CN115710349B - Aliphatic-aromatic copolyester and application thereof - Google Patents

Aliphatic-aromatic copolyester and application thereof Download PDF

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CN115710349B
CN115710349B CN202210304833.1A CN202210304833A CN115710349B CN 115710349 B CN115710349 B CN 115710349B CN 202210304833 A CN202210304833 A CN 202210304833A CN 115710349 B CN115710349 B CN 115710349B
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containing compound
aliphatic
acid
magnesium
zinc
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CN115710349A (en
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李凌云
张长礼
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Polycarbon Oxygen New Material Technology Wuxi Co ltd
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Polycarbon Oxygen New Material Technology Wuxi Co ltd
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Abstract

An aliphatic-aromatic copolyester and its application are disclosed. The copolyester is obtained by the following method: in the presence of the first catalyst and/or the second catalyst, the aliphatic dibasic acid, the aromatic dibasic acid and the aliphatic dihydric alcohol are subjected to esterification reaction, polycondensation reaction and chain extension reaction. Wherein the first catalyst comprises the reaction product of a titanium-containing compound, a magnesium-containing compound, a zinc-containing compound, a hydroxyl-containing compound, and a carboxyl-containing compound; the second catalyst comprises the reaction product of a titanium-containing compound, a magnesium-containing compound, a zinc-containing compound, a hydroxyl-containing compound, and an epoxy-containing compound. The auxiliary agent for chain extension reaction comprises a molecular weight extender selected from isocyanate compounds, carbodiimide compounds, glyceryl ether/ester compounds, oxazoline compounds, coupling agent compounds or alkyl metal compounds. The copolyester of the invention has adjustable biodegradation period, less surface smooth gel point, high molecular weight and narrow molecular weight distribution when being prepared into films/sheets.

Description

Aliphatic-aromatic copolyester and application thereof
Technical Field
The invention belongs to the field of synthesis and application of high polymer materials, and particularly relates to aliphatic-aromatic copolyester and application thereof.
Technical Field
In recent years, the problems of white pollution and micro plastic pollution and the global sustainable development goal all push biodegradable materials to the tip of the wind port. Before the day, commercial commercialization of aliphatic-aromatic biodegradable copolyester is most successful by taking Basoff Ecoflex as a representative, and the aliphatic-aromatic biodegradable copolyester can replace part of linear Low Density Polyethylene (LDPE) to be applied to the field of soft film materials, so that the problems of white pollution and microplastic pollution are relieved.
Currently, biodegradable polyester films/sheets have the following problems: 1. the degradation rate is too fast, namely the carboxyl end is high, so that the shelf life of the material is short, and the practical application is limited; 2. the roughness of the surface of the biodegradable polyester film/sheet is expressed as a large number of gel points on the surface of the film/sheet, which results in poor processing stability of the downstream film/sheet and influences the printing effect. Therefore, development of low carboxyl end group, low gel point biodegradable aliphatic/aromatic copolyesters is necessary.
In the Chinese patent application with publication number CN103497316A, a polyester product with high molecular weight and low carboxyl end of about 5-20 mmol/kg can be prepared by adding a polyepoxy compound into a polymerization reactor for melt adhesion reaction. In the Chinese patent application with publication number CN103665777A, a double-screw extruder is used for melt reaction extrusion of polyester and reaction auxiliaries such as epoxy, imine and the like, so that a low-end carboxyl polyester product can be prepared. In chinese patent application publication No. CN111363131a, a process of melt mixing and solid phase adhesion promotion using a dynamic mixer is disclosed to prepare low-end carboxyl aliphatic-aromatic copolyester. The above patents all realize the preparation of low-end carboxyl polyester, but local overreaction between the auxiliary agent and the polyester in the melting reaction cannot be avoided, and the gel point is more.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides the aliphatic-aromatic copolyester, the biodegradation period of which is adjustable, and the film/sheet prepared from the aliphatic-aromatic copolyester has the advantages of less surface smoothness gel point, high molecular weight and narrow molecular weight distribution.
In a first aspect the present invention provides an aliphatic-aromatic copolyester obtainable by a process comprising the steps of:
s1: in the presence of a first catalyst and/or a second catalyst, respectively carrying out esterification reaction on aliphatic dibasic acid and aromatic dibasic acid and aliphatic dihydric alcohol to obtain esterification reaction products;
s2: carrying out polycondensation reaction on the esterified product of the S1 to obtain a polyester intermediate;
s3: in the presence of an auxiliary agent, enabling the polyester intermediate of the S2 to undergo a chain growth reaction to obtain the aliphatic-aromatic copolyester;
wherein the first catalyst comprises the reaction product of a titanium-containing compound, a magnesium-containing compound, a zinc-containing compound, a hydroxyl-containing compound, and a carboxyl-containing compound; the second catalyst comprises the reaction product of a titanium-containing compound, a magnesium-containing compound, a zinc-containing compound, a hydroxyl-containing compound, and an epoxy-containing compound;
the auxiliary agent comprises a molecular weight extender and a dispersing agent, wherein the molecular weight extender comprises one or more of isocyanate compounds, carbodiimide compounds, glycerol ether compounds, glycerol ester compounds, oxazoline compounds, coupling agent compounds and alkyl metal compounds.
According to some embodiments of the invention, the aliphatic-aromatic copolyester has a carboxyl end group content of 4-15mmol/kg, e.g. 5mmol/kg, 6mmol/kg, 7mmol/kg, 8mmol/kg, 9mmol/kg, 10mmol/kg, 11mmol/kg, 12mmol/kg, 13mmol/kg, 14mmol/kg or any value in between.
According to some embodiments of the invention, the gel point of the aliphatic-aromatic copolyester is 10/m or less 2 For example 1/m 2 2/m 2 3/m 2 4/m 2 5/m 2 6/m 2 7/m 2 8/m 2 9/m 2 Or any value therebetween.
According to some embodiments of the invention, the aliphatic-aromatic copolyester has a mass average molecular weight of 7.0X10 4 -15.0×10 4 For example 7.5X10 4 、8.0×10 4 、9.0×10 4 、9.5×10 4 、10.×10 4 、10.5×10 4 、11.0×10 4 、11.5×10 4 、12.0×10 4 、12.5×10 4 、13.0×10 4 、13.5×10 4 、14.0×10 4 、14.5×10 4 Or any value therebetween. In some embodiments, the aliphatic-aromatic copolyester has a mass average molecular weight of 9.1X10 4 -15.0×10 4 。
According to some embodiments of the invention, the aliphatic-aromatic copolyester has a molecular weight distribution of 1.8 to 2.2, for example 1.85, 1.9, 1.95, 2.05, 2.1, 2.15 or any value in between.
According to some embodiments of the invention, the isocyanate compound has a structure as shown in formula I,
in the formula I, R 1 Is C 1 ～C 20 Hydrocarbyl radicals, x > 1. In some embodiments, R 1 Selected from monovalent C 1 ～C 20 Hydrocarbyl, divalent C 1 ～C 20 Hydrocarbyl or multivalent C 1 ～C 20 A hydrocarbon group. In some embodiments, the monovalent C 1 ～C 20 The hydrocarbon radical being selected from C 1 ～C 20 Alkyl (e.g. C 1 ～C 6 Alkyl, C 5 ～C 8 Alkyl, C 9 ～C 12 Alkyl, C 13 ～C 16 Alkyl, C 17 ～C 20 Alkyl group, C 6 ～C 20 Aryl, C 7 -C 20 Alkylaryl and C 7 -C 20 Aralkyl groups. In some embodiments, the divalent C 1 ～C 20 The hydrocarbon radical being selected from C 1 ～C 20 Alkylene (e.g. C 1 ～C 6 Alkylene, C 5 ～C 8 Alkylene, C 9 ～C 12 Alkylene, C 13 ～C 16 Alkylene, C 17 ～C 20 Alkylene group, C 6 ～C 20 Arylene group, C 7 -C 20 Alkarylene and C 7 -C 20 Aralkylene radicals. In some embodiments, the multivalent C 1 ～C 20 The hydrocarbon radical being selected from C 1 ～C 20 Trivalent alkyl groups (e.g. C 1 ～C 6 Trivalent alkyl, C 5 ～C 8 Trivalent alkyl, C 9 ～C 12 Trivalent alkyl, C 13 ～C 16 Trivalent alkyl, C 17 ～C 20 Trivalent alkyl group), C 6 ～C 20 Trivalent aryl, C 7 -C 20 Trivalent alkylaryl and C 7 -C 20 Trivalent aralkyl groups. In some embodiments, x is 1, 2, 3, 4, or 5.
According to some embodiments of the invention, the isocyanate-based compound includes one or more of 2, 4-toluene diisocyanate and its trimer, 2, 6-toluene diisocyanate and its trimer, tetramethyl dimethylene benzene diisocyanate, trimethyl hexamethylene diisocyanate, xylylene diisocyanate, methylcyclohexane diisocyanate, 1, 6-hexamethylene diisocyanate and its trimer, 4 '-diphenylmethane diisocyanate, 2,4' -diphenylmethane diisocyanate, 2 '-diphenylmethane diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, or lysine diisocyanate.
According to some embodiments of the invention, the carbodiimide compound has a structure according to formula II,
R 2 -N＝C＝N-R 3 II (II)
In formula II, R 2 And R is 3 Identical or different, each independently selected from C 1 ～C 20 A hydrocarbon group. In some embodiments, R 2 And R is 3 Each independently selected from C 1 ～C 10 A hydrocarbon group. According to some embodiments of the invention, R 2 And R is 3 Each independently selected from C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 10 Aryl, C 7 -C 10 Alkylaryl and C 7 -C 10 Aralkyl groups. In some embodiments, R 2 And R is 3 Each independently selected from C 1 ～C 20 Alkyl radicals, e.g. C 1 ～C 6 Alkyl, C 5 ～C 8 Alkyl, C 9 ～C 12 Alkyl, C 13 ～C 16 Alkyl, C 17 ～C 20 An alkyl group.
According to some embodiments of the invention, the carbodiimide-based compound includes one or more of N, -dicyclohexylcarbodiimide, N, -diisopropylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, 1-ethyl- (3-dimethylaminopropyl) carbodiimide, bis (3-isopropenyl-dimethylbenzyl) carbodiimide, diphenylcarbodiimide, bis (2, 6-diisopropylphenyl) carbodiimide, or bis (3-benzyl) carbodiimide.
According to some embodiments of the invention, the structure of the glyceryl ether compound is shown in formula III,
in formula III, R 4 Selected from C 1 ～C 20 Hydrocarbyl, m > 1. In some embodiments, R 4 Selected from monovalent C 1 ～C 20 Hydrocarbyl, divalent C 1 ～C 20 Hydrocarbyl or multivalent C 1 ～C 20 A hydrocarbon group. In some embodiments, the monovalent C 1 ～C 20 The hydrocarbon radical being selected from C 1 ～C 20 Alkyl (e.g. C 1 ～C 6 Alkyl, C 5 ～C 8 Alkyl, C 9 ～C 12 Alkyl, C 13 ～C 16 Alkyl, C 17 ～C 20 Alkyl group, C 6 ～C 20 Aryl, C 7 -C 20 Alkylaryl and C 7 -C 20 Aralkyl groups. In some embodiments, the divalent C 1 ～C 20 The hydrocarbon radical being selected from C 1 ～C 20 Alkylene (e.g. C 1 ～C 6 Alkylene, C 5 ～C 8 Alkylene, C 9 ～C 12 Alkylene, C 13 ～C 16 Alkylene, C 17 ～C 20 Alkylene group, C 6 ～C 20 Arylene group, C 7 -C 20 Alkarylene and C 7 -C 20 Aralkylene radicals. In some embodiments, the multivalent C 1 ～C 20 The hydrocarbon radical being selected from C 1 ～C 20 Trivalent alkyl groups (e.g. C 1 ～C 6 Trivalent alkyl, C 5 ～C 8 Trivalent alkyl, C 9 ～C 12 Trivalent alkyl, C 13 ～C 16 Trivalent alkyl, C 17 ～C 20 Trivalent alkyl group), C 6 ～C 20 Trivalent aryl, C 7 -C 20 Trivalent alkylaryl and C 7 -C 20 Trivalent aralkyl groups. In some embodiments, m is 1, 2, 3, 4, or 5.
According to some embodiments of the invention, the glycerol ether compound comprises one or more of ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, trimethylolpropane triglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 5-pentanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, bisphenol a diglycidyl ether, or resorcinol diglycidyl ether.
According to some embodiments of the invention, the glyceride compound has a structural formula shown in formula IV,
in formula IV, R 5 Selected from C 1 ～C 20 Hydrocarbyl, t > 1. In some embodiments, R 5 Selected from monovalent C 1 ～C 20 Hydrocarbyl, divalent C 1 ～C 20 Hydrocarbyl or multivalent C 1 ～C 20 A hydrocarbon group. In some embodiments, the monovalent C 1 ～C 20 The hydrocarbon radical being selected from C 1 ～C 20 Alkyl (e.g. C 1 ～C 6 Alkyl, C 5 ～C 8 Alkyl, C 9 ～C 12 Alkyl, C 13 ～C 16 Alkyl, C 17 ～C 20 Alkyl group, C 6 ～C 20 Aryl, C 7 -C 20 Alkylaryl and C 7 -C 20 Aralkyl groups. In some embodiments, the divalent C 1 ～C 20 The hydrocarbon radical being selected from C 1 ～C 20 Alkylene (e.g. C 1 ～C 6 Alkylene, C 5 ～C 8 Alkylene, C 9 ～C 12 Alkylene, C 13 ～C 16 Alkylene, C 17 ～C 20 Alkylene group, C 6 ～C 20 Arylene group, C 7 -C 20 Alkarylene and C 7 -C 20 Aralkylene radicals. In some embodiments, the multivalent C 1 ～C 20 The hydrocarbon radical being selected from C 1 ～C 20 Trivalent alkyl groups (e.g. C 1 ～C 6 Trivalent alkyl, C 5 ～C 8 Trivalent alkyl, C 9 ～C 12 Trivalent alkyl, C 13 ～C 16 Trivalent alkyl, C 17 ～C 20 Trivalent alkyl group), C 6 ～C 20 Trivalent aryl, C 7 -C 20 Trivalent alkylaryl and C 7 -C 20 Trivalent aralkyl groups. In some embodiments, t is 1, 2, 3, 4, or 5.
According to some embodiments of the invention, the glyceride compounds include one or more of diglycidyl oxalate, diglycidyl 1, 3-malonate, diglycidyl succinate, diglycidyl 1, 5-glutarate, diglycidyl adipate, diglycidyl sebacate, or triglycidyl citrate.
According to some embodiments of the invention, the oxazoline compound has a structure as shown in formula V,
in the formula I, R 6 、R 7 、R 8 、R 9 Identical or different, each independently selected from hydrogen or a C1-C20 hydrocarbon radical, R being absent or selected from a C2-C10 alkylene radical or a C6-C20 arylene radical.
According to some embodiments of the invention, R is selected from C2-C6 alkylene or C3-C8 cycloalkylene.
According to some embodiments of the invention, R is selected from the group consisting of C6-C15 arylene groups, preferably C6-C12 arylene groups. In some embodiments, R is selected from phenylene, biphenylene, methyl-substituted phenylene, ethyl-substituted phenylene, propyl-substituted phenylene, or butyl-substituted phenylene.
According to some embodiments of the invention, R 6 、R 7 、R 8 、R 9 The same or different are each independently selected from hydrogen or C1-C6 alkyl. In some embodiments, R 6 、R 7 、R 8 、R 9 The same applies to hydrogen. In some embodiments, R 6 And R is 9 The same are all hydrogen, R 7 And R is 8 The same or different are each independently selected from C1-C10 alkyl groups, preferably C1-C6 alkyl groups.
According to some embodiments of the present invention, the oxazoline compound comprises 2,2' -bis (2-oxazoline), 2' -bis (4-methyl-2-oxazoline), 2' -ethylenebis (4-methyl-2-oxazoline), and 2,2' -butylidenebis (2-oxazoline), 2' -butylidenebis (4, 4' -dimethyl-2-oxazoline), 2' -bis (4-butyl-2-oxazoline), 2' -hexylidenebis (2-oxazoline), and one or more of 2,2' -cyclohexylidene bis (2-oxazoline), 1, 3-bis (2-oxazoline) benzene, 2' - (1, 3-phenylene) -bisoxazoline, 2' - (1, 4-phenylene) -bisoxazoline, 2' -p-phenylene-bis (4-methyl-2-oxazoline), 2' -p-phenylene-bis (4, 4' -dimethyl-2-oxazoline), and 2,2' -diphenylidene bis (4-methyl-2-oxazoline).
According to some embodiments of the invention, the coupling agent comprises one or more of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a phosphate coupling agent, or a borate coupling agent.
According to some embodiments of the invention, the silane coupling agent has the general structural formula Y (CH 2 ) k SiZ 3 Wherein k=0 to 5, e.g. 1, 2, 3 or 4; y is vinyl, amino, epoxy, methacryloxy, mercapto or ureido; z is chloro, methoxy, ethoxy, methoxyethoxy and acetoxy. In some embodiments, the silane coupling agent includes one or more of vinyltris (β -methoxyethoxy) silane, vinyltrimethylsilane, vinyltriethoxysilane, γ -mercaptopropyltrimethoxysilane, γ -methacryloxypropyl trimethoxysilane, γ -glycidoxypropyl trimethoxysilane, N- (β -aminoethyl) - γ -aminopropyl trimethoxysilane, γ -aminopropyl triethoxysilane.
According to some embodiments of the invention, the titanateThe structural general formula of the coupling agent is (R) 10 O) a -Ti(OA-R1-Q) b ，R 10 Is C 1 ～C 20 A hydrocarbon group; OA is carboxyl, sulfonic acid, sulfone, phosphate, pyrophosphate and phosphite; r1 is C 1 ～C 20 Alkylene radicals of (C) 1 ～C 6 Alkylene, C 6 ～C 8 Alkylene, C 9 ～C 12 Alkylene, C 13 ～C 16 Alkylene, C 17 ～C 20 An alkylene group; q is C 1 ～C 6 Alkyl, hydroxy, amino, epoxy, vinyl; a.gtoreq.1, for example 2, 3, 4 or 5; b.gtoreq.1, for example 2, 3, 4 or 5. In some embodiments, R 10 Is C 1 ～C 20 Alkyl radicals, e.g. C 1 ～C 6 Alkyl, C 6 ～C 8 Alkyl, C 9 ～C 12 Alkyl, C 13 ～C 16 Alkyl, C 17 ～C 20 An alkyl group. In some embodiments, the titanate coupling agent comprises one or more of triisostearoyl isopropyl titanate, bis (dioctyl oxy pyrophosphate) ethylene titanate, isopropyl dioleoyl (dioctyl phosphate) titanate, diethyl propyl di (acetylacetonate) titanate, tetraisopropyl di (dioctyl phosphite) titanate, diisopropyl bis (acetoacetate) titanate, isopropyl tri (dodecylbenzenesulfonyl) titanate.
According to some embodiments of the invention, the aluminate coupling agent has the general structural formula (R) 11 O) a -Al(Dn)(R 12 COO) b A.gtoreq.1, for example 2, 3, 4 or 5; b.gtoreq.1, for example 2, 3, 4 or 5; r is R 11 And R is 12 Identical or different, each independently selected from C 1 ～C 20 A hydrocarbon group; dn is an N-or O-containing coordinating group. In some embodiments, R 11 And R is 12 Identical or different, each independently selected from C 1 ～C 20 Alkyl radicals, e.g. C 1 ～C 6 Alkyl, C 6 ～C 8 Alkyl, C 9 ～C 12 Alkyl, C 13 ～C 16 Alkyl, C 17 ～C 20 An alkyl group. In some embodiments, the aluminate coupling agent comprises one or more of distearoyloxy isopropyl aluminate, aluminum diisopropoxyacetoacetate, isopropyl bis (glyceryl distearate) aluminate, isopropyl bis (diethylene glycol oleate) aluminate, isopropyl bis (pentaerythritol tristearate) aluminate.
According to some embodiments of the invention, the phosphate coupling agent comprises one or more of 2-hydroxyethyl methacrylate phosphate, di (methacryloxyethyl) hydrogen phosphate, bis (dioctyl oxyphosphate) ethylene titanate, isopropyl dioleoyl (dioctyl phophophoxyoxy) titanate, diethyl propyl di (acetylacetonate) titanate, or tetra isopropyl di (dioctyl phophoxyoxy) titanate.
According to some embodiments of the present application, the borate coupling agent has the general structural formula ((R) 13 O) a -B(Dn)(R 14 COO) b A.gtoreq.1, for example 2, 3, 4 or 5; b.gtoreq.1, for example 2, 3, 4 or 5; r is R 13 And R is 14 Identical or different, each independently C 1 ～C 20 A hydrocarbon group; dn is an N-or O-containing coordinating group. In some embodiments, R 13 And R is 14 Identical or different, each independently selected from C 1 ～C 20 Alkyl radicals, e.g. C 1 ～C 6 Alkyl, C 6 ～C 8 Alkyl, C 9 ～C 12 Alkyl, C 13 ～C 16 Alkyl, C 17 ～C 20 An alkyl group. In some embodiments, the borate coupling agent comprises one or more of isostearyloxy isopropyl borate, isopropyl bis (diglycol distearate), isopropyl bis (diglycol oleate), isopropyl bis (pentaerythritol tristearate) borate.
According to some embodiments of the invention, the metal alkyl compound comprises a metal having the general formula (R 15 ) y M, wherein R 15 Selected from C1-C20 alkyl, M is Ti, zn, mg,Sn or Al, y > 1. In some embodiments, R 15 Selected from C1-C15 alkyl groups. In some embodiments, R 15 Selected from C1-C10 alkyl groups. In some embodiments, R 15 Selected from C1-C6 alkyl groups. According to some embodiments of the invention, y is a positive integer between 1 and 4, for example 1, 2, 3 or 4. In some embodiments, the metal alkyl compound includes one or more of ethylzinc, triethylaluminum, tetrabutyltin, dibutylzinc, or n-butylethylmagnesium.
According to some embodiments of the invention, the diffusing agent comprises a polymer having R 16 -O-R 17 Ether compounds of the general formula, wherein R 16 And R is 17 Identical or different, each independently selected from C 1 ～C 20 A hydrocarbon group. In some embodiments, R 16 And R is 17 Each independently selected from C 1 ～C 10 A hydrocarbon group. In some embodiments, R 16 And R is 17 Each independently selected from C1-C20 alkyl (e.g., C 1 ～C 6 Alkyl, C 5 ～C 8 Alkyl, C 9 ～C 12 Alkyl, C 13 ～C 16 Alkyl, C 17 ～C 20 Alkyl), C3-C10 cycloalkyl, C6-C10 aryl, C7-C10 alkylaryl, and C7-C10 arylalkyl.
According to some embodiments of the invention, the diffusing agent comprises a polymer having R 18 COOR 19 、 One or more of the ester compounds of the general formula, R 18 、R 19 And R' are each independently selected from C 1 ～C 20 Hydrocarbyl radicals G being divalent or trivalent C 1 ～C 20 Hydrocarbyl, optionally G is substituted with hydroxy. In some embodiments, R 18 And R is 19 Each independently selected from C 1 ～C 20 Alkyl radicals, e.g. C 1 ～C 6 Alkyl, C 5 ～C 8 Alkyl, C 9 ～C 12 Alkyl, C 13 ～C 16 Alkyl, C 17 ～C 20 An alkyl group. In some embodiments, R 18 And R is 19 Each independently selected from C 1 ～C 10 A hydrocarbon group. In some embodiments, R 18 And R is 19 Each independently selected from the group consisting of C3-C10 cycloalkyl, C6-C10 aryl, C7-C10 alkylaryl, and C7-C10 arylalkyl. In some embodiments, G is C 1 ～C 20 Alkylene of (C), e.g. C 1 ～C 6 Alkylene group, C 5 ～C 8 Alkylene group, C 9 ～C 12 Alkylene group, C 13 ～C 16 Alkylene group, C 17 ～C 20 Alkylene groups of (a).
According to some embodiments of the invention, the diffusing agent comprises a polymer havingOne or more of the ketones of the general formula, wherein R 20 And R is 21 Identical or different, each independently selected from C 1 ～C 20 A hydrocarbon group. In some embodiments, R 20 And R is 21 Each independently selected from C 1 ～C 10 A hydrocarbon group. In some embodiments, R 20 And R is 21 Each independently selected from C1-C20 alkyl (e.g., C 1 ～C 6 Alkyl, C 5 ～C 8 Alkyl, C 9 ～C 12 Alkyl, C 13 ～C 16 Alkyl, C 17 ～C 20 Alkyl), C3-C10 cycloalkyl, C6-C10 aryl, C7-C10 alkylaryl, and C7-C10 arylalkyl.
According to some embodiments of the invention, the diffusing agent comprises one or more of n-butyl ether, n-pentyl ether, hexyl ether, octyl ether, tributyl citrate, dioctyl succinate, dibutyl glutarate, dioctyl adipate, dibutyl sebacate, acetophenone, methyl ethyl ketone, methyl amyl ketone, butanone, hexanone.
According to some embodiments of the invention, the adjuvant further comprises an accelerator. In some embodiments, theThe accelerator comprises a catalyst havingOne or more of the metal-organic compounds of the formula R 22 Selected from C 1 ～C 20 A hydrocarbon group; m is M 2 Is Zn, mg, sn, al, ti; z > 1, for example 1, 2, 3, 4 or 5. In some embodiments, R 22 Selected from C1-C20 alkyl (e.g. C 1 ～C 6 Alkyl, C 5 ～C 8 Alkyl, C 9 ～C 12 Alkyl, C 13 ～C 16 Alkyl, C 17 ～C 20 Alkyl), C3-C10 cycloalkyl, C6-C10 aryl, C7-C10 alkylaryl, and C7-C10 arylalkyl.
According to some embodiments of the invention, the accelerator comprises a catalyst having (R 23 ) q M 2 One or more of the metal-organic compounds of the formula R 23 Selected from C 1 ～C 20 Hydrocarbyl, M 2 Is Zn, mg, sn, al, ti; q is greater than 1; for example 1, 2, 3, 4 or 5. In some embodiments, R 23 Selected from C1-C20 alkyl (e.g. C 1 ～C 6 Alkyl, C 5 ～C 8 Alkyl, C 9 ～C 12 Alkyl, C 13 ～C 16 Alkyl, C 17 ～C 20 Alkyl), C3-C10 cycloalkyl, C6-C10 aryl, C7-C10 alkylaryl, and C7-C10 arylalkyl.
According to some embodiments of the invention, the accelerator comprises a catalyst havingOne or more of the metal-organic compounds of the formula R 24 Selected from C 1 ～C 20 Hydrocarbyl, M 2 Is Zn, mg, sn, al, ti; i > 1, for example 1, 2, 3, 4 or 5. In some embodiments, R 24 Selected from C1-C20 alkyl (e.g. C 1 ～C 6 Alkyl, C 5 ～C 8 Alkyl, C 9 ～C 12 Alkyl, C 13 ～C 16 Alkyl, C 17 ～C 20 Alkyl), C3-C10 cycloalkyl, C6-C10 aryl, C7-C10 alkylarylAnd C7-C10 aralkyl.
According to some embodiments of the invention, the accelerator comprises one or more of titanium tetraethoxide, titanium tetrabutoxide, stannous octoate, magnesium acetate, magnesium 2-ethylbutyrate, aluminum ethoxide, tin acetate, zinc glutarate, zinc adipate, magnesium glutarate, tin glutarate, magnesium laurate, magnesium stearate, dibutyl zinc, tetrabutyl tin, aluminum triisopropoxide, magnesium tert-butoxide, or n-butylethyl magnesium.
According to some embodiments of the invention, the dispersing agent, molecular weight increasing agent and accelerator comprise 0.1-2%, 0.5-5% and 5×10% of the mass of the polyester intermediate, respectively -4 ～15×10 -4 ％。
According to some embodiments of the invention, the magnesium-containing compound is 0.01 to 10 moles per mole of titanium-containing compound, which may be, for example, 0.05 moles, 0.1 moles, 0.3 moles, 0.5 moles, 0.7 moles, 0.9 moles, 1.5 moles, 2.0 moles, 3.0 moles, 4.0 moles, 5.0 moles, 6.0 moles, 7.0 moles, 8.0 moles, 9.0 moles, or any value therebetween. In some embodiments, the magnesium-containing compound is present in an amount of 0.2 to 5 moles, for example 0.2 to 1 mole, per mole of titanium-containing compound.
In some embodiments, the zinc-containing compound is 0.01 to 10 moles per mole of titanium-containing compound, and may be, for example, 0.05 moles, 0.1 moles, 0.3 moles, 0.5 moles, 0.7 moles, 0.9 moles, 1.5 moles, 2.0 moles, 3.0 moles, 4.0 moles, 5.0 moles, 6.0 moles, 7.0 moles, 8.0 moles, 9.0 moles, or any value therebetween. In some embodiments, the zinc-containing compound is present in an amount of 0.1 to 5 moles, for example 0.1 to 1 mole, per mole of titanium-containing compound.
In some embodiments, the hydroxyl-containing compound is 1 to 20 moles per mole of titanium-containing compound, which may be, for example, 1.5 moles, 2.0 moles, 2.5 moles, 3.0 moles, 3.5 moles, 4.0 moles, 4.5 moles, 6.0 moles, 7.0 moles, 8.0 moles, 10.0 moles, 12.0 moles, 14.0 moles, 16.0 moles, 18.0 moles, or any value therebetween. In some embodiments, the hydroxyl-containing compound is present in an amount of 1 to 10 moles, for example 1 to 5 moles, per mole of titanium-containing compound.
In some embodiments, the carboxylic-containing compound is 0.01 to 0.5 mole per mole of titanium-containing compound, which may be, for example, 0.05 mole, 0.07 mole, 0.09 mole, 0.15 mole, 0.20 mole, 0.25 mole, 0.30 mole, 0.35 mole, 0.40 mole, 0.45 mole, or any value therebetween. In some embodiments, the carboxyl-containing compound is in the range of 0.1 to 0.5 moles per mole of titanium-containing compound.
In some embodiments, the epoxy-containing compound is 0.01 to 1 mole per mole of titanium-containing compound, which may be, for example, 0.05 mole, 0.07 mole, 0.09 mole, 0.15 mole, 0.20 mole, 0.25 mole, 0.30 mole, 0.35 mole, 0.40 mole, 0.45 mole, or any value therebetween. In some embodiments, the epoxy-containing compound is present in an amount of 0.1 to 0.5 moles per mole of titanium-containing compound.
In some embodiments, the concentration of elemental titanium in the catalyst is 1 to 10wt%, e.g., 1.5wt%, 2.0wt%, 2.5wt%, 3.0wt%, 3.5wt%, 4.0wt%, 4.5wt%, 5.0wt%, 5.5wt%, 6.0wt%, 6.5wt%, 7.0wt%, 7.5wt%, 8.0wt%, 8.5wt%, 9.0wt%, 9.5wt%, or any value therebetween. In some embodiments, the concentration of elemental titanium in the catalyst is from 3 to 10wt%.
According to some embodiments of the invention, the titanium-containing compound is selected from the group consisting of the general formula Ti (OR 1 ) m X 4-m One OR more of the compounds shown and titanium oxides, of the general formula Ti (OR 1 ) m X 4-m Wherein R is 1 Is C 2 -C 10 Is a hydrocarbon group of (2); x is halogen, such as chlorine, bromine or iodine; m is an integer from 0 to 4, for example 0, 1, 2, 3 or 4. In some embodiments, R 1 Is C 2 -C 10 Is a hydrocarbon group of (a). In some embodiments, R 1 Is C 2 -C 6 For example ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl or hexyl.
According to some embodiments of the invention, the titanium-containing compound is selected from one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, and titanium dioxide.
According to some embodiments of the invention, the magnesium-containing compound is selected from the group consisting of compounds of the general formula Mg (OR 2 ) 2 X 2-n Compounds of the formula Mg (OOR) 3 ) 2 One OR more of the compounds shown, of the general formula Mg (OR 2 ) 2 X 2-n Wherein R is 2 Is C 2 -C 10 X is halogen, such as chlorine, bromine or iodine; n is an integer from 0 to 2, for example 0, 1 or 2; the general formula Mg (OOR) 3 ) 2 Wherein R is 3 Is C 2 -C 10 Is a hydrocarbon group of (a). In some embodiments, R 2 Is C 2 -C 6 For example ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl or hexyl. In some embodiments, R 3 Is C 2 -C 6 For example ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl or hexyl.
According to some embodiments of the invention, the magnesium-containing compound is selected from one or more of magnesium dichloride, magnesium dibromide, magnesium diiodide, magnesium diethoxide, magnesium dipropoxide, magnesium diisopropyloxide, magnesium dibutoxide, magnesium diisobutoxide, magnesium acetate, magnesium propionate, and magnesium butyrate.
According to some embodiments of the invention, the zinc-containing compound is selected from the group consisting of general formula Zn (OOR 4 ) 2 One or more of the compounds shown and zinc halides, the general formula Zn (OOR 4 ) 2 Wherein R is 4 Is C 2 -C 20 Is a hydrocarbon group of (a). In some embodiments, R 4 Is C 2 -C 10 Is a hydrocarbon group of (a). In some embodiments, R 4 Is C 2 -C 6 For example ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl or hexyl.
According to some embodiments of the invention, the zinc-containing compound is selected from one or more of zinc dichloride, zinc dibromide, zinc diiodide, zinc acetate, zinc propionate, zinc butyrate, and zinc stearate.
According to some embodiments of the invention, the hydroxyl-containing compound is selected from one or more of a monohydric alcohol and a polyhydric alcohol. In some embodiments, the monohydric alcohol is C 1 -C 10 Is a monohydric alcohol of (a). In some embodiments, the polyol is a 2-6-polyol, e.g., C 2 -C 10 Glycol, C 3 -C 15 Is (C) a triol 4 -C 20 Tetrahydric alcohol, C 5 -C 20 Five-membered alcohol or C 6 -C 20 Is a polyol.
According to some embodiments of the invention, the hydroxyl-containing compound is selected from one or more of methanol, ethanol, isopropanol, n-butanol, n-pentanol, 2-pentanol, 3-pentanol, ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, pentaerythritol, and sorbitol.
According to some embodiments of the invention, the carboxyl-containing compound is selected from one or more of monocarboxylic acids and polycarboxylic acids. In some embodiments, the monocarboxylic acid is C 1 -C 20 Is a monocarboxylic acid of (2). In some embodiments the polycarboxylic acid is C 2 -C 20 Dicarboxylic acids or C 3 -C 20 Is a tricarboxylic acid of (2).
According to some embodiments of the invention, the carboxyl group containing compound is selected from at least one of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, stearic acid, oxalic acid, malonic acid, succinic acid, glutaric acid and adipic acid.
According to some embodiments of the invention, the epoxy-containing compound is selected from the group consisting of general formulasOne or more of the compounds indicated, the formula>Wherein R is 5 And R is 6 The same or different, each independently selected from hydrogen or a C1-C20 hydrocarbyl group. In some embodiments, R 5 And R is 6 Each independently selected from hydrogen or a C1-C10 hydrocarbyl group. In some embodiments, R 5 And R is 6 Each independently selected from hydrogen or C1-C10 alkyl, such as C1-C6 alkyl. According to some embodiments of the invention, the epoxy-containing compound is selected from one or more of ethylene oxide, propylene oxide, 1, 2-butylene oxide, 1, 4-butylene oxide, or 1, 2-pentane oxide.
In this application, the C1-C6 alkyl is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl or hexyl. The C1-C6 alkylene is selected from methylene, ethylene, propylene, isopropylene, butylene, isobutylene, tertbutylene, n-pentylene, isopentylene, tertbentylene, hexylene, cyclopentylene or cyclohexylene. The C6-C20 aryl is selected from phenyl, biphenyl, methyl-substituted phenyl, ethyl-substituted phenyl, propyl-substituted phenyl or butyl-substituted phenyl.
According to some embodiments of the invention, the method of preparing the first catalyst comprises the steps of:
step A: reacting a portion of the hydroxyl-containing compound with the carboxyl-containing compound to obtain a first solution;
and (B) step (B): and (C) adding the rest of the hydroxyl-containing compound, the magnesium-containing compound, the zinc-containing compound and the titanium-containing compound into the first solution in the step (A), and reacting to obtain a second solution.
According to some embodiments of the invention, the method further comprises step C: and standing and curing the second solution.
According to some embodiments of the invention, in step a, the reaction temperature is 60-200 ℃, e.g. 70 ℃, 90 ℃, 100 ℃, 110 ℃, 130 ℃, 150 ℃, 170 ℃, 190 ℃ or any value in between. In some embodiments, in step a, the reaction time is 0.5 to 5 hours, for example 1 hour, 2 hours, 3 hours or 4 hours. According to some embodiments of the invention, in step B, the reaction temperature is 40-100 ℃, e.g. 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or any value in between. In some embodiments, in step B, the reaction time is 0.5 to 5 hours, for example 1 hour, 2 hours, 3 hours or 4 hours. According to some embodiments of the invention, the curing temperature is 20-60 ℃, e.g. 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃ or any value in between. According to some embodiments of the invention, in step C, the maturation time is between 5 and 24 hours. In some embodiments, in step C, the maturation time is 7h, 9h, 10h, 13h, 15h, 17h, 19h, 20h, or 22h.
The first catalyst of the invention ensures the catalytic activity and selectivity of the catalyst by compounding the magnesium-containing compound, the zinc-containing compound and the titanium-containing compound and dispersing the product obtained by the reaction of the hydroxyl-containing compound and the carboxyl-containing compound. The preparation process of the first catalyst is simple and convenient, the configuration condition is mild, and the raw material cost is low.
According to some embodiments of the invention, the method of preparing the second catalyst comprises the steps of:
step M: reacting a hydroxyl group-containing compound, an epoxy group-containing compound, and one selected from a zinc-containing compound and a magnesium-containing compound to obtain a third solution;
step N: adding another zinc-containing compound and magnesium-containing compound, a titanium-containing compound and optionally a hydroxyl-containing compound into the third solution in the step M, and reacting to obtain a fourth solution.
According to some embodiments of the invention, the method of preparation comprises the steps of:
step M1: reacting a hydroxyl group-containing compound, an epoxy group-containing compound with a zinc-containing compound to obtain a third solution,
step N1: adding a magnesium-containing compound, a titanium-containing compound and an optional hydroxyl-containing compound into the third solution in the step M1, and reacting to obtain a fourth solution.
According to some embodiments of the invention, the method of preparation comprises the steps of:
step M1: reacting a portion of the hydroxyl-containing compound, the epoxy-containing compound, and the zinc-containing compound to obtain a third solution, preferably step M1 comprises mixing a portion of the hydroxyl-containing compound and the epoxy-containing compound to obtain a first mixture, which is reacted with the zinc-containing compound to obtain the third solution, more preferably at a temperature of 30-80 ℃, such as 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or any value therebetween. In some embodiments, the mixing is for a period of time ranging from 0.5 to 5 hours, such as 1 hour, 2 hours, 3 hours, or 4 hours;
step N1: and (3) adding a magnesium-containing compound, a titanium-containing compound and the rest of hydroxyl-containing compounds into the third solution in the step M1, and reacting to obtain a fourth solution.
According to some embodiments of the invention, the method of preparation comprises the steps of:
step M1: reacting the hydroxyl-containing compound, the epoxy-containing compound and the zinc-containing compound to obtain a third solution, preferably step M1 comprises mixing the hydroxyl-containing compound and the epoxy-containing compound to obtain a first mixture, which is reacted with the zinc-containing compound to obtain the third solution, more preferably at a temperature of 30-80 ℃, such as 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or any value therebetween. In some embodiments, the mixing is for a period of time ranging from 0.5 to 5 hours, such as 1 hour, 2 hours, 3 hours, or 4 hours;
Step N1: and adding a magnesium-containing compound and a titanium-containing compound into the third solution in the step M1, and reacting to obtain a fourth solution.
According to some embodiments of the invention, the method of preparation comprises the steps of:
step M2: reacting a hydroxyl group-containing compound, an epoxy group-containing compound and a magnesium-containing compound to obtain a third solution,
step N2: and adding a zinc-containing compound, a titanium-containing compound and an optional hydroxyl-containing compound into the third solution in the step M2, and reacting to obtain a fourth solution.
According to some embodiments of the invention, the method of preparation comprises the steps of:
step M2: reacting a portion of the hydroxyl-containing compound, the epoxy-containing compound, and the magnesium-containing compound to obtain a third solution, preferably step M2 comprises mixing a portion of the hydroxyl-containing compound and the epoxy-containing compound to obtain a first mixture, the first mixture being reacted with the magnesium-containing compound to obtain the third solution, more preferably at a temperature of 30-80 ℃, such as 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or any value therebetween. In some embodiments, the mixing is for a period of time ranging from 0.5 to 5 hours, such as 1 hour, 2 hours, 3 hours, or 4 hours;
Step N2: and adding the zinc-containing compound, the titanium-containing compound and the rest of the hydroxyl-containing compound into the third solution in the step M2, and reacting to obtain a fourth solution.
According to some embodiments of the invention, the method of preparation comprises the steps of:
step M2: reacting the hydroxyl-containing compound, the epoxy-containing compound and the magnesium-containing compound to obtain a third solution, preferably step M2 comprises mixing the hydroxyl-containing compound and the epoxy-containing compound to obtain a first mixture, which is reacted with the magnesium-containing compound to obtain the third solution, more preferably at a temperature of 30-80 ℃, such as 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or any value therebetween. In some embodiments, the mixing is for a period of time ranging from 0.5 to 5 hours, such as 1 hour, 2 hours, 3 hours, or 4 hours;
step N2: and adding a zinc-containing compound and a titanium-containing compound into the third solution in the step M2, and reacting to obtain a fourth solution.
According to some embodiments of the invention, the method further comprises step O: and standing and curing the fourth solution.
According to some implementations of the invention, the reaction temperature in steps M, M, M2 is 0-100 ℃, e.g., 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, or any value therebetween. In some embodiments, in steps M, M, M2, the reaction time is from 0.5 to 5 hours, e.g., 1 hour, 2 hours, 3 hours, or 4 hours. In some embodiments, in steps N, N, N2, the reaction temperature is 25-100 ℃, e.g., 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, or any value therebetween. In some embodiments, in steps N, N, N2, the reaction time is from 0.5 to 5 hours, e.g., 1 hour, 2 hours, 3 hours, or 4 hours. In some embodiments, in step O, the curing temperature is 20 to 60 ℃, e.g., 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, or any value therebetween. In some embodiments, in step O, the maturation time is 5-24 hours, for example 7 hours, 9 hours, 10 hours, 13 hours, 15 hours, 17 hours, 19 hours, 20 hours or 22 hours.
The second catalyst of the invention disperses and complexes the magnesium-containing compound, the zinc-containing compound and the titanium compound through the product obtained by the reaction of the hydroxyl-containing compound and the epoxy-containing compound, thereby regulating and controlling the catalytic activity and the selectivity of the titanium-based catalyst. The method has the advantages of simple process, mild configuration conditions and low raw material cost.
According to some embodiments of the invention, the aliphatic dibasic acid is C 2 ～C 16 Dibasic acid of C 2 ～C 16 Aliphatic dibasic acid anhydride or C 2 ～C 16 One or more of the aliphatic dibasic acid halides of (a). According to some embodiments of the invention, the aliphatic dibasic acid is C 2 ～C 10 Dibasic acid of C 2 ～C 10 Aliphatic dibasic acid anhydride or C 2 ～C 10 One or more of the aliphatic dibasic acid halides of (a). In some embodiments of the invention, the aliphatic dibasic acid comprises one or more of succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1, 4-cyclohexanedicarboxylic acid, glutaric anhydride, or malonyl chloride.
According to some embodiments of the invention, the aromatic diacid is selected from C 8 ～C 16 Aromatic dibasic acid, C 8 ～C 16 Aromatic dibasic acid anhydride or C 8 ～C 16 One or more of the aromatic dicarboxylic acid halides of (a). In some embodiments of the invention, the aromatic diacid includes one or more of terephthalic acid, terephthalic anhydride, terephthaloyl halide, isophthalic acid, isophthalic anhydride, isophthaloyl halide, naphthalene dicarboxylic acid, naphthalene dicarboxylic anhydride, naphthalene dicarboxylic acid halide.
According to some embodiments of the invention, the aliphatic diol is selected from C 2 ～C 10 One or more of the aliphatic diols of (a). According to some embodiments of the invention, the aliphatic diol is C 2 ～C 6 One or more of the aliphatic diols of (a). In some embodiments of the invention, the aliphatic diol comprises one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, or a polyether diol.
According to some embodiments of the invention, the molar content ratio of hydroxyl functional groups to the total functional groups of carboxylic acid, anhydride and acid halide in the aliphatic dibasic acid, aromatic dibasic acid and aliphatic diol is (1.1-2.5): 1. and/or
According to some embodiments of the invention, in step S1, the esterification reaction is carried out at a temperature of 150 ℃ to 250 ℃, at an absolute pressure of 40KPa to 110KPa, and for a reaction time of 2h to 6h. According to some embodiments of the invention, the temperature of the esterification reaction is 150 ℃, 170 ℃, 190 ℃, 210 ℃, 230 ℃, 250 ℃ and any value in between. According to some embodiments of the invention, the absolute pressure of the esterification reaction is 40KPa, 60KPa, 80KPa, 100KPa, 110KPa and any value between them. According to some embodiments of the invention, the time of the esterification reaction is 2h, 3h, 4h, 5h, 6h and any value therebetween.
According to some embodiments of the invention, in step S2, the polycondensation reaction comprises a first polycondensation reaction and a second polycondensation reaction that are performed sequentially. According to some embodiments of the invention, the temperature of the first polycondensation reaction is 200 ℃ to 250 ℃, the absolute pressure is 1KPa to 5KPa, and the reaction time is 1h to 3h. According to some embodiments of the invention, the temperature of the second polycondensation reaction is 200 ℃ to 250 ℃, the absolute pressure is 10Pa to 300Pa, and the reaction time is 1h to 3h. According to some embodiments of the invention, the temperature of the first and/or second polycondensation reaction is 205 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃ and any value therebetween. According to some embodiments of the invention, the absolute pressure of the first polycondensation reaction is 1.5KPa, 2KPa, 2.5KPa, 3KPa, 4KPa and any value therebetween. According to some embodiments of the invention, the absolute pressure of the second polycondensation reaction is 50Pa, 100Pa, 150Pa, 200Pa, 250Pa, and any value therebetween. According to some embodiments of the invention, the first and/or second polycondensation reaction is carried out for a time of 1.5h, 2h, 2.5h and any value therebetween.
According to some embodiments of the invention, step S2 further comprises granulating and drying after the polycondensation reaction to obtain the polyester intermediate.
According to some embodiments of the invention, in step S3, the chain extension reaction is carried out at a temperature of 25 ℃ to 100 ℃ for a time of 4 hours to 24 hours. According to some embodiments of the invention, the temperature of the chain extension reaction is 25 ℃, 35 ℃, 45 ℃, 55 ℃, 65 ℃, 75 ℃, 85 ℃, 95 ℃, 100 ℃ and any value therebetween. According to some embodiments of the invention, the time of the chain growth reaction is 4h, 8h, 12h, 16h, 20h, 24h and any value in between.
The inventor of the invention finds that the polycondensation of polyester is an equilibrium reaction in the polymerization process of biodegradable aliphatic-aromatic copolyester, the chain extension, chain breakage and chain transfer reaction are carried out simultaneously, when the three reactions reach equilibrium, the polyester has a certain viscosity and a lower carboxyl end group, the polycondensation reaction is stopped at the moment, and the chain extension reaction is carried out under the low temperature and the low temperature condition, so that the polyester product with low carboxyl end group, less gel point and high molecular weight can be prepared.
A second aspect of the invention provides the use of an aliphatic-aromatic copolyester according to the first aspect in a polyester film material or a polyester sheet material.
The invention has the following beneficial effects:
(1) The biodegradable aliphatic-aromatic copolyester has high molecular weight and narrow molecular weight distribution, and can be applied to the field of films/sheets; and compared with the prior art, the carboxyl end group of the product is lower, and has excellent biodegradation controllability.
(2) The biodegradable aliphatic-aromatic copolyester film/sheet has the advantages of smooth surface, less gel point, and excellent downstream modified processing stability and printability.
Detailed Description
The present invention will be further illustrated by the following specific examples, but the scope of the present invention is not limited thereto.
The carboxyl end groups of the polymers were tested by acid-base titration, as specified in GB/T32366-2015. The mixed solution is phenol-chloroform with a volume ratio of 2:3. The standard titration solution was potassium hydroxide-benzyl alcohol at a concentration of 0.01mol/L, and was prepared and calibrated with reference to 4.24 in GB/T601-2002. The bromophenol blue indicator concentration was 0.2%. And (3) test preparation: 0.5g of the sample was dissolved in 25.00ml of a phenol-chloroform mixed solvent.
Testing gel point of polyester sample film/sheet by projection method, wherein the test comprises 4 layers of film/sheet, each film size is at least 200mm 2 At 254mm 2 For the best, to the size >Counting and counting the gel points of 0.6mm or 0.3-0.6 mm respectively.
The molecular weight and molecular weight distribution of the polymer are determined by gel permeation chromatography, chloroform is used as a solvent, a Waters-e2695 instrument is used for testing, and polystyrene is used as a standard sample.
Catalyst preparation example
Preparation example 1
54.9g of 1, 4-butanediol, 3.4g of acetic acid and heating at 90 ℃ for 0.5h are sequentially added into the reactor to obtain a transparent solution A1; then 10.1g of butanol, 5.2g of ethanol, 5.2g of magnesium bromide, 7.9g of zinc bromide and 26.9g of titanium tetrachloride are sequentially added, the mixture is stirred uniformly and heated for 2 hours at 60 ℃ to obtain a transparent solution B1, and the transparent solution B is kept stand and cured for 12 hours at 50 ℃ to obtain a catalyst solution C1.
Preparation example 2
36.0g of ethylene glycol, 8.2g of adipic acid and heating at 110 ℃ for 1 hour are added into the reactor to obtain a transparent solution A2; then 10.1g of propanol, 5.2g of ethanol, 9.3g of magnesium butoxide, 4.8g of zinc chloride and 11.6g of titanium dioxide are sequentially added, and the mixture is uniformly stirred and heated at 90 ℃ for 3 hours to obtain a solution B2; standing and curing for 20 hours at 40 ℃ to obtain a catalyst solution C2.
Preparation example 3
Adding 32.7g of 1, 3-propanediol into a reactor, heating 16.0g of stearic acid at 180 ℃ for 2 hours to obtain a transparent solution A3; then 10.2g of sorbitol, 7.8g of magnesium acetate, 11.2g of zinc iodide and 41.1g of tetraisopropyl titanate are sequentially added, and the mixture is uniformly stirred and heated at 80 ℃ for 4 hours to obtain a transparent solution B3; standing and curing for 24 hours at the temperature of 25 ℃ to obtain a catalyst solution C3.
Preparation example 4
Adding 31.6g of 1, 5-pentanediol and 7.2g of succinic acid into a reactor, and heating for 1h at 135 ℃ to obtain a transparent solution A4; then 10.1g of pentaerythritol, 5.2g of ethanol, 7.8g of magnesium acetate, 7.9g of zinc acetate and 49.2g of tetrabutyl titanate are sequentially added, and the mixture is uniformly stirred and heated at 70 ℃ for 3 hours to obtain a transparent solution B4; standing and curing for 20 hours at the temperature of 30 ℃ to obtain a catalyst solution C4.
Preparation example 5
62.8g of 1, 4-butanediol, 3.4g of acetic acid and heating at 90 ℃ for 0.5h are sequentially added into the reactor to obtain a transparent solution A5; then 10.1g of butanol, 5.2g of ethanol, 26.9g of titanium tetrachloride and 5.2g of magnesium bromide are sequentially added, and the mixture is stirred uniformly and heated for 2 hours at 60 ℃ to obtain a transparent solution B5, and the transparent solution B5 is kept stand and cured for 12 hours at 50 ℃ to obtain a catalyst solution C5.
Preparation example 6
60.1g of 1, 4-butanediol, 3.4g of acetic acid and heating at 90 ℃ for 0.5h are sequentially added into the reactor to obtain a transparent solution A6; then 10.1g of butanol, 5.2g of ethanol, 26.9g of titanium tetrachloride and 7.9g of zinc bromide are sequentially added, and the mixture is stirred uniformly and heated for 2 hours at 60 ℃ to obtain a transparent solution B6, and the transparent solution B6 is kept stand and cured for 12 hours at 50 ℃ to obtain a catalyst solution C6.
Preparation example 7
58.3g of 1, 4-butanediol is sequentially added into the reactor, the mixture is heated for 0.5h at 90 ℃, 10.1g of butanol, 5.2g of ethanol, 26.9g of titanium tetrachloride, 5.2g of magnesium bromide and 7.9g of zinc bromide are sequentially added, the mixture is stirred and heated uniformly for 2h at 60 ℃ to obtain a transparent solution B7, and the transparent solution B7 is stood and cured for 12h at 50 ℃ to obtain a catalyst solution C7.
Preparation example 8
57.3g of 1, 4-butanediol, 6.4g of zinc acetate and 2.5g of ethylene oxide are sequentially added into the reactor, heated and stirred for 4 hours at 60 ℃, and then 2 hours of zinc oxide is slowly added into the reactor for reaction at 10 ℃ for 4 hours to obtain a solution A8; then 10.1g of butanol, 5.2g of ethanol, 5.2g of magnesium bromide and 26.9g of titanium tetrachloride are sequentially added, evenly stirred, heated at 60 ℃ for reaction for 2 hours to obtain a solution B8, and the solution B8 is obtained after standing and curing for 24 hours at 25 ℃.
Preparation example 9
48.1g of ethylene glycol, 7.4g of zinc propionate and 3.3g of propylene oxide are sequentially added into a reactor, heated and stirred at 60 ℃ for 4 hours, and then reacted at 40 ℃ for 1 hour to obtain a solution A9; then 8.2g of propanol, 5.2g of ethanol, 9.3g of magnesium butoxide and 26.9g of titanium tetrachloride are sequentially added, and the mixture is stirred uniformly and heated at 60 ℃ for reaction for 2 hours to obtain a solution B9; and (3) standing and curing for 20 hours at 40 ℃ to obtain a catalyst solution C9.
Preparation example 10
34.2g of 1, 3-propanediol, 22.0g of zinc stearate and 4 hours of heating and stirring at 60 ℃ are sequentially added into a reactor, 4.1g of butylene oxide is slowly added, and the reaction is carried out at 50 ℃ for 1 hour to obtain a solution A10; then 8.2g of amyl alcohol, 5.2g of ethanol, 7.8g of magnesium acetate and 26.9g of titanium tetrachloride are sequentially added, and the mixture is stirred uniformly and heated at 60 ℃ for reaction for 2 hours to obtain a solution B10; and standing and curing for 20 hours at 50 ℃ to obtain a catalyst solution C10.
PREPARATION EXAMPLE 11
61.7g of 1, 4-butanediol, 5.9g of zinc chloride and 2.5g of ethylene oxide are added into the reactor, heated and stirred at 60 ℃ for 4 hours, and then 2 hours of zinc oxide is slowly added into the reactor to react at 10 ℃ for 4 hours to obtain a solution A11; then 7.8g of magnesium acetate and 41.09g of tetraisopropyl titanate are sequentially added, and the mixture is uniformly stirred and heated at 80 ℃ for 2 hours to obtain a solution B11; and standing and curing for 24 hours at 25 ℃ to obtain a catalyst solution C11.
Preparation example 12
62.5g of 1, 4-butanediol, 6.4g of zinc acetate and heating and stirring for 4 hours at 60 ℃ are sequentially added into a reactor, 2.5g of ethylene oxide is slowly added, and the reaction is carried out for 4 hours at 10 ℃ to obtain a solution A12; then 10.1g of butanol, 5.2g of ethanol, 26.9g of titanium tetrachloride and stirring uniformly are added in sequence, the mixture is heated and reacted for 2 hours at 60 ℃ to obtain a solution B12, and the solution B12 is obtained after standing and curing for 24 hours at 25 ℃.
Preparation example 13
59.8g of 1, 4-butanediol, 6.4g of zinc acetate and heating and stirring at 60 ℃ for 4 hours, and reacting at 10 ℃ for 4 hours to obtain a solution A13; then 10.1g of butanol, 5.2g of ethanol, 5.2g of magnesium bromide, 26.9g of titanium tetrachloride and the like are sequentially added, stirred uniformly at 60 ℃ and heated for reaction for 2 hours to obtain a solution B13, and the solution B13 is obtained after standing and curing for 24 hours at 25 ℃.
PREPARATION EXAMPLE 14
63.7g of 1, 4-butanediol is added into the reactor, 2.5g of ethylene oxide is slowly added into the reactor, and the reaction is carried out for 4 hours at the temperature of 10 ℃ to obtain a solution A14; then 10.1g of butanol, 5.2g of ethanol, 5.2g of magnesium bromide, 26.9g of titanium tetrachloride and the like are sequentially added, stirred uniformly at 60 ℃ and heated for reaction for 2 hours to obtain a solution B14, and the solution B14 is obtained after standing and curing for 24 hours at 25 ℃.
Examples
Example 1
38.01kg/h of terephthalic acid, 36.22kg/h of adipic acid and 68.70kg/h of 1, 4-butanediol are mixed and stirred, the mixture enters an esterification unit for esterification, the material temperature is 220 ℃, the absolute pressure is 60KPa, the esterified substance is obtained when the esterification rate reaches 98%, the esterified substance continuously enters a polycondensation unit, the reaction temperature is 240 ℃, the absolute pressure is 3KPa, the reaction time is 2h, the absolute pressure is regulated to 200Pa, the polycondensation reaction is continued for 3h, the cooled granulation and drying are carried out to obtain 100kg/h of polyester intermediate, and the polyester intermediate is fully mixed with 0.3kg/h of butyl ether, 3.0kg/h of 2, 4-diphenylmethane diisocyanate and 0.5g/h of tetrabutyltin, and then the polyester product is obtained after the reaction for 4h at 60 ℃.
Example 2
Mixing 43.25kg/h of terephthalic acid, 42.45kg/h of adipic acid, 57.95kg/h of glycol and 0.20kg/h of catalyst solution C, entering an esterification unit for esterification reaction, under the condition of 220 ℃ of material temperature, obtaining an esterified substance when the esterification rate reaches 98%, continuously entering a polycondensation unit for reaction at 200 ℃ and 2KPa of absolute pressure for 1.5h, adjusting the absolute pressure to 200Pa for polycondensation reaction for 3h, cooling, granulating and drying to obtain 100kg/h of polyester intermediate, and fully mixing with 0.3kg/h of tributyl citrate, 1.25g/h of bis (3-isopropenyl-dimethylbenzyl) carbodiimide and 6h of tetraethoxytitanium at 80 ℃ to obtain a polyester product.
Example 3
40.85kg/h of terephthalic acid, 31.46kg/h of succinic acid and 73.83kg/h of 1, 4-butanediol, and 0.18kg/h of catalyst solution C, and then, the mixture is fed into an esterification unit for esterification, the material temperature is 225 ℃ and the absolute pressure is 50KPa, an esterified substance is obtained when the esterification rate reaches 98%, the esterified substance continuously enters a polycondensation unit, the reaction temperature is 230 ℃, the absolute pressure is 3KPa, the reaction time is 2h, the absolute pressure is regulated to 100Pa for polycondensation reaction 3h, 100kg/h of polyester intermediate is obtained by cooling, granulating and drying, and then, after being fully mixed with 0.5kg/h of methyl tertiary butyl ether, 0.9kg/h of 1, 6-hexanediol diglycidyl ether and 1.5g/h of zinc acetate, the polyester product is obtained by reacting for 8h at 60 ℃.
Example 4
Mixing 52.25kg/h of 2, 6-naphthalene dicarboxylic acid chloride, 53.85kg/h of malonyl chloride and 61.2kg/h of ethylene glycol, adding a catalyst solution C1.18 kg/h into an esterification unit for esterification reaction, obtaining an esterified substance when the absolute pressure is 90KPa at 180 ℃, obtaining the esterified substance when the esterification rate reaches 98%, continuously adding the esterified substance into a polycondensation unit at 210 ℃, and obtaining the polycondensation reaction at 2KPa and 1.5h of absolute pressure, adjusting the absolute pressure to 150Pa for polycondensation reaction for 2h, cooling, granulating and drying to obtain 100kg/h of a polyester intermediate, and fully mixing with 0.5kg/h of butanone, 3.4kg/h of 2,2' -bis (4-methyl-2-oxazoline) and 0.75g/h of aluminum ethoxide for reaction for 6h at 70 ℃ to obtain a polyester product.
Example 5
49.25kg/h of terephthaloyl chloride, 31.65kg/h of succinic anhydride, 71.7kg/h of 1, 3-propylene glycol and 0.25kg/h of catalyst solution C are mixed, the mixture enters an esterification unit for esterification reaction, the material temperature is 180 ℃, the absolute pressure is 40KPa, an esterified substance is obtained when the esterification rate reaches 98%, the esterified substance continuously enters a polycondensation unit, the reaction temperature is 220 ℃, the absolute pressure is 2KPa, the reaction time is 1.5h, the absolute pressure is regulated to 80Pa for polycondensation 2.5h, the cooled granulation and drying are carried out to obtain 100kg/h of polyester intermediate, and the polyester intermediate, the octyl ether, the triisostearyl isopropyl titanate and the tin acetate are fully mixed, and then the polyester product is obtained after the reaction is carried out for 8h at 60 ℃.
Example 6
38.05kg/h of 2, 3-naphthalene dicarboxylic acid, 36.75kg/h of azelaic acid and 65.4kg/h of 1, 5-pentanediol are mixed with 0.25kg/h of catalyst solution C, the mixture is put into an esterification unit for esterification reaction, the material temperature is 250 ℃, the absolute pressure is 60KPa, the esterified substance is obtained when the esterification rate reaches 98%, the esterified substance continuously enters a polycondensation unit, the reaction temperature is 250 ℃, the absolute pressure is 1.5KPa, the reaction time is 1h, the absolute pressure is regulated to 60Pa for polycondensation for 3h, 100kg/h of polyester intermediate is obtained by cooling, granulating and drying, and the polyester product is obtained by reacting for 4h at 40 ℃ after the mixture is fully mixed with 0.50kg/h of hexyl ether and 0.82kg/h of ethyl zinc.
Example 7
Mixing 43.25kg/h of terephthalic acid, 42.45kg/h of adipic acid, 57.95kg/h of glycol and 0.20kg/h of catalyst solution C, entering an esterification unit for esterification reaction, wherein the material temperature is 220 ℃, the absolute pressure is 40KPa, obtaining an esterified substance when the esterification rate reaches 98%, continuously entering a polycondensation unit, the reaction temperature is 200 ℃, the absolute pressure is 2KPa, the reaction time is 1.5h, adjusting the absolute pressure to 200Pa for polycondensation reaction for 3h, cooling, granulating and drying to obtain 100kg/h of polyester intermediate, fully mixing with 0.3kg/h of tributyl citrate and 0.9kg/h of bis (3-isopropenyl-dimethylbenzyl) carbodiimide, and reacting for 6h at 80 ℃ to obtain a polyester product.
Example 8-example 10
The only difference from example 1 is that the catalyst was replaced by the respective catalyst solutions C2-C4 to prepare a polyester product.
Comparative example 1-comparative example 3
The only difference from example 1 is that the catalyst was replaced by the respective catalyst solutions C5-C7 to prepare a polyester product.
Example 12-example 15
The only difference from example 1 is that the catalyst was replaced by the respective catalyst solutions C8-C11 to prepare a polyester product.
Comparative example 4-comparative example 6
The only difference from example 1 is that the catalyst was replaced by the respective catalyst solutions C12-C14 to prepare a polyester product.
Comparative example 7
Mixing 38.01kg/h of terephthalic acid, 36.22kg/h of adipic acid and 68.70kg/h of 1, 4-butanediol, adding a catalyst solution C1.18 kg/h, performing esterification reaction in an esterification unit, wherein the material temperature is 220 ℃, the absolute pressure is 80KPa, obtaining an esterified substance when the esterification rate reaches 98%, continuously feeding the esterified substance into a polycondensation unit, the reaction temperature is 240 ℃, the absolute pressure is 3KPa, the reaction time is 2h, continuously performing polycondensation reaction under the condition that the absolute pressure is adjusted to 200Pa for 3.5h, waiting until the torque of a polymerization stirrer rises to the maximum value, finishing the polycondensation reaction, cooling and granulating, and drying to obtain 100kg/h of polyester product.
Comparative example 8
38.01kg/h of terephthalic acid, 36.22kg/h of adipic acid and 68.70kg/h of 1, 4-butanediol are mixed according to the proportion, the mixture enters an esterification unit for esterification, the material temperature is 220 ℃, the absolute pressure is 80KPa, the esterified substance is obtained when the esterification rate reaches 98%, the esterified substance continuously enters a polycondensation unit, the reaction temperature is 240 ℃, the absolute pressure is 3KPa, the reaction time is 2h, the absolute pressure is regulated to 200Pa, the polycondensation reaction is continued for 3h, 100kg/h of polyester intermediate is obtained after cooling, granulating and drying, 1.0kg/h of 2,2' - (1, 3-phenylene) -bisoxazoline and 2.5kg/h of 2, 4-diphenylmethane diisocyanate are fully mixed through a high-speed stirring mixer, and the polyester product is obtained after the reaction extrusion under the condition of 190 ℃ of the same direction double screw.
Comparative example 9
38.01kg/h of terephthalic acid, 36.22kg/h of adipic acid and 68.70kg/h of 1, 4-butanediol are mixed according to the proportion of 0.18kg/h of catalyst solution C, the mixture enters an esterification unit for esterification, the material temperature is 220 ℃, the absolute pressure is 80KPa, an esterified substance is obtained when the esterification rate reaches 98%, the esterified substance continuously enters a polycondensation unit, the reaction temperature is 240 ℃, the absolute pressure is 3KPa, the reaction time is 2h, the absolute pressure is regulated to 200Pa, the polycondensation reaction is continued for 3h, 100kg/h of polyester intermediate melt is obtained, the melt is fully mixed with 3.0kg/h of 2, 4-diphenylmethane diisocyanate through a dynamic mixer, the polyester intermediate is obtained through cooling and granulating and drying, and the polyester product is obtained through reaction for 50h at 80 ℃.
Comparative example 10
The preparation method comprises the steps of mixing 38.01Kg/h of terephthalic acid, 36.22Kg/h of adipic acid, 68.70Kg/h of 1, 4-butanediol, 0.18Kg/h of tetrabutyl titanate 1, 4-butanediol solution (tetrabutyl titanate concentration is 40 wt%) with the mixture, carrying out esterification reaction by an esterification unit, obtaining an esterified substance when the esterification rate reaches 98%, continuously feeding the esterified substance into a polycondensation unit, carrying out polycondensation reaction at the reaction temperature of 240 ℃ and the absolute pressure of 3KPa for 2h, adjusting the absolute pressure to 200Pa for 3h, cooling, granulating and drying to obtain 100Kg/h of polyester intermediate, fully mixing with 0.3Kg/h of butyl ether, 3.0Kg/h of 2, 4-diphenylmethane diisocyanate and 0.5g/h of tetrabutyltin, and carrying out reaction for 4h at the temperature of 60 ℃ to obtain a polyester product.
Comparative example 11
38.01kg/h of terephthalic acid, 36.22kg/h of adipic acid and 68.70kg/h of 1, 4-butanediol are mixed according to the proportion of 0.18kg/h of catalyst solution C, an esterification reaction is carried out by an esterification unit, the material temperature is 220 ℃, the absolute pressure is 80KPa, an esterified substance is obtained when the esterification rate reaches 98%, the esterified substance continuously enters a polycondensation unit, the temperature is 240 ℃, the absolute pressure is 3KPa, the reaction time is 2h, the absolute pressure is regulated to 200Pa, the polycondensation reaction is carried out for 3h, 100kg/h of polyester intermediate is obtained by cooling, granulating and drying, and the polyester product is obtained by reacting for 4h at 60 ℃ after the mixture is fully mixed with 3.0kg/h of 2, 4-diphenylmethane diisocyanate and 0.5g/h of tetrabutyltin.
Comparative example 12
49.25kg/h of terephthaloyl chloride, 31.65kg/h of succinic anhydride, 71.7kg/h of 1, 3-propylene glycol and 0.25kg/h of catalyst solution C are mixed, the mixture enters an esterification unit for esterification reaction, the material temperature is 180 ℃, the absolute pressure is 40KPa, the esterified substance is obtained when the esterification rate reaches 98%, the esterified substance continuously enters a polycondensation unit, the reaction temperature is 220 ℃, the absolute pressure is 2KPa, the reaction time is 1.5h, the absolute pressure is regulated to 80Pa for polycondensation 2.5h, the cooled granulation and drying are carried out to obtain 100kg/h of polyester intermediate, and the polyester intermediate is fully mixed with 3.5kg/h of isopropyl triisostearoyl titanate and then reacted for 8h at 60 ℃ to obtain a polyester product.
The preparation method of the biodegradable aliphatic-aromatic copolyester sample film/sheet of the above examples and comparative examples comprises the following steps: the polyester sample particles are subjected to melt extrusion through a single-screw extrusion film blowing machine at 150 ℃, then are cooled, blown and pulled to prepare a film with the thickness of 20+/-5 mu m, the blowing ratio is 3, or the single-screw extrusion film blowing machine is subjected to melt extrusion, and then are cooled and pulled to prepare a sheet with the thickness of 200+/-10 mu m, wherein the specific performance parameters are shown in the following table:
TABLE 1
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In conclusion, the aliphatic-aromatic copolyester has excellent product quality, namely 4-15 mmol/kg of carboxyl end groups of the resin, and the gel points in the resin film/sheet are less than or equal to 10/m 2 Mass average molecular weight 7.0-15.0X10 4 The molecular weight distribution is 1.8-2.2.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.

Claims (16)

1. An aliphatic-aromatic copolyester obtained by a process comprising the steps of:
s1: in the presence of a first catalyst and/or a second catalyst, respectively carrying out esterification reaction on aliphatic dibasic acid and aromatic dibasic acid and aliphatic dihydric alcohol to obtain esterification reaction products;
s2: carrying out polycondensation reaction on the esterified product of the S1 to obtain a polyester intermediate;
s3: in the presence of an auxiliary agent, enabling the polyester intermediate of the S2 to undergo a chain growth reaction to obtain the aliphatic-aromatic copolyester;
wherein the first catalyst comprises a reaction product of a titanium-containing compound, a magnesium-containing compound, a zinc-containing compound, a hydroxyl-containing compound and a carboxyl-containing compound, wherein the magnesium-containing compound is 0.01-10 mol and the zinc-containing compound is 0.01-10 mol per mol of the titanium-containing compound; the hydroxyl-containing compound is 1 to 20 moles; the carboxyl-containing compound is 0.01 to 0.5 mol; the second catalyst comprises a reaction product of a titanium-containing compound, a magnesium-containing compound, a zinc-containing compound, a hydroxyl-containing compound and an epoxy-containing compound, wherein the magnesium-containing compound is 0.01-10 mol per mol of the titanium-containing compound; the zinc-containing compound is 0.01 to 10 mol; 1 to 20 moles of the hydroxyl group-containing compound, and 0.01 to 1 mole of the epoxy group-containing compound;
The titanium-containing compound is selected from the group consisting of compounds of the general formula Ti (OR) 1 ) m X 4-m One OR more of the compounds shown and titanium oxide, a general formula Ti (OR 1 ) m X 4-m Wherein R is 1 Is C 2 ～C 10 Is a hydrocarbon group of (2); x is halogen; m is 0, 1, 2, 3 or 4;
the magnesium-containing compound is selected from the group consisting of compounds of the general formula Mg (OR) 2 ) 2 X 2-n Compounds of the formula Mg (OOR) 3 ) 2 One OR more of the compounds shown, the general formula Mg (OR 2 ) 2 X 2-n Wherein R is 2 Is C 2 ～C 10 X is halogen; n is 0, 1 or 2; general formula Mg (OOR) 3 ) 2 Wherein R is 3 Is C 2 ～C 10 Is a hydrocarbon group of (2);
the zinc-containing compound is selected from the general formula Zn (OOR) 4 ) 2 One or more of the compounds shown and zinc halides,the general formula Zn (OOR) 4 ) 2 Wherein R is 4 Is C 2 ～C 20 Is a hydrocarbon group of (2);
the hydroxyl-containing compound is selected from C 1 ～C 10 Monohydric alcohol, C 2 ～C 10 Glycol, C 3 ～C 15 Is (C) a triol 4 ～C 20 Tetrahydric alcohol, C 5 ～C 20 Five-membered alcohol or C 6 ～C 20 Is a hexahydric alcohol of (2);
the carboxyl group-containing compound is selected from C 1 ～C 20 Monocarboxylic acid of C 2 ～C 20 Dicarboxylic acids or C 3 ～C 20 Is a tricarboxylic acid of (2);
the epoxy group-containing compound is selected from the general formulaOne or more of the compounds shown, the general formulaWherein R is 5 And R is 6 The same or different, each independently selected from hydrogen or C 1 ～C 20 Is a hydrocarbon group of (2);
the preparation method of the first catalyst comprises the following steps:
step A: reacting a portion of the hydroxyl-containing compound with the carboxyl-containing compound to obtain a first solution;
And (B) step (B): adding the rest of hydroxyl-containing compound, magnesium-containing compound, zinc-containing compound and titanium-containing compound into the first solution, and reacting to obtain a second solution;
the preparation method of the second catalyst comprises the following steps:
step M: reacting a portion of the hydroxyl-containing compound, the epoxy-containing compound, and the zinc-containing compound to obtain a third solution;
step N: adding a magnesium-containing compound, a titanium-containing compound and the rest of hydroxyl-containing compound into the third solution in the step M, and reacting to obtain a fourth solution;
the aliphatic groupDibasic acid is C 2 ～C 16 Dibasic acid of C 2 ～C 16 Aliphatic dibasic acid anhydride or C 2 ～C 16 One or more of the aliphatic dibasic acid halides of (a);
the aromatic diacid is selected from C 8 ～C 16 Aromatic dibasic acid, C 8 ～C 16 Aromatic dibasic acid anhydride or C 8 ～C 16 One or more of the aromatic dibasic acid halides of (a);
the aliphatic diol is selected from C 2 ～C 10 One or more of the aliphatic diols of (a);
the auxiliary agent comprises a molecular weight extender and a dispersing agent, wherein the molecular weight extender comprises one or more of isocyanate compounds, carbodiimide compounds, glycerol ether compounds, glycerol ester compounds, oxazoline compounds, coupling agent compounds and alkyl metal compounds;
The structure of the isocyanate compound is shown as a formula I,
in the formula I, R 1 Is C 1 ～C 20 Hydrocarbyl, x > 1;
the structure of the carbodiimide compound is shown as a formula II,
R 2 -N＝C＝N-R 3 II type
In formula II, R 2 And R is 3 Identical or different, each independently selected from C 1 ～C 20 A hydrocarbon group;
the structure of the glycerol ether compound is shown as a formula III,
in formula III, R 4 Selected from C 1 ～C 20 Hydrocarbyl, m > 1; and/or
The structural formula of the glyceride compound is shown as a formula IV,
in formula IV, R 5 Selected from C 1 ～C 20 Hydrocarbyl, t > 1;
the structure of the oxazoline compound is shown as a formula V,
in the formula I, R 6 、R 7 、R 8 、R 9 Identical or different, each independently selected from hydrogen or a C1-C20 hydrocarbon radical, R being absent or selected from a C2-C10 alkylene radical or a C6-C20 arylene radical;
the coupling agent comprises one or more of silane coupling agent, titanate coupling agent, aluminate coupling agent, phosphate coupling agent or borate coupling agent;
the metal alkyl compound includes a metal alkyl having the general formula (R 15 ) y M, wherein R 15 Selected from C1-C20 alkyl, M is Ti, zn, mg, sn or Al, y > 1;
the dispersing agent comprises a dispersing agent with R 16 -O-R 17 Ether compounds of the general formula, having R 18 COOR 19 、 Ester compounds of the general formula or having +.>One or more of the ketones of the general formula, wherein R 16 、R 17 、R 18 、R 19 、R 20 、R 21 And R' are each independently selected from C 1 ～C 20 Hydrocarbyl radicals G being divalent or trivalent C 1 ～C 20 Hydrocarbyl, optionally G is substituted with hydroxy.
2. The aliphatic-aromatic copolyester according to claim 1, characterized in that the carboxyl end group content of said aliphatic-aromatic copolyester is 4-15mmol/kg; and/or
The gel point of the aliphatic-aromatic copolyester is less than or equal to 10/m 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or
The mass average molecular weight of the aliphatic-aromatic copolyester is 7.0x10 4 -15.0×10 4 The method comprises the steps of carrying out a first treatment on the surface of the And/or
The molecular weight distribution of the aliphatic-aromatic copolyester is 1.8-2.2.
3. The aliphatic-aromatic copolyester according to claim 1, wherein the aliphatic-aromatic copolyester has a mass average molecular weight of 9.1×10 4 -15.0×10 4 。
4. The aliphatic-aromatic copolyester according to claim 1, wherein X is selected from chlorine, bromine or iodine; and/or R 2 Is C 2 ～C 6 Is a hydrocarbon group of (2); and/or R 3 Is C 2 ～C 6 Is a hydrocarbon group of (2); and/or R 4 Is C 2 ～C 10 Is a hydrocarbon group of (2); and/or R 5 And R is 6 Selected from hydrogen or C 1 ～C 10 Is a hydrocarbon group of (a).
5. The aliphatic-aromatic copolyester according to claim 1, wherein said silane coupling agent has the general structural formula Y (CH) 2 ) k SiZ 3 Wherein k=0 to 5; y is vinyl, amino, epoxy, methacryloxy, mercapto or ureido; z is chloro, methoxy, ethoxy, methoxyethoxy, acetoxy; and/or
The structural general formula of the titanate coupling agent is (R 10 O) a -Ti(OA-R1-Q) b ，R 10 Is C 1 ～C 20 A hydrocarbon group; OA is carboxyl, sulfonic acid, sulfone, phosphate, pyrophosphate and phosphite; r1 is C 1 ～C 20 Alkylene groups of (a); q is C 1 ～C 6 Alkyl, hydroxy, amino, epoxy, vinyl; a is more than or equal to 1, b is more than or equal to 1; and/or
The structural general formula of the aluminate coupling agent is (R) 11 O) a -Al(Dn)(R 12 COO) b ，a≥1，b≥1，R 11 And R is 12 Identical or different, each independently selected from C 1 ～C 20 A hydrocarbon group; dn is a group containing N or O ligands, and/or
The structural general formula of the borate coupling agent is ((R) 13 O) a -B(Dn)(R 14 COO) b ，a≥1，b≥1，R 13 And R is 14 Identical or different, each independently C 1 ～C 20 A hydrocarbon group; dn is an N-or O-containing coordinating group.
6. The aliphatic-aromatic copolyester according to claim 1, wherein said isocyanate-based compound comprises one or more of 2, 4-toluene diisocyanate and its trimer, 2, 6-toluene diisocyanate and its trimer, tetramethyl-dimethylene benzene diisocyanate, trimethyl-hexamethylene diisocyanate, xylylene diisocyanate, methylcyclohexane diisocyanate, 1, 6-hexamethylene diisocyanate and its trimer, 4 '-diphenylmethane diisocyanate, 2,4' -diphenylmethane diisocyanate, 2 '-diphenylmethane diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate or lysine diisocyanate; and/or
The carbodiimide compound comprises one or more of N, N, -dicyclohexylcarbodiimide, N, -diisopropylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, 1-ethyl- (3-dimethylaminopropyl) carbodiimide, bis (3-isopropenyl-dimethylbenzyl) carbodiimide, diphenylcarbodiimide, bis (2, 6-diisopropylphenyl) carbodiimide or bis (3-benzyl) carbodiimide; and/or
The glycerol ether compound comprises one or more of ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, trimethylolpropane triglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 5-pentanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, bisphenol A diglycidyl ether or resorcinol diglycidyl ether; and/or
The glyceride compounds comprise one or more of diglycidyl oxalate, diglycidyl 1, 3-malonate, diglycidyl succinate, diglycidyl 1, 5-glutarate, diglycidyl adipate, diglycidyl sebacate or triglycidyl citrate; and/or
The silane coupling agent comprises one or more of vinyl tri (beta-methoxyethoxy) silane, vinyl trimethyl silane, vinyl triethoxy silane, gamma-mercaptopropyl trimethoxy silane, gamma-methacryloxypropyl trimethoxy silane, gamma-glycidol ether oxypropyl trimethoxy silane, N- (beta-aminoethyl) -gamma-aminopropyl trimethoxy silane, gamma-aminopropyl trimethoxy silane and gamma-aminopropyl triethoxy silane; and/or
The titanate coupling agent comprises one or more of triisostearoyl isopropyl titanate, bis (dioctyl oxy pyrophosphato) ethylene titanate, isopropyl dioleate acyloxy (dioctyl phosphoryloxy) titanate, diethyl propyl di (acetylacetonato) titanate, tetraisopropyl di (dioctyl phosphite acyloxy) titanate, diisopropyl bis (acetoacetate) titanate and isopropyl tri (dodecylbenzenesulfonyl) titanate; and/or
The aluminate coupling agent comprises one or more of distearoyl oxygen isopropyl aluminate, aluminum diisopropoxy acetoacetate, isopropyl bis (glyceryl distearate group) aluminate, isopropyl bis (diethylene glycol oleate group) aluminate and isopropyl bis (pentaerythritol tristearate group) aluminate; and/or
The phosphate coupling agent comprises one or more of 2-hydroxyethyl methacrylate phosphate, di (methacryloyloxyethyl) phosphate, bis (dioctyl oxyphosphate) ethylene titanate, isopropyl dioleoyl (dioctyl phosphoryloxy) titanate, diethyl propyl di (acetylacetonato) titanate or tetraisopropyl di (dioctyl phosphoryloxy) titanate; and/or
The borate coupling agent comprises one or more of distearoyl oxygen isopropyl borate, di (diethylene glycol distearate group) isopropyl borate, di (diethylene glycol oleate group) isopropyl borate and di (pentaerythritol tristearate group) isopropyl borate; and/or
The alkyl metal compound comprises one or more of ethyl zinc, triethyl aluminum, tetrabutyl tin, dibutyl zinc or n-butyl ethyl magnesium.
7. The aliphatic-aromatic copolyester according to any one of claims 1 to 6, wherein said diffusing agent comprises one or more of n-butyl ether, n-pentyl ether, hexyl ether, octyl ether, tributyl citrate, dioctyl succinate, dibutyl glutarate, dioctyl adipate, dibutyl sebacate, acetophenone, methyl ethyl ketone, methyl amyl ketone, butanone, hexanone; and/or
The auxiliary agent also comprises an accelerator, wherein the accelerator comprises a catalyst having the following components(R 23 ) q M 2 Or (b)One or more of the metal-organic compounds of the formula R 22 、R 23 And R is 24 Each independently selected from C 1 ～C 20 Hydrocarbyl, M 2 Is Zn, mg, sn, al, ti; z is > 1; q is greater than 1; i > 1.
8. The aliphatic-aromatic copolyester of claim 7, wherein the promoter comprises one or more of tetraethoxytitanium, tetrabutoxytitanium, stannous octoate, magnesium acetate, magnesium 2-ethylbutyrate, aluminum ethoxide, tin acetate, zinc glutarate, zinc adipate, magnesium glutarate, tin glutarate, magnesium laurate, magnesium stearate, dibutyl zinc, tetrabutyl tin, aluminum triisopropoxide, magnesium tert-butoxide, or n-butylethylmagnesium.
9. The aliphatic-aromatic copolyester according to claim 7, wherein said diffusing agent, molecular weight increasing agent and accelerator are 0.1 to 2%, 0.5 to 5% and 5X 10- 4 ～15×10- 4 ％。
10. The aliphatic-aromatic copolyester according to anyone of claims 1 to 6, characterized in that said magnesium-containing compound is present in an amount of 0.2 to 5 moles per mole of titanium-containing compound; and/or the zinc-containing compound is 0.1 to 5 mol; and/or 1 to 10 moles of the hydroxyl group-containing compound; and/or the carboxyl group-containing compound is 0.1 to 0.5 mol; and/or the epoxy group-containing compound is 0.1 to 0.5 mol.
11. The aliphatic-aromatic copolyester according to any one of claims 1 to 6, characterised in that said titanium-containing compound is selected from one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate and titanium dioxide; and/or
The magnesium-containing compound is selected from one or more of magnesium dichloride, magnesium dibromide, magnesium diiodide, magnesium diethoxide, magnesium dipropoxide, magnesium diisopropyloxide, magnesium dibutoxide, magnesium diisobutoxide, magnesium acetate, magnesium propionate and magnesium butyrate; and/or
The zinc-containing compound is selected from one or more of zinc dichloride, zinc dibromide, zinc diiodide, zinc acetate, zinc propionate, zinc butyrate and zinc stearate; and/or
The hydroxyl-containing compound is selected from one or more of methanol, ethanol, isopropanol, n-butanol, n-amyl alcohol, 2-amyl alcohol, 3-amyl alcohol, ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, pentaerythritol and sorbitol; and/or
The carboxyl-containing compound is at least one of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, stearic acid, oxalic acid, malonic acid, succinic acid, glutaric acid and adipic acid; and/or
The epoxy group-containing compound is selected from one or more of ethylene oxide, propylene oxide, 1, 2-butylene oxide, 1, 4-butylene oxide or 1, 2-pentane oxide.
12. The aliphatic-aromatic copolyester according to anyone of claims 1 to 6, characterised in that said aliphatic dibasic acid is selected from C 2 ～C 10 Aliphatic dibasic acid, C 2 ～C 10 Aliphatic dibasic acid anhydride or C 2 ～C 10 One or more of the aliphatic dibasic acid halides of (a).
13. The aliphatic-aromatic copolyester according to any one of claims 1 to 6, wherein said aliphatic dibasic acid comprises one or more of succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1, 4-cyclohexanedicarboxylic acid, glutaric anhydride or malonyl chloride;
the aromatic diacid comprises one or more of terephthalic acid, terephthalic anhydride, terephthaloyl halide, isophthalic acid, isophthalic anhydride, isophthaloyl halide, naphthalene dicarboxylic acid, naphthalene dicarboxylic anhydride and naphthalene dicarboxylic acid halide;
the aliphatic diol comprises one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol or polyether diol.
14. The aliphatic-aromatic copolyester according to any one of claims 1 to 6, wherein the molar ratio of the hydroxyl functional groups to the total functional groups of carboxylic acid, anhydride and acid halide in the aliphatic dibasic acid, aromatic dibasic acid and aliphatic glycol is (1.1 to 2.5): 1.
15. the aliphatic-aromatic copolyester according to any one of claims 1 to 6, wherein in step S1, the esterification reaction temperature is 150 to 250 ℃, the absolute pressure is 40 to 110KPa, and the reaction time is 2 to 6 hours;
in the step S2, the polycondensation reaction comprises a first polycondensation reaction and a second polycondensation reaction which are sequentially carried out, wherein the temperature of the first polycondensation reaction is 200-250 ℃, the absolute pressure is 1 KPa-5 KPa, the time is 1-3 h, the temperature of the second polycondensation reaction is 200-250 ℃, the absolute pressure is 10-300 Pa, and the reaction time is 1-3 h; and/or step S2 further comprises granulating and drying after the polycondensation reaction to obtain the polyester intermediate;
in the step S3, the temperature of the chain growth reaction is 25-100 ℃ and the time is 4-24 h.
16. Use of the aliphatic-aromatic copolyester according to any one of claims 1-15 in a polyester film material or a polyester sheet material.
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TW418216B (en) * 1995-12-19 2001-01-11 Borealis As Procatalyst, procatalyst precursor, and process for the preparation of a multimodal ethylene polymer
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