CN101293958A - Appropriately crosslinked biodegradable polyester-amides random block copolymer - Google Patents
Appropriately crosslinked biodegradable polyester-amides random block copolymer Download PDFInfo
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Abstract
The invention relates to a proper cross-linking biodegradable polyester amide atactic block copolymer and a synthetic method thereof. The structure of the atactic block copolymer is shown as the figure. The copolymer has the advantages of excellent mechanical and thermal properties and good biodegradability. Additionally, the atactic block copolymer is amphiphilic and compatible to other polymer materials. The atactic block copolymer is particularly suitable for being used as a biodegradable material.
Description
Technical field
The present invention relates to a kind of biodegradable polyester acid amides macromolecular material, specifically a kind of appropriately crosslinked biodegradable polyester-amides random block copolymer and synthetic method thereof.
Background technology
Aliphatics or aliphatic-aromatic copolymerized type polyester acid amides are the novel biodegradable polymers in environment of a class, it has the advantage of polyester and polymeric amide concurrently, aliphatic poly esteramides segment makes material have the favorable biological degradability energy, the existence of polyamide segment simultaneously makes material have intensity and the mechanical property more excellent than simple polyester, exist in the time of ester bond and amido linkage, given the amphiphilic of polyesteramide.So this type of polyesteramide is with a wide range of applications.
In the present existing polyesteramide synthetic patented technology, the synthetic technology that includes random and block type polyesteramide is many, as CN1173190A, CN1285853A.In order to improve the molecular weight of synthesis of polyester amide, many investigators have adopted the way of chain extension, as Chinese patent application open CN1293214A, CN1310194A, CN1310193A, they have reported the chain extension method of thermoplastic biologically degradable polyester amide and multipolymer, but all used the bigger vulcabond of toxicity or other virose compounds as chainextender in the preparation of these polyesteramides, brought disadvantage and inconvenience to suitability for industrialized production.Minnesota Mining and Manufacturing Company obtains the acid amides dibasic alcohol with oxyacetic acid or lactic acid and diamine reaction, then itself and acyl chlorides are reacted in solvent and obtain polyester-amide copolymer, yet because the active reaction of acyl chlorides is restive, reactor and environment are brought pollution in such reaction.Journal of chemistry, 72,867 (1972) have reported the polyesteramide that contains L-lactic acid, but it is monomeric synthetic comparatively complicated, polymkeric substance shows as the random copolymerization of poly (l-lactic acid) and poly-L-lactic amide, Chinese invention patent 98121899.7 has been reported the polyester-amide copolymer that contains DL-lactic acid link, takes place but these polyesteramides synthetic all complicated and being difficult to overcomes the side reaction of transesterify, makes polymkeric substance or multipolymer darker color occur.Bayer A.G sells polyesteramide with the BAK brand 1991～calendar year 2001, but because cost height, and the material legislation problem of German renewable resources manufacturing etc., cause the said firm to abandon this business (Zhu Cenghui, some new argument and developments of current relevant biodegradable material.New Chemical Materials, 2004,32 (8): 44-45).EP-A717064, JP04306229, JP07010988 and JP07157557 disclose transesterify by higher molecular weight polymeric amide and higher molecular weight polyester-/polyesteramide of acid amides permutoid reaction acquisition block structure.This reaction depends on operational condition to a great extent, and circulation ratio is poor, and the polyesteramide with this kind block structure does not have enough biodegradabilities.
In sum, exist in the synthetic method of existing Biodegradable polyester amides that raw material is toxic, speed of response is slow, side reaction is many, react difficult operation, poor reproducibility, degradation property deficiency, the product color is dark, cost is high and other variety of problems and deficiency.
Summary of the invention
Purpose of the present invention is intended to overcome above-mentioned deficiency of the prior art, and a kind of appropriately crosslinked biodegradable polyester-amides random block copolymer and synthetic method thereof are provided.
Another object of the present invention is to provide the preparation method of above-mentioned polymkeric substance, the synthetic method of this polymkeric substance is simply effective, and the productive rate height can synthesize product of higher molecular weight at short notice, both save the energy, solved the darker problem of high molecular weight products color again.
Subject polymer of the present invention is realized by the following technical solutions: its structural formula is:
M is 2～10 integer in the structural formula, and n is 2～12 integer, and p is 2～12 integer, m, and n, p can be identical or different, and x is 1～10 integer, and y is 1～10 integer, and molecular weight is 4～150,000.
The present invention's technical scheme preferably is that m is 4～6 integer in the structural formula, and n is 2～4 integer, and p is 4～6 integer, m, and n, p can be identical or different, and x is 1～10 integer, and y is 1～10 integer, and molecular weight is 5～100,000.
Preparation method of the present invention, it may further comprise the steps:
1) 5～50 parts of aliphatic dibasic acid or derivatives thereofs, 5～50 parts of aliphatic dihydroxy alcohols, 0～50 part of aromatic acid or derivatives thereof, 0～30 part of aliphatic diamine, 0～50 part of hydroxycarboxylic acid or derivatives thereof, 0～30 part of amino alcohol, 0～30 part in amino acid, 0～30 part of cyclic lactames, 0.01～1 part of catalyzer, oxidation inhibitor are joined in the reactor for 0.01～2 part, feed nitrogen, be warmed up to 120～200 ℃, carry out esterification and transesterification reaction, reacted 1～3 hour.
2) after reaction was finished, polycondensation was carried out in beginning progressively decompression again, the while elevated temperature, and temperature of reaction is 150～300 ℃, the reaction system vacuum ranges is≤200Pa polycondensation 3～8 hours.
3) after polycondensation finishes, add 0.5～10 part linking agent in reaction system, carry out crosslinking reaction, keeping temperature of reaction is 120～200 ℃, 0.5～2 hour reaction times.
Preparation method of the present invention technical scheme preferably is: described aliphatic dibasic acid or derivatives thereof is alicyclic lactone, acid anhydrides or their mixture with the aliphatic dibasic acid of 2～12 carbon atoms or its ester or its acid anhydrides, 5～10 carbon atoms; Described aromatic acid or derivatives thereof is to benzene diprotic acid, a benzene diprotic acid, adjacent benzene diprotic acid and ester or its acid anhydrides; Described aliphatic dihydroxy alcohol is ethylene glycol, glycol ether, 1, ammediol, 1,4-butyleneglycol, 1,6-hexylene glycol, cyclohexanedimethanol; Described aliphatic diamine is a quadrol, 1,3-propylene diamine, 1,4-butanediamine, 1,6-hexanediamine or urea; Described hydroxycarboxylic acid or derivatives thereof is oxyacetic acid, hydroxy-propionic acid (lactic acid), hydroxybutyric acid, hydroxypentanoic acid or their derivative; Described amino alcohol is thanomin, diethanolamine or Yi Bingchunan; Amino acid is Padil, alanine or hexosamine; Cyclic lactames is hexanolactam or laurolactam; Described linking agent is a tung oil acid anhydride.
Described catalyzer is organo-tin compound, organic titanic compound, phosphorus compound, organic germanium compounds, organic zinc compound or its mixture.
Described oxidation inhibitor is antioxidant 1010, antioxidant 3114 or oxidation inhibitor 245.
Ester class formation unit of the present invention and amides structural unit are to form polyester fragment and polymeric amide fragment in target product, and are that the random block sequence distributes.With these polyesteramide macromole that forms by the polyester fragment and the copolymerization of polymeric amide fragment of the distribution of random block sequence, suitably be cross-linked into the flowable polymer that contains the suitable degree of branching again with small amount of trifunctional group compound.Cross-link bond can be the comprehensive use of ester bond, ehter bond, amido linkage, C-C or these several keys.The degree of crosslinking of polymerisate will be controlled at 20%-1%, still has the flowability of melt-processable to guarantee the synthetic polymkeric substance.Measured by the GPC method, its molecular weight is 4～150,000, and melt temperature is at 120～150 ℃, tensile strength 15～30MPa, elongation at break 500～1500%.
Wherein, no more than 50% (mole) of the shared total carboxylic acid's of aromatic acid (or derivatives thereof) (or derivatives thereof) share.
In the technical solution of the present invention: described catalyzer is organo-tin compound, organic titanic compound, phosphorus compound, organic germanium compounds, organic zinc compound etc. or its mixture.
In the technical solution of the present invention: described oxidation inhibitor is antioxidant 1010, antioxidant 3114, oxidation inhibitor 245 etc.
Compared with prior art, the present invention has following characteristics:
1) adopt the appropriately crosslinked polyester-amides random block copolymer product of the present invention's preparation, be white or faint yellow solid, fusing point is at 120～150 ℃, tensile strength 15～30MPa, elongation at break 500～1500%.
2) the appropriately crosslinked polyester-amides random block copolymer product of the present invention's preparation, the uncrosslinked polyesteramide molecular weight of synthetic obviously improves 2～3 times under its molecular weight ratio same reaction conditions.
3) the appropriately crosslinked polyester-amides random block copolymer product of the present invention's preparation is the random block structure, has both avoided the unstable of random structure product, and the degradation property than segmented copolymer is good again.
4) the appropriately crosslinked polyester-amides random block copolymer product of the present invention's preparation, ester bond and amido linkage are random block and distribute, appropriately crosslinked again, both had excellent mechanical property and thermal characteristics, the favorable biological degradability energy is arranged again, have simultaneously amphipathic, good with the consistency of other macromolecular material blend.
5) the appropriately crosslinked polyester-amides random block copolymer product of the present invention's preparation, owing to contain a certain amount of branched polymer, help improving processing characteristics, and, can in very large range control the structure and the performance of product by regulating the proportioning of starting raw material.
6) preparation method of appropriately crosslinked polyester-amides random block copolymer of the present invention finished by melt polymerization one step, the reaction yield height, and method is simply effective.Present method can synthesize the higher polyesteramide of molecular weight within a short period of time, helps save energy, reduces cost.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment 1:
Under the room temperature with 174g dimethyl adipate, 194g dimethyl terephthalate (DMT), 120g1,4-butyleneglycol, 40.7g thanomin, 340mg tetrabutyl titanate, 5g antioxidant 1010 add in the four neck flasks that nitrogen inlet, agitator, prolong are housed successively, feed nitrogen, be warming up to 140～160 ℃, stirring reaction 1～3 hour.Slowly decompression then, and progressively improve temperature to 220～260 ℃, vacuum degree control was reacted 3～6 hours in 200Pa.Add the 78.1g tung oil acid anhydride then in reaction system, keeping temperature of reaction is 120～200 ℃, reacts 0.5～2 hour again.Products therefrom is a white, and GPC method determining molecular weight Mw is 9.15 ten thousand, and molecular weight distribution is 6.57.
Embodiment 2:
Under the room temperature with 174g dimethyl adipate, 194g dimethyl terephthalate (DMT), 153g 1,4 butyleneglycols, 18.3g thanomin, 340mg tetrabutyl titanate, 5g antioxidant 1010 add in the four neck flasks that nitrogen inlet, agitator, prolong are housed successively, feed nitrogen, be warming up to 140～160 ℃, stirring reaction 1～3 hour.Slowly decompression then, and progressively improve temperature to 220～260 ℃, vacuum degree control was reacted 3～6 hours in 200Pa.Add the 78.1g tung oil acid anhydride then in reaction system, keeping temperature of reaction is 120～200 ℃, reacts 0.5～2 hour again.Products therefrom is faint yellow, and GPC method determining molecular weight Mw is 9.63 ten thousand, and molecular weight distribution is 5.16.
Embodiment 3:
Under the room temperature with 146g dimethyl succinate, 194g dimethyl terephthalate (DMT), 108g 1,4-butyleneglycol, 63.6g glycol ether, 23.2g hexanediamine, 340mg tetrabutyl titanate, 5g antioxidant 1010 add in the four neck flasks that nitrogen inlet, agitator, prolong are housed successively, feed nitrogen, be warming up to 140～160 ℃, stirring reaction 1～3 hour.Slowly decompression then, and progressively improve temperature to 220～260 ℃, vacuum degree control was reacted 3～6 hours in 200Pa.Add the 78.1g tung oil acid anhydride then in reaction system, keeping temperature of reaction is 120～200 ℃, reacts 0.5～2 hour again.Products therefrom is a white, and GPC method determining molecular weight Mw is 8.79 ten thousand, and molecular weight distribution is 6.21.
Embodiment 4:
Under the room temperature with 146g hexanodioic acid, 194g dimethyl terephthalate (DMT), 108g 1,4-butyleneglycol, 63.6g glycol ether, 23.2g hexanediamine, 340mg tetrabutyl titanate, 5g antioxidant 1010 add in the four neck flasks that nitrogen inlet, agitator, prolong are housed successively, feed nitrogen, be warming up to 140～160 ℃, stirring reaction 1～3 hour.Slowly decompression then, and progressively improve temperature to 220～260 ℃, vacuum degree control was reacted 3～6 hours in 200Pa.Add the 78.1g tung oil acid anhydride then in reaction system, keeping temperature of reaction is 120～200 ℃, reacts 0.5～2 hour again.Products therefrom is a white, and GPC method determining molecular weight Mw is 9.79 ten thousand, and molecular weight distribution is 5.93.
Embodiment 5:
Under the room temperature with 146g dimethyl succinate, 194g dimethyl terephthalate (DMT), 180g 1,4-butyleneglycol, 37.5g Padil, 340mg tetrabutyl titanate, 5g antioxidant 1010 add in the four neck flasks that nitrogen inlet, agitator, prolong are housed successively, feed nitrogen, be warming up to 140～160 ℃, stirring reaction 1～3 hour.Slowly decompression then, and progressively improve temperature to 220～260 ℃, vacuum degree control was reacted 3～6 hours in 200Pa.Add the 87.9g tung oil acid anhydride then in reaction system, keeping temperature of reaction is 120～200 ℃, reacts 0.5～2 hour again.Products therefrom is a white, and GPC method determining molecular weight Mw is 10.45 ten thousand, and molecular weight distribution is 7.41.
Embodiment 6:
Under the room temperature with 118g Succinic Acid, 194g dimethyl terephthalate (DMT), 144g 1,4-butyleneglycol, 45g hydroxy-propionic acid (lactic acid), 30g urea, 340mg tetrabutyl titanate, 5g antioxidant 1010 add in the four neck flasks that nitrogen inlet, agitator, prolong are housed successively, feed nitrogen, be warming up to 140～160 ℃, stirring reaction 1～3 hour.Slowly decompression then, and progressively improve temperature to 220～260 ℃, vacuum degree control was reacted 3～6 hours in 200Pa.Add the 78.1g tung oil acid anhydride then in reaction system, keeping temperature of reaction is 120～200 ℃, reacts 0.5～2 hour again.Products therefrom is faint yellow look, and GPC method determining molecular weight Mw is 14.65 ten thousand, and molecular weight distribution is 7.74.
Embodiment 7:
Under the room temperature with 118g Succinic Acid, 194g dimethyl terephthalate (DMT), 117g 1,4-butyleneglycol, 30.5g thanomin, 23.2g hexanediamine, 340mg tetrabutyl titanate, 5g antioxidant 1010 add in the four neck flasks that nitrogen inlet, agitator, prolong are housed successively, feed nitrogen, be warming up to 140～160 ℃, stirring reaction 1～3 hour.Slowly decompression then, and progressively improve temperature to 220～260 ℃, vacuum degree control was reacted 3～6 hours in 200Pa.Add the 78.1g tung oil acid anhydride then in reaction system, keeping temperature of reaction is 120～200 ℃, reacts 0.5～2 hour again.Products therefrom is faint yellow, and GPC method determining molecular weight Mw is 9.09 ten thousand, and molecular weight distribution is 5.62.
Embodiment 8:
Under the room temperature with 146g hexanodioic acid, 194g dimethyl terephthalate (DMT), 135g1,4-butyleneglycol, 30.5g thanomin, 33.9g hexanolactam, 340mg tetrabutyl titanate, 5g antioxidant 1010 add in the four neck flasks that nitrogen inlet, agitator, prolong are housed successively, feed nitrogen, be warming up to 140～160 ℃, stirring reaction 1～3 hour.Slowly decompression then, and progressively improve temperature to 220～260 ℃, vacuum degree control was reacted 3～6 hours in 200Pa.Add the 78.1g tung oil acid anhydride then in reaction system, keeping temperature of reaction is 120～200 ℃, reacts 0.5～2 hour again.Products therefrom is faint yellow, and GPC method determining molecular weight Mw is 8.15 ten thousand, and molecular weight distribution is 5.36.
Embodiment 9:
Under the room temperature with 118g Succinic Acid, 194g dimethyl terephthalate (DMT), 99g 1,4-butyleneglycol, 30.5g thanomin, 23.2g hexanediamine, 300mg zincic acid dimethyl ester, 5g antioxidant 1010 add in the four neck flasks that nitrogen inlet, agitator, prolong are housed successively, feed nitrogen, be warming up to 140～160 ℃, stirring reaction 1～3 hour.Slowly decompression then, and progressively improve temperature to 220～260 ℃, vacuum degree control was reacted 3～6 hours in 200Pa.Add the 78.1g tung oil acid anhydride then in reaction system, keeping temperature of reaction is 120～200 ℃, reacts 0.5～2 hour again.Products therefrom is faint yellow, and GPC method determining molecular weight Mw is 9.09 ten thousand, and molecular weight distribution is 5.62.
Embodiment 10:
Under the room temperature with 146g hexanodioic acid, 194g terephthalic acid, 135g1,4-butyleneglycol, 30.5g thanomin, 33.9g Valerolactim, 340mg stannic acid four butyl esters, 5g antioxidant 1010 add in the four neck flasks that nitrogen inlet, agitator, prolong are housed successively, feed nitrogen, be warming up to 140～160 ℃, stirring reaction 1～3 hour.Slowly decompression then, and progressively improve temperature to 220～260 ℃, vacuum degree control was reacted 3～6 hours in 200Pa.Add the 78.1g tung oil acid anhydride then in reaction system, keeping temperature of reaction is 120～200 ℃, reacts 0.5～2 hour again.Products therefrom is faint yellow, and GPC method determining molecular weight Mw is 7.65 ten thousand, and molecular weight distribution is 5.2.
Claims (8)
1, a kind of appropriately crosslinked biodegradable polyester-amides random block copolymer, its structural formula is:
M is 2～10 integer in the structural formula, and n is 2～12 integer, and p is 2～12 integer, m, and n, p can be identical or different, and x is 1～10 integer, and y is 1～10 integer, and molecular weight is 4～150,000.
2, according to a kind of appropriately crosslinked biodegradable polyester-amides random block copolymer of claim 1, wherein m is 4～6 integer in the structural formula, n is 2～4 integer, p is 4～6 integer, m, n, p can be identical or different, x is 1～10 integer, and y is 1～10 integer, and molecular weight is 5～100,000.
3, a kind of preparation method of appropriately crosslinked biodegradable polyester-amides random block copolymer, it may further comprise the steps:
1) 5～50 parts of aliphatic dibasic acid or derivatives thereofs, 5～50 parts of aliphatic dihydroxy alcohols, 0～50 part of aromatic acid or derivatives thereof, 0～30 part of aliphatic diamine, 0～50 part of hydroxycarboxylic acid or derivatives thereof, 0～30 part of amino alcohol, 0～30 part in amino acid, 0～30 part of cyclic lactames, 0.01～1 part of catalyzer, oxidation inhibitor are joined in the reactor for 0.01～2 part, feed nitrogen, be warmed up to 120～200 ℃, carry out esterification and transesterification reaction, reacted 1～3 hour.
2) after reaction was finished, polycondensation was carried out in beginning progressively decompression again, the while elevated temperature, and temperature of reaction is 150～300 ℃, the reaction system vacuum ranges is≤200Pa polycondensation 3～8 hours.
3) after polycondensation finishes, add 0.5～10 part linking agent in reaction system, carry out crosslinking reaction, keeping temperature of reaction is 120～200 ℃, 0.5～2 hour reaction times.
4, the preparation method of a kind of appropriately crosslinked biodegradable polyester-amides random block copolymer according to claim 3, wherein said aliphatic dibasic acid or derivatives thereof is alicyclic lactone, acid anhydrides or their mixture with the aliphatic dibasic acid of 2～12 carbon atoms or its ester or its acid anhydrides, 5～10 carbon atoms; Described aromatic acid or derivatives thereof is to benzene diprotic acid, a benzene diprotic acid, adjacent benzene diprotic acid and ester or its acid anhydrides; Described aliphatic dihydroxy alcohol is ethylene glycol, glycol ether, 1, ammediol, 1,4-butyleneglycol, 1,6-hexylene glycol, cyclohexanedimethanol.
5, the preparation method of a kind of appropriately crosslinked biodegradable polyester-amides random block copolymer according to claim 3, wherein said aliphatic diamine is a quadrol, 1,3-propylene diamine, 1,4-butanediamine, 1,6-hexanediamine or urea; Described hydroxycarboxylic acid or derivatives thereof is oxyacetic acid, hydroxy-propionic acid (lactic acid), hydroxybutyric acid, hydroxypentanoic acid or their derivative; Described amino alcohol is thanomin, diethanolamine or Yi Bingchunan; Amino acid is Padil, alanine or hexosamine; Cyclic lactames is hexanolactam or laurolactam.
6, the preparation method of a kind of appropriately crosslinked biodegradable polyester-amides random block copolymer according to claim 3, wherein said linking agent is a tung oil acid anhydride.
7, the preparation method of a kind of appropriately crosslinked biodegradable polyester-amides random block copolymer according to claim 3, wherein said catalyzer is organo-tin compound, organic titanic compound, phosphorus compound, organic germanium compounds, organic zinc compound or its mixture.
8, the preparation method of a kind of appropriately crosslinked biodegradable polyester-amides random block copolymer according to claim 3, wherein said oxidation inhibitor is antioxidant 1010, antioxidant 3114 or oxidation inhibitor 245.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010111898A1 (en) * | 2009-03-31 | 2010-10-07 | 武汉华丽生物材料有限公司 | Environmentally degradable polymer composite |
| CN111303409A (en) * | 2020-03-04 | 2020-06-19 | 东华大学 | Biodegradable alternating aromatic polyester amide and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4327024A1 (en) * | 1993-08-12 | 1995-02-16 | Bayer Ag | Thermoplastically processable and biodegradable aliphatic polyesteramides |
| DE19800698A1 (en) * | 1998-01-10 | 1999-07-15 | Bayer Ag | Biodegradable polyester amides with block-like polyester and polyamide segments |
| CN1256280A (en) * | 1998-12-09 | 2000-06-14 | 中国科学院成都有机化学研究所 | Biologically degradable polyester-polyamide copolymer and its preparation |
| CN1594396A (en) * | 2004-06-25 | 2005-03-16 | 绵阳东方特种工程塑料有限公司 | Biodegradable ternary random polyester amide and process for preparing same |
| CN101168595A (en) * | 2006-10-27 | 2008-04-30 | 湖南大学 | Degradable unsaturated polyesteramide resin and synthesis method thereof |
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2008
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010111898A1 (en) * | 2009-03-31 | 2010-10-07 | 武汉华丽生物材料有限公司 | Environmentally degradable polymer composite |
| JP2011516719A (en) * | 2009-03-31 | 2011-05-26 | 武▲漢華麗▼生物材料有限公司 | Environmentally degradable polymer composite material and production method |
| AU2010230796B2 (en) * | 2009-03-31 | 2013-08-29 | Wuhan Huali Environmental Protection Industry Co., Ltd. | Environmentally degradable polymer composite |
| CN111303409A (en) * | 2020-03-04 | 2020-06-19 | 东华大学 | Biodegradable alternating aromatic polyester amide and preparation method thereof |
| CN111303409B (en) * | 2020-03-04 | 2021-07-06 | 东华大学 | Biodegradable alternating aromatic polyester amide and preparation method thereof |
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