CN115667361A - Autocatalytic rapid degradation polyester polymer and preparation method and application thereof - Google Patents
Autocatalytic rapid degradation polyester polymer and preparation method and application thereof Download PDFInfo
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- CN115667361A CN115667361A CN202180034136.2A CN202180034136A CN115667361A CN 115667361 A CN115667361 A CN 115667361A CN 202180034136 A CN202180034136 A CN 202180034136A CN 115667361 A CN115667361 A CN 115667361A
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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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
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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
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
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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
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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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
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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
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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
- C08G63/78—Preparation processes
Abstract
The invention discloses an autocatalytic fast degradation polyester polymer and a preparation method and application thereof. The polyester polymer provided by the invention not only has good machining performance, but also can be rapidly degraded in a proper water environment, and the degradation does not depend on microorganisms or bacteria, so that the problem of environmental pollution generated in the application of the polyester polymer is effectively solved. It meets a wide range of application requirements, particularly ensuring that such polymers can be applied to beverage bottles, food packaging films, especially mulching films, shopping bags and other food packaging containers. In addition, the preparation method of the invention is simple and low in cost, and the raw materials are easy to obtain at low price. It is suitable for batch production and has practical value and application potential.
Description
Technical Field
The invention relates to a preparation method and application of an autocatalytic fast degradation polyester polymer. In particular, the invention relates to the preparation and use of condensed copolyesters by embedding small biodegradable blocks and catalytic blocks in the polymer backbone. It belongs to the field of functional polymer material.
Background
Polyester is a generic name of polymers prepared by polycondensation of polyol (polyvinyl alcohol) with polybasic acid, and typical polyester is aromatic polyester represented by polyethylene terephthalate (PET), which is widely used in various fiber, packaging and other industries due to its excellent chemical stability, proper mechanical properties, transparency and health properties. At present, the growth momentum of polyester production and sale is still strong, especially in the field of carbonated beverage packaging. With the breakthrough of the barrier research of the polyester, the application of the polyester in the field of beer, food and cosmetic packaging will expand the market of the polyester. However, polyester (PET) waste is difficult to naturally degrade in nature. In an environment with humidity of 45% to 100% and temperature of 20 ℃, the PET bottle can exist for 30 to 40 years, and the mechanical property of the PET bottle is only lost by 50%; under the same conditions, the polyester film may exist for 90 to 100 years. Therefore, the large amount of polyester waste will put a great pressure on our environment.
In the prior art, polyesters are disclosed which contain degradable blocks in the polymer backbone, which show mechanical and thermal properties similar to conventional polyesters, but degrade very rapidly, especially in the presence of hydrolysis catalysts such as acids or bases. Thus, polymers with degradable segments can degrade naturally within an estimated 5-10 years, and can also be recovered and degraded at the plant, a so-called tertiary recycle mode.
However, in practice, the 5 to 10 year degradation time of plastics is still too long for environmental protection, especially for special applications such as agricultural films, disposable food packaging and tableware, disposable clothing and the like. Therefore, it is highly desirable to develop a polymer that degrades more rapidly.
On the other hand, toluene sulfonic acid or cationic ion exchange resins are often used as hydrolysis catalysts for hydrolyzing small molecular esters. Sodium dimethyl 5-sulfoisophthalate or its derivative sodium 5-diethylisophthalate or diethylene glycol 5-sulfoisophthalate is used as comonomer of polyethylene terephthalate, and the sulfophthalate is included in the main polymer chain as the dye combining site to raise the dyeing performance of polyester. However, sulfoisophthalate is not used as a hydrolysis catalyst in polyesters because the ester bond in polyethylene terephthalate is not easily hydrolyzed even in the presence of sulfoisophthalate.
In the present invention, both the fast degrading block hydroxy acid ester, which is easily hydrolyzed with a catalyst, and the catalytic block sulfoisophthalate are contained in the same polyester backbone, resulting in faster hydrolysis of the hydroxy acid ester and thus faster cleavage of the polyester backbone.
Disclosure of Invention
In order to solve the above problems of the prior art, an object of the present invention is to provide a rapidly degradable polyester polymer, a method for preparing the same and use thereof, to achieve the object of rapidly degrading a polyester polymer such as PET under special conditions, and to solve the problem of environmental pollution caused by the use of such a polymer.
It is to be understood by one of ordinary skill in the art that the present invention has been described by way of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention. Each aspect so described may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with one or more other features indicated as being preferred or advantageous. For the above purpose of the present invention, the technical method used in the present invention is as follows:
in one aspect, the present invention provides an autocatalytic fast degrading polyester polymer comprising recurring units- [ (A) n1 -(B) n2 -(C) n3 -(D) n4 -(E) n5 ] n -prepared by polycondensation of recurring structural units comprising a non-degradable rigid block a, a degradable soft block B, a fast degrading block C, a soft block D and a catalytic block E, wherein the non-degradable rigid block a has the structure of formula (I):
the degradable soft block B has a structure of formula (II):
the fast degrading block C has a structure of formula (IIIa) or formula (IIIb) or formula (IIIc) or formula (iiid):
the soft block D has the structure of formula (IV):
the catalytic block E has the structure of formula (V):
repeating units of the polyester Polymer- [ (A) n1 -(B) n2 -(C) n3 -(D) n4 -(E) n5 ] n -, having formula (VIa) or formula (VIb) or formula (VIc) or formula ((VId):
wherein in the repeating unit- [ (A) n1 -(B) n2 -(C) n3 -(D) n4 -(E) n5 ] n -the sequence of blocks a, B, C, D and E is randomly arranged and any block may occur multiple times; n, n 1 And n is 3 Each independently is an integer greater than 0; n is a radical of an alkyl radical 2 ,n 4 And n 5 Each independently 0 or an integer greater than 0; p, q and y are each independently 0 or 1; r is 1 ,r 2 ,r 3 S, t, u, v, w, x and z are each independently integers greater than 0 and less than 50; m is an integer greater than 0 and less than 200; r is 1 ,R 2 ,R 3 ,R 4 ,R 5 ,R 6 ,R 7, R 8 ,R 9 ,R 10 ,R 11 ,R 12 ,R 13 ,R 14 ,R 15 ,R 16 ,R 17 ,R 18 Is independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl, substituted or unsubstituted alkoxy, ester, nitro, amine, amide, or thiol in each structural unit; and R ', R' and R 4 Independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl.
In some embodiments, the R is 1 ,R 2 ,R 3 ,R 4 ,R 5 ,R 6 ,R 7, R 8 ,R 9 ,R 10 ,R 11 ,R 12 ,R 13 ,R 14 ,R 15 ,R 16 ,R 17 ,R 18 Independently selected from hydrogen or C1-C10 alkyl in each structural unit.
In some embodiments, the R is 1 ,R 2 ,R 3 ,R 4 ,R 5 ,R 6 ,R 7, R 8 ,R 9 ,R 10 ,R 11 ,R 12 ,R 13 ,R 14 ,R 15 ,R 16 ,R 17 ,R 18 Independently selected from hydrogen or methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl in each structural unit; r ', R' and R 4 Selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, and substituted or unsubstituted heterocycloalkyl.
In some embodiments, the R is 1 ,R 2 ,R 3 ,R 4 ,R 5 ,R 6 ,R 7, R 8 ,R 9 ,R 10 ,R 11 ,R 12 ,R 13 ,R 14 ,R 15 ,R 16 ,R 17 ,R 18 Is hydrogen; r is 9 、R 10 Is hydrogen or methyl; r is 1 、r 2 、r 3 S, t, w, x and z are any integer independently selected from 2, 3, 4; u and v are any integer independently selected from 1, 2, 3 or 4.
In another aspect, the present invention provides a method for preparing an autocatalytic fast degrading polyester polymer, comprising the steps of:
(a) Mixing comonomers or oligomers of the non-degradable rigid block A, the degradable soft block B, the rapidly degradable block C, the soft block D and the catalytic block E together in the same reactor at the same time, and esterifying at 220-260 ℃; and
(b) Melt polymerization or solution polymerization is carried out, preferably melt polymerization.
In a preferred embodiment, the step (a) may be implemented by:
1) Mixing terephthalic acid, dihydric alcohol, dibasic acid, hydroxy acid or methyl hydroxy acid ester or ethyl hydroxy acid ester or glycolide (1, 4-dioxane-2, 5-diketone) or lactide, polyether and dimethyl sodium 5-sulfoisophthalate according to the required MA/MD molar ratio of 1/1-1/5, stirring and fully mixing with a catalyst; wherein MA represents the combined molar amounts of all acids and esters and MD is the molar amount of all diols;
2) First esterification: esterification of the mixture in step 1) at 220 to 260 ℃ with removal of methanol or ethanol and water by fractional distillation (schemes VIIIa to VIIIf); and
3) And (3) second esterification: the mixture in step 2) continues to be esterified at 220 to 260 ℃ and methanol or ethanol and water are removed by fractional distillation until no more alcohol or water is removed (schemes IXa to IXc).
According to the present invention, the method for preparing the autocatalytic fast degradation polyester polymer may comprise the steps of:
(a) Firstly, synthesizing a monomer or an oligomer of a non-degradable rigid block A; and
(b) Adding monomers or oligomers of degradable soft block B, fast degradable block C, soft block D and catalytic block E to carry out solution polymerization or melt polymerization.
According to the present invention, the method for preparing the autocatalytic fast degradation polyester polymer may comprise the steps of:
(a) Firstly, simultaneously synthesizing monomers or oligomers of an undegradable rigid block A, a degradable soft block B, a fast degradable block C and a catalytic block E; and
(b) Monomers or oligomers of the soft block D are added to carry out solution polymerization or melt polymerization (see schemes VIa to VId below).
Wherein R is independently selected from hydrogen or methyl or ethyl or C3-C10 alkyl or ethylene glycol (HOCH) 2 CH 2 -)，R 1 ,R 2 ,R 3 ,R 4 ,R 5 ,R 6 ,R 7, R 8 ,R 9 ,R 10 ,R 11 ,R 12 ,R 13 ,R 14 ,R 15 ,R 16 ,R 17 ,R 18, n,n 1 ,n 2 ,n 3 ,n 4 ,n 5 ,p,q,y,r 1 ,r 2 ,r 3 S, t, u, v, w, x, z and m are as defined above.
In a preferred embodiment, the conditions for melt polymerization in the present invention are polymerization at 200 to 290 ℃ for 2 to 7 hours under vacuum.
In a preferred embodiment, the melt polymerization in the present invention may be carried out as follows:
1) Prepolymerizing at 200 ℃ to 250 ℃ under vacuum;
2) The final polymerization is carried out under high vacuum at 200 ℃ to 290 ℃ until the desired viscosity is reached.
In a preferred embodiment, the desired viscosity is from 0.6 to 1.2dL/g.
In some embodiments, the synthesis of the monomers or oligomers of the non-degradable rigid block a comprises the steps of:
wherein, R', R 1 ,R 2 ,R 3 ,r 1 And n is 1 As defined above.
In some embodiments, the synthesis of the monomer or oligomer of the fast degrading block C may be achieved from the alkyl hydroxy acid ester by scheme IIIa or scheme IIIb or scheme IIIc or scheme IIId as follows:
wherein R is independently selected from hydrogen or C1-C10 alkyl or ethylene glycol (HOCH) in each structural unit 2 CH 2 -)，u、v、R 9 、R 10 、R 11 、R 12 As defined above;
wherein R is independently selected from hydrogen or C1-C10 alkyl or ethylene glycol (HOCH) in each structural unit 2 CH 2 -)，u、v、R 9 、R 10 、R 11 、R 12 As defined above; r is 4 Selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl;
wherein R is independently selected from hydrogen or C3-C10 alkyl or ethylene glycol (HOCH) in each structural unit 2 CH 2 -)，u、v、R 9 、R 10 、R 11 、R 12 As defined above; the catalyst in scheme IIIc is selected from any transesterification catalyst including, but not limited to: h 2 SO 4 Or a lewis acid or zinc acetate or tert-butyl titanate or butyl (oxo) tin nanol or mixtures thereof;
wherein R and R' are independently selected from hydrogen or C3-C10 alkyl or ethylene glycol (HOCH) in each structural unit 2 CH 2 -)，u、v、R 9 、R 10 、R 11 、R 12 As defined above; r 4 Selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl; the catalyst in scheme IIId is selected from any transesterification catalyst including, but not limited to: h 2 SO 4 Or Lewis acids or zinc or titanium acetateTert-butyl or butyl (oxo) tin nanoalcohols or mixtures thereof;
in some embodiments, the synthesis of the monomers or oligomers of the degradable soft block B comprises the steps of:
wherein R is 2 ,R 3 ,R 5 ,R 6 ,R 7 ,R 8 ,r 2 S, and n 2 As defined above.
In some embodiments, the synthesis of the monomer or oligomer of catalytic block E comprises the steps of:
wherein R is independently selected from hydrogen or methyl or ethyl or C3-C10 alkyl, R 15 、R 16 And w is as defined above, the catalyst in scheme V is selected from one of the liquid acids of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, p-toluenesulfonic acid or lewis acids; or one or two or more solid acid catalysts; or a mixture of a liquid acid and one or two or more solid acid catalysts, preferably Lewis acids, zinc acetate, tetrabutyl titanate, monobutyl tin oxide, calcium carbonate or mixtures thereof.
In some embodiments, the alkyl hydroxy acid ester (VII)
Can be prepared by the following method:
wherein R is independently selected from hydrogen or methyl or ethyl in each structural unitOr C3-C10 alkyl or ethylene glycol (HOCH) 2 CH 2 -, R' are independently selected from hydrogen or methyl or ethyl; r 9 、R 10 And v are as defined above; the catalyst in scheme VIIa is one of the liquid acids of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, p-toluenesulfonic acid, or Lewis acid; or one or two or more solid acid catalysts; or a mixture of one liquid acid and one or two or more solid acid catalysts, specifically cationic ion exchange resins, antimony glycol, antimony trioxide, antimony acetate, aluminum glycol, aluminum hydroxide, aluminum chloride, aluminum acetate, aluminum oxide, trimethylaluminum, triethylaluminum, aluminum ethoxide, aluminum triisopropoxide, aluminum stearate, sodium aluminate, aluminum oxide, aluminum sulfate, titanium glycol, ethyl titanate, tetrabutyl titanate, isopropyl titanate, titanium tetrachloride, potassium hexafluorotitanate, potassium oxalate, lithium titanate, titanium carboxylate, titanium dioxide, titanium acetylacetonate, tetraphenyl titanate, titanium chloride, diisopropoxy-diacetylacetyl titanium, di-n-butoxy-bis (triethanol-amine) titanium, tributyl monoacetyltitanium, triisopropyl monoacetyltitanium, titanium tetrabenzoate, germanium dioxide, tetrabutoxygermanium, stannous oxalate, monobutyltin oxide, stannous octoate, tin acetylacetonate, stannous chloride, tin powder, tin oxide, tin acetate, butylstannoic acid, monobutyltin oxide, dibutyldiisooctyl tin oxide, dimethyltin oxide, dibutyltin oxide, triphenyltin acetate, triphenyltin trichloride, tributyltin acetate, triethyltin chloride, triethyltin hydroxide, triethyltin chloride or triethyltin bromide; preferably, one or two or more of Lewis acid, monobutyl tin oxide, dibutyl tin oxide and tributyl tin acetate; more preferably sulfuric acid, p-toluenesulfonic acid, cationic ion exchange resins, lewis acids, zinc acetate, tetrabutyl titanate, monobutyl tin oxide, or mixtures thereof; the solvent is benzene or toluene or any other solvent that azeotropes with water.
In some embodiments, wherein the alkyl hydroxy acid ester (VII)
Can be prepared by the following method:
wherein R is independently selected from hydrogen or methyl or ethyl or C3-C10 alkyl or ethylene glycol (HOCH) in each structural unit 2 CH 2 -, R' are independently selected from hydrogen or methyl or ethyl; r 9 、R 10 And v is as defined above; the catalyst in scheme VIIb is one of the liquid acids of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, p-toluenesulfonic acid, or lewis acids; or one or two or more solid acid catalysts; or a mixture of one liquid acid and one or two or more solid acid catalysts, specifically cationic ion exchange resins, antimony glycol, antimony trioxide, antimony acetate, aluminum glycol, aluminum hydroxide, aluminum chloride, aluminum acetate, aluminum oxide, trimethylaluminum, triethylaluminum, aluminum ethoxide, aluminum triisopropoxide, aluminum stearate, sodium aluminate, aluminum oxide, aluminum sulfate, titanium glycol ethylene glycol, ethyl titanate, tetrabutyl titanate, isopropyl titanate, titanium tetrachloride, potassium hexafluorotitanate, potassium oxalate, lithium titanate, titanium carboxylate, titanium dioxide, titanium acetylacetonate, tetraphenyl titanate, titanium chloride, diisopropoxy-diacetone titanium, di-n-butoxy-bis (triethanolamine) titanium, tributylmonoacetyl titanium, triisopropylmonoacetyl titanium, titanium tetrabenzoate, germanium dioxide, tetrabutoxygermanium, stannous oxalate, monobutyltin oxide, stannous octoate, tin acetylacetonate, stannous chloride, tin powder, tin oxide, tin acetate, butylstannic acid, monobutyltin oxide, dibutyl diisooctyltin, dimethyl tin oxide, dibutyl tin oxide, bisphenyltin oxide, tributyltin acetate, tributyltin fluoride, triethyl tin chloride, trimethyl tin bromide, one or more of triethyl tin acetate, trimethyl tin hydroxide, triphenyl tin chloride, triphenyl tin bromide, triphenyl tin acetate, and zinc acetate; superior foodOptionally, one or two or more of Lewis acid, monobutyl tin oxide, dibutyl tin oxide and tributyl tin acetate; more preferably sulfuric acid, p-toluenesulfonic acid, cationic ion exchange resins, lewis acids, zinc acetate, tetrabutyl titanate, monobutyltin oxide or mixtures thereof.
In a preferred embodiment, the moles of hydroxyl groups comprised in the non-degradable rigid block a are greater than the moles of hydroxyl groups comprised in the rapidly degradable block C; and the number of moles of hydroxyl groups contained in the fast degradation block C is greater than that contained in the catalytic block E because the excess ethylene glycol in the non-fast degradation block can be removed under vacuum at high temperature and thus self-polycondensed to form a high molecular polymer.
In another aspect of the invention, there is provided the use of the autocatalytic fast degradable polyester polymer or the process for preparing an autocatalytic fast degradable polyester polymer in shopping bags, greenhouse films, mulching films, medical devices, beverage packaging bottles, food packaging films and other food containers.
Compared with the prior art, the polymer main chain of the polyester polymer disclosed by the invention comprises degradable blocks, soft blocks and catalytic blocks with different structures, so that the crystallinity of the polyester polymer is reduced, and the melting temperature of the polyester polymer is far lower than that of the conventional polyester polymer; in addition, since the soft segment of the polymer is lengthened due to the inclusion of other blocks, the glass transition temperature of the polymer is also lower than that of the conventional polyester polymer. Thus, the polyester polymers of the present invention not only have excellent processability, but also can be rapidly degraded under appropriate circumstances (e.g., the presence of water) into many short non-degradable chains, followed by further complete degradation of the non-degradable short chain segments. It effectively solves the problem of environmental pollution caused by the application of the polymer and meets the requirement of wide application of the polymer material. In particular, it can ensure that such polymers are suitable for application to greenhouse films, mulching films, beverage bottles, food packaging films, shopping bags and other food packaging containers; in addition, the preparation method of the invention is simple, the cost is low, and the raw materials are easily obtained at low price. It is suitable for batch production and has practical value and application potential.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The following examples are intended to illustrate, but not limit, the scope of the invention. The scope of the invention is not limited by the embodiments, but is defined in the appended claims. All ingredients and percentages are on a weight basis unless otherwise indicated.
Example 1
1. Synthesis of comonomer in catalytic Block E (formula V): 1, 3-diethylene glycol 5-sodium sulfoisophthalate.
To a solution of sodium 1, 3-dimethyl 5-sulfoisophthalate (1.0 mole) in ethylene glycol (1.5 moles) was added the catalyst CaCO 3 (0.01 mol) and sodium acetate (0.0015 mol). The solution was stirred at a temperature of 130 to 150 ℃ for 5 hours, and methanol (2.0 moles) was collected by fractional distillation. The residue solution is ready for polymerization.
2. Synthesis of fast degrading Block C comonomer (IIIa and/or IIIb):
A. to a solution of ethyl lactate or methyl lactate (1 mole) in ethylene glycol (2 moles) was added the catalyst, monobutyl tin oxide (0.2 mole) with stirring, the solution temperature was raised to 135 to 180 ℃, and the reaction was maintained for 3 to 4 hours. The ethanol or methanol as the byproduct is slowly fractionated, and the temperature at the top of the fractionating tower is controlled below 80 ℃. The transesterification reaction is a reversible reaction, so the reactant ethylene glycol is in excess during the reaction, and the reaction by-product ethanol or methanol should be removed in time to force the reaction to proceed in a forward direction. When ethanol or methanol was not distilled off any more in the system, excess ethylene glycol and unreacted ethyl 2-hydroxypropionate were distilled off under reduced pressure; the residue in the reactor is the reaction product, the formula is as described above, the boiling point of the reaction product is 274 to 275 ℃, and the yield is 84 to 86%.
B. To the above product (product of step A, 1 mole) is added a diacid such as adipic acid, succinic acid or terephthalic acid (0.5 mole) under nitrogen protection, the pressure is maintained at 0.05MPa, the temperature of the mixture is raised to 180-200 ℃ and the reaction is maintained at 0.05MPa for 2-3 hours. Collecting by-product H by fractional distillation 2 O until H can no longer be distilled off 2 And O. MixingThe material is ready for polymerization.
3. Synthesis of fast degradable Block C comonomer (IIIc)
To a solution of ethylene glycol (1 mole) in ethyl lactate or methyl lactate (2 moles) was added the catalyst, monobutyl tin oxide (0.2 moles) with stirring, the temperature of the solution was raised to 135 to 180 ℃, and the reaction was maintained for 3 to 4 hours. The ethanol or methanol as the byproduct is slowly fractionated, and the temperature at the top of the fractionating tower is controlled below 80 ℃. When ethanol or methanol is not distilled off any more in the system, the residue in the reactor is a reaction product, and the structural formula is as described above.
4. Synthesis of fast degradable Block C comonomer (IIId)
A、Synthesis of ethylene glycol lactate: the same procedure as in step 2A of example 1.
B、Synthesis of lactic acid ethylene glycol: to rich H 2 SO 4 (98%, 2 ml) to a solution in benzene or toluene (100 ml) were added lactic acid (80%, 225 g) and ethylene glycol (490 g). Heating the solution to boiling, and collecting H with Dean Stark or similar device 2 O/benzene (toluene) mixture. When distillation of H is no longer necessary 2 O, the system temperature was raised and the solvent benzene or toluene and excess ethylene glycol were removed in vacuo.
C. Commercially available lactide or glycolide was used as it was.
5. Synthesis (II) of degradable Soft Block B comonomer
To the catalyst (e.g. Sb) with agitation 2 O 3 0.1 wt.%) to a solution in ethylene glycol (2.0 moles) was added a diacid such as adipic acid or succinic acid (1.0 mole). The mixture is reacted at 250 ℃ until no more H is distilled off 2 And O. The residue is the product.
6. Synthesis of polyester polymers of the invention
A、Esterification of terephthalic acid (PTA): to the catalyst (e.g. Sb) with stirring 2 O 3 0.1 wt%) and stabilizer (0.05 wt%) were added to a solution of terephthalic acid in ethylene glycol. Mixing ofThe mixture was reacted at 250 ℃ until no more H could be distilled off 2 O, more catalyst and stabilizer are added.
B、Pre-polymerization: comonomers of the catalytic block E, any fast degrading block C (IIIa, IIIb, IIIc or IIId), the degradable soft block B and the commercially available soft block D (such as polyethylene glycol or polytetrahydrofuran) are added to the above step a mixture in the desired molar ratio, the mixture is polymerized at 200 to 240 ℃ for about 1 hour under vacuum (20 KPa), and then the temperature of the mixture is raised to 210 to 250 ℃. The ethylene glycol was removed by vacuum.
C、Final polymerization: the mixture in step B is further polymerized at 220 to 270 ℃ under very high vacuum (50 to 100 Pa) until the viscosity reaches the desired value.
Example 2
1. Synthesis of the polyester Polymer of the invention:
A、esterification of a non-degradable rigid block A, a degradable soft block B, a rapidly degradable block C and a catalytic block E together: to catalysts (e.g. Sb) 2 O 3 0.1% by weight) and stabilizer (0.05% by weight) in ethylene glycol were added terephthalic acid, adipic acid or succinic acid, alkyl glycolate or lactate (where the alkyl group is methyl or ethyl or any other alkyl group) or ethylene lactate (product of a or B in step 4 of example 1) or glycolide or lactide, and sodium 1, 3-dimethyl 5-sulfoisophthalate or sodium 1, 3-diethylene glycol 5-sulfoisophthalate. Reacting the mixture at 250 ℃ to collect methanol, ethanol and H 2 O until no more H can be distilled off 2 O, addition of further catalyst and stabilizer, and soft block D (e.g. polyethylene glycol or polytetrahydrofuran).
B、Pre-polymerization: the mixture of step a was polymerized under vacuum (20 KPa) at 200 to 240 ℃ for about 1 hour, then the temperature of the mixture was raised to 210 to 250 ℃ and reacted under vacuum (10 KPa) for another half hour. The ethylene glycol was removed by vacuum.
C、Final polymerization: the mixture from step B is further polymerized at 220 to 270 ℃ under very high vacuum (50 to 100 Pa) untilUntil the viscosity reaches the desired value.
In conclusion, the polyester polymer provided in the present invention has not only excellent mechanical processability but also rapid degradation whenever water or moisture is present, thereby effectively solving the problem of environmental pollution caused by such polymer. It meets a wide range of application requirements, particularly ensuring that such polymers can be applied to beverage bottles, food packaging films, agricultural films (greenhouse films and/or mulching films), shopping bags and other food packaging containers. In addition, the preparation method of the invention is simple, the cost is low, and the raw materials are easily obtained at low price. It is suitable for batch production and has practical value and application potential.
Finally, it is necessary here to state: the above examples are only for further illustrating the technical demonstration of the present invention in detail, and should not be construed as limiting the scope of the invention, and any unnecessary modifications and adaptations by anyone skilled in the art based on the contents of the present invention will fall within the scope of the invention.
Claims (18)
1. An autocatalytic fast degrading polyester polymer comprising recurring units- [ (A) n1 -(B) n2 -(C) n3 -(D) n4 -(E) n5 ] n -prepared by polycondensation of recurring structural units comprising a non-degradable rigid block a, a degradable soft block B, a fast degrading block C, a soft block D and a catalytic block E, wherein the non-degradable rigid block a has the structure of formula (I):
the degradable soft block B has a structure of formula (II):
the fast degrading block C has a structure of formula (IIIa) or formula (IIIb) or formula (IIIc) or formula (iiid):
the soft block D has the structure of formula (IV):
the catalytic block E has the structure of formula (V):
repeating units of the polyester Polymer- [ (A) n1 -(B) n2 -(C) n3 -(D) n4 -(E) n5 ] n -, having formula (VIa) or formula (VIb) or formula (VIc) or formula ((VId):
wherein:
in the repeating unit- [ (A) n1 -(B) n2 -(C) n3 -(D) n4 -(E) n5 ] n -the sequence of blocks a, B, C, D and E is randomly arranged and any block may occur multiple times;
n,n 1 and n is 3 Each independently is an integer greater than 0;
n 2 ,n 4 and n 5 Each independently is 0 or an integer greater than 0;
p, q and y are each independently 0 or 1;
r 1 ,r 2 ,r 3 s, t, u, v, w, x and z are each independently integers greater than 0 and less than 50;
m is an integer greater than 0 and less than 200;
R 1 ,R 2 ,R 3 ,R 4 ,R 5 ,R 6 ,R 7, R 8 ,R 9 ,R 10 ,R 11 ,R 12 ,R 13 ,R 14 ,R 15 ,R 16 ,R 17 ,R 18 is independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl, substituted or unsubstituted alkoxy, ester, nitro, amine, amide, or thiol in each structural unit; and is
R ', R' and R 4 Independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl.
2. The autocatalytic fast degrading polyester polymer of claim 1 wherein said R 1 ,R 2 ,R 3 ,R 4 ,R 5 ,R 6 ,R 7, R 8 ,R 9 ,R 10 ,R 11 ,R 12 ,R 13 ,R 14 ,R 15 ,R 16 ,R 17 ,R 18 Independently selected from hydrogen or C1-C10 alkyl in each structural unit.
3. The autocatalytic fast degrading polyester polymer of claim 2 wherein said R 1 ,R 2 ,R 3 ,R 4 ,R 5 ,R 6 ,R 7, R 8 ,R 9 ,R 10 ,R 11 ,R 12 ,R 13 ,R 14 ,R 15 ,R 16 ,R 17 ,R 18 Independently selected from hydrogen or methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl in each structural unit; r ', R ", R'" and R 4 Selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, and substituted or unsubstituted heterocycloalkyl.
4. The autocatalytic fast degrading polyester polymer of claim 2 wherein said R 1 ,R 2 ,R 3 ,R 4 ,R 5 ,R 6 ,R 7, R 8 ,R 9 ,R 10 ,R 11 ,R 12 ,R 13 ,R 14 ,R 15 ,R 16 ,R 17 ,R 18 Is hydrogen; r is 9 、R 10 Is hydrogen or methyl; r is 1 、r 2 、r 3 S, t, w, x and z are any integer independently selected from 2, 3, 4; u and v are any integer independently selected from 1, 2, 3 or 4.
5. The method for preparing autocatalytic fast degrading polyester polymer according to any of claims 1 to 4, comprising the steps of:
(a) Mixing comonomers or oligomers of the nondegradable rigid block A, the degradable soft block B, the rapidly degradable block C, the soft block D and the catalytic block E together in the same reactor at the same time, and esterifying at 220-260 ℃; and
(b) Melt polymerization or solution polymerization is carried out.
6. The preparation method of the autocatalytic fast degrading polyester polymer according to claim 5, said step (a) can be achieved by:
1) Mixing terephthalic acid, dihydric alcohol, dibasic acid, hydroxy acid or methyl hydroxy acid ester or ethyl hydroxy acid ester or glycolide (1, 4-dioxane-2, 5-diketone), or lactide, polyether and 5-sulfoisophthalic acid dimethyl ester sodium according to the required MA/MD molar ratio of 1/1-1/5, stirring and fully mixing with a catalyst; wherein MA represents the combined molar amount of all acids and esters and MD is the molar amount of all diols;
2) First esterification: esterification of the mixture in step 1) at 220 to 260 ℃ with removal of methanol or ethanol and water by fractional distillation (schemes VIIIa to VIIIf); and
3) And (3) second esterification: the mixture in step 2) is continued to be esterified at 220 to 260 ℃ and methanol or ethanol and water are removed by fractional distillation until no more alcohol or water is removed.
7. The method for preparing autocatalytic fast degrading polyester polymer according to any of claims 1 to 4, comprising the steps of:
(a) Firstly, synthesizing monomers or oligomers of a non-degradable rigid block A; and
(b) Adding monomers or oligomers of degradable soft block B, fast degradable block C, soft block D and catalytic block E to carry out solution polymerization or melt polymerization.
8. The method for preparing autocatalytic fast degrading polyester polymer according to any of claims 1 to 4, comprising the steps of:
(a) Firstly, simultaneously synthesizing monomers or oligomers of a non-degradable rigid block A, a degradable soft block B, a fast degradable block C and a catalytic block E; and
(b) The monomer or oligomer of the soft block D is added to perform solution polymerization or melt polymerization.
9. The method for preparing autocatalytically fast degrading polyester polymer according to any of claims 5 to 8, melt polymerizing under conditions of 200 to 290 ℃ for 2 to 7 hours under vacuum.
10. The method for preparing autocatalytic fast degrading polyester polymer according to claim 9, wherein the melt polymerization step is performed as follows:
1) Prepolymerizing at 200 ℃ to 250 ℃ under vacuum;
2) The final polymerization is carried out under high vacuum at 200 ℃ to 290 ℃ until the desired viscosity is reached.
11. The process for the preparation of autocatalytic fast degrading polyester polymer according to any of claims 5 to 8, the synthesis of the monomer or oligomer of non-degradable hard block a comprising the steps of:
wherein, R', R 1 ,R 2 ,R 3 ,r 1 And n is 1 As defined in the preceding claims 1 to 4.
12. The preparation process of an autocatalytic fast degrading polyester polymer according to anyone of claims 5 to 8, the synthesis of the monomer or oligomer of the fast degrading block C is achieved from an alkyl hydroxy acid ester by the following scheme (IIIa) or scheme (IIIb) or scheme (IIIc) or scheme (IIId):
wherein R is independently selected from hydrogen or C1-C10 alkyl or ethylene glycol (HOCH) in each structural unit 2 CH 2 -)，u、v、R 9 、R 10 、R 11 、R 12 The same as defined in claims 1 to 4;
wherein R is independently selected from hydrogen or C1-C10 alkyl or ethylene glycol (HOCH) in each structural unit 2 CH 2 -)，u、v、R 9 、R 10 、R 11 、R 12 As defined in claims 1 to 4; r 4 Selected from hydrogen, substituted or unsubstitutedSubstituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl;
wherein R is independently selected from hydrogen or C3-C10 alkyl or ethylene glycol (HOCH) in each structural unit 2 CH 2 -)，u、v、R 9 、R 10 、R 11 、R 12 The same as defined in claims 1 to 4; the catalyst in scheme (IIIc) is selected from any transesterification catalyst;
wherein R and R' are independently selected from hydrogen or C3-C10 alkyl or ethylene glycol (HOCH) in each structural unit 2 CH 2 -)，u、v、R 9 、R 10 、R 11 、R 12 The same as defined in claims 1 to 4; r 4 Selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl; the catalyst in scheme (IIId) is selected from any transesterification catalyst.
13. The method for preparing autocatalytically fast degrading polyester polymer according to any one of claims 5 to 8, wherein the synthesis of said monomer or oligomer of degradable soft block B comprises the steps of:
wherein R is 2 ,R 3 ,R 5 ,R 6 ,R 7 ,R 8 ,r 2 S, and n 2 As defined in claims 1 to 4.
14. The process for the preparation of an autocatalytic fast degrading polyester polymer according to anyone of claims 5 to 8, the synthesis of the monomer or oligomer of the catalytic block E comprising the steps of:
wherein R is independently selected from hydrogen or methyl or ethyl or C3-C10 alkyl, R 15 、R 16 And w are as defined in claims 1 to 4, the catalyst in scheme V being selected from one of the liquid acids of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, p-toluenesulfonic acid or Lewis acid; or one or two or more solid acid catalysts; or a mixture of a liquid acid and one or two or more solid acid catalysts, preferably Lewis acids, zinc acetate, tetrabutyl titanate, monobutyl tin oxide, calcium carbonate or mixtures thereof.
15. The method for preparing autocatalytically fast degrading polyester polymer according to claim 12, said alkyl hydroxy acid ester (VII)
The preparation method comprises the following steps:
wherein R is independently selected from hydrogen or methyl or ethyl or C3-C10 alkyl or ethylene glycol (HOCH) in each structural unit 2 CH 2 -, R' are independently selected from hydrogen or methyl or ethyl; r 9 、R 10 And v is as defined in claims 1 to 5; the catalyst in scheme VIIa is one of the liquid acids of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, p-toluenesulfonic acid, or lewis acids; or one or two or moreA solid acid catalyst; or a mixture of one liquid acid and one or two or more solid acid catalysts, specifically cationic ion exchange resins, antimony glycol, antimony trioxide, antimony acetate, aluminum glycol, aluminum hydroxide, aluminum chloride, aluminum acetate, aluminum oxide, trimethylaluminum, triethylaluminum, aluminum ethoxide, aluminum triisopropoxide, aluminum stearate, sodium aluminate, aluminum oxide, aluminum sulfate, titanium glycol ethylene glycol, ethyl titanate, tetrabutyl titanate, isopropyl titanate, titanium tetrachloride, potassium hexafluorotitanate, potassium oxalate, lithium titanate, titanium carboxylate, titanium dioxide, titanium acetylacetonate, tetraphenyl titanate, titanium chloride, diisopropoxy-diacetoacetyltitanium, di-n-butoxy-bis (triethanolamine) titanium, tributylmonoacetyltitanium, triisopropylmonoacetyltitanium, titanium tetrabenzoate, germanium dioxide, tetrabutoxygermanium, stannous oxalate, monobutyltin oxide, stannous octoate, tin acetylacetonate, stannous chloride, tin powder, tin oxide, tin acetate, butylstannoic acid, monobutyltin oxide, dibutyldiisooctyltin, dimethyltin oxide, dibutyltin oxide, diphenyltin oxide, tributyltin acetate, tributyltin fluoride, triethyltin chloride, tributyltin bromide, one or more of triethyltin acetate, trimethyltin hydroxide, triphenyltin chloride, triphenyltin bromide, triphenyltin acetate, and zinc acetate; preferably, one or two or more of Lewis acid, monobutyl tin oxide, dibutyl tin oxide and tributyl tin acetate; more preferably sulfuric acid, p-toluenesulfonic acid, cationic ion exchange resins, lewis acids, zinc acetate, tetrabutyl titanate, monobutyltin oxide or mixtures thereof; the solvent is benzene or toluene or any other solvent that azeotropes with water.
16. The method for preparing autocatalytic fast degrading polyester polymer according to claim 12, said alkyl hydroxy acid ester (VII)
The preparation method comprises the following steps:
wherein R is independently selected from hydrogen or methyl or ethyl or C3-C10 alkyl or ethylene glycol (HOCH) in each structural unit 2 CH 2 -, R' are independently selected from hydrogen or methyl or ethyl; r 9 、R 10 And v is as defined in claims 1 to 5; the catalyst in scheme VIIb is one of the liquid acids of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, p-toluenesulfonic acid, or lewis acids; or one or two or more solid acid catalysts; or a mixture of one liquid acid and one or two or more solid acid catalysts, specifically cationic ion exchange resins, antimony glycol, antimony trioxide, antimony acetate, aluminum glycol, aluminum hydroxide, aluminum chloride, aluminum acetate, aluminum oxide, trimethylaluminum, triethylaluminum, aluminum ethoxide, aluminum triisopropoxide, aluminum stearate, sodium aluminate, aluminum oxide, aluminum sulfate, titanium glycol, ethyl titanate, tetrabutyl titanate, isopropyl titanate, titanium tetrachloride, potassium hexafluorotitanate, potassium oxalate, lithium titanate, titanium carboxylate, titanium dioxide, titanium acetylacetonate, tetraphenyl titanate, titanium chloride, diisopropoxy-diacetonattitanium, di-n-butoxy-bis (triethanolaminato) titanium, tributylmonoacetyltitanium, triisopropylmonoacetyltitanium, titanium tetrabenzoate, germanium dioxide, tetrabutoxygermanium, stannous oxalate, monobutyltin oxide, stannous octoate, tin acetylacetonate, stannous chloride, tin powder, tin oxide, tin acetate, butylstannoic acid, monobutyltin oxide, dibutyldiisooctyltin oxide, dimethyltin oxide, dibutyltin oxide, triphenyltin acetate, triethyltin hydroxide, triethyltin chloride, and triethyltin bromide; preferably, one or two or more of Lewis acid, monobutyl tin oxide, dibutyl tin oxide and tributyl tin acetate; more preferably sulfuric acid, p-toluenesulfonic acid, cationIon exchange resins, lewis acids, zinc acetate, tetrabutyl titanate, monobutyl tin oxide, or mixtures thereof.
17. The process for preparing an autocatalytic fast degrading polyester polymer according to any of claims 5 to 9, wherein the moles of hydroxyl groups contained in the non-degradable rigid block a is greater than the moles of hydroxyl groups contained in the fast degrading block C; and the number of moles of hydroxyl groups contained in the fast degrading block C is greater than the number of moles of hydroxyl groups contained in the catalytic block E.
18. Use of the autocatalytically fast degradable polyester polymer of any of claims 1 to 4 or the process for the preparation of autocatalytically fast degradable polyester polymer of any of claims 5 to 15 in shopping bags, greenhouse films, mulching films, medical devices, beverage packaging bottles, food packaging films and other food containers.
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