Bio-based pest material with side chain containing heterocyclic structure

Abstract

Provided in the present invention is a bio-based PEST material with a side chain containing a heterocyclic structure. The bio-based PEST material with the side chain containing a heterocyclic structure comprises a chain segment unit obtained by polymerizing diols containing side-chain heterocyclic structures and / or diacids containing side-chain heterocyclic structures. By means of copolymerization modification, the mechanical properties and thermal properties of the PEST material are improved, and the PEST material has a better application in products having high barrier properties.

Description

Bio-based PEST material with side chain containing heterocyclic structure TECHNICAL FIELD

[0001] The present application belongs to the field of high polymer materials, and particularly relates to a PEST material with side chain containing heterocyclic structure. BACKGROUND

[0002] PET is the largest polyester material in global production, and has high mechanical strength and good transparency, and can be widely applied to bottle materials, spinning polyester, food packaging and other fields. In today's call for plastic pollution control, the non-degradable disadvantage of PET has become the number one product of marine pollution. Although PET is easy to recycle, the recycling rate is less than 30%, and the secondary pollution caused by recycling further increases the harm to the environment. Therefore, how to improve the degradation of PET is also a research hotspot in recent years.

[0003] PEST material is a polyester formed by copolymerization of terephthalic acid, ethylene glycol and succinic acid, which has high rigidity and strength of PET polyester and degradation characteristics of PES polyester, and is an excellent degradable material. The degradation characteristics are related to the proportion of T content in terephthalic acid. The higher the T content, the slower the degradation rate. And the succinic acid of PEST can be obtained by biological fermentation, so PEST is a biobased degradable polyester material.

[0004] PETG (CHDM content 20%-70%) and PCT (CHDM content 100%) materials formed by adding appropriate amount of CHDM monomer to PET material by Eastman Company have high transparency, good barrier property and good thermal performance. The monomer of 1,4-cyclohexane dimethanol has high rigidity, large steric hindrance and good heat resistance. The addition of the monomer to the polyester main chain breaks the regular crystallization of the original PET, and the glass transition temperature is obviously lower than that of PET. However, the barrier property is twice that of PET, and the temperature resistance is also obviously improved.

[0005] The polyester PEF formed by furan dicarboxylic acid (FDCA) and ethylene glycol and the polyester PETF material formed by part of FDCA and ethylene glycol and terephthalic acid have better performance improvement compared with the original PEF material. The PETF material has certain biodegradability, but the degradation rate is relatively slow. The PETF material formed by the conjugated structure of furan ring has one time higher barrier property and about 10℃ higher heat distortion temperature than PET, reaching 85℃. SUMMARY

[0006] In view of this, the present application provides the following technical solutions:

[0007] In a first aspect, the present application provides a PEST material with side chain containing heterocyclic structure, which is a polymer containing copolymerization units of terephthalic acid, succinic acid and ethylene glycol, and contains repeating unit segments of the following formula XI to formula XIII:

[0008] characterized in that the PEST material containing side chains with heterocyclic structures comprises segment units obtained by polymerization of a heterocyclic structure diol and / or a heterocyclic structure diacid; the segment unit obtained by polymerization of the heterocyclic structure diol is as shown in the following formula (I):

[0009] wherein:

[0010] R1 is selected from at least one of C2-C6 alkylene, C3-C6 cycloalkylene or C5-C6 arylene, and optionally can be substituted with 1-5 halogen, nitro or C2-C6 alkyl, C3-C6 cycloalkyl or C5-C6 aryl; 10 10 10 10 10 10

[0011] R2 is selected from C2-C6 alkylene, and optionally can be substituted with 1-5 halogen, nitro or C2-C6 alkyl, C3-C6 cycloalkyl or C5-C6 aryl; 10 10 10

[0012] the segment unit obtained by polymerization of the heterocyclic structure diacid is as shown in the following formula (II):

[0013] wherein: Asp is

[0014] X is -C=C-; or selected from at least one of C2-C6 alkylene, C3-C6 cycloalkylene or C5-C6 arylene, and optionally can be substituted with 1-5 halogen, nitro or C2-C6 alkyl, C3-C6 cycloalkyl or C5-C6 aryl; 10 10 10 10 10 10

[0015] Preferably, X is -C=C-.

[0016] n is a non-negative integer, and the segment unit obtained by polymerization of the heterocyclic structure diacid comprises segment units with n being a positive integer.

[0017] Preferably, n is any integer from 0 to 7.

[0018] Preferably, the segment unit obtained by polymerization of the heterocyclic structure diacid further comprises structures as shown in formula VII and / or formula VIII: ​​​​​​​​​​​​​​​

[0019] n is 0 or an integer greater than 0, preferably n is any integer from 0 to 7; n1 and n2 are non-negative integers less than n, preferably n1 and n2 are any integer from 0 to 6; preferably, the N value is the value of n, n1 or n2, and the content of monomers with N value greater than 0 is greater than 0.

[0020] Preferably, n is any integer from 0 to 7, such as n is 0, 1, 2, 3, 4, 5, 6 or 7.

[0021] n1 or n2 is independently any integer from 0 to 6, such as 0, 1, 2, 3, 4, 5 or 6.

[0022] Preferably, the segment unit obtained by polymerization of the diol of the heterocyclic structure in the side chain of the PEST material containing the heterocyclic structure is as follows (III):

[0023] wherein R3 is selected from at least one of C2-C 10 alkylene, C3-C 10 cycloalkylene or C5-C 10 aromatic.

[0024] Preferably, R1 is selected from at least one of ethylene, propylene, 1,2-phenylene or 1,2-cyclohexylene; R2 is selected from at least one of 2-N-1,3-O-propylene or 1-N-2,3-O-propylene.

[0025] More preferably, R3 is 1,4-butylene and / or 1,4-phenylene, and R1 is 1,2-ethylene.

[0026] Preferably, the segment unit obtained by polymerization of the diacid of the heterocyclic structure in the side chain of the PEST material containing the heterocyclic structure is as follows (IV):

[0027] wherein R4 is selected from at least one of C2-C 10 alkylene, C3-C 10 cycloalkylene or C5-C 10 aromatic; preferably, X is selected from at least one of ethylene, propylene, 1,2-phenylene or 1,2-cyclohexylene; more preferably, R4 is ethylene and X is 1,2-ethylene.

[0028] Preferably, the segment unit obtained by polymerization of the diacid of the heterocyclic structure in the side chain of the PEST material containing the heterocyclic structure further comprises a polyester structure as shown in (VII-1) and / or (VIII-1):

[0029] Preferably, the segment units obtained after polymerization of the heterocyclic structure diols and / or heterocyclic structure diacids form branched and / or crosslinked structures through the double bonds and / or or carboxyl groups on the side chains.

[0030] Preferably, the proportion of the heterocyclic structure diols and / or heterocyclic structure diacids in the side chain heterocyclic structure-containing PEST material is 0.5-90 mol%, preferably 3-50 mol%, and further preferably 5-50 mol%.

[0031] Preferably, the proportion of terephthalic acid in the total diacids in the side chain heterocyclic structure-containing PEST material can be arbitrarily selected by those skilled in the art, for example 20-90%, for the application of biodegradability, preferably 20-60%, more preferably 40-60%, and for the application of mechanical properties, preferably 60-90%.

[0032] In a second aspect, the present application provides a polymer alloy comprising the side chain heterocyclic structure-containing PEST material according to any one of the preceding aspects.

[0033] In a third aspect, the present application provides a composition or a shaped body comprising the side chain heterocyclic structure-containing PEST material according to any one of the preceding aspects.

[0034] In a fourth aspect, the present application provides a use of the side chain heterocyclic structure-containing PEST material, or the polymer alloy, or the composition or the shaped body according to any one of the preceding aspects, wherein the use is at least one of biodegradable mulching film, paper-plastic composite coating film, double-pull transparent barrier packaging film, degradable transparent adhesive tape, and metal encapsulation material.

[0035] In a fifth aspect, the present application provides a method for preparing the side chain heterocyclic structure-containing PEST material according to any one of the preceding aspects, comprising the following steps:

[0036] S1: preparing a heterocyclic structure diol and / or heterocyclic structure diacid monomer; the structure of the heterocyclic structure diol monomer is shown in formula V:

[0037] wherein R1 and R2 are as defined in any one of the preceding aspects;

[0038] The structure of the heterocyclic structure diacid monomer is shown in formula VI:

[0039] wherein Asp, X and n are as defined in any one of the preceding aspects;

[0040] Preferably, the heterocyclic structure diacid monomer further comprises one or more structures obtained after ring-opening of part of the ring imide in the heterocyclic structure diacid-containing monomer shown in formula VI, and / or a structure terminated by a double bond of the terminal ring imide (i.e. X is -C=C-).

[0041] S2: esterification / ester exchange reaction of the above-mentioned heterocyclic structure diol and / or heterocyclic structure diacid monomer and terephthalic acid / ester / anhydride, succinic acid / ester / anhydride, ethylene glycol and optional other diols or diacids that can be used for polyester synthesis; or esterification / ester exchange reaction of the above-mentioned heterocyclic structure diol and / or heterocyclic structure diacid monomer and a prepolymer obtained by esterification / ester exchange reaction of terephthalic acid / ester / anhydride, succinic acid / ester / anhydride, ethylene glycol and optional other diols or diacids that can be used for polyester synthesis.

[0042] Beneficial technical effects

[0043] The present application forms a PEST material with functional structure monomer characteristics by the introduction of a heterocyclic structure diol or diacid, the introduction of a side chain heterocyclic ring, the increase of product steric hindrance, the improvement of barrier properties, and the improvement of mechanical strength and crystallization rate of the product by the imide structure BRIEF DESCRIPTION OF DRAWINGS

[0044] Figure 1: NMR chart of 2-amino-silanol functional monomer.

[0045] Figure 2: NMR chart of 3-amino-silanol functional monomer.

[0046] Figure 3: NMR chart of aspartic acid functional monomer.

[0047] Figure 4: Infrared spectrum of PEST modified by aspartic acid functional monomer with different proportions.

[0048] Figure 5: Infrared spectrum of PEST modified by aspartic acid functional monomer with different proportions (partial enlargement).

[0049] Figure 6: Thermal decomposition temperature of PEST modified by 5% 2-amino-silanol monomer.

[0050] Figure 7: Thermal decomposition temperature of PEST modified by 10% 2-amino-silanol monomer.

[0051] Figure 8: Thermal decomposition temperature of PEST modified by 15% 2-amino-silanol monomer.

[0052] Figure 9: Thermal decomposition temperature of PEST modified by 20% 2-amino-silanol monomer. DETAILED DESCRIPTION

[0053] In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application. However, it will be apparent to one skilled in the art that the present application can be practiced without one or more of these specific details. In other instances, well-known features have not been described in detail to avoid obscuring the present application.

[0054] Unless otherwise specified, the percentages or dosage ratios in this invention are all molar percentages.

[0055] The implementation of this invention is described in detail below with reference to the definitions of terms:

[0056] I heterocyclic diol modified PEST material

[0057] The synthesis method of heterocyclic diols can be found in Chinese patent application CN202311583766.2, which first involves preparing heterocyclic diol monomers.

[0058] The structural formula of the heterocyclic diol monomer of the present invention is shown in Formula V:

[0059] in:

[0060] R1 is selected from C2-C 10 Alkylene, C3-C 10 Cycloalkyl or C5-C 10 At least one of the aromatic groups and optionally 1-5 halogens, nitro groups, or C2-C groups. 10 Alkyl, C3-C 10 cycloalkyl or C5-C 10 Aromatic group substitution;

[0061] R2 is selected from C2-C6 pentaalkyl groups and may optionally be 1-5 halogens, nitro groups, or C2-C6 groups. 10 Alkyl, C3-C 10 cycloalkyl or C5-C 10 Aromatic group substitution.

[0062] In some embodiments, R1 is selected from at least one of C2-C6 alkylene, C3-C6 cycloalkylene, or C5-C6 aromaticyl groups and may optionally be substituted with one or two halogens, nitro groups, or C2-C6 alkyl, C3-C6 cycloalkyl, or C5-C6 aromaticyl groups.

[0063] In some embodiments, R1 is selected from at least one of C2-C6 alkylene, C3-C6 cycloalkylene, or C5-C6 aromaticylene.

[0064] R2 is selected from C2-C6 pentaalkyl groups and may optionally be 1-5 halogens, nitro groups, or C2-C6 groups. 10 Alkyl, C3-C 10 cycloalkyl or C5-C 10 Aromatic group substitution.

[0065] In some embodiments, R1 is selected from at least one of ethylene, propylene, 1,2-phenylene, or 1,2-cyclohexylene.

[0066] In some embodiments, R2 is selected from at least one of 2-N-l,3-O-propylene or 1-N-2,3-O-propylene.

[0067] In some embodiments, R1 is 1,2-ethylene.

[0068] In some embodiments, the heterocyclic structural diol monomers of the present application can be prepared from an aminodiol and a dibasic acid. For example, the following representative heterocyclic structural diol monomers can be prepared from the reaction of 2-amino-l,3-propanediol (2-amino-threitol) or 3-amino-l,2-propanediol and succinic acid (3-amino-threitol):

[0069] In some embodiments, the heterocyclic structural diols of the present application can be directly copolymerized as monomers with other monomers to form segment units in PEST materials through the conventional steps of polyester synthesis.

[0070] In some embodiments, the above heterocyclic structural diols and optionally any of the heterocyclic structural diacid monomers of the present application described below, and terephthalic acid / ester / anhydride, succinic acid / ester / anhydride, ethylene glycol, and optionally other diols or dibasic acids useful in polyester synthesis are esterified / transesterified to produce modified PEST materials of the present application.

[0071] In some embodiments, the above heterocyclic structural diols and optionally any of the heterocyclic structural diacid monomers of the present application described below, and prepolymers, which are produced by esterification / transesterification of terephthalic acid / ester / anhydride, succinic acid / ester / anhydride, ethylene glycol, and optionally other diols or dibasic acids useful in polyester synthesis, are esterified / transesterified to produce modified PEST materials of the present application.

[0072] In some embodiments, the above heterocyclic structural diols and terephthalic acid / ester / anhydride, succinic acid / ester / anhydride, ethylene glycol are esterified / transesterified to produce modified PEST materials of the present application.

[0073] In some embodiments, the above heterocyclic structural diols and prepolymers, which are produced by esterification / transesterification of terephthalic acid / ester / anhydride, succinic acid / ester / anhydride, ethylene glycol, are esterified / transesterified to produce modified PEST materials of the present application.

[0074] In some embodiments, the segment units produced by polymerization of the heterocyclic structural diols of the present application are of the following formula (I):

[0075] wherein R1 and R2 are as previously described.

[0076] In some embodiments, the heterocyclic structure diol of the present application forms the following structure (III) in the PEST material after polymerization:

[0077] wherein R3 is selected from at least one of C2-C6 alkylene, C3-C6 cycloalkylene or C5-C6 arylene. 10 10 10

[0078] In some embodiments, R3 is selected from at least one of C2-C6 alkylene, C3-C6 cycloalkylene or C5-C6 arylene.

[0079] In some embodiments, R3 is 1,4-butylene and / or 1,4-phenylene.

[0080] In some embodiments, R1 is 1,2-ethylene, R2 is selected from at least one of 2-N-1,3-O-propylidene or 1-N-2,3-O-propylidene, and R3 is 1,4-butylene and / or 1,4-phenylene.

[0081] In some embodiments, the proportion of the heterocyclic structure diol in the modified PEST material is 0.5-90 mol%, preferably 5-50 mol%, more preferably 5-30 mol%, for example, it can be 1%, 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%.

[0082] II Heterocyclic structure diacid modified PEST material

[0083] The synthesis method of the heterocyclic structure diacid can refer to Chinese patent application CN202311738254.9, and first, a heterocyclic structure diacid monomer is prepared.

[0084] The structural formula of the heterocyclic structure diacid monomer of the present application is shown in formula V:

[0085] wherein:

[0086] Asp is

[0087] X is -C=C, or is selected from at least one of C2-C6 alkylene, C3-C6 cycloalkylene or C5-C6 arylene and can be optionally substituted by 1-5 halogen, nitro or C2-C6 alkyl, C3-C6 cycloalkyl or C5-C6 aryl; 10 10 10 10 10 10 ​​​​​​​​​

[0088] n is a non-negative integer, and the chain segment unit obtained after polymerization of the heterocyclic structure diacid contains a chain segment unit with n being a positive integer.

[0089] In some embodiments, X is selected from at least one of C2-C6 alkylene, C3-C6 cycloalkylene, or C5-C6 arylene. 10 10 In some embodiments, X is selected from at least one of C2-C6 alkylene, C3-C6 cycloalkylene, or C5-C6 arylene. 10

[0090] In some embodiments, X is selected from at least one of C2-C6 alkylene, C3-C6 cycloalkylene, or C5-C6 arylene.

[0091] In some embodiments, X is selected from at least one of ethylene, propylene, 1,2-phenylene, or 1,2-cyclohexylene.

[0092] In some embodiments, X is 1,2-ethylene.

[0093] In some embodiments, the heterocyclic structure diacid monomers of the present application can be prepared from aspartic acid and a diacid. For example, a representative compound of Formula IV can have the structure:

[0094] and the like.

[0095] In some embodiments, the heterocyclic structure diacid monomers of the present application have a structure that includes one or more of the structures of the monomers containing imide ring structure shown in Formula VI after ring-opening of part of the imide ring, and / or the structure of the terminal double bond end-capped, for example:

[0096] In some embodiments, the heterocyclic structure diacid of the present application can be directly copolymerized with other monomers to form chain segment units in PEST materials through conventional steps of polyester synthesis.

[0097] In some embodiments, the above-mentioned heterocyclic structure diacid and optionally the heterocyclic structure diol monomer of the present application of any one of the foregoing, and terephthalic acid / ester / anhydride, succinic acid / ester / anhydride, ethylene glycol, and optionally other diols or diacids that can be used in polyester synthesis are subjected to esterification / ester exchange reaction to obtain a modified PEST material of the present application.

[0098] In some embodiments, the above-mentioned heterocyclic structure diacid and optionally the heterocyclic structure diol monomer of any one of the foregoing, and a prepolymer obtained by esterification / ester exchange reaction of terephthalic acid / ester / anhydride, succinic acid / ester / anhydride, ethylene glycol, and optionally other diols or diacids that can be used in polyester synthesis are subjected to esterification / ester exchange reaction to obtain a modified PEST material of the present application.​​

[0099] In some embodiments, the above-mentioned heterocyclic structural diacid and terephthalic acid / ester / anhydride, succinic acid / ester / anhydride, ethylene glycol are subjected to esterification / ester exchange reaction to obtain the modified PEST material of the present application.

[0100] In some embodiments, the above-mentioned heterocyclic structural diacid and pre-polymer, which is obtained by subjecting terephthalic acid / ester / anhydride, succinic acid / ester / anhydride, ethylene glycol to esterification / ester exchange reaction, are subjected to esterification / ester exchange reaction to obtain the modified PEST material of the present application.

[0101] In some embodiments, the above-mentioned heterocyclic structural diacid, any one of the above-mentioned heterocyclic structural diol monomers, and terephthalic acid / ester / anhydride, succinic acid / ester / anhydride, ethylene glycol are subjected to esterification / ester exchange reaction to obtain the modified PEST material of the present application.

[0102] In some embodiments, the above-mentioned heterocyclic structural diacid, any one of the above-mentioned heterocyclic structural diol monomers, and pre-polymer, which is obtained by subjecting terephthalic acid / ester / anhydride, succinic acid / ester / anhydride, ethylene glycol to esterification / ester exchange reaction, are subjected to esterification / ester exchange reaction to obtain the modified PEST material of the present application.

[0103] In some embodiments, the segment unit obtained after polymerization of the heterocyclic structural diacid of the present application has the following formula (II):

[0104] wherein X and n are defined as described above.

[0105] In some embodiments, the heterocyclic structural diacid of the present application forms the following formula (IV) in the PEST material after polymerization:

[0106] wherein R4 is selected from at least one of C2-C6 alkylene, C3-C6 cycloalkylene, or C5-C6 arylene. 10 10 10

[0107] In some embodiments, R4 is selected from at least one of C2-C6 alkylene, C3-C6 cycloalkylene, or C5-C6 arylene.

[0108] In some embodiments, R4 is ethylene.

[0109] In some embodiments, X is 1,2-ethylene, Asp is R4 is ethylene, n is a non-negative integer, n is a non-negative integer and the segment unit obtained after polymerization of the heterocyclic structural diacid contains a segment unit with a positive integer n. ​​​

[0110] Preferably, the heterocyclic structure diacid after polymerization forms further structures in the PEST material as shown in the following formula (IV) structure, and / or the structures obtained after polymerization of the terminal cyclic imide double bond capped structure (i.e. X is -C=C-), which are further contained in one or more of the monomers containing heterocyclic structure diacids as shown in formulae VI-4 to VI-9 after ring-opening of part of the cyclic imide ring.

[0111] In some embodiments, the heterocyclic structure diacid accounts for 0.5-90 mol%, preferably 5-50 mol%, for example, it can be 1%, 2%, 5%, 10%, 15%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% in the modified PEST material.

[0112] III PEST material

[0113] The PEST material of the present application is a polymer containing terephthalic acid, succinic acid and ethylene glycol copolymer units, containing the following formula XI to formula XIII repeating unit segments:

[0114] IV Other diols or diacids that can be used for polyester synthesis

[0115] In some embodiments, the other diols that can be used for polyester synthesis in the present application refer to at least one of alkylene glycol containing 2-18 carbons, polyethylene glycol, polypropylene glycol, polytetrahydrofuran diol, N-methyldiethanolamine, N-ethyldiethanolamine. The other diols that can be used for polyester synthesis in the present application can be preferably selected from at least one of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,18-octadecanediol, polyethylene glycol, 1,4-cyclohexanedimethanol.

[0116] In some embodiments, the above-mentioned diols for polymer synthesis can account for 0-99% in the final PEST material containing heterocyclic structure side chains, for example, it can be 0.1%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 95%.

[0117] In some embodiments, the diacids used in the present application for polyester synthesis are selected from at least one of succinic acid, 2-methylsuccinic acid, 2- phenylsuccinic acid, 2-benzylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3- dimethylsuccinic acid, 2,3-diphenylsuccinic acid, 1,2-cyclobutane dicarboxylic acid, 2,2,3,3-tetramethylsuccinic acid, oxalic acid, malonic acid, 1,6-hexanedioic acid, 1,10-decanedioic acid, 1,18-octadecanedioc acid, maleic acid, methylmaleic acid, dimethylmaleic acid, phthalic acid, hexahydrophthalic acid, norbornene dicarboxylic acid, tetrahydrophthalic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 3-phenylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, diglycolic acid, 2,3-furandicarboxylic acid, 3,4-furandicarboxylic acid, 2,3-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, terephthalic acid, 2,5-furandicarboxylic acid.

[0118] In some embodiments, the diacids used in the above polymer synthesis can be present in the final PEST material with a heterocyclic structure in the side chain in an amount of 0-99%, for example, 0.1%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95%.

[0119] IV Polymer alloy

[0120] The polymers of the present application form alloys with each other or, optionally, with other polymers.

[0121] V Polymer composition and molded body

[0122] The present application also provides a composition or a molded body of the above-mentioned polymers, and the method of processing or molding each type of polymer is known in the art.

[0123] The polymer composition of the present application can further contain other polymers, plasticizers, nucleating agents, or hydrolysis inhibitors.

[0124] In the polymer composition of the present application, as other components other than the above, fillers, flame retardants, antioxidants, lubricants, ultraviolet absorbers, antistatic agents, anti-haze agents, light stabilizers, and the like can be contained within a range that does not impair the effects of the present application.

[0125] The aromatic polyester composition containing a cyclic imide structure of the present application can be prepared into a molded body such as a sheet by extrusion molding, press molding; and the obtained sheet can be further thermoformed, for example, stretched into a film or a fiber, in a temperature range above the glass transition temperature (Tg) and below the melting point (Tm) of the aromatic polyester composition containing a cyclic imide structure.

[0126] VI Article and use

[0127] The polymer, alloy or composition or shaped body of the present application is suitable for preparing biodegradable mulching film, paper-plastic composite coating film, double-pull transparent barrier packaging film, degradable transparent adhesive tape, metal encapsulating material, etc.

[0128] Hereinafter, the present application will be further described in detail through specific examples.

[0129] Preparation Example

[0130] Preparation Example 1 Synthesis of aspartic acid / succinic acid modified PEST

[0131] First step: A five-kettle polyester synthesis device is used. Two beating kettles are preheated to 60°C, and two esterification kettles are preheated to 120°C. The modified unit synthesis monomer aspartic acid and succinic acid are put into beating kettle 1 at a molar ratio of 1:3, and 200 ppm of antioxidant and heat stabilizer are added, and slowly stirred to melt to liquid state in a nitrogen atmosphere; then the material is discharged into esterification kettle 1, which is heated to 160°C, and kept at this temperature for 3 h (typical monomer nuclear magnetic resonance chart is shown in FIG. 3). At the same time of the synthesis of the functional monomer, 1,4-benzenedicarboxylic acid, succinic acid and ethylene glycol are added to beating kettle 2. (1,4-benzenedicarboxylic acid + succinic acid): ethylene glycol = 1:1.2. And 200 ppm of antioxidant and heat stabilizer are added, and the material is discharged into esterification kettle 2 after beating is completed, and kept at 220°C under 400 kPa to reflux for 3 h.

[0132] Second step: The modified monomer in esterification kettle 1 is discharged into esterification kettle 2, 200 ppm of anhydrous zinc acetate is added, and ethylene glycol is supplemented to control the diol:diacid ratio of the system to 1.2:1, and the temperature is raised to 225°C, and the co-esterification reaction is continued until more than 95% of the theoretical distillation amount of the fraction is reached.

[0133] Third step: After the co-esterification is completed, the material is discharged into a final kettle for polycondensation reaction, and 300 ppm of tetrabutyl titanate is added, the vacuum degree in the kettle is slowly reduced, and the temperature is further raised to 245°C, and the reaction is kept at a vacuum degree below 20 Pa for 4-6 h, and then the reaction is ended, the material is discharged, water-cooled, drawn into strips, and pelletized to obtain the modified PEST polyester.

[0134] The infrared spectra of PEST polyesters modified by aspartic acid monomers with different proportions are shown in FIGS. 4-5. It can be found that typical C=O bond absorption peaks (1720 cm -1 ) and C-N bond absorption peaks (1376 cm -1 ) appear in the spectra. The results show that the PEST polyester is successfully synthesized. In comparison with different amounts of addition, the C-N bond absorption peak gradually increases with the increase of the functional monomer, indicating that more functional monomers are successfully introduced into the material.

[0135] When the modified unit ratio exceeds 15%, the functional monomer is prepared by feeding aspartic acid: succinic acid = 1:1.

[0136] Preparation of Example 2: Synthesis of serinol (2-amino-1,3-propanediol) / succinic acid modified PEST

[0137] First step: five-kettle polyester synthesis device was used. Two pulp kettles were preheated to 60°C, and two esterification kettles were preheated to 120°C. The modified unit synthesis monomer serinol was fed into pulp kettle 1 at a molar ratio of 1:2 with succinic acid, and 200 ppm of antioxidant and heat stabilizer was added. Slow stirring was carried out under nitrogen atmosphere to melt to liquid state, and then the material was discharged into esterification kettle 1. The temperature was raised to 160°C, and the reaction was kept for 3h (typical monomer nuclear magnetic resonance spectrum is shown in Figure 1, and the functional monomer nuclear magnetic resonance spectrum obtained from 3-amino-serine alcohol is shown in Figure 2). At the same time of functional monomer synthesis, 1,4-benzenedicarboxylic acid, succinic acid and ethylene glycol were added to pulp kettle 2, (1,4-benzenedicarboxylic acid + succinic acid): ethylene glycol = 1:1.2, and 200 ppm of antioxidant and heat stabilizer was added. After the pulp was finished, the material was discharged into esterification kettle 2, and the reaction was kept for 3h under 400kPa at 220°C.

[0138] Second step: the modified monomer in esterification kettle 1 was fed into esterification kettle 2, 200 ppm of anhydrous zinc acetate was added, and ethylene glycol was supplemented to control the diol: diacid ratio of the system to 1.2:1. The temperature was raised to 225°C, and the co-esterification reaction was continued until more than 95% of the theoretical distillation amount of the fraction was reached.

[0139] Third step: after the co-esterification was completed, the material was fed into the final kettle for polycondensation reaction, and 300 ppm of tetrabutyl titanate was added. The vacuum degree in the kettle was slowly reduced, and the temperature was further raised to 245°C. The reaction was kept for 4-6h under a vacuum degree of less than 20Pa, and then the reaction was ended. The material was discharged, water-cooled, drawn, and pelletized to obtain the modified PEST polyester.

[0140] Effect example

[0141] 1. Water vapor transmission rate test standard: PEST film was cast using a flat plate curing machine, with a thickness of 30um. The water vapor / oxygen test conditions were 38°C, and the positive cup method was used.

[0142] 2. The tensile strength and elongation at break of the resin materials obtained in the examples and comparative examples were tested according to GB / T1040.2-2006. The melting temperature (Tm) of the resin materials obtained in the examples and comparative examples was tested according to GB / T 19466.2-2004. The melting flow index (MFI) was tested according to the standard ASTM-D1238-2010.

[0143] 3. Thermogravimetric analysis: Turn on the TG instrument, and after the panel is zeroed, the initial temperature is set to 60°C. Take 5g of PEST sample with different modification ratios, and place it in the weighing crucible. Introduce nitrogen gas. Slowly increase the temperature at a rate of 10°C / min, and the final temperature is 600°C. After the weight loss is complete, the thermogravimetric curve is exported and analyzed.

[0144] The performance test data is shown in the following table: Note 1: The modification unit ratio is the molar ratio of aspartic acid or serinol functional monomer repeat units to the total repeat units of the polymer; Note 2: The terephthalic acid ratio is the proportion of terephthalic acid monomer to the total mass of the polymer. In the * group, the molar ratio of terephthalic acid is 90% of the total diacid, and in the other groups, the molar ratio of terephthalic acid is 45% of the total diacid.

[0145] As shown in the results, when the aspartic acid content is between 5-15%, the Rockwell hardness and impact strength of the material gradually increase with the increase of aspartic acid content, and reach the optimum at 15%. The elongation at break of the material gradually decreases with the increase of the modification unit, which is related to the increase of the rigid imide ring, which increases the rigidity of the material. The water vapor transmission rate and oxygen transmission rate show that the water vapor barrier performance and oxygen barrier performance of the material are better with the increase of the modification unit ratio.

[0146] In the serinol modification system, when the modification unit is between 5-15%, the Rockwell hardness and impact strength of the material increase with the increase of the unit addition amount. When the content exceeds 15%, the hardness and impact strength of the material gradually decrease. The water vapor and oxygen barrier performance gradually increases with the increase of the modification unit.

[0147] In addition, with the increase of the addition amount of functional monomer (Figures 6-9), the thermal decomposition temperature of the product increases, indicating that the thermal stability of the modified PEST increases with the increase of the content of the functional monomer.

Claims

1. A PEST material with side chain heterocyclic structure, the PEST material being a polymer comprising copolymerized units of terephthalic acid, succinic acid and ethylene glycol, comprising repeating unit segments of the following formulae XI to XIII: characterized in that The PEST material containing side chains with heterocyclic structures contains chain segment units obtained by polymerization of a heterocyclic structure diol and / or a heterocyclic structure diacid; the chain segment unit obtained by polymerization of the heterocyclic structure diol is as follows: wherein: R1is selected from at least one of C2-C 10 alkylene, C3-C 10 cycloalkylene or C5-C 10 arylene and can optionally be substituted with 1-5 halogen, nitro or C2-C 10 alkyl, C3-C 10 cycloalkyl or C5-C 10 aromatic groups; R2 is selected from C2-C6 pentaalkyl groups and may optionally be 1-5 halogens, nitro groups, or C2-C6 groups. 10 Alkyl, C3-C 10 cycloalkyl or C5-C 10 Aromatic group substitution; The chain segment unit obtained after polymerization of the heterocyclic structure diacid is as follows: wherein: Asp is X is selected from at least one of C2-C 10 alkylene, C3-C 10 cycloalkylene or C5-C 10 arylene and can optionally be substituted with 1-5 halogen, nitro or C2-C 10 alkyl, C3-C 10 cycloalkyl or C5-C 10 aromatic groups; n is a non-negative integer, and the chain segment unit obtained after the polymerization of the heterocyclic structure diacid contains a chain segment unit with n being a positive integer; Preferably, n is any integer from 0 to 7.

2. The side chain heterocyclic structure containing PEST material according to claim 1, wherein the segment unit obtained after polymerization of the heterocyclic structure diol is of the following formula (III): wherein, R3is selected from at least one of C2-C 10 alkylene, C3-C 10 cycloalkylene or C5-C 10 arylene; Preferably, R1 is selected from at least one of ethylene, propylene, 1,2-phenylene or 1,2-cyclohexylene; and R2 is selected from at least one of 2-N-1,3-O-propylene or 1-N-2,3-O-propylene. More preferably, R3 is 1,4-butylene and / or 1,4-phenylene, and R1 is 1,2-ethylene.

3. The side chain heterocyclic structure containing PEST material of claim 1, wherein the heterocyclic structure diacid after polymerization gives a segment unit of the following formula (IV): wherein: R4is selected from at least one of C2-C 10 alkylene, C3-C 10 cycloalkylene or C5-C 10 arylene; preferably, X is selected from at least one of ethylene, propylene, 1,2- phenylene or 1,2-cyclohexylene; more preferably, R4is ethylene and X is 1,2- ethylene.

4. The side-chain heterocyclic structure-containing PEST material according to claim 1, wherein the proportion of the heterocyclic structure diol and / or heterocyclic structure diacid in the side-chain heterocyclic structure-containing PEST material is 0.5-90 mol%, preferably 3-50 mol%, and further preferably 5-50 mol%. It is also preferable that the molar proportion of terephthalic acid in the total diacid in the side-chain heterocyclic structure-containing PEST material is 20-90%, further preferably 20-60%, and more preferably 40-60%; and it is also preferable that the molar proportion of terephthalic acid in the total diacid in the side-chain heterocyclic structure-containing PEST material is 60-90%.

5. A polymer alloy comprising the side-chain heterocyclic structure-containing PEST material according to any one of claims 1-4.

6. A composition or shaped body comprising the side-chain heterocyclic structure-containing PEST material according to any one of claims 1-4.

7. Use of the side-chain heterocyclic structure-containing PEST material according to any one of claims 1-4, or the polymer alloy according to claim 5, or the composition or shaped body according to claim 6, wherein the use is at least one of biodegradable mulching film, paper-plastic composite coating film, double-pull transparent barrier packaging film, degradable transparent adhesive tape, or metal-coated material.

8. A method for preparing the side-chain heterocyclic structure-containing PEST material according to any one of claims 1-4, comprising the following steps: S1 : preparing a heterocyclic structure diol and / or a heterocyclic structure diacid monomer; the structure of the heterocyclic structure diol monomer is shown as formula V: wherein R1 and R2 are as defined in any one of claims 1-4; The heterocyclic structure diacid monomer structure is shown in Formula VI: wherein Asp, X and n are as defined in any one of claims 1-4; S2: esterification / ester exchange reaction of the above-mentioned heterocyclic structure diol and / or heterocyclic structure diacid monomer and terephthalic acid / ester / anhydride, succinic acid / ester / anhydride, ethylene glycol, and optionally other diols or diacids that can be used for polyester synthesis; or esterification / ester exchange reaction of the above-mentioned heterocyclic structure diol and / or heterocyclic structure diacid monomer and a prepolymer obtained by esterification / ester exchange reaction of terephthalic acid / ester / anhydride, succinic acid / ester / anhydride, ethylene glycol, and optionally other diols or diacids that can be used for polyester synthesis.

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