CN102453243A - Preparation method of polyester and polyester prepared by preparation method - Google Patents
Preparation method of polyester and polyester prepared by preparation method Download PDFInfo
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- CN102453243A CN102453243A CN2010105169056A CN201010516905A CN102453243A CN 102453243 A CN102453243 A CN 102453243A CN 2010105169056 A CN2010105169056 A CN 2010105169056A CN 201010516905 A CN201010516905 A CN 201010516905A CN 102453243 A CN102453243 A CN 102453243A
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Abstract
The invention provides a preparation method of polyester, which comprises the following steps that: with a first catalyst, a component a and a component b are contacted and reacted with a component c, and the product after the reaction is contacted to react with a second catalyst; the component a is at least one of C11-C20 dicarboxylic acid, ester of C11-C20 dicarboxylic acid and acid anhydride of C11-C20 dicarboxylic acid, the component b is aliphatic dihydric alcohol and/or alicyclic dihydric alcohol, the component c is at least one of C3-C10 unsaturated dicarboxylic acid, C3-C10 unsaturated dicarboxylic ester, C3-C10 unsaturated dicarboxylic acid anhydride and an epoxy compound, the first catalyst is one or more than one of M oxide, M(OR1)n and M(-OOCR2)n, and the chemical formula of the second catalyst is one or more than one of RE(R3)3. The invention also provides the polyester prepared by the method. The polyester prepared by the method has better processing property and quicker degradation rate.
Description
Technical field
The present invention relates to a kind of preparation method of polyester and the polyester for preparing by this method.
Background technology
The Biodegradable material of the synthetic of exploitation mainly comprises POLYACTIC ACID (PLA), PHA (PHA), CO at present
2With the multipolymer polymerized thylene carbonate ethyl ester (PEC) of epoxy alkane or poly (propylene carbonate) (PPC), aliphatic-aromatic copolyester as gathering (hexanodioic acid butyleneglycol-terephthalic acid butyleneglycol) ester (PBTA) or gathering polycondensation product such as poly butylene succinate (PBS) of (Succinic Acid butyleneglycol-terephthalic acid butyleneglycol) ester (PBTS) and aliphatic dicarboxylic acid and aliphatic dihydroxy alcohol etc.The degradation speed of these macromolecular materials all relatively slowly (be that about 50%, temperature is under 58 ± 2 ℃ the condition in humidity usually, fully about 6 months of degraded needs-even several years), and toughness is bad.
Long-chain binary hydroxy acid (Long chain dicarboxylic acids); Be meant the aliphatic dicarboxylic acid that contains 10 above carbon atoms in the carbochain; Comprise saturated and unsaturated dicarboxylic acid; Long-chain binary hydroxy acid be a kind of very important with the fine chemical product of extensive use is arranged, it is an important source material of making senior spices, high performance nylon engineering plastics, high-grade nylon hot-melt adhesive, high-temperature electrolysis matter, senior lubricant, senior paint and coating, cold-resistant plasticizer, resin, medicine and agricultural chemicals.
A kind of equal polyester based on long-chain binary hydroxy acid is disclosed among the CN1854167A; Wherein, The monomer that is used to prepare said equal polyester comprises: A, a kind of carbon atom quantity are di-carboxylic acid or its acid anhydrides or its diester of 11-18, and wherein carbonatoms is that 12 di-carboxylic acid is made by biological process; B, a kind of carbon atom quantity be 2-12 normal carbon chain or contain side chain divalent alcohol; Wherein, the ratio of the carboxyl functional group of reaction mixture and hydroxy functional group is 1: 0.9-1.3.
Though the polyester according to above-mentioned patented claim has the toughness of obvious raising with respect to the polyester by the preparation of short carbon chain di-carboxylic acid; Yet; Polyester according to above-mentioned patented claim is linear long-chain because of main chain, causes the product processing characteristics bad, can't use as product separately.
Summary of the invention
The objective of the invention is to overcome the above-mentioned defective of existing polyester, the polyester that a kind of preparation method of polyester is provided and has adopted the preparation of this method adopts the polyester of this method preparation to have better machining property and degradation speed faster.
The invention provides a kind of preparation method of polyester; Wherein, This method comprises: under the condition of esterification and/or transesterification reaction, in the presence of first catalyzer, make component a, components b and amount of component b contact reacts; Under the polycondensation condition, with the product and the second catalyzer contact reacts that obtain after the reaction; Said component a is C
11-C
20Di-carboxylic acid, C
11-C
20The ester and the C of di-carboxylic acid
11-C
20The acid anhydrides of di-carboxylic acid at least a, said b is aliphatic dihydroxy alcohol and/or alicyclic divalent alcohol, said amount of component b is C
3-C
10Unsaturated dicarboxylic acid, C
3-C
10Ester, the C of unsaturated dicarboxylic acid
3-C
10Unsaturated dicarboxylic acid anhydride and epoxy compounds at least a; Said first catalyzer is oxide compound, the M (OR that is selected from M
1)
nAnd M (OOCR
2)
nIn one or more, wherein, M is titanium, antimony or zinc, the value of n is identical with the valence state of M, R
1Be C
1-C
10Alkyl, R
2Be C
1-C
30Alkyl; Said second catalyzer is that chemical formula is RE (R
3)
3Compound in one or more, wherein, RE is one or more in the thulium, R
3For being selected from halogen, C
1-C
30Alkoxyl group, C
1-C
30Aryloxy, acetylacetone based and R
4A kind of in the COO-group, R
4Be C
1-C
30Alkyl.
The present invention also provides a kind of polyester that is made by the method for preparing polyester provided by the invention.
Have better machining property and degradation speed faster according to the polyester of said method preparation provided by the invention, its reason possibly be, by C
11-C
20Long-chain binary hydroxy acid prepare and add a spot of C in the process of polyester
3-C
10Unsaturated monomer or epoxy compounds, can on polyester, introduce some side chains, make the polyester of preparation like this have higher elongation at break, and degradation speed faster.
Embodiment
According to said method provided by the invention, said component a is C
11-C
20Di-carboxylic acid, C
11-C
20The ester and the C of di-carboxylic acid
11-C
20The acid anhydrides of di-carboxylic acid at least a.In the present invention, said C
11-C
20Di-carboxylic acid can be saturated dicarboxylic acid, also can be undersaturated di-carboxylic acid.
Under preferable case, said component a is C
12-C
18Di-carboxylic acid, C
12-C
18The ester and the C of di-carboxylic acid
12-C
18The acid anhydrides of di-carboxylic acid at least a, for example can be in 12 carbon di-carboxylic acid, 13 carbon di-carboxylic acid, 14 carbon di-carboxylic acid, 15 carbon di-carboxylic acid, 16 carbon di-carboxylic acid, 17 carbon di-carboxylic acid, 18 carbon di-carboxylic acid and their ester and the acid anhydrides at least a.
According to said method provided by the invention, said components b is aliphatic dihydroxy alcohol and/or alicyclic divalent alcohol.The carbonatoms of preferred ingredient b is 2-10.Said aliphatic dihydroxy alcohol for example can be in terepthaloyl moietie, Ucar 35, butyleneglycol, pinakon and the pentanediol at least a; Said alicyclic divalent alcohol for example can be in 1,4 cyclohexane dimethanol, three ring 12 carbon dimethanols, 12 carbon naphthenes, the two pure and mild the spiroglycols (like volution terepthaloyl moietie) at least a.
According to said method provided by the invention, said amount of component b is C
3-C
10Unsaturated dicarboxylic acid, C
3-C
10Ester, the C of unsaturated dicarboxylic acid
3-C
10Unsaturated dicarboxylic acid anhydride and epoxy compounds at least a.Said C
3-C
10Unsaturated dicarboxylic acid for example can be in fumaric acid, maleic acid, methylene-succinic acid, citraconic acid and the chloro maleic acid at least a, said C
3-C
10The ester of unsaturated dicarboxylic acid can be above-mentioned various C
3-C
10The methyl esters or the ethyl ester of unsaturated dicarboxylic acid, said C
3-C
10Unsaturated dicarboxylic acid anhydride can be above-mentioned various C
3-C
10The acid anhydrides of unsaturated dicarboxylic acid.Said epoxy compounds can be in epoxy soybean oil, oxyethane and the propylene oxide at least a.
According to said method provided by the invention, said first catalyzer is oxide compound, the M (OR that is selected from M
1)
nAnd M (OOCR
2)
nIn one or more, wherein, M is titanium, antimony or zinc, the value of n is identical with the valence state of M, R
1Be C
1-C
10Alkyl, R
2Be C
1-C
30Alkyl.In order further to improve the processing characteristics and the degradation speed of the polyester of final preparation, said first catalyzer is preferably at least a in oxide compound and the titanyl compound of the oxide compound that is selected from titan-alkoxide, antimony acetate, zinc acetate, zinc, antimony.Further under the preferable case, said first catalyzer is for being selected from tetrabutyl titanate (Ti (OC
4H
9)
4), at least a in tetraisopropoxy titanium, titanium oxide, Antimony Trioxide: 99.5Min, antimony acetate and the zinc acetate.
According to said method provided by the invention, said second catalyzer is that chemical formula is RE (R
3)
3Compound in one or more, wherein, RE is one or more in the thulium, R
3For being selected from halogen, C
1-C
30Alkoxyl group, C
1-C
30Aryloxy, acetylacetone based and R
4A kind of in the COO-group, R
4Be C
1-C
30Alkyl.In order further to improve the processing characteristics and the degradation speed of the polyester of final preparation, in said second catalyzer, be RE (R at chemical formula
3)
3Compound in, RE is preferably lanthanum, cerium, praseodymium, neodymium, terbium, ytterbium, dysprosium, samarium or scandium; Said halogen is a chlorine or bromine, and said alkoxyl group is C
3-C
6Alkoxyl group, said aryloxy is the aryloxy that comprises at least one phenyl ring and/or naphthalene nucleus, R
4R in the COO-group
4Be C
1-C
20Alkyl.Further under the preferable case, RE is for being selected from lanthanum, cerium, praseodymium, neodymium or scandium, and said halogen is a chlorine or bromine, and the alkyl in the said alkoxyl group is sec.-propyl, normal-butyl or isopentyl, and said aryloxy is 2,6-di-t-butyl-4-methylphenoxy or 4-butyl phenoxy, R
4R in the COO-group
4Be C
3-C
18Alkyl.Under the preferred situation; Said second catalyzer is one or more in methyl ethyl diketone lanthanum, methyl ethyl diketone neodymium, isopropoxy neodymium, isopropoxy lanthanum, isopropoxy scandium, Triple Pressed Stearic Acid lanthanum, Triple Pressed Stearic Acid neodymium, Lanthanum trichloride and three (2, the 6-di-t-butyl-4-methylphenoxy) lanthanum.
According to said method provided by the invention, the condition of said esterification and/or transesterification reaction can comprise that temperature of reaction is 150-220 ℃, and the reaction times was at least 30-300 minute.Under the preferable case, the condition of said esterification and/or transesterification reaction comprises that temperature of reaction is 160-200 ℃, and the reaction times was at least 60-150 minute.
According to said method provided by the invention; The mol ratio of said component a and components b can be 1: 0.5-10; The mol ratio of said amount of component b and component a can be 1: 10-10000, the mol ratio of said first catalyzer and said component a can be 1: 1000-10000.Under the preferable case, the mol ratio of said component a and components b is 1: 0.8-3, the mol ratio of said amount of component b and component a is 1: 20-1000, the mol ratio of said first catalyzer and said component a is 1: 2000-6000.
According to said method provided by the invention; Can produce water in the said esterification reaction process; Can produce monohydroxy-alcohol (like methyl alcohol, ethanol etc.) in the said ester-exchange reaction; Decidable esterification and transesterification reaction were accomplished when therefore, said esterification and/or said transesterification reaction proceeded to water and monohydroxy-alcohol in the reaction system separately and steam fully.
According to said method provided by the invention, said polycondensation condition can comprise that temperature of reaction is 200-300 ℃, and the reaction absolute pressure is 0-800Pa, and the reaction times is 3-10 hour.Under the preferable case, said polycondensation condition comprises that temperature of reaction is 240-260 ℃, and the reaction absolute pressure is 10-300Pa, and the reaction times is 4-7 hour.
According to said method provided by the invention, the mol ratio of said second catalyzer and first catalyzer can be 0.1-10: 1, be preferably 0.3-3: and 1,0.6-1.5 more preferably: 1.
The present invention also provides a kind of polyester by method for preparing provided by the invention.
In a kind of preferred implementation, the second-order transition temperature of this polyester is-80 ℃ to-20 ℃, and fusing point is 70-100 ℃.In this case, this polyester has very high elongation at tear, thereby has better machining property, and this polyester also has very fast degradation speed simultaneously.
Below through embodiment the present invention is described further, but protection scope of the present invention is not limited only to this.
In following examples, the methyl ethyl diketone lanthanum makes according to the method for embodiment A among the CN1807485A 2; The isopropoxy scandium makes according to the method for embodiment A among the CN1807485A 3; Three (2,6-di-t-butyl-4-methylphenoxy) lanthanum makes according to the method for embodiment A among the CN1807485A 4; Cerous acetate makes according to the method according to embodiment A among the CN1807485A 6.
Embodiment 1
Present embodiment is used to explain the preparation method of said polyester of the present invention and the polyester that is prepared by this method.
The bay diacid (available from sea, Ningbo safe heavy chemicals ltd) of 0.8mol, the terepthaloyl moietie of 0.97mol, fumaric acid (selling ltd available from the rich horse chemical industry in Zibo) and the tetrabutyl titanate (available from Beijing chemical reagents corporation) of 0.293mmol of 0.008mol are added in the there-necked flask of 500ml; Under nitrogen protection; Be heated with stirring to backflow, temperature of reaction be adjusted to 180 ℃ and about 100 minutes of reaction under this temperature, when the water that question response generates steams fully; The methyl ethyl diketone lanthanum that in this there-necked flask, adds 0.175mmol; There-necked flask is vacuumized, and temperature wherein is increased to 250 ℃, make absolute pressure≤200Pa wherein; Reaction 6h obtains white solid polymer P1 under this temperature and pressure.
Comparative Examples 1
Method according to embodiment 1 prepares polyester, and different is in said there-necked flask, not add fumaric acid, thereby make white solid polymkeric substance DP1.
Comparative Examples 2
Method according to embodiment 1 prepares polyester, and different is with the tetrabutyl titanate replacement methyl ethyl diketone lanthanum wherein of same molar, thereby to make white solid polymkeric substance DP2.
Embodiment 2
Present embodiment is used to explain the preparation method of said polyester of the present invention and the polyester that is prepared by this method.
With 1 of the 13 carbon di-carboxylic acid dimethyl esters (straight chain is available from Zibo Guangtong Chemical Industry) of 1.0mol, 0.5mol, the Antimony Trioxide: 99.5Min (available from Beijing chemical reagents corporation) of the epoxy soybean oil of 4-butyleneglycol, 0.001mol (available from the triumphant chemical industry in Zibo ltd) and 0.333mmol adds in the there-necked flask of 500ml; Under nitrogen protection, be heated with stirring to backflow, and with temperature of reaction be adjusted to 160 ℃ and under this temperature the reaction about 150 minutes; When the methyl alcohol that question response generates steams fully; In this there-necked flask, add three (2,6-di-t-butyl-4-methylphenoxy) lanthanum of 0.32mmol, there-necked flask is vacuumized; And the temperature of inciting somebody to action wherein is increased to 240 ℃; Make absolute pressure≤150Pa wherein, reaction 7h obtains white solid polymer P2 under this temperature and pressure.
Embodiment 3
Present embodiment is used to explain the preparation method of said polyester of the present invention and the polyester that is prepared by this method.
With 1 of the ten four-carbon dicarboxylic acid acid anhydrides (straight chain is available from Zibo Guangtong Chemical Industry) of 0.6mol, 1.8mol, in the there-necked flask of zinc acetate (available from Beijing chemical reagents corporation) the adding 500ml of the fumaric acid of 6-pinakon, 0.03mol (selling ltd) and 0.1mmol available from the rich horse chemical industry in Zibo; Under nitrogen protection; Be heated with stirring to backflow, and temperature of reaction is adjusted to 200 ℃ and about 50 minutes of reaction under this temperature, when the water that question response generates steams fully; The isopropoxy scandium that in this there-necked flask, adds 0.15mmol; There-necked flask is vacuumized, and temperature wherein is increased to 260 ℃, make absolute pressure≤100Pa wherein; Reaction 4h obtains white solid polymer P3 under this temperature and pressure.
Embodiment 4
Present embodiment is used to explain the preparation method of said polyester of the present invention and the polyester that is prepared by this method.
Method according to embodiment 3 prepares polyester, and different is, with 15 carbon dicarboxylic acid (straight chains of same molar; Available from Zibo Guangtong Chemical Industry) replacement ten four-carbon dicarboxylic acid acid anhydrides wherein; With 1 of same molar, the 5-pentanediol replace wherein 1, the 6-pinakon; Maleic acid (containing chemical industry ltd available from Wenzhou City's hat) with same molar replaces fumaric acid wherein, thereby makes white solid polymer P 4.
Embodiment 5
Present embodiment is used to explain the preparation method of said polyester of the present invention and the polyester that is prepared by this method.
Method according to embodiment 3 prepares polyester, and different is, with the 16-dicarboxylic acid (straight chain of same molar; Available from Zibo Guangtong Chemical Industry) replacement ten four-carbon dicarboxylic acid acid anhydrides wherein; With 1 of same molar, the 7-heptanediol replace wherein 1, the 6-pinakon; Maleic acid (containing chemical industry ltd available from Wenzhou City's hat) with same molar replaces fumaric acid wherein, thereby makes white solid polymer P 5.
Embodiment 6
Present embodiment is used to explain the preparation method of said polyester of the present invention and the polyester that is prepared by this method.
Method according to embodiment 3 prepares polyester, and different is with the cerous acetate replacement isopropoxy scandium wherein of same molar, thereby to make white solid polymer P 6.
Embodiment 7
Present embodiment is used to explain the preparation method of said polyester of the present invention and the polyester that is prepared by this method.
Method according to embodiment 3 prepares polyester, and different is with tetraisopropoxy titanium (available from Beijing chemical reagents corporation) the replacement zinc acetate wherein of same molar, thereby to make white solid polymer P 7.
Test case 1
Detect weight-average molecular weight and the MWD coefficient of polymer P 1-P7 and DP1-DP2 according to GPC (GPC); With THF (THF) is solvent; At Waters-208 (band Waters 2410RI detector; 1.5ml/min flow velocity, 30 ℃) to measure on the instrument, weight-average molecular weight is calibrated with the vinylbenzene standard specimen;
Detect second-order transition temperature and the fusing point of polymer P 1-P7 and DP1-DP2 according to DSC (DSC) assay method; On Perkin Elmer Pyris 1 determinator; Each sample is heated to 250 ℃ from-100 ℃, adds heat scan through both sides, and heating rate is 20 ℃/min;
Detect tensile mechanical properties such as stretching yield stress, tensile break stress and the tension fracture elongation rate of polymer P 1-P7 and DP1-DP2 according to the method for ASTM D638-03;
Its detected result is as shown in table 1 below.
Table 1
Data by table 1 can find out that the prepared according to the methods of the invention polyester has lower second-order transition temperature and fusing point, and have higher tensile mechanical properties, thereby have better machining property.
Test case 2
Adopt following mode to detect the degradation property of polymer P 1-P7 and DP1-DP2: the film that polymer samples is hot pressed into 15 μ m; Be cut into the print that surface-area is 2cm * 2cm, imbed in the petridish that composting soil is housed, put into the incubator of fixed temperature and humidity together; Keeping humidity is about 50%; Temperature is 58 ± 2 ℃, the weightlessness of period sampling measuring sample, and its detected result is as shown in table 2 below.
Table 2
| Polymkeric substance | One week weightless (weight %) | Two weeks weightless (weight %) | Three weeks weightless (weight %) | Weightless (weight %) all around |
| P1 | 70 | 100 | - | - |
| DP1 | 30 | 60 | 80 | 100 |
| DP2 | 45 | 80 | 95 | 100 |
| P2 | 65 | 100 | - | - |
| P3 | 70 | 100 | - | - |
| P4 | 65 | 100 | - | - |
| P5 | 65 | 100 | - | - |
| P6 | 65 | 100 | - | - |
| P7 | 65 | 100 | - | - |
Data by table 2 can find out that the prepared according to the methods of the invention polyester has degradation rate faster.
Claims (13)
1. the preparation method of a polyester; It is characterized in that; This method comprises: under the condition of esterification and/or transesterification reaction, in the presence of first catalyzer, make component a, components b and amount of component b contact reacts; Under the polycondensation condition, with the product and the second catalyzer contact reacts that obtain after the reaction;
Said component a is C
11-C
20Di-carboxylic acid, C
11-C
20The ester and the C of di-carboxylic acid
11-C
20The acid anhydrides of di-carboxylic acid at least a, said components b is aliphatic dihydroxy alcohol and/or alicyclic divalent alcohol, said amount of component b is C
3-C
10Unsaturated dicarboxylic acid, C
3-C
10Ester, the C of unsaturated dicarboxylic acid
3-C
10Unsaturated dicarboxylic acid anhydride and epoxy compounds at least a;
Said first catalyzer is oxide compound, the M (OR that is selected from M
1)
nAnd M (OOCR
2)
nIn one or more, wherein, M is titanium, antimony or zinc, the value of n is identical with the valence state of M, R
1Be C
1-C
10Alkyl, R
2Be C
1-C
30Alkyl; Said second catalyzer is that chemical formula is RE (R
3)
3Compound in one or more, wherein, RE is one or more in the thulium, R
3For being selected from halogen, C
1-C
30Alkoxyl group, C
1-C
30Aryloxy, acetylacetone based and R
4A kind of in the COO-group, R
4Be C
1-C
30Alkyl.
2. method according to claim 1; Wherein, The condition of said esterification and/or transesterification reaction comprises that temperature of reaction is 150-220 ℃, and the reaction times was at least 30-300 minute, and the mol ratio of said component a and components b is 1: 0.5-10; The mol ratio of said amount of component b and component a is 1: 10-10000, and the mol ratio of said first catalyzer and said component a is 1: 1000-10000; Said polycondensation condition comprises that temperature of reaction is 200-300 ℃, and the reaction absolute pressure is 0-800Pa, and the reaction times is 3-10 hour, and the mol ratio of second catalyzer and first catalyzer is 0.1-10: 1.
3. method according to claim 2; Wherein, The condition of said esterification and/or transesterification reaction comprises that temperature of reaction is 160-200 ℃, and the reaction times was at least 30-150 minute, and the mol ratio of said component a and components b is 1: 0.8-3; The mol ratio of said amount of component b and component a is 1: 20-1000, and the mol ratio of said first catalyzer and said component a is 1: 1500-6000; Said polycondensation condition comprises that temperature of reaction is 220-260 ℃, and the reaction absolute pressure is 10-400Pa, and the reaction times is 4-7 hour, and the mol ratio of second catalyzer and first catalyzer is 0.3-3: 1.
4. according to any described method among the claim 1-3, wherein, said first catalyzer is at least a in oxide compound and the titanyl compound of the oxide compound that is selected from titan-alkoxide, antimony acetate, zinc acetate, zinc, antimony.
5. method according to claim 4, wherein, said first catalyzer is to be selected from least a in tetrabutyl titanate, tetraisopropoxy titanium, titanium oxide, Antimony Trioxide: 99.5Min, antimony acetate and the zinc acetate.
6. method according to claim 1, wherein, RE is selected from lanthanum, cerium, praseodymium, neodymium, terbium, ytterbium, dysprosium, samarium or scandium.
7. method according to claim 6, wherein, RE is selected from lanthanum, cerium, praseodymium, neodymium or scandium.
8. according to claim 1 or 6 described methods, wherein, said halogen is a chlorine or bromine, and said alkoxyl group is C
3-C
6Alkoxyl group, said aryloxy is the aryloxy that comprises at least one phenyl ring and/or naphthalene nucleus, R
4R in the COO-group
4Be C
1-C
20Alkyl.
9. method according to claim 8, wherein, the alkyl in the said alkoxyl group is sec.-propyl, normal-butyl or isopentyl, said aryloxy is 2,6-di-t-butyl-4-methylphenoxy or 4-butyl phenoxy, R
4R in the COO-group
4Be C
3-C
18Alkyl.
10. method according to claim 1; Wherein, said component a is at least a in 12 carbon di-carboxylic acid, 13 carbon di-carboxylic acid, 14 carbon di-carboxylic acid, 15 carbon di-carboxylic acid, 16 carbon di-carboxylic acid, 17 carbon di-carboxylic acid, 18 carbon di-carboxylic acid and their ester and the acid anhydrides; Said components b is at least a in terepthaloyl moietie, Ucar 35, butyleneglycol, pinakon, pentanediol, 1,4 cyclohexane dimethanol, three rings, 12 carbon dimethanols, 12 carbon naphthenes, the two pure and mild the spiroglycols; Said amount of component b is at least a in fumaric acid, fumaric acid anhydride, maleic acid, maleic anhydride, methylene-succinic acid, citraconic acid, chloro maleic acid, epoxy soybean oil, oxyethane and the propylene oxide.
11. polyester by any described method preparation among the claim 1-10.
12. polyester according to claim 11, wherein, the second-order transition temperature of this polyester is-80 ℃ to-20 ℃.
13. according to claim 11 or 12 described polyester, wherein, the fusing point of this polyester is 70-100 ℃.
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| CN103113563A (en) * | 2013-01-18 | 2013-05-22 | 清华大学 | Branched aliphatic polyester and synthetic method thereof |
| CN110437430A (en) * | 2018-05-02 | 2019-11-12 | 中国石油化工股份有限公司 | A kind of modified poly ester and preparation method thereof |
| CN113088234A (en) * | 2019-12-23 | 2021-07-09 | 上海理日化工新材料有限公司 | Low-shrinkage high-melting-point light hot melt adhesive composition and preparation method thereof |
| CN115260470A (en) * | 2022-03-23 | 2022-11-01 | 旭科新材料(山东)有限责任公司 | Composition for preparing polyester film material, polyester film material and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1556142A (en) * | 2004-01-09 | 2004-12-22 | 中国科学院长春应用化学研究所 | Preparation method of biodegradable polyester composite material |
| CN1796433A (en) * | 2004-12-23 | 2006-07-05 | 中国石油化工股份有限公司 | Method for synthesizing polyester by using rare earth catalyst |
| CN101704943A (en) * | 2009-11-12 | 2010-05-12 | 浙江大学 | Rare earth catalyst of condensation and polymerization synthesis of polyester and linear functionalization polyester and application thereof |
-
2010
- 2010-10-15 CN CN 201010516905 patent/CN102453243B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1556142A (en) * | 2004-01-09 | 2004-12-22 | 中国科学院长春应用化学研究所 | Preparation method of biodegradable polyester composite material |
| CN1796433A (en) * | 2004-12-23 | 2006-07-05 | 中国石油化工股份有限公司 | Method for synthesizing polyester by using rare earth catalyst |
| CN101704943A (en) * | 2009-11-12 | 2010-05-12 | 浙江大学 | Rare earth catalyst of condensation and polymerization synthesis of polyester and linear functionalization polyester and application thereof |
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| CN103113563B (en) * | 2013-01-18 | 2015-08-19 | 清华大学 | A kind of cladodification aliphatic polyester and synthetic method thereof |
| CN110437430A (en) * | 2018-05-02 | 2019-11-12 | 中国石油化工股份有限公司 | A kind of modified poly ester and preparation method thereof |
| CN113088234A (en) * | 2019-12-23 | 2021-07-09 | 上海理日化工新材料有限公司 | Low-shrinkage high-melting-point light hot melt adhesive composition and preparation method thereof |
| CN115260470A (en) * | 2022-03-23 | 2022-11-01 | 旭科新材料(山东)有限责任公司 | Composition for preparing polyester film material, polyester film material and application thereof |
| CN115260470B (en) * | 2022-03-23 | 2023-11-17 | 旭科新材料(山东)有限责任公司 | Composition for preparing polyester film material, polyester film material and application thereof |
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