CN1796435A - Modified butanediol ester poly succinic acid and synthetic method - Google Patents
Modified butanediol ester poly succinic acid and synthetic method Download PDFInfo
- Publication number
- CN1796435A CN1796435A CNA200410098973XA CN200410098973A CN1796435A CN 1796435 A CN1796435 A CN 1796435A CN A200410098973X A CNA200410098973X A CN A200410098973XA CN 200410098973 A CN200410098973 A CN 200410098973A CN 1796435 A CN1796435 A CN 1796435A
- Authority
- CN
- China
- Prior art keywords
- succinic acid
- acid
- butanediol ester
- maleopimaric
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
This invention relates to a cyclic compound, especially poly (butylenes succinate) modified by copolymerization with maleopimaric anhydride and its synthesis method. Succinic acid, 1,4-butanediol are mixed at a mole ratio of 1:1~4, and 4~20g maleopimaric imine dicarboxylic ester oligomers are added per 163g succinic acid/1,4-butanediol mixture. The system is stirred at a temperature of 160~200 deg.C in the presence of inert gas, and cadmium acetate, zincum acetate, stibium oxide, butyl titanate or their optional combinations are added as catalysts at a mass fraction of 0.1~3% for a polymerization at a temperature of 230~280 deg.C and a pressure of 5~10Pa to produce modified poly(butylenes succinate) with a following structure. Such an environmentally friendly polymer performs a good elongation rate at break, impact-resistance strength and bending strength.
Description
Technical field
This patent relates to a kind of ring compound, particularly maleopimaric anhydride modification by copolymerization poly butylene succinate and synthetic method thereof.
Background technology
In recent years, because the development of plastics industry and people are to the pay attention to day by day of environmental problem, " white pollution " problem that is caused by plastics more and more is subjected to people's attention, how to seek a kind of can the degraded, environmental friendliness and can satisfy the difficult problem that the plastics of the different demands of people have become numerous scientific workers to face jointly.Aliphatic polyester more and more is subjected to people's favor as a kind of bio-degradable plastics that everybody generally acknowledges.
Poly butylene succinate (PBS) is a kind of fusing point and the intensity higher aliphatic polyester that all compares, and most possibly replaces other existing non-biodegradation plastics and becomes a kind of general type material.Early several years ago, clear and polymer company of Japan and the S.K.Ind trade(brand)name that just released one after another is respectively: the commercialization poly butylene succinate of Bionolle and Skygreen, but fail to obtain in a large number, promote the use of widely always.Mainly be because aliphatic polyester for other non-biodegradation plastics, has the shortcoming that intensity is low, price is high, the cost performance that therefore how to improve aliphatic polyester has become urgent problem.People such as In.kwon.jung [J.Appl.Polym.Sci, Vol 72,553-561 (1999)] with 1,4-cyclohexanedimethanol (CHDM) structure is found after introducing the PBS main chain, increase along with the CHDM structural content, when the elongation at break of material increased a little, its fusing point, biodegradability and tensile strength all significantly reduced.Darwin P.R.Kint[Polymer 44 (2003) 1321-1330] and Wilt, U[Macromol.Chem.Phy.1996,197,1525] etc. the people's studies show that, common aromatic series phenyl ring (as phenylglycol structure, terephthalic acid structure) be introduced in the relevant mechanical property that can improve aliphatic polyester to a certain extent, but its biodegradability can be subjected to very big influence, and degraded product is under a cloud to the environment toxic side effect.
Summary of the invention
One of purpose of the present invention provides a kind of environment-friendly modified poly butylene succinate that is expected to suitability for industrialized production, and this modified butanediol ester poly succinic acid is cheap, and fusing point, biodegradability and resistance to impact shock and flexural strength height.
Two of purpose of the present invention provides a kind of synthetic method of modified butanediol ester poly succinic acid.
The chemical structural formula of modified butanediol ester poly succinic acid of the present invention is as follows:
Wherein,
Or
N=2～21; M=50～250; Hydrogen phenanthrene ring structure molar content 0.5%～8%.Limiting viscosity: 0.6～1.5dl/g.
Maleopimaric acid imidodicarboxylic acid ester oligomer related among the present invention can synthesize as follows:
Wherein:
Or
(1) with maleopimaric anhydride (RMA), amino acid [H
2N-R-COOH, R=(CH
2)
N1N1=1～18, or
Be dissolved in an amount of N in 1: 1 in molar ratio; behind the dinethylformamide (DMF); add and have in the reactor of thermometer, stirring, nitrogen protection device; after the stirring at room 3～18 hours, be warming up to 130～150 ℃ and stirred 2～4 hours, be cooled to room temperature; become the yellowish brown solid; add an amount of distilled water, stir, have yellow mercury oxide to produce.Filter washing, vacuum-drying 3～5 hours, with DMF and water recrystallization repeatedly, final product becomes the white powder solid, inserts in the vacuum drying oven 90 ℃～100 ℃ following vacuum-dryings 8～10 hours, obtain maleopimaric acid imide dicarboxylic acid (RMID), standby, productive rate 60%～86%.
(2) the maleopimaric acid imide dicarboxylic acid that step (1) is made and excessive 1; the 4-butyleneglycol joins and has stirring; heating; in the reactor of nitrogen protection device; temperature be under 230～300 ℃ with zinc oxide, zinc acetate, antimonous oxide or their mixture as catalyzer; react after 5～8 hours extract out with vacuum pump unnecessary 1, the 4-butyleneglycol.Pour out viscous liquid under the nitrogen protection, be cooled to room temperature, become the reddish-brown brittle solid.Product is with DMF and methyl alcohol repeatedly behind the recrystallization, 80～100 ℃ of following vacuum-dryings 4～8 hours, maleopimaric acid imidodicarboxylic acid ester oligomer, standby, productive rate 42%～52.3%.Polymerization degree n=8～21 wherein.
Maleopimaric anhydride structural formula of the present invention is as follows:
The maleopimaric acid imide dicarboxylic acid structure is identified (is example with para-amino benzoic acid and RMA reaction), sees Fig. 1, Fig. 2, Fig. 3, Fig. 4.
Above IR, ultimate analysis shows that successfully preparing maleopimaric acid imide dicarboxylic acid maleopimaric acid imidodicarboxylic acid ester oligomer structure identifies (is example with para-amino benzoic acid and RMA reaction), sees Fig. 5, Fig. 6.
H
1-NMR(CDCl
3，300MHz)
| Chemical shift (ppm) | Ownership is explained |
| δ5.4(s) | A position (1H) |
| δ4.3(t) | X position (2H) |
| δ4.1(t) | Y position (2H) |
Infrared spectra (KBr compressing tablet)
Above IR, H
1-NMR shows and successfully prepares maleopimaric acid imidodicarboxylic acid ester oligomer
The synthetic route of modified butanediol ester poly succinic acid of the present invention is as follows:
With Succinic Acid; 1; 4-butyleneglycol 1: 1 in molar ratio～4 mixes; every 163g Succinic Acid in reactor; 1; the mixture of 4-butyleneglycol adds 4～20g maleopimaric acid imidodicarboxylic acid ester oligomer; under protection of inert gas; in 160～200 ℃ of following heated and stirred after 3～5 hours; use cadmium acetate; zinc acetate; antimonous oxide; butyl (tetra) titanate or their any mixture are as catalyzer; put in the reactor by 0.1%～3% of the quality that always feeds intake; at 230～280 ℃; polymerization is 4～9 hours under 5～10Pa; obtain thick modified butanediol ester poly succinic acid melt, cooling crystallizes into pale solid.Record 113～105 ℃ of fusing points, limiting viscosity 0.6～1.5dl/g.
Described rare gas element is nitrogen or argon gas etc.
Wherein:
Or
The modified butanediol ester poly succinic acid structure is identified: (is example with para-amino benzoic acid and RMA reaction), see Fig. 7, Fig. 8.
Above IR, H
1-MR shows and successfully prepares polymkeric substance.
People introduced the PBS segment with simple ring texture (as common phenyl ring or cyclohexane structure) before the present invention was different from, with the derivative of natural rosin acid---and hydrogen phenanthrene ring huge in the maleopimaric anhydride has been introduced the PBS main chain.The carboxyl activity is low having solved on the polymerization process on the hydrogen phenanthrene ring, is difficult to the difficult problem that copolymerization obtains high molecular weight product, has successfully prepared high-molecular weight modification PBS.By its property research being found the introducing of a small amount of hydrogen phenanthrene ring has significantly improved the crystallization behavior of PBS, greatly reduces its crystallization velocity and Tc, has improved its elongation at break, shock strength and flexural strength.Simultaneously, the material that is used for modification comes from nontoxic natural product, can avoid the toxic side effect of degraded product to environment.In addition, rosin is as the rich renewable natural resource of a kind of cheapness that produce of China, and its deep processed product is less relatively, and the present invention has further opened up its application new way.
Description of drawings:
Fig. 1. maleopimaric anhydride (RMA) H
1-nmr spectrum (solvent: CDCl
3, 300MHZ);
Fig. 2. maleopimaric anhydride (RMA) infrared spectrum (KBr compressing tablet);
Fig. 3. maleopimaric acid imide dicarboxylic acid (RMID) H
1-nmr spectrum (solvent: CDCl
3, 300MHZ);
Fig. 4. maleopimaric acid imide dicarboxylic acid (RMID) infrared spectrum (KBr compressing tablet);
Fig. 5. maleopimaric acid imide dicarboxylic acid oligopolymer H
1-nmr spectrum (solvent: CDCl
3, 300MHZ);
Fig. 6. maleopimaric acid imide dicarboxylic acid oligopolymer infrared spectrum (KBr compressing tablet);
Fig. 7. final modified butanediol ester poly succinic acid polymkeric substance H
1-nmr spectrum (solvent: CDCl
3, 300MHZ);
Fig. 8. final modified butanediol ester poly succinic acid polymkeric substance infrared spectra (polymeric film).
Embodiment
With maleopimaric anhydride (RMA) 0.1mol, Padil 0.1mol, N; dinethylformamide 150ml (DMF) adds and has in the four-hole bottle of thermometer, stirring, nitrogen protection device; after the stirring at room 8 hours; being warming up to 130 ℃ stirred 4 hours; be cooled to room temperature, become the yellowish brown solid, add 200ml water; stir, have yellow mercury oxide to produce.Filter, washing, vacuum-drying 3 hours, with DMF and water recrystallization repeatedly, final product becomes the white powder solid, inserts in the vacuum drying oven 90 ℃ of vacuum-dryings 10 hours, obtains maleopimaric acid imide dicarboxylic acid (RMID), and is standby, productive rate 56%.
Get the maleopimaric acid imide dicarboxylic acid 0.05mol that makes of step and excessive 1; the 4-butyleneglycol adds and has stirring; heating; in the four-hole bottle of nitrogen protection device; under 230～300 ℃ with the mixture of zinc acetate, antimonous oxide as catalyzer; react after 5～8 hours, it is unnecessary 1 to extract out with vacuum pump, the 4-butyleneglycol.Pour out viscous liquid under the nitrogen protection, be cooled to room temperature, become the reddish-brown brittle solid.Product is with DMF and methyl alcohol repeatedly behind the recrystallization, 80 ℃ of following vacuum-dryings 4 hours, oligopolymer, standby, productive rate 42.3%.Polymerization degree n=8～18 wherein.
With Succinic Acid and 1,4-butyleneglycol 1: 2 in molar ratio is 163g altogether, and the above-mentioned oligopolymer of 10g adds and has heating, stir and the four-hole bottle of nitrogen protection device in, in 180 ℃ of following heated and stirred after three hours, it is unnecessary 1 to steam, the 4-butyleneglycol.Add 0.1～0.2g butyl (tetra) titanate and zinc acetate as catalyzer, 270 ℃ of following vacuum polymerizations 6 hours, obtain thick melt, cooling crystallizes into pale solid 110g.Record 107 ℃ of fusing points, limiting viscosity 0.9dl/g; After 110 ℃ of injection mouldings, record material impact intensity: 48.5J/m by ASTM; Flexural strength: 37.4MPa; Elongation at break: 360%.Corresponding unmodified PBS shock strength is that 38.9J/m, flexural strength are that 37.5MPa, elongation at break are 272%.
Embodiment 2,
With maleopimaric anhydride (RMA) 0.1mol, 6-aminocaprolc acid 0.1mol, N; dinethylformamide 150ml (DMF) adds and has in the four-hole bottle of thermometer, stirring, nitrogen protection device; after the stirring at room 18 hours; being warming up to 140 ℃ stirred 4 hours; be cooled to room temperature, become the yellowish brown solid, add 200ml water; stir, have yellow mercury oxide to produce.Filter, washing, vacuum-drying 5 hours, with DMF and water recrystallization repeatedly, final product becomes the white powder solid, inserts in the vacuum drying oven 90 ℃ of vacuum-dryings 10 hours, obtains the maleopimaric acid imide dicarboxylic acid, and is standby, productive rate 70%.
Get the maleopimaric acid imide dicarboxylic acid 0.05mol that makes of step with excessive 1, the 4-butyleneglycol adds and has stirring, heats; in the four-hole bottle of nitrogen protection device, under 230～300 ℃ with antimonous oxide as catalyzer, react after 8 hours; it is unnecessary 1 to extract out with vacuum pump, the 4-butyleneglycol.Pour out viscous liquid under the nitrogen protection, be cooled to room temperature, become the reddish-brown solid.Product is with DMF and methyl alcohol repeatedly behind the recrystallization, 80 ℃ of following vacuum-dryings 4 hours, oligopolymer, standby, productive rate 47.1%.Polymerization degree n=3～15 wherein.
With Succinic Acid and 1,4-butyleneglycol 1: 3 in molar ratio is 195g altogether, and the above-mentioned oligopolymer of 4g adds and has heating, stirs and the four-hole bottle of nitrogen protection device, and in 200 ℃ of following heated and stirred after four hours, it is unnecessary 1 to steam, the 4-butyleneglycol.Add 0.2～0.3g butyl (tetra) titanate as catalyzer, 230 ℃ of following vacuum polymerizations 10 hours obtain thick melt, and cooling crystallizes into pale solid 90g.Record 112.5 ℃ of fusing points, limiting viscosity 1.2dl/g; After 110 ℃ of injection mouldings, record material impact intensity: 41.7J/m by ASTM; Flexural strength: 38.2MPa; Elongation at break: 320%; Corresponding unmodified PBS shock strength is that 38.9J/m, flexural strength are that 37.5MPa, elongation at break are 272%.
Embodiment 3,
With maleopimaric anhydride (RMA) 0.1mol, para-amino benzoic acid 0.1mol, N; dinethylformamide 150ml (DMF) adds and has in the four-hole bottle of thermometer, stirring, nitrogen protection device; after the stirring at room 3 hours; being warming up to 150 ℃ stirred 2 hours; be cooled to room temperature, become the yellowish brown solid, add 200ml water; stir, have yellow mercury oxide to produce.Filtration washing, vacuum-drying 3 hours, DMF and water is recrystallization repeatedly, and final product becomes the white powder solid, inserts in the vacuum drying oven 90 ℃ of vacuum-dryings 10 hours, obtains maleopimaric acid imide dicarboxylic acid (RMID), and is standby, productive rate 86%.See Fig. 1～4.
Get the maleopimaric acid imide dicarboxylic acid 0.05mol that makes of step and excessive 1; the 4-butyleneglycol adds and has stirring; heating; in the four-hole bottle of nitrogen protection device; under 230～300 ℃ with the mixture of zinc oxide, zinc acetate as catalyzer; react after 5 hours extract out with vacuum pump unnecessary 1, the 4-butyleneglycol.Pour out viscous liquid under the nitrogen protection, be cooled to room temperature, become the reddish-brown brittle solid.Product is with DMF and methyl alcohol repeatedly behind the recrystallization, 80 ℃ of following vacuum-dryings 4 hours, oligopolymer, standby, productive rate 52.3%.Polymerization degree n=8～21 wherein.See Fig. 5～6.
With Succinic Acid and 1,4-butyleneglycol 1: 4 in molar ratio is 240g altogether, and the above-mentioned oligopolymer of 25g adds and has heating, stirs and the four-hole bottle of nitrogen protection device, and in 160 ℃ of following heated and stirred after five hours, it is unnecessary 1 to steam, the 4-butyleneglycol.Add 0.3～0.4g cadmium acetate, zinc acetate, butyl (tetra) titanate as catalyzer, 280 ℃ of following vacuum polymerizations 4 hours, obtain thick melt, cooling crystallizes into pale solid 113g.Record 105 ℃ of fusing points, limiting viscosity 0.7dl/g; After 110 ℃ of injection mouldings, record material impact intensity: 48.5J/m by ASTM; Flexural strength: 35.6MPa; Elongation at break: 380%; Corresponding unmodified PBS shock strength is 38.9J/m; Flexural strength is 37.5MPa; Elongation at break is 272%.See Fig. 7～8.
Embodiment 4,
With the amino stearic acid 0.1mol of maleopimaric anhydride (RMA) 0.1mol, 18-, N; dinethylformamide 150ml (DMF) adds and has in the four-hole bottle of thermometer, stirring, nitrogen protection device; after the stirring at room 16 hours; being warming up to 130 ℃ stirred 4 hours; be cooled to room temperature, become the yellowish brown solid, add 160ml water; stir, have yellow mercury oxide to produce.Filtration washing, vacuum-drying 3 hours, with DMF and water recrystallization repeatedly, final product becomes the white powder solid, inserts in the vacuum drying oven 90 ℃ of vacuum-dryings 10 hours, obtains the maleopimaric acid imide dicarboxylic acid, and is standby, productive rate 73.2%.
Get the maleopimaric acid imide dicarboxylic acid 0.05mol that makes of step and excessive 1; the 4-butyleneglycol adds and has stirring; heating; in the four-hole bottle of nitrogen protection device; under 230～300 ℃ with the mixture of zinc oxide, antimonous oxide, zinc acetate as catalyzer; react after 6 hours extract out with vacuum pump unnecessary 1, the 4-butyleneglycol.Pour out viscous liquid under the nitrogen protection, be cooled to room temperature, become the reddish-brown brittle solid.Product is with DMF and methyl alcohol repeatedly behind the recrystallization, 80 ℃ of following vacuum-dryings 4 hours, oligopolymer, standby, productive rate 43.5%.Polymerization degree n=12～17 wherein.
With Succinic Acid and 1,4-butyleneglycol 1: 1 in molar ratio is 198g altogether, and the above-mentioned oligopolymer of 8g adds and has heating, stir and the four-hole bottle of nitrogen protection device in, in 190 ℃ of following heated and stirred after 5 hours, it is unnecessary 1 to steam, the 4-butyleneglycol.Add 0.2～0.3g zinc acetate and zinc oxide as catalyzer, 250 ℃ of following vacuum polymerizations 9 hours, obtain thick melt, cooling crystallizes into pale solid 163g.Record 109 ℃ of fusing points, limiting viscosity 1.06dl/g; After 110 ℃ of injection mouldings, record material impact intensity: 44.2J/m by ASTM; Flexural strength: 40.3MPa; Elongation at break: 330%; Corresponding unmodified PBS shock strength is 38.9J/m; Flexural strength is 37.5MPa; Elongation at break is 272%.
Claims (9)
1. a modified butanediol ester poly succinic acid is characterized in that, described modified butanediol ester poly succinic acid has following structure:
Wherein,
N1=1～18; N=2～21; M=50～250.
2. modified butanediol ester poly succinic acid according to claim 1 is characterized in that: the hydrogen phenanthrene ring structure molar content 0.5%～8% of described modified butanediol ester poly succinic acid.
3. modified butanediol ester poly succinic acid according to claim 1 and 2 is characterized in that: the limiting viscosity of described modified butanediol ester poly succinic acid: 0.6～1.5dl/g.
4. synthetic method according to each described modified butanediol ester poly succinic acid of claim 1～3 is characterized in that:
With Succinic Acid; 1; 4-butyleneglycol 1: 1 in molar ratio～4 mixes; every 163g Succinic Acid in the reactor; 1; the mixture of 4-butyleneglycol adds 4～20g maleopimaric acid imidodicarboxylic acid ester oligomer; under protection of inert gas; in 160～200 ℃ of following heated and stirred reactions; use cadmium acetate; zinc acetate; antimonous oxide; butyl (tetra) titanate or their any mixture are as catalyzer; put in the reactor by 0.1%～3% of the quality that always feeds intake; at 230～280 ℃; polymerization obtains thick modified butanediol ester poly succinic acid melt under 5～10Pa; cooling crystallizes into pale solid.
5. method according to claim 4 is characterized in that: described 160～200 ℃ of following heated and stirred 3～5 hours.
6. method according to claim 4 is characterized in that: described polymerization time is 4～9 hours.
7. method according to claim 4 is characterized in that: described modified butanediol ester poly succinic acid has following structure:
Wherein,
N1=1～18; N=2～21; M=50～250.
8. according to claim 6 or 7 described methods, it is characterized in that: the hydrogen phenanthrene ring structure molar content 0.5%～8% of described modified butanediol ester poly succinic acid, limiting viscosity: 0.6～1.5dl/g.
9. method according to claim 6, it is characterized in that: described maleopimaric acid imidodicarboxylic acid ester oligomer is with maleopimaric acid imide dicarboxylic acid and excessive 1, the 4-butyleneglycol joins in the reactor that has nitrogen protection device, temperature be under 230～300 ℃ with zinc oxide, zinc acetate, antimonous oxide or their mixture as catalyzer, react after 5～8 hours extract out unnecessary 1, the 4-butyleneglycol; Pour out viscous liquid under the nitrogen protection, be cooled to room temperature, become the reddish-brown brittle solid; Product is with DMF and methyl alcohol repeatedly behind the recrystallization, 80～100 ℃ of following vacuum-dryings, maleopimaric acid imidodicarboxylic acid ester oligomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410098973XA CN1332996C (en) | 2004-12-22 | 2004-12-22 | Modified butanediol ester poly succinic acid and synthetic method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410098973XA CN1332996C (en) | 2004-12-22 | 2004-12-22 | Modified butanediol ester poly succinic acid and synthetic method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1796435A true CN1796435A (en) | 2006-07-05 |
| CN1332996C CN1332996C (en) | 2007-08-22 |
Family
ID=36817761
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200410098973XA Expired - Fee Related CN1332996C (en) | 2004-12-22 | 2004-12-22 | Modified butanediol ester poly succinic acid and synthetic method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1332996C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311544A (en) * | 2010-07-09 | 2012-01-11 | 中国科学院宁波材料技术与工程研究所 | Rosinyl plasticizer and preparation method thereof |
| CN102643198A (en) * | 2012-04-01 | 2012-08-22 | 山东万图高分子材料有限公司 | Preparation method of tripalmitin citrate |
| CN102702525A (en) * | 2012-06-21 | 2012-10-03 | 东莞市信诺橡塑工业有限公司 | Biological based long-carbon-chain semi-alicyclic polyamidoimide copolymer and synthetic method of copolymer |
| CN102718950A (en) * | 2012-07-09 | 2012-10-10 | 北京旭阳化工技术研究院有限公司 | Preparation method of biodegradable polybutylene succinate |
| CN102718949A (en) * | 2012-07-09 | 2012-10-10 | 北京旭阳化工技术研究院有限公司 | Preparation method of polybutylene succinate |
| CN102746493A (en) * | 2012-07-09 | 2012-10-24 | 北京旭阳化工技术研究院有限公司 | Preparation method of all-biological-base poly butylenes succinate (PBS) |
| CN103113552A (en) * | 2013-01-22 | 2013-05-22 | 中国科学院宁波材料技术与工程研究所 | Rosin-based chain extender and preparation method thereof |
| CN104370773A (en) * | 2013-06-05 | 2015-02-25 | 中国林业科学研究院林产化学工业研究所 | Rosinyl carbamate and preparation method thereof |
| CN112029078A (en) * | 2020-09-11 | 2020-12-04 | 长春市联禹化学科技有限公司 | Copolyester and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3506521B2 (en) * | 1995-03-08 | 2004-03-15 | ユニチカ株式会社 | Biodegradable core-sheath composite long fiber and method for producing the same |
| CN1073545C (en) * | 1998-10-27 | 2001-10-24 | 中国科学院广州化学研究所 | Process for catalytic esterification of maleopimaric acid |
| JP2003213529A (en) * | 2002-01-11 | 2003-07-30 | Chisso Corp | Biodegradable conjugated fiber and fiber structure and absorption article using the same |
-
2004
- 2004-12-22 CN CNB200410098973XA patent/CN1332996C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311544A (en) * | 2010-07-09 | 2012-01-11 | 中国科学院宁波材料技术与工程研究所 | Rosinyl plasticizer and preparation method thereof |
| CN102311544B (en) * | 2010-07-09 | 2012-12-12 | 中国科学院宁波材料技术与工程研究所 | Rosinyl plasticizer and preparation method thereof |
| CN102643198A (en) * | 2012-04-01 | 2012-08-22 | 山东万图高分子材料有限公司 | Preparation method of tripalmitin citrate |
| CN102702525A (en) * | 2012-06-21 | 2012-10-03 | 东莞市信诺橡塑工业有限公司 | Biological based long-carbon-chain semi-alicyclic polyamidoimide copolymer and synthetic method of copolymer |
| CN102718950A (en) * | 2012-07-09 | 2012-10-10 | 北京旭阳化工技术研究院有限公司 | Preparation method of biodegradable polybutylene succinate |
| CN102718949A (en) * | 2012-07-09 | 2012-10-10 | 北京旭阳化工技术研究院有限公司 | Preparation method of polybutylene succinate |
| CN102746493A (en) * | 2012-07-09 | 2012-10-24 | 北京旭阳化工技术研究院有限公司 | Preparation method of all-biological-base poly butylenes succinate (PBS) |
| CN103113552A (en) * | 2013-01-22 | 2013-05-22 | 中国科学院宁波材料技术与工程研究所 | Rosin-based chain extender and preparation method thereof |
| CN104370773A (en) * | 2013-06-05 | 2015-02-25 | 中国林业科学研究院林产化学工业研究所 | Rosinyl carbamate and preparation method thereof |
| CN104370774A (en) * | 2013-06-05 | 2015-02-25 | 中国林业科学研究院林产化学工业研究所 | Rosinyl carbamate quaternary ammonium salt derivative and preparation method thereof |
| CN104370774B (en) * | 2013-06-05 | 2016-01-20 | 中国林业科学研究院林产化学工业研究所 | A kind of rosinyl carbamate quaternary ammonium salt derivative and preparation method thereof |
| CN112029078A (en) * | 2020-09-11 | 2020-12-04 | 长春市联禹化学科技有限公司 | Copolyester and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1332996C (en) | 2007-08-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109776773B (en) | Preparation method of biodegradable block copolymer | |
| JP3426064B2 (en) | Manufacturing method of macrocyclic polyester oligomer | |
| US20070293629A1 (en) | Preparation of polamide block copolymers | |
| CN111423580B (en) | Shape memory resin based on biomass benzoxazine and preparation method and application thereof | |
| CN1796435A (en) | Modified butanediol ester poly succinic acid and synthetic method | |
| CN107722262B (en) | Polycarbodiimide polymer and preparation method and application thereof | |
| WO2012049044A2 (en) | Polycarbonates as nucleating agents for polylactides. | |
| CN102491874A (en) | Metallic alkoxy complex, catalyst composition and preparation method of poly-caprolactone or poly-lactide | |
| JP2004511595A (en) | Copolymer containing alkylene carbonate and method for producing the same | |
| CN101525411B (en) | Method for producing poly-lactic acid products | |
| CN105368023B (en) | Supermolecule stereoblock polylactic acid that easily Stereocomplex is crystallized and preparation method thereof | |
| CN101538361A (en) | Cyclic esters compound polymerization catalyst, preparation method and application thereof | |
| CN102627760A (en) | Catalyst composition and preparation method of polylactic acid | |
| JP2012523472A (en) | Method for producing heat-resistant polyamide | |
| CN110467726B (en) | High-melting-point bio-based polyesteramide and preparation method thereof | |
| CN101130599A (en) | Heat-resistance polylactic acid copolymer and ring opening polymerization method for preparing the same | |
| CN116789946A (en) | High-temperature-resistant polylactic acid block elastomer and preparation method thereof | |
| CN113621095A (en) | Degradable polymer initiator and preparation method thereof | |
| CN102791764A (en) | Polylactide resin, a production method for the same and a polylactide resin composition comprising the same | |
| CN1903917A (en) | Polyacrylic acid grafted methoxy polyethylene glycol comb shaped copolymer and its synthesis method | |
| CN101041711A (en) | Method for preparing malic acid containing unit functional polyester by biological catalysis in organic medium | |
| CN114479093B (en) | Low molecular weight metal coordination supermolecule triblock copolymer thermoplastic elastomer film | |
| TWI603995B (en) | Copolymer based on dimethyl carbonate and method of preparing the same | |
| CN110818894B (en) | Polyester amide and preparation method thereof | |
| CN115785414B (en) | Polyfurandicarboxylic acid-carbonic acid-butanediol ester and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Zhejiang Chancing Packaging Materials Co., Ltd. Assignor: Institute of Chemistry, Chinese Academy of Sciences Contract fulfillment period: 2007.9.1 to 2013.8.31 contract change Contract record no.: 2008330002317 Denomination of invention: Modified butanediol ester poly succinic acid and synthetic method Granted publication date: 20070822 License type: Exclusive license Record date: 20081124 |
|
| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.9.1 TO 2013.8.31; CHANGE OF CONTRACT Name of requester: ZHEJIANG PROVINCE INTEGRITY PACKAGING MATERIALS CO Effective date: 20081124 |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070822 Termination date: 20131222 |