysilane and dicarboxylic acids the copolymerization gained of hydroxy alkyl, the anti-hydrolytic performance of resulting copolymer are improved, but its Resistance to low temperature and hydrophobic performance do not refer to.
In the modification application of engineering plastics, organic siliconresin is usually utilized to enhance the release property of final modified material, This is because the organosilicon being added all is small molecule material, it is modified by the way that after blending extrusion, silicone molecules are easy migration To the surface of material, so that the surface tension of material is reduced, so that it is easier injection molding.But its disadvantage is exactly to have The additional amount of machine silicone resin cannot be excessively high, and the organosilicon small molecule being otherwise added is migrated to article surface, forms oil mark and defect. Also it has been proposed that adding other low surface energy auxiliary agents, such as by way of blending extrusion, by organic silicon rubber and nylon resin Extruding pelletization is carried out, it, can not to reach the low-temperature impact-resistant performance for improving resin, but since the otherness of two kinds of resins is too big Reach uniform mixing, silicon rubber disperses unevenly in nylon resin, and performance generates fluctuation, often also difficult in process of production With control, for the application field of the product or spinning film that require comparison accurate, then it is unable to reach stable production, limited Its application.As can the organosilicon of small molecule or oligomer and polyester are copolymerized by way of polymerization, then organosilicon It can be uniformly dispersed in polyester resin, the higher mechanical performance and silicone resin that new material will have simultaneously polyester resin Resistance to low temperature and hydrophobicity, and silicone molecules are dispersed in resin with the rank of molecule, and the performance of material will become Must be stable, fluctuation becomes smaller, and performance is more excellent, has expanded its application field significantly.Preceding sections patent is referred to containing poly- The copolymer of silane, but there is no the resistance to low temperatures and hydrophobic performance that solve material.Meanwhile the patent CN102382307A, which only has studied, forms Copolycarbonate with phosgene reaction；The patent US4927895A uses end It reacts to obtain copolymer with polyester end for the polysilane of epoxy group, which is unable to the moisture absorption, seriously to environmental requirement harshness Affect its use；The patent US5132392A and US4894427A uses end be copolymerized for the polysilane of hydroxyl New polymer has been arrived, hydrophilicity and anti-hydrolytic performance are improved, but due to the one-step polymerization that it is used, polysilane and two The difference of the reaction rate of first alcohol results in polysilane being unevenly distributed in the copolymer, and the other performance of material is by shadow It rings, Gu Wenzhong does not refer to the resistance to low temperature and hydrophobic performance of obtained polymer.In conclusion in open source literature, Fail the open report that discovery is able to solve above-mentioned polyester material resistance to low temperature and hydrophobic performance.
Summary of the invention
The object of the invention is to be intended to overcome the deficiencies in the prior art described above, by way of copolymerization, provide a kind of resistance to Cold, hydrophobic polyester block copolymer.New polyester block polymer prepared by the present invention, at the same impart new material compared with Low surface tension and impact strength higher at low temperature, provides possibility for the application extension of material.
The present invention is obtained a kind of poly- by introducing polysilane molecule in the molecular structure of polyester by the method for copolymerization Ester block copolymer, prepared polyester block copolyesters have structure shown in following general formula (1):
An-Bt (I)
In formula (I):
A block is the polyester that binary acid and diol reaction obtain；Wherein, the binary acid is selected from aromatic dicarboxylic carboxylic One of acid, aliphatic dicarboxylic acid are several；The dihydric alcohol is in aliphatic dihydroxy alcohol, cycloaliphatic diols It is one or several kinds of；
Shown in B block structure such as formula (II):
In formula (II): R4、R5It is each independently selected from methyl, ethyl, propyl, phenyl, Alpha-Methyl phenyl or to methylbenzene Base；R6Indicate (CH2)2、(CH2)3、(CH2)4、(CH2)6、One or more of；S is whole greater than 1 Number；
In the block copolymer, n is the integer greater than 1, and t is the integer greater than 1.
Polyester block copolymer of the present invention meets A block and accounts for the percentage of the copolymer gross mass to be accounted for B block The sum of percentage of the copolymer gross mass is 100%；Preferably, the quality of the B block accounts for the copolymer gross mass Percentage be 0.1%~50%, more preferably 0.5%~30%, further preferably 3%~20%, still more preferably It is 10%~15%.
In the A block of the polyester block copolymer, the aromatic binary carboxylic acid is selected from terephthalic acid (TPA), isophthalic diformazan One or more of acid, naphthalene diacid；The aliphatic dicarboxylic acid be selected from one of succinic acid, adipic acid, suberic acid or It is several；The cycloaliphatic diols are selected from one of ethylene glycol, propylene glycol, butanediol, hexylene glycol, 1,4 cyclohexane dimethanol Or it is several.
In the B block of the polyester block copolymer, 1≤s≤100；Preferably, 1≤s≤50；It is highly preferred that 1≤s≤ 30；It is further preferred that 1≤s≤50.The R4、R5Structure it is identical or different, preferably identical, more preferable R4With R5It is Methyl.
The inherent viscosity of polyester block copolymer provided by the invention be 0.6~2.0dL/g, preferably 0.79~ 1.33dL/g.It is such as indicated without special, intrinsic viscosity of the present invention is measured according to ASTM D445 standard method.
As a preferred solution of the present invention, the polyester block copolymer is selected from the one or more of such as flowering structure:
Polyester block copolymer resistance to low temperature provided by the invention is excellent, and cold temperature impact is good, and performance tension is small, can use In fields such as cold resistance and hydrophobic application field, such as fiber, film, Bottle & Can, engineering plastics.
Invention also provides a kind of preparation methods of polyester block copolymer, including esterification, prepolymerization reaction And polycondensation reaction；Further, solid-phase tack producing reaction can also be carried out as needed.
Specifically, the described method comprises the following steps:
(1) dicarboxylic acids and dihydric alcohol are placed in reaction kettle, carry out esterification；
Dicarboxylic acids described in this step is selected from one of aromatic binary carboxylic acid, aliphatic dicarboxylic acid or several； Dihydric alcohol described in this step is selected from one of aliphatic dihydroxy alcohol, cycloaliphatic diols or several；
(2) will the α as shown in formula (III), ω-dicarboxyl polysilane and dihydric alcohol are placed in reaction kettle, be esterified anti- It answers；
In formula (III), R4、R5It is each independently selected from methyl, ethyl, propyl, phenyl, Alpha-Methyl phenyl or to methylbenzene Base；S is the integer greater than 1；
Dihydric alcohol described in this step is selected from one of aliphatic dihydroxy alcohol, cycloaliphatic diols or several；
(3) step (1) products therefrom and step (2) products therefrom are placed in reaction kettle, carry out prepolymerization reaction, generated Precondensation product；
(4) precondensation product obtained by step (3) is placed in reaction kettle, carries out polycondensation reaction, obtains polyester block copolymer.
In order to improve the viscosity of the polyester block copolymer, the method for the invention can also include making step (4) The product obtained carries out solid-phase tack producing reaction.Solid-phase tack producing reaction can vacuum state (3-100Pa) or inert gas It is carried out under the state (flow velocity of inert gas is 0.5-5L/ [minKG viscosifies particle]) of protection.Preferably, the solid phase increases The temperature of viscous reaction is 100-260 DEG C, and the General reactions time is 4-36 hours.Make obtained polyester by solid-phase tack producing reaction The inherent viscosity of block copolymer is 0.8-2.0dL/g, preferably 0.79~1.33dL/g.Specific reaction condition can be according to reality Depending on border needs.
In the step (1), the dicarboxylic acids can be selected from phthalic acid (PTA), M-phthalic acid (PIA), 2,6- Naphthalenedicarboxylic acid (NDA), 1,4- succinic acid (SA), adipic acid or the one such or several mixture of suberic acid；It is described Dihydric alcohol is that ethylene glycol, 1,3- propylene glycol, 1,4- butanediol, 1,6-HD and 1,4 cyclohexane dimethanol (CHDM) are therein One or several kinds of mixtures.
The present invention further carries out preferably, specifically: institute the combination of dicarboxylic acids and dihydric alcohol in step (1) The dicarboxylic acids stated is terephthalic acid (TPA), the dihydric alcohol is ethylene glycol；Alternatively, the dicarboxylic acids be terephthalic acid (TPA), The dihydric alcohol is 1,3- propylene glycol；Alternatively, the dicarboxylic acids is terephthalic acid (TPA), the dihydric alcohol is Isosorbide-5-Nitrae-fourth two Alcohol；Alternatively, the dicarboxylic acids is terephthalic acid (TPA), the dihydric alcohol is 1,4-CHDM (CHDM)；Alternatively, institute The dicarboxylic acids stated is 2,6- naphthalenedicarboxylic acid (NDA), the dihydric alcohol is ethylene glycol；Alternatively, the dicarboxylic acids is 2,6- Naphthalenedicarboxylic acid, the dihydric alcohol are 1,4- butanediol；Alternatively, the dicarboxylic acids is 1, 4- succinic acid (SA), the binary Alcohol is 1,4- butanediol；Alternatively, the dicarboxylic acids is terephthalic acid (TPA), the dihydric alcohol is ethylene glycol and Isosorbide-5-Nitrae-hexamethylene Dimethanol.
In the step (2), formula (III) compound represented can be selected from α, ω-dicarboxyethyl dimethyl silicone polymer, α, ω-dicarboxyethyl polydiethylsiloxane, α, ω-dicarboxyethyl polymethylphenylsiloxane, α, ω-dicarboxyethyl Polydiphenylsiloxane etc..The dihydric alcohol is ethylene glycol, 1,3- propylene glycol, 1,4- butanediol, 1,6-HD and 1,4- ring The one such or several mixture of hexane dimethanol (CHDM).
The present invention carries out preferably, thus the polyester block copolymer being had excellent performance the dosage of each step raw material.Tool For body, in the step (1), the molar ratio of dicarboxylic acids and dihydric alcohol is 1:1~1:1.5.In the step (2), formula (III) compound represented and the molar ratio of dihydric alcohol are 1:1.2~1:1.5.In the step (3), step (2) products therefrom Dosage account for the sum of step (1), (2) product dosage ratio be 0.1%~50%, preferably 0.5%~30%, more preferably 3%~20%, further preferably 10%~15%.
The step (1), step (2) esterification in, it is preferred to use catalyst is catalyzed.The catalyst is optional One of autoxidation germanium, manganese acetate, zinc acetate, butyl titanate, antimony oxide, antimony glycol, titanium ethylene glycolate are several The compound of kind.The quality of the catalyst preferably accounts for the 0.01%-0.1% of reaction raw materials gross mass.
The present invention is preferably in esterification using the mixed system of above-mentioned catalyst and dihydric alcohol, the catalyst mixture The preparation method of system includes: to be placed in the dihydric alcohol and the catalyst in reaction kettle according to the ratio, and boiling is heated under vacuum state It rises 2-4 hours, vacuum degree 20-30KPa, temperature is 170-200 DEG C, cooling.Wherein, the dihydric alcohol is urged with described The molar ratio of agent is 1:3~1:6.
The esterification carries out according to normal conditions.As a preferred embodiment: step (1) described esterification Condition it is preferred are as follows: 160~245 DEG C of temperature, 40~45KPa of vacuum degree；Step (2) the esterification condition are as follows: temperature 160 ~245 DEG C, 40~45KPa of vacuum degree.
The present invention is in order to improve the polymerization effect and comprehensive performance of products therefrom, using first carrying out prepolymerization reaction, then The scheme of polycondensation reaction is carried out, and the reaction condition of two one-step polycondensations is optimized.
Specifically: step (3) the prepolymerization reaction condition are as follows: 180~310 DEG C of temperature, vacuum degree 1.5~ 2.5KPa, General reactions time are 30-60min；Step (4) the polycondensation reaction condition are as follows: 180~310 DEG C of temperature, vacuum degree 100~200Pa, General reactions time are 60-240min.
The polycondensation process started in esterification continues in precondensation kettle, and prepolymerization reaction generates low molecular weight Polyester copolymer, precondensation product by precondensation discharging pump, precondensation discharge filter, precondensation discharge cooler it is laggard Enter polycondensation reactor.The polyester block copolymer of polycondensation reaction generation high molecular weight.Polycondensation product passes through polycondensation discharging pump, polymerization Enter pelleter system after object viscosimeter, polycondensation discharging filter, polycondensation discharging distributing valve.High score has been obtained after cooling and dicing The polyester block copolymer product of son amount.The inherent viscosity of gained polyester block copolymer is 0.5-1.0dL/g.
When the method also further progress solid-phase tack producing reacts, the temperature of solid-phase tack producing reaction is 100~260 DEG C.
As a preferred solution of the present invention, the method includes steps in detail below:
S1: slurry preparation
Dicarboxylic acids and dihydric alcohol are placed in container (preparing tank), stirred evenly, mixed material S1 is made；Wherein, two Molar ratio 1:1~1:1.5 of first carboxylic acid and dihydric alcohol；
Formula (III) compound represented and dihydric alcohol are placed in container (preparing tank), stirred evenly, mixed material is made S2；Wherein, molar ratio 1:1.2~1:1.5 of formula (III) compound represented and dihydric alcohol；
S2: catalyst preparation
The dihydric alcohol and the catalyst are added in container (preparing tank) according to the ratio of molar ratio 1:3~1:6, Ebuillition of heated 2-4 hours, vacuum degree 20-30KPa under vacuum state, temperature is 170-200 DEG C, cooling；It is mixed that catalyst is made Zoarium system；
S3: esterification
Mixed material S1 is placed in reaction kettle (esterifying kettle), the catalyst mixed system for adding step S2 preparation carries out Esterification, reaction there is no water until generating；Generate oligomer OM1；Wherein, the quality of added catalyst is mixed with described The mass ratio of material S1 is 0.01%-0.1%；Esterification condition are as follows: 160-245 DEG C of temperature, vacuum degree 40-45KPa, instead It is 1-3 hours between seasonable；
Mixed material S2 is placed in reaction kettle (esterifying kettle), the catalyst mixed system for adding step S2 preparation carries out Esterification, reaction there is no water until generating；Generate oligomer OM2, i.e. formula (III) compound represented；
Wherein, the mass ratio of the quality of added catalyst and the mixed material S2 are 0.01%-0.1%；Esterification is anti- Answer condition are as follows: 160-245 DEG C of temperature, vacuum degree 40-45KPa, the reaction time is 1-3 hours；
S4: prepolymerization reaction
Oligomer OM1 and oligomer OM2 are placed in reaction kettle (precondensation kettle), prepolymerization reaction is carried out, generates preshrunk Poly- product (i.e. the polyester copolymer of low molecular weight)；Wherein, the matter of the quality of oligomer OM1 and oligomer OM1, oligomer OM2 The ratio of the sum of amount is 0.1%-50%；Prepolymerization reaction condition are as follows: 180-310 DEG C of temperature, vacuum degree 1.5-2.5KPa, reaction Time is 30-60min.
S5: polycondensation reaction
Precondensation product obtained by step S4 is placed in reaction kettle (polycondensation reactor), polycondensation reaction is carried out, generates formula (I) Compound represented (i.e. the polyester block copolymer of high molecular weight)；Polycondensation reaction condition are as follows: 180-310 DEG C of temperature, vacuum degree 100-200Pa, reaction time 60-240min；The inherent viscosity of gained polyester block copolymer is 0.5-1.0dL/g；
S6: solid-phase tack producing reaction
The polyester block copolymer particle that polycondensation reaction is obtained is sent into thickening kettle, 3-100Pa vacuum state or In the state of person's inert gas shielding, the flow velocity of inert gas is 0.5-5L/ [minKG viscosifies particle], in the temperature of setting Solid phase reaction is carried out at 100-260 DEG C, the reaction time is 4-36 hours；The inherent viscosity of obtained polyester block copolymer is 0.8-2.0dL/g。
The present invention is optimized reaction condition further directed to the characteristic of raw material.Specifically:
When step (1) dicarboxylic acids is 2,6-naphthalenedicarboxylic acid, prepolymerization reaction temperature range is 250~310 DEG C, Polycondensation reaction temperature is 250~310 DEG C, and preferably solid-phase tack producing reaction temperature is 200~240 DEG C.
When step (1) described dicarboxylic acids is terephthalic acid (TPA), the dihydric alcohol is 1,4 cyclohexane dimethanol (CHDM) When, prepolymerization reaction temperature range is 280~310 DEG C, and polycondensation reaction temperature is 280~310 DEG C, preferably solid-phase tack producing reaction temperature Degree is 240~260 DEG C.
When step (1) described dicarboxylic acids is terephthalic acid (TPA), the dihydric alcohol is except 1,4 cyclohexane dimethanol (CHDM) a kind of dihydric alcohol except or for two or more dihydric alcohols mixture when, prepolymerization reaction temperature range is 200 ~250 DEG C, polycondensation reaction temperature is 200~250 DEG C, and preferably solid-phase tack producing reaction temperature is 180~220 DEG C.
When step (1) dicarboxylic acids is succinic acid, prepolymerization reaction temperature range is 100~200 DEG C, and polycondensation is anti- Answering temperature is 100~200 DEG C, and solid-phase tack producing reaction temperature is 100~110 DEG C.
Each raw material that the present invention uses is commercially available to be bought.
The polyester block copolymer that the present invention protects the polyester block copolymer or the method to be prepared simultaneously exists Prepare the application in terms of fiber, film, Bottle & Can, engineering plastics.
Compared with prior art, the present invention having the advantage that
The first, the polyester copolymer prepared by the present invention containing silicon unit, inherent viscosity is high, directly reflects copolymer point Son measures higher, excellent in mechanical performance, while imparting the excellent resistance to low temperature of material and lower surface tension, can be very big The existing polyester of expansion application range.
The second, the polyester copolymer prepared by the present invention containing silicon unit is to be prepared using the method for direct polymerization, made Silicon molecule is evenly distributed in the strand of polyester resin in standby polyester copolymer.It compares by the way of being blended, it will Silicon rubber or silicone resin with polyester resin in such a way that double screw extruder is blended, since consistency problem generates meeting Layering or incompatible phenomenon；In addition, if using small molecule the silicone molecules and polyester resin containing reactive group It is blended by double screw extruder, since the residence time is shorter in twin-screw, reacts insufficient, more small molecule will be remained In last blend, volatile matter is higher.
Third, preparation method of the present invention, after by silicon-containing monomer and silicon-containing monomer is not esterified respectively again Polymerization makes reaction be easier to be controlled as requested, convenient for obtaining the polyester block copolymer of certain regularity；Meanwhile containing Silicon monomer is first esterified, and reaction is more easily controlled.
4th, preparation method provided by the invention uses the mild solid phase mode of reaction condition finally to synthesize Direct polycondensation cannot high molecular weight obtained polyester copolymer, thus not only produce a desired effect, but also avoid Conventional polycondensation mode consumes energy greatly, and reaction condition is more harsh, the high requirements on the equipment, it is difficult to control the disadvantage of Product Process condition Disease.The preparation method of polyester copolymer provided by the present invention is optimized on the basis of the production method of existing polyester, Method is simple and convenient, easily controllable and realization industrialized production.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..It is not specified in embodiment specific Technology or conditions person, described technology or conditions according to the literature in the art, or carried out according to product description.It is used Production firm person is not specified in reagent or instrument, is the conventional products that can be commercially available by regular distributor.
Following detection method:
Intrinsic viscosity: it is measured according to ASTM D445 standard.
Impact strength: it is measured according to ASTM D256 standard.
End carboxyl group content: it is measured according to GB/T 14190-2008 standard.
Solution constant temperature thermal weight loss: weighing appropriate amount of sample, and in air atmosphere heating furnace, initial temperature is room temperature, heating speed Rate is 20 DEG C/min, and temperature programming keeps 120min to 260 DEG C.By the curvilinear motion of sample quality and temperature relation, calculate The content of volatile matter in sample.
Surface tension: it is measured according to GB/T 14216-2008 standard.
The preparation of PBT copolyesters of the embodiment 1 containing silicon unit
Slurry preparation: 1) terephthalic acid (TPA) (PTA) and 1,4 butanediols (BDO) respectively by metering system is entered into slurry Preparing tank U1, stirs evenly, and is denoted as slurry S1, and wherein PTA is 773G (G meaning is mass unit gram, similarly hereinafter), BDO 520G. 2) α, ω-dicarboxyethyl dimethyl silicone polymer and 1,4 butanediols (BDO) are entered into slurry preparation by metering system respectively Tank U2, stirs evenly, and is denoted as slurry S2, wherein α, and ω-dicarboxyethyl dimethyl silicone polymer is 210G, Isosorbide-5-Nitrae butanediol It (BDO) is 30G.
Catalyst preparation: 1,4 butanediols (BDO) 100G and catalyst C (butyl titanate) 158.9G is added to preparation In tank U3, ebuillition of heated 2-3 hours, vacuum degree 20-30KPa under vacuum state, temperature is 180 DEG C, will be configured after cooling Catalyst be transferred in catalyst shot tank.
Esterification: the slurry S1 in slurry tank U1 is sent into esterifying kettle E1 by mashing pump, by configured catalyst C It is pumped into esterifying kettle E1 by gear, esterification occurs under the effect of the catalyst, esterification is to there is no water generations Until, the oligomer OM1 of generation.The mass ratio C/S1 that the amount of added catalyst accounts for slurry is 0.05%.The reaction of esterifying kettle Condition are as follows: temperature is 245 DEG C, vacuum degree 42KPa, and the reaction time is 2 hours, and esterification yield is up to 99.2%.
Esterification: the slurry S2 in slurry tank U2 is sent into esterifying kettle E2 by mashing pump, by configured catalyst It is pumped into esterifying kettle E2 by gear, esterification occurs under the effect of the catalyst, esterification is to there is no water generations Until, the oligomer OM2 of generation.The mass ratio C/S2 that the amount of added catalyst accounts for slurry is 0.05%.The reaction of esterifying kettle Condition are as follows: temperature is 245 DEG C, vacuum degree 42KPa, and the reaction time is 2 hours, esterification yield 99%.
Prepolymerization reaction: the oligomer in esterifying kettle E1 and E2 is sent into precondensation kettle in proportion respectively, wherein being esterified The ratio OM2/ (OM1+OM2) that OM2 is added in kettle E2 is 10%.The polycondensation process started in esterification is in precondensation kettle Continue, prepolymerization reaction temperature is 245 DEG C, and vacuum degree is -2KPa, reaction time 40min, generates the poly- of low molecular weight Ester copolymer, precondensation product is by entering contracting after precondensation discharging pump, precondensation discharging filter, precondensation discharging cooler Poly- reactor.
Polycondensation reaction: precondensation product is admitted to polycondensation reactor from precondensation unit, and the reaction was continued for prepolymer, and polycondensation is anti- It answers temperature to be 248 DEG C, vacuum degree 120Pa, reaction time 200min and generates the polyester block copolymer of high molecular weight.Contracting Poly- product is by entering pelleter system after polycondensation discharging pump, polymer viscosity meter, polycondensation discharging filter, polycondensation discharging distributing valve System.The polyester block copolymer product of high molecular weight has been obtained after cooling and dicing.The characteristic of gained polyester block copolymer is viscous Degree is 0.61dL/g.
The structure of obtained polyester block copolymer is shown below:
Solid-phase tack producing reaction: the polyester block copolymer particle that polycondensation reaction is obtained is sent into thickening kettle, 10Pa's In the state of vacuum state or inert gas shielding, solid phase reaction is carried out at a temperature of setting, the reaction time is 20 hours.
The inherent viscosity of obtained polyester block copolymer is 0.92dL/g.Temperature is set as 200 DEG C.
The preparation of PBT copolyesters of the embodiment 2 containing silicon unit
Slurry preparation: 1) terephthalic acid (TPA) (PTA) and 1,4 butanediols (BDO) respectively by metering system is entered into slurry Preparing tank U1, stirs evenly, and is denoted as slurry S1, and wherein PTA is 773G, BDO 520G.2) by α, ω-dicarboxyethyl poly- two Methylsiloxane and Isosorbide-5-Nitrae butanediol (BDO) enter slurry preparation U2 by metering system respectively, stir evenly, are denoted as slurry S2, wherein α, ω-dicarboxyethyl dimethyl silicone polymer are 300G, and Isosorbide-5-Nitrae butanediol (BDO) is 45G.
Catalyst preparation: 1,4 butanediols (BDO) 100G and catalyst C (butyl titanate) 158.9G is added to preparation In tank U3, ebuillition of heated 2-3 hours, vacuum degree 20-30KPa under vacuum state, temperature is 180 DEG C, will be configured after cooling Catalyst be transferred in catalyst shot tank.
Esterification: the slurry S1 in slurry tank U1 is sent into esterifying kettle E1 by mashing pump, by configured catalyst C It is pumped into esterifying kettle E1 by gear, esterification occurs under the effect of the catalyst, esterification is to there is no water generations Until, the oligomer OM1 of generation.The mass ratio C/S1 that the amount of added catalyst accounts for slurry is 0.05%.The reaction of esterifying kettle Condition are as follows: temperature is 245 DEG C, vacuum degree 42KPa, and the reaction time is 2 hours, and esterification yield is up to 99.2%.
Esterification: the slurry S2 in slurry tank U2 is sent into esterifying kettle E2 by mashing pump, by configured catalyst It is pumped into esterifying kettle E2 by gear, esterification occurs under the effect of the catalyst, esterification is to there is no water generations Until, the oligomer OM2 of generation.The mass ratio C/S2 that the amount of added catalyst accounts for slurry is 0.05%.The reaction of esterifying kettle Condition are as follows: temperature is 245 DEG C, vacuum degree 42KPa, and the reaction time is 2 hours, esterification yield 99%.
Prepolymerization reaction: the oligomer in esterifying kettle E1 and E2 is sent into precondensation kettle in proportion respectively, wherein being esterified The ratio OM2/ (OM1+OM2) that OM2 is added in kettle E2 is 20%.The polycondensation process started in esterification is in precondensation kettle Continue, prepolymerization reaction temperature is 245 DEG C, and vacuum degree is -2KPa, reaction time 50min, generates the poly- of low molecular weight Ester copolymer, precondensation product is by entering contracting after precondensation discharging pump, precondensation discharging filter, precondensation discharging cooler Poly- reactor.
Polycondensation reaction: precondensation product is admitted to polycondensation reactor from precondensation unit, and the reaction was continued for prepolymer, and polycondensation is anti- It answers temperature to be 248 DEG C, vacuum degree 120Pa, reaction time 200min and generates the polyester block copolymer of high molecular weight.Contracting Poly- product is by entering pelleter system after polycondensation discharging pump, polymer viscosity meter, polycondensation discharging filter, polycondensation discharging distributing valve System.The polyester block copolymer product of high molecular weight has been obtained after cooling and dicing.The characteristic of gained polyester block copolymer is viscous Degree is 0.6dL/g.
The structure of obtained polyester block copolymer is shown below:
Solid-phase tack producing reaction: the polyester block copolymer particle that polycondensation reaction is obtained is sent into thickening kettle, 10Pa's In the state of vacuum state or inert gas shielding, solid phase reaction is carried out at a temperature of setting, the reaction time is 25 hours.
The inherent viscosity of obtained polyester block copolymer is 0.90dL/g.Temperature is set as 200 DEG C.
The preparation of PBT copolyesters of the embodiment 3 containing silicon unit
Slurry preparation: 1) terephthalic acid (TPA) (PTA) and 1,4 butanediols (BDO) respectively by metering system is entered into slurry Preparing tank U1, stirs evenly, and is denoted as slurry S1, and wherein PTA is 773G, BDO 520G.2) by α, ω-dicarboxyethyl poly- two Methylsiloxane and Isosorbide-5-Nitrae butanediol (BDO) enter slurry preparation U2 by metering system respectively, stir evenly, are denoted as slurry S2, wherein α, ω-dicarboxyethyl dimethyl silicone polymer are 420G, and Isosorbide-5-Nitrae butanediol (BDO) is 60G.
Catalyst preparation: 1,4 butanediols (BDO) 100G and catalyst C (butyl titanate) 158.9G is added to preparation In tank U3, ebuillition of heated 2-3 hours, vacuum degree 20-30KPa under vacuum state, temperature is 180 DEG C, will be configured after cooling Catalyst be transferred in catalyst shot tank.
Esterification: the slurry S1 in slurry tank U1 is sent into esterifying kettle E1 by mashing pump, by configured catalyst C It is pumped into esterifying kettle E1 by gear, esterification occurs under the effect of the catalyst, esterification is to there is no water generations Until, the oligomer OM1 of generation.The mass ratio C/S1 that the amount of added catalyst accounts for slurry is 0.05%.The reaction of esterifying kettle Condition are as follows: temperature is 245 DEG C, vacuum degree 42KPa, and the reaction time is 2 hours, and esterification yield is up to 99.2%.
Esterification: the slurry S2 in slurry tank U2 is sent into esterifying kettle E2 by mashing pump, by configured catalyst It is pumped into esterifying kettle E2 by gear, esterification occurs under the effect of the catalyst, esterification is to there is no water generations Until, the oligomer OM2 of generation.The mass ratio C/S2 that the amount of added catalyst accounts for slurry is 0.05%.The reaction of esterifying kettle Condition are as follows: temperature is 245 DEG C, vacuum degree 42KPa, and the reaction time is 2 hours, esterification yield 99%.
Prepolymerization reaction: the oligomer in esterifying kettle E1 and E2 is sent into precondensation kettle in proportion respectively, wherein being esterified The ratio OM2/ (OM1+OM2) that OM2 is added in kettle E2 is 30%.The polycondensation process started in esterification is in precondensation kettle Continue, prepolymerization reaction temperature is 245 DEG C, and vacuum degree is -2KPa, reaction time 50min, generates the poly- of low molecular weight Ester copolymer, precondensation product is by entering contracting after precondensation discharging pump, precondensation discharging filter, precondensation discharging cooler Poly- reactor.
Polycondensation reaction: precondensation product is admitted to polycondensation reactor from precondensation unit, and the reaction was continued for prepolymer, and polycondensation is anti- It answers temperature to be 248 DEG C, vacuum degree 120Pa, reaction time 200min and generates the polyester block copolymer of high molecular weight.Contracting Poly- product is by entering pelleter system after polycondensation discharging pump, polymer viscosity meter, polycondensation discharging filter, polycondensation discharging distributing valve System.The polyester block copolymer product of high molecular weight has been obtained after cooling and dicing.The characteristic of gained polyester block copolymer is viscous Degree is 0.55dL/g.
The structure of obtained polyester block copolymer is shown below:
Solid-phase tack producing reaction: the polyester block copolymer particle that polycondensation reaction is obtained is sent into thickening kettle, 10Pa's In the state of vacuum state or inert gas shielding, solid phase reaction is carried out at a temperature of setting, the reaction time is 30 hours.
The inherent viscosity of obtained polyester block copolymer is 0.88dL/g.Temperature is set as 200 DEG C.
The preparation of PBT copolyesters of the embodiment 4 containing silicon unit
Slurry preparation: 1) terephthalic acid (TPA) (PTA) and 1,4 butanediols (BDO) respectively by metering system is entered into slurry Preparing tank U1, stirs evenly, and is denoted as slurry S1, and wherein PTA is 773G, BDO 520G.2) by α, ω-dicarboxyethyl poly- two Methylsiloxane and Isosorbide-5-Nitrae butanediol (BDO) enter slurry preparation U2 by metering system respectively, stir evenly, are denoted as slurry S2, wherein α, ω-dicarboxyethyl dimethyl silicone polymer are 100G, and Isosorbide-5-Nitrae butanediol (BDO) is 20G.
Catalyst preparation: 1,4 butanediols (BDO) 100G and catalyst C (butyl titanate) 158.9G is added to preparation In tank U3, ebuillition of heated 2-3 hours, vacuum degree 20-30KPa under vacuum state, temperature is 180 DEG C, will be configured after cooling Catalyst be transferred in catalyst shot tank.
Esterification: the slurry S1 in slurry tank U1 is sent into esterifying kettle E1 by mashing pump, by configured catalyst C It is pumped into esterifying kettle E1 by gear, esterification occurs under the effect of the catalyst, esterification is to there is no water generations Until, the oligomer OM1 of generation.The mass ratio C/S1 that the amount of added catalyst accounts for slurry is 0.05%.The reaction of esterifying kettle Condition are as follows: temperature is 245 DEG C, vacuum degree 42KPa, and the reaction time is 2 hours, and esterification yield is up to 99.2%.
Esterification: the slurry S2 in slurry tank U2 is sent into esterifying kettle E2 by mashing pump, by configured catalyst It is pumped into esterifying kettle E2 by gear, esterification occurs under the effect of the catalyst, esterification is to there is no water generations Until, the oligomer OM2 of generation.The mass ratio C/S2 that the amount of added catalyst accounts for slurry is 0.05%.The reaction of esterifying kettle Condition are as follows: temperature is 245 DEG C, vacuum degree 42KPa, and the reaction time is 2 hours, esterification yield 99%.
Prepolymerization reaction: the oligomer in esterifying kettle E1 and E2 is sent into precondensation kettle in proportion respectively, wherein being esterified The ratio OM2/ (OM1+OM2) that OM2 is added in kettle E2 is 5%.The polycondensation process started in esterification is in precondensation kettle Continue, prepolymerization reaction temperature is 245 DEG C, and vacuum degree is -2KPa, reaction time 40min, generates the poly- of low molecular weight Ester copolymer, precondensation product is by entering contracting after precondensation discharging pump, precondensation discharging filter, precondensation discharging cooler Poly- reactor.
Polycondensation reaction: precondensation product is admitted to polycondensation reactor from precondensation unit, and the reaction was continued for prepolymer, and polycondensation is anti- It answers temperature to be 248 DEG C, vacuum degree 120Pa, reaction time 200min and generates the polyester block copolymer of high molecular weight.Contracting Poly- product is by entering pelleter system after polycondensation discharging pump, polymer viscosity meter, polycondensation discharging filter, polycondensation discharging distributing valve System.The polyester block copolymer product of high molecular weight has been obtained after cooling and dicing.The characteristic of gained polyester block copolymer is viscous Degree is 0.65dL/g.
The structure of obtained polyester block copolymer is shown below:
Solid-phase tack producing reaction: the polyester block copolymer particle that polycondensation reaction is obtained is sent into thickening kettle, 10Pa's In the state of vacuum state or inert gas shielding, solid phase reaction is carried out at a temperature of setting, the reaction time is 20 hours.
The inherent viscosity of obtained polyester block copolymer is 0.93dL/g.Temperature is set as 200 DEG C.
The preparation of PBT polyester of the comparative example 1 without containing silicon unit
Slurry preparation: 1) terephthalic acid (TPA) (PTA) and 1,4 butanediols (BDO) respectively by metering system is entered into slurry Preparing tank U1, stirs evenly, and is denoted as slurry S1, and wherein PTA is 773G, BDO 520G.
Catalyst preparation: 1,4 butanediols (BDO) 100G and catalyst C (butyl titanate) 158.9G is added to preparation In tank U3, ebuillition of heated 2-3 hours, vacuum degree 20-30KPa under vacuum state, temperature is 180 DEG C, will be configured after cooling Catalyst be transferred in catalyst shot tank.
Esterification: the slurry S1 in slurry tank U1 is sent into esterifying kettle E1 by mashing pump, by configured catalyst C It is pumped into esterifying kettle E1 by gear, esterification occurs under the effect of the catalyst, esterification is to there is no water generations Until, the oligomer OM1 of generation.The mass ratio C/S1 that the amount of added catalyst accounts for slurry is 0.05%.The reaction of esterifying kettle Condition are as follows: temperature is 245 DEG C, vacuum degree 42KPa, and the reaction time is 2 hours, and esterification yield is up to 99.2%.
Prepolymerization reaction: the oligomer in esterifying kettle E1 is sent into precondensation kettle, the polycondensation started in esterification Process continues in precondensation kettle, prepolymerization reaction temperature be 245 DEG C, vacuum degree be -2KPa, reaction time 40min, The polyester copolymer of low molecular weight is generated, precondensation product is gone out by precondensation discharging pump, precondensation discharging filter, precondensation Enter polycondensation reactor after expecting cooler.
Polycondensation reaction: precondensation product is admitted to polycondensation reactor from precondensation unit, and the reaction was continued for prepolymer, and polycondensation is anti- It answers temperature to be 248 DEG C, vacuum degree 120Pa, reaction time 200min and generates the polyester block copolymer of high molecular weight.Contracting Poly- product is by entering pelleter system after polycondensation discharging pump, polymer viscosity meter, polycondensation discharging filter, polycondensation discharging distributing valve System.The polyester block copolymer product of high molecular weight has been obtained after cooling and dicing.The characteristic of gained polyester block copolymer is viscous Degree is 0.75dL/g.
Solid-phase tack producing reaction: the polyester block copolymer particle that polycondensation reaction is obtained is sent into thickening kettle, 10Pa's In the state of vacuum state or inert gas shielding, solid phase reaction is carried out at a temperature of setting, the reaction time is 20 hours.
The inherent viscosity of obtained polyester block copolymer is 0.95dL/g.Temperature is set as 200 DEG C.
The preparation of PCT copolyesters of the embodiment 5 containing silicon unit
Slurry preparation: 1) terephthalic acid (TPA) (PTA) and 1,4 cyclohexane dimethanol (CHDM) is respectively passed through into metering system It into slurry preparation U1, stirs evenly, is denoted as slurry S1, wherein PTA is 773G, CHDM 670G.2) by α, ω-dicarboxyl Ethyl dimethyl silicone polymer and slurry 1) used in 1,4 cyclohexane dimethanol (CHDM) respectively pass through metering system enter Slurry preparation U2, stirs evenly, and is denoted as slurry S2, wherein α, and ω-dicarboxyethyl dimethyl silicone polymer is 100G, Isosorbide-5-Nitrae- Cyclohexanedimethanol (CHDM) is 30G.
Catalyst preparation: by 1,4 cyclohexane dimethanol (CHDM) 128.89G and catalyst C (butyl titanate) 158.9G It is added in preparing tank U3, is slowly ramped to 200 DEG C, ebuillition of heated 2-3 hours, vacuum degree 20-30KPa under vacuum state, Configured catalyst is transferred in catalyst shot tank after cooling.
Esterification: the slurry S1 in slurry tank U1 is sent into esterifying kettle E1 by mashing pump, by configured catalyst C It is pumped into esterifying kettle E1 by gear, esterification occurs under the effect of the catalyst, esterification is to there is no water generations Until, the oligomer OM1 of generation.The mass ratio C/S1 that the amount of added catalyst accounts for slurry is 0.05%.The reaction of esterifying kettle Condition are as follows: temperature is 280 DEG C, vacuum degree 42KPa, and the reaction time is 2 hours, and esterification yield is up to 99.1%.
Esterification: the slurry S2 in slurry tank U2 is sent into esterifying kettle E2 by mashing pump, by configured catalyst It is pumped into esterifying kettle E2 by gear, esterification occurs under the effect of the catalyst, esterification is to there is no water generations Until, the oligomer OM2 of generation.The mass ratio C/S2 that the amount of added catalyst accounts for slurry is 0.05%.The reaction of esterifying kettle Condition are as follows: temperature is 245 DEG C, vacuum degree 42KPa, and the reaction time is 2 hours, esterification yield 99%.
Prepolymerization reaction: the oligomer in esterifying kettle E1 and E2 is sent into precondensation kettle in proportion respectively, wherein being esterified The ratio OM2/ (OM1+OM2) that OM2 is added in kettle E2 is 5%.The polycondensation process started in esterification is in precondensation kettle Continue, prepolymerization reaction temperature is 300 DEG C, and vacuum degree is -2KPa, reaction time 40min, generates the poly- of low molecular weight Ester copolymer, precondensation product is by entering contracting after precondensation discharging pump, precondensation discharging filter, precondensation discharging cooler Poly- reactor.
Polycondensation reaction: precondensation product is admitted to polycondensation reactor from precondensation unit, and the reaction was continued for prepolymer, and polycondensation is anti- It answers temperature to be 300 DEG C, vacuum degree 120Pa, reaction time 200min and generates the polyester block copolymer of high molecular weight.Contracting Poly- product is by entering pelleter system after polycondensation discharging pump, polymer viscosity meter, polycondensation discharging filter, polycondensation discharging distributing valve System.The polyester block copolymer product of high molecular weight has been obtained after cooling and dicing.The characteristic of gained polyester block copolymer is viscous Degree is 0.56dL/g.
The structure of obtained polyester block copolymer is shown below:
Solid-phase tack producing reaction: the polyester block copolymer particle that polycondensation reaction is obtained is sent into thickening kettle, 10Pa's In the state of vacuum state or inert gas shielding, solid phase reaction is carried out at a temperature of setting, the reaction time is 20 hours.
The inherent viscosity of obtained polyester block copolymer is 0.82dL/g.Temperature is set as 260 DEG C.
The preparation of PCT polyester of the comparative example 2 without containing silicon unit
Slurry preparation: 1) terephthalic acid (TPA) (PTA) and 1,4 cyclohexane dimethanol (CHDM) is respectively passed through into metering system It into slurry preparation U1, stirs evenly, is denoted as slurry S1, wherein PTA is 773G, CHDM 670G.
Catalyst preparation: by 1,4 cyclohexane dimethanol (CHDM) 128.89G and catalyst C (butyl titanate) 158.9G It is added in preparing tank U3, is slowly ramped to 200 DEG C, ebuillition of heated 2-3 hours, vacuum degree 20-30KPa under vacuum state, Configured catalyst is transferred in catalyst shot tank after cooling.
Esterification: the slurry S1 in slurry tank U1 is sent into esterifying kettle E1 by mashing pump, by configured catalyst C It is pumped into esterifying kettle E1 by gear, esterification occurs under the effect of the catalyst, esterification is to there is no water generations Until, the oligomer OM1 of generation.The mass ratio C/S1 that the amount of added catalyst accounts for slurry is 0.05%.The reaction of esterifying kettle Condition are as follows: temperature is 280 DEG C, vacuum degree 42KPa, and the reaction time is 2 hours, and esterification yield is up to 99.1%.
Prepolymerization reaction: the oligomer of esterifying kettle E1 is sent into precondensation kettle, the polycondensation started in esterification Journey continues in precondensation kettle, and prepolymerization reaction temperature is 300 DEG C, and vacuum degree is -2KPa, reaction time 40min, life At the polyester copolymer of low molecular weight, precondensation product passes through precondensation discharging pump, precondensation discharging filter, precondensation discharging Enter polycondensation reactor after cooler.
Polycondensation reaction: precondensation product is admitted to polycondensation reactor from precondensation unit, and the reaction was continued for prepolymer, and polycondensation is anti- It answers temperature to be 300 DEG C, vacuum degree 120Pa, reaction time 200min and generates the polyester block copolymer of high molecular weight.Contracting Poly- product is by entering pelleter system after polycondensation discharging pump, polymer viscosity meter, polycondensation discharging filter, polycondensation discharging distributing valve System.The polyester block copolymer product of high molecular weight has been obtained after cooling and dicing.The characteristic of gained polyester block copolymer is viscous Degree is 0.61dL/g.
Solid-phase tack producing reaction: the polyester block copolymer particle that polycondensation reaction is obtained is sent into thickening kettle, 10Pa's In the state of vacuum state or inert gas shielding, solid phase reaction is carried out at a temperature of setting, the reaction time is 20 hours.
The inherent viscosity of obtained polyester block copolymer is 0.85dL/g.Temperature is set as 260 DEG C.
The preparation of PBN copolyesters of the embodiment 6 containing silicon unit
Slurry preparation: 1) 2,6- naphthalenedicarboxylic acid (NDA) and 1,4 butanediols (BDO) respectively by metering system is entered into slurry Expect preparing tank U1, stir evenly, be denoted as slurry S1, wherein NDA is 997G, BDO 520G.2) by α, ω-dicarboxyethyl is poly- Dimethyl siloxane and Isosorbide-5-Nitrae butanediol (BDO) enter slurry preparation U2 by metering system respectively, stir evenly, are denoted as slurry Expect S2, wherein α, ω-dicarboxyethyl dimethyl silicone polymer is 80G, and Isosorbide-5-Nitrae butanediol (BDO) is 20G.
Catalyst preparation: 1,4 butanediols (BDO) 100G and catalyst C (butyl titanate) 158.9G is added to preparation In tank U3, ebuillition of heated 2-3 hours, vacuum degree 20-30KPa under vacuum state, temperature is 180 DEG C, will be configured after cooling Catalyst be transferred in catalyst shot tank.
Esterification: the slurry S1 in slurry tank U1 is sent into esterifying kettle E1 by mashing pump, by configured catalyst C It is pumped into esterifying kettle E1 by gear, esterification occurs under the effect of the catalyst, esterification is to there is no water generations Until, the oligomer OM1 of generation.The mass ratio C/S1 that the amount of added catalyst accounts for slurry is 0.05%.The reaction of esterifying kettle Condition are as follows: temperature is 265 DEG C, vacuum degree 42KPa, and the reaction time is 2 hours, and esterification yield is up to 99.2%.
Esterification: the slurry S2 in slurry tank U2 is sent into esterifying kettle E2 by mashing pump, by configured catalyst It is pumped into esterifying kettle E2 by gear, esterification occurs under the effect of the catalyst, esterification is to there is no water generations Until, the oligomer OM2 of generation.The mass ratio C/S2 that the amount of added catalyst accounts for slurry is 0.05%.The reaction of esterifying kettle Condition are as follows: temperature is 265 DEG C, vacuum degree 42KPa, and the reaction time is 2 hours, esterification yield 98.6%.
Prepolymerization reaction: the oligomer in esterifying kettle E1 and E2 is sent into precondensation kettle in proportion respectively, wherein being esterified The ratio OM2/ (OM1+OM2) that OM2 is added in kettle E2 is 5%.The polycondensation process started in esterification is in precondensation kettle Continue, prepolymerization reaction temperature is 265 DEG C, and vacuum degree is -2KPa, reaction time 40min, generates the poly- of low molecular weight Ester copolymer, precondensation product is by entering contracting after precondensation discharging pump, precondensation discharging filter, precondensation discharging cooler Poly- reactor.
Polycondensation reaction: precondensation product is admitted to polycondensation reactor from precondensation unit, and the reaction was continued for prepolymer, and polycondensation is anti- It answers temperature to be 268 DEG C, vacuum degree 120Pa, reaction time 200min and generates the polyester block copolymer of high molecular weight.Contracting Poly- product is by entering pelleter system after polycondensation discharging pump, polymer viscosity meter, polycondensation discharging filter, polycondensation discharging distributing valve System.The polyester block copolymer product of high molecular weight has been obtained after cooling and dicing.The characteristic of gained polyester block copolymer is viscous Degree is 0.66dL/g.
The structure of obtained polyester block copolymer is shown below:
Solid-phase tack producing reaction: the polyester block copolymer particle that polycondensation reaction is obtained is sent into thickening kettle, 10Pa's In the state of vacuum state or inert gas shielding, solid phase reaction is carried out at a temperature of setting, the reaction time is 20 hours.
The inherent viscosity of obtained polyester block copolymer is 0.79dL/g.Temperature is set as 200 DEG C.
The preparation of PBN polyester of the comparative example 3 without containing silicon unit
Slurry preparation: 1) 2,6- naphthalenedicarboxylic acid (NDA) and 1,4 butanediols (BDO) respectively by metering system is entered into slurry Expect preparing tank U1, stir evenly, be denoted as slurry S1, wherein NDA is 997G, BDO 520G.
Catalyst preparation: 1,4 butanediols (BDO) 100G and catalyst C (butyl titanate) 158.9G is added to preparation In tank U3, ebuillition of heated 2-3 hours, vacuum degree 20-30KPa under vacuum state, temperature is 180 DEG C, will be configured after cooling Catalyst be transferred in catalyst shot tank.
Esterification: the slurry S1 in slurry tank U1 is sent into esterifying kettle E1 by mashing pump, by configured catalyst C It is pumped into esterifying kettle E1 by gear, esterification occurs under the effect of the catalyst, esterification is to there is no water generations Until, the oligomer OM1 of generation.The mass ratio C/S1 that the amount of added catalyst accounts for slurry is 0.05%.The reaction of esterifying kettle Condition are as follows: temperature is 265 DEG C, vacuum degree 42KPa, and the reaction time is 2 hours, and esterification yield is up to 99.2%.
Prepolymerization reaction: the oligomer in esterifying kettle E1 is sent into precondensation kettle, the polycondensation started in esterification Process continues in precondensation kettle, prepolymerization reaction temperature be 265 DEG C, vacuum degree be -2KPa, reaction time 40min, The polyester copolymer of low molecular weight is generated, precondensation product is gone out by precondensation discharging pump, precondensation discharging filter, precondensation Enter polycondensation reactor after expecting cooler.
Polycondensation reaction: precondensation product is admitted to polycondensation reactor from precondensation unit, and the reaction was continued for prepolymer, and polycondensation is anti- It answers temperature to be 268 DEG C, vacuum degree 120Pa, reaction time 200min and generates the polyester block copolymer of high molecular weight.Contracting Poly- product is by entering pelleter system after polycondensation discharging pump, polymer viscosity meter, polycondensation discharging filter, polycondensation discharging distributing valve System.The polyester block copolymer product of high molecular weight has been obtained after cooling and dicing.The characteristic of gained polyester block copolymer is viscous Degree is 0.75dL/g.
Solid-phase tack producing reaction: the polyester block copolymer particle that polycondensation reaction is obtained is sent into thickening kettle, 10Pa's In the state of vacuum state or inert gas shielding, solid phase reaction is carried out at a temperature of setting, the reaction time is 20 hours.
The inherent viscosity of obtained polyester block copolymer is 0.85dL/g.Temperature is set as 200 DEG C.
Experimental example
The polyester block copolymer analysis and characterization of above embodiments 1-6 and comparative example 1-3 preparation see the table below with evaluation result 1-3。
Table 1
Table 2
Performance Unit Comparative example 2# Embodiment 5#
Intrinsic viscosity DL/g 0.85 0.82
Content of carboxyl end group Mmol/Kg 18 17
Impact strength (23 DEG C) KJ/m2 4 16
Impact strength (- 40 DEG C) KJ/m2 2 12
Thermal weight loss % 1.6 1.5
Surface tension mN/m 39 27
Table 3
Performance Unit Comparative example 3# Embodiment 6#
Intrinsic viscosity DL/g 0.85 0.79
Content of carboxyl end group Mmol/Kg 17 16
Impact strength (23 DEG C) KJ/m2 4 18
Impact strength (- 40 DEG C) KJ/m2 3 13
Thermal weight loss % 1.7 1.6
Surface tension mN/m 42 27
As table 1-3 it is found that polyester block copolymer prepared by the present invention has lower surface tension and preferable resistance to Low temperature impact properties, lower thermal weight loss rate, the performance for compensating for normal polyester resin is insufficient, has expanded its application field.
Although above having used general explanation, specific embodiment and test, the present invention is made to retouch in detail It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art 's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed Range.

Claims (10)

1. a kind of polyester block copolymer, which is characterized in that shown in its structure such as following formula (I):
An-Bt (I)
In formula (I):
A block is the polyester that binary acid and diol reaction obtain；Wherein, the binary acid is selected from aromatic binary carboxylic acid, rouge One of fat race dicarboxylic acids is several；The dihydric alcohol is selected from one of aliphatic dihydroxy alcohol, cycloaliphatic diols Or it is several；
Shown in B block structure such as formula (II):
In formula (II): R4、R5It is each independently selected from methyl, ethyl, propyl, phenyl, Alpha-Methyl phenyl or p-methylphenyl；R6 Indicate (CH2)2、(CH2)3、(CH2)4、(CH2)6、One or more of；S is the integer greater than 1；
In the block copolymer, n is the integer greater than 1, and t is the integer greater than 1；
The polyester block copolymer meets that A block accounts for the percentage of the copolymer gross mass and B block accounts for the copolymer The sum of percentage of gross mass is 100%；
Preferably, it is 0.1%~50% that the quality of the B block, which accounts for the percentage of the copolymer gross mass, more preferably 0.5%~30%, further preferably 3%~20%, it is still more preferably 10%~15%.
2. polyester block copolymer according to claim 1, which is characterized in that in A block, the aromatic binary carboxylic acid Selected from one or more of terephthalic acid (TPA), M-phthalic acid, naphthalene diacid；The aliphatic dicarboxylic acid be selected from succinic acid, One or more of adipic acid, suberic acid；The cycloaliphatic diols be selected from ethylene glycol, propylene glycol, butanediol, hexylene glycol, One or more of 1,4 cyclohexane dimethanol；
It is preferred that in the A block: the dicarboxylic acids is terephthalic acid (TPA), the dihydric alcohol is ethylene glycol；Alternatively, described Dicarboxylic acids is terephthalic acid (TPA), the dihydric alcohol is 1,3- propylene glycol；Alternatively, the dicarboxylic acids be terephthalic acid (TPA), The dihydric alcohol is 1,4- butanediol；Alternatively, the dicarboxylic acids is terephthalic acid (TPA), the dihydric alcohol is Isosorbide-5-Nitrae-hexamethylene Dimethanol；Alternatively, the dicarboxylic acids is 2,6-naphthalenedicarboxylic acid, the dihydric alcohol is ethylene glycol；Alternatively, the binary carboxylic Acid is 2,6- naphthalenedicarboxylic acid, the dihydric alcohol is 1,4- butanediol；Alternatively, the dicarboxylic acids is 1, 4- succinic acid, described Dihydric alcohol is 1,4- butanediol；Alternatively, the dicarboxylic acids is terephthalic acid (TPA), the dihydric alcohol is ethylene glycol and Isosorbide-5-Nitrae-ring Hexane dimethanol；
In B block, 1≤s≤100, preferably 1≤s≤50, more preferably 1≤s≤30, further preferably 1≤s≤50； And/or R4、R5Structure it is identical, preferably R4With R5It is methyl.
3. polyester block copolymer according to claim 1 or 2, which is characterized in that the spy of the polyester block copolymer Property viscosity be 0.6~2.0dL/g, preferably 0.79~1.33dL/g.
4. polyester block copolymer according to any one of claims 1 to 3, which is characterized in that selected from such as flowering structure It is one or more:
5. a kind of preparation method of polyester block copolymer, which comprises the following steps:
(1) dicarboxylic acids and dihydric alcohol are placed in reaction kettle, carry out esterification；
Dicarboxylic acids described in this step is selected from one of aromatic binary carboxylic acid, aliphatic dicarboxylic acid or several；This step The rapid dihydric alcohol is selected from one of aliphatic dihydroxy alcohol, cycloaliphatic diols or several；
(2) will the α as shown in formula (III), ω-dicarboxyl polysilane and dihydric alcohol be placed in reaction kettle, carries out esterification；
In formula (III), R4、R5It is each independently selected from methyl, ethyl, propyl, phenyl, Alpha-Methyl phenyl or p-methylphenyl；s For the integer greater than 1；
Dihydric alcohol described in this step is selected from one of aliphatic dihydroxy alcohol, cycloaliphatic diols or several, preferably second two One or more of alcohol, 1,3- propylene glycol, 1,4- butanediol, 1,6-HD, 1,4 cyclohexane dimethanol；
(3) step (1) products therefrom and step (2) products therefrom are placed in reaction kettle, carry out prepolymerization reaction, generate preshrunk Poly- product；
(4) precondensation product obtained by step (3) is placed in reaction kettle, carries out polycondensation reaction, obtains polyester block copolymer；
Preferably, the method also includes product made from step (4) is carried out solid-phase tack producing reaction, obtaining inherent viscosity is The polyester block copolymer of 0.8~2.0dL/g, preferably 0.79~1.33dL/g.
6. preparation method according to claim 5, which is characterized in that in the step (1), dicarboxylic acids and dihydric alcohol Molar ratio is 1:1~1:1.5；
And/or in the step (2), the molar ratio of formula (III) compound represented and dihydric alcohol is 1:1.2~1:1.5；
And/or in the step (3), the dosage of step (2) products therefrom accounts for the ratio of the sum of step (1), (2) product dosage It is 0.1%~50%, preferably 0.5%~30%, more preferably 3%~20%, further preferably 10%~15%.
7. preparation method according to claim 5 or 6, which is characterized in that step (3) the prepolymerization reaction condition are as follows: 180~310 DEG C of temperature, 1.5~2.5KPa of vacuum degree；Step (4) the polycondensation reaction condition are as follows: 180~310 DEG C of temperature, very 100~200Pa of reciprocal of duty cycle；
Preferably, the temperature of the solid-phase tack producing reaction is 100-260 DEG C.
8. preparation method according to claim 7, which is characterized in that when step (1) dicarboxylic acids is 2,6- naphthalene two When formic acid, prepolymerization reaction temperature range is 250~310 DEG C, and polycondensation reaction temperature is 250~310 DEG C, and preferably solid-phase tack producing is anti- Answering temperature is 200~240 DEG C；
When step (1) described dicarboxylic acids is terephthalic acid (TPA), the dihydric alcohol is 1,4-CHDM, precondensation is anti- Answer temperature range be 280~310 DEG C, polycondensation reaction temperature be 280~310 DEG C, preferably solid-phase tack producing reaction temperature be 240~ 260℃；
When step (1) described dicarboxylic acids is terephthalic acid (TPA), the dihydric alcohol is one in addition to 1,4 cyclohexane dimethanol Kind of dihydric alcohol or for two or more dihydric alcohols mixture when, prepolymerization reaction temperature range is 200~250 DEG C, and polycondensation is anti- Answering temperature is 200~250 DEG C, and preferably solid-phase tack producing reaction temperature is 180~220 DEG C；
When step (1) dicarboxylic acids is succinic acid, prepolymerization reaction temperature range is 100~200 DEG C, polycondensation reaction temperature Degree is 100~200 DEG C, and solid-phase tack producing reaction temperature is 100~110 DEG C.
9. the polyester block copolymer that any one of claim 5~8 preparation method is prepared.
10. polyester block copolymer described in any one of Claims 1 to 4 polyester block copolymer or claim 9 is being made Application in terms of standby fiber, film, Bottle & Can, engineering plastics.
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