CN106117529A - The biodegradable copolyester of low moisture-inhibiting - Google Patents

The biodegradable copolyester of low moisture-inhibiting Download PDF

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Publication number
CN106117529A
CN106117529A CN201610598663.7A CN201610598663A CN106117529A CN 106117529 A CN106117529 A CN 106117529A CN 201610598663 A CN201610598663 A CN 201610598663A CN 106117529 A CN106117529 A CN 106117529A
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CN
China
Prior art keywords
inhibiting
dimer
low moisture
acid
biodegradable copolyester
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.)
Pending
Application number
CN201610598663.7A
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Chinese (zh)
Inventor
瞿锋
瞿一锋
胡军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JIANGSU HESHILI NEW MATERIAL CO Ltd
Jiangyin Hechuang Elastomers New Materials Technology Co Ltd
Original Assignee
JIANGSU HESHILI NEW MATERIAL CO Ltd
Jiangyin Hechuang Elastomers New Materials Technology Co Ltd
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Filing date
Publication date
Application filed by JIANGSU HESHILI NEW MATERIAL CO Ltd, Jiangyin Hechuang Elastomers New Materials Technology Co Ltd filed Critical JIANGSU HESHILI NEW MATERIAL CO Ltd
Priority to CN201610598663.7A priority Critical patent/CN106117529A/en
Publication of CN106117529A publication Critical patent/CN106117529A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G13/00—Protecting plants
    • A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
    • A01G13/0256—Ground coverings
    • A01G13/0268—Mats or sheets, e.g. nets or fabrics
    • A01G13/0275—Films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2230/00—Compositions for preparing biodegradable polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

Abstract

The present invention relates to polymeric material field, the biodegradable copolyester of a kind of low moisture-inhibiting, aklylene glycol, mixed acid and dimer (fatty acid) yl or derivatives thereof copolymerization form.The biodegradable copolyester of the low moisture-inhibiting of the present invention, is a kind of thermoplastic flexible polyester, has good mechanical performance, and elastic and biodegradability, fusing point, between 90 150 DEG C, has relatively low steam penetrating capacity as thin film.The hydrophobic performance of the copolyesters of the present invention is more excellent, and adjustable weatherability and hydrolytic resistance, is particularly suitable for manufacturing Farm mulch.

Description

The biodegradable copolyester of low moisture-inhibiting
Technical field
The present invention relates to technical field of polymer materials, specifically, be to can be applicable in agricultural film, reduce steam Transmitance, improves the biodegradable copolyester of the low vapor transfer rate of crop moisture retention.
Background technology
Poly-(mutual-phenenyl two acid bromide two alcohol ester's-co-tetramethylene adipate) (PBAT) is a kind of biodegradable thermoplastic Copolyesters, has polybutylene terephthalate (PBT) (PBT) thermostability and intensity and the softness of poly adipate succinic acid ester (PBA) concurrently Property, ductility.And for contrasting other Biodegradable material, cost is relatively low, stable mechanical property, it is commonly applied to shopping Bag, agricultural film etc..Use PBAT do agricultural film can in soil natural degradation, replace conventional polyethylene film and be difficult to recovery and make The problem becoming white pollution, but PBAT has many weak points as agricultural film, if PBAT is hydrophilic material steam Transmitance is higher, as agricultural film, not enough to crop moisture retention, and each crop local climate is different, material degradation mistake sometimes Hurry up, more cause agricultural film to use.
Summary of the invention
It is an object of the invention to provide the biodegradable copolyester of a kind of low-moisture permeability, the hydrophobic performance of this copolyesters More excellent, and adjustable weatherability and hydrolytic resistance.
To achieve these goals, the technical scheme is that
A first aspect of the present invention, it is provided that the biodegradable copolyester of a kind of low moisture-inhibiting, by aklylene glycol, mixing Acid and dimer (fatty acid) yl or derivatives thereof copolymerization form；Described aklylene glycol, mixed acid and dimer (fatty acid) yl or its derive The percentage by weight of thing is respectively 25-45%, 40-70% and 1-25%；
Described mixed acid includes:
(1) carboxylate of p-phthalic acid, p-phthalic acid, or their mixture, the weight percent in mixed acid Ratio is 30-70%；With
(2) carboxylate of adipic acid, adipic acid, or their mixture, the percentage by weight in mixed acid is 30- 70%.
Preferably, described aklylene glycol is selected from: ethylene glycol, propylene glycol or BDO, more preferably propylene glycol, 1, 4-butanediol, most preferably uses BDO.
Preferably, described mixed acid is the mixed acid of p-phthalic acid and adipic acid, wherein p-phthalic acid and oneself two The mass ratio of acid is 1:1.
Preferably, described dimer (fatty acid) yl can be obtained by oligomerization by monomer unsaturated fatty acid.More preferably Saturated dimer (fatty acid) yl (hydrogenated dimer acids) after over hydrogenation.
Described dimer fatty acid derivative includes the carboxylic group in this dimer (fatty acid) yl or its ester group base prepared The derivant that group is converted into amide groups, itrile group, amido etc. and obtains.In the production of polyester containing dimer (fatty acid) yl or derivatives thereof In, dimer (fatty acid) yl or derivatives thereof can be individually or to use with the form of arbitrary proportion composition.
Preferably, described dimer (fatty acid) yl can comprise 30～50 carbon atoms.It is furthermore preferred that described dimer (fatty acid) yl Comprise 36 carbon atoms.It is furthermore preferred that the dimer (fatty acid) yl (dimeric dibasic acid Pripol 1009) of structure as shown in Figure 1 can be used, tool Body data can pass through the Presentation Hans Ridderikhoff-BPM of CRODA company (East Yorkshire, UK) Symposium 15-06-2011 secured data finds.
Owing to dimer (fatty acid) yl has a Long carbon chain alkyl side chain, therefore dimer (fatty acid) yl has a repellency, dimer (fatty acid) yl or The addition of its derivant can improve the weatherability of copolyesters of the present invention and hydrophobicity and reduce poisture-penetrability.
Described dimer (fatty acid) yl or derivatives thereof accounting is 1wt%-25wt%, preferably 2wt%-15wt%, more preferably 4wt%-12wt%.The biological degradability of this copolyesters can be had a strong impact on when dimer (fatty acid) yl is more than 25wt%.
Preferably, the preparation method of the biodegradable copolyester of described low moisture-inhibiting comprises the following steps: proportionally Add BDO, p-phthalic acid, adipic acid, dimeric dibasic acid Pripol 1009, catalyst butyl titanate in the reactor TBT (optional DuPont TYZOR TBT), is then purged with nitrogen, carries out esterification, first esterification temperature is maintained at 210 DEG C, until removing all moisture.Again temperature is risen to 230 DEG C, then add TBT and stabilizer phosphorous acid, contract subsequently Close reaction, react about 40 minutes, is warming up to 245 DEG C and is slowly evacuated to 100Pa, and the most about 2-4 hour until react extremely Required viscosity.
The catalyst TBT added during preparation is 300-1800ppm, the preferably 500-1300ppm of raw mixture gross mass, Phosphorous acid is the 100-1200ppm of raw mixture gross mass, preferably 200-800ppm.
A second aspect of the present invention, it is provided that the biodegradable copolyester of above-mentioned low moisture-inhibiting answering in preparing agricultural film With.
A third aspect of the present invention, it is provided that a kind of agricultural uses water conservation weather-resistance film much, by the biodegradable of above-mentioned low moisture-inhibiting Copolyesters prepares.In agricultural film application, it is resistance to that the interpolation of dimer (fatty acid) yl or derivatives thereof can effectively improve moisture retention Time property and hydrolytic resistance, can adjust the consumption of dimer (fatty acid) yl or derivatives thereof, to adjust according to the region of agricultural film application The moisture retention of whole timber material and degradability.
The biodegradable copolyester of the low moisture-inhibiting of the present invention, is a kind of thermoplastic flexible polyester, has good machine Tool performance, elastic and biodegradability, fusing point, between 90-150 DEG C, has relatively low steam as thin film and passes through Amount.The hydrophobic performance of the copolyesters of the present invention is more excellent, and adjustable weatherability and hydrolytic resistance, is particularly suitable for manufacturing agricultural use Mulch film.
Accompanying drawing explanation
Fig. 1 is the structural representation of dimer (fatty acid) yl.
Detailed description of the invention
The detailed description of the invention provided the present invention below in conjunction with embodiment elaborates.
Embodiment 1
Copolymer is prepared by: use 30L reactor, adds BDO 9.2kg, p-phthalic acid 3.4kg, Adipic acid 3.4kg, dimeric dibasic acid Pripol 1009 0.52kg, catalyst butyl titanate (TBT) 7g, be then purged with nitrogen, Carry out esterification, first esterification temperature is maintained at 210 DEG C, until removing all moisture.Again temperature is risen to 230 DEG C, then Add TBT 4g, stabilizer phosphorous acid 2g, carry out condensation reaction subsequently, react about 40 minutes, be warming up to 245 DEG C and slowly take out Vacuum to 100Pa, and the most about 2-4 hour until reaction is to required viscosity.
Embodiment 2
Copolymer preparation method is same as in Example 1, but dimeric dibasic acid Pripol 1009 is added to 1.04kg.
Comparative example 1
Copolymer preparation method is same as in Example 1, but without dimeric dibasic acid Pripol 1009.
Comparative example 2
Directly use polyethylene film.
Performance test
Film is prepared by: make the granule of polymer be extruded through annular slot die through single screw extrusion machine, and And on standard blown equipment, be blow molded a diameter of 150mm, thickness is the circular membrane of 100 μm.
Concrete method of testing is as follows:
1, thickness (μm), uses film thickness gauge test.
2, fusing point (Tm, DEG C), utilizes TA Instruments Q100 DSC to measure.By the about 5mg material in polymer beads Material is placed in specimen disc.Being subsequently placed in DSC device, be heated to 250 DEG C and be again cooled to room temperature, the two process is with l The speed of TC/min is carried out.Hereafter, temperature raises with 10 DEG C/min.Fusing point is determined by the maximum at the heat peak crystallized.
3, surface tension mN/m: by arcotest dyne reagent test.
4, moisture-vapor transmission (g/m2* 24hr): measure according to ISO 15106.
Test result is shown in Table 1:
The performance comparison of table 1 embodiment 1-2 and comparative example 1-2
Below preferred embodiment to the invention is illustrated, but the invention is not limited to described Embodiment, those of ordinary skill in the art it may also be made that all equivalents on the premise of the invention spirit Modification or replacement, modification or the replacement of these equivalents are all contained in the application claim limited range.

Claims (10)

1. the biodegradable copolyester of a low moisture-inhibiting, it is characterised in that by aklylene glycol, mixed acid and dimer fatty Acid or derivatives thereof copolymerization forms, described aklylene glycol, mixed acid and the weight percent of dimer (fatty acid) yl or derivatives thereof Ratio respectively 25-45%, 40-70% and 1-25%；
Described mixed acid is by the p-phthalic acid of percentage by weight 30-70% or its carboxylate, and percentage by weight 30-70% Adipic acid or its carboxylate composition；
Described aklylene glycol is selected from: ethylene glycol, propylene glycol or 1,4-butanediol.
The biodegradable copolyester of low moisture-inhibiting the most according to claim 1, it is characterised in that described aklylene glycol For 1,4-butanediol.
The biodegradable copolyester of low moisture-inhibiting the most according to claim 1, it is characterised in that described dimer (fatty acid) yl Or derivatives thereof is dimer (fatty acid) yl, dimeric fatty alcohol or dimer fatty polyhydric alcohol.
The biodegradable copolyester of low moisture-inhibiting the most according to claim 3, it is characterised in that described dimer (fatty acid) yl Or derivatives thereof contains 30～50 carbon atoms.
The biodegradable copolyester of low moisture-inhibiting the most according to claim 4, it is characterised in that described dimer (fatty acid) yl Or derivatives thereof contains 36 carbon atoms.
The biodegradable copolyester of low moisture-inhibiting the most according to claim 5, it is characterised in that described dimer (fatty acid) yl Or derivatives thereof is hydrogenated dimer acids.
The biodegradable copolyester of low moisture-inhibiting the most according to claim 1, it is characterised in that described mixed acid is right The mass ratio of phthalic acid and adipic acid is 1:1.
The biodegradable copolyester of low moisture-inhibiting the most according to claim 1, it is characterised in that described dimer (fatty acid) yl The percentage by weight of or derivatives thereof is 2-15%.
9. according to biodegradable copolyester the answering in preparing agricultural film of the arbitrary described low moisture-inhibiting of claim 1-8 With.
10. agricultural uses a water conservation weather-resistance film much, by the biodegradable copolyester of the arbitrary described low moisture-inhibiting of claim 1-8 Prepare.
CN201610598663.7A 2016-07-27 2016-07-27 The biodegradable copolyester of low moisture-inhibiting Pending CN106117529A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107254240A (en) * 2017-04-20 2017-10-17 浙江传化天松新材料有限公司 A kind of high decorative surface of curable epoxide, enhanced water resistance polyester resin for powder coating and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1898294A (en) * 2003-12-18 2007-01-17 伊斯曼化学公司 High clarity films with improved thermal properties
CN103122129A (en) * 2003-12-22 2013-05-29 伊士曼化工公司 Polymer blends with improved notched impact strength
CN104629663A (en) * 2013-11-11 2015-05-20 上海轻工业研究所有限公司 Polyester hot melt adhesive
CN104822728A (en) * 2012-09-26 2015-08-05 陶氏环球技术有限责任公司 Polyurethane based insulated glass sealant

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1898294A (en) * 2003-12-18 2007-01-17 伊斯曼化学公司 High clarity films with improved thermal properties
CN103122129A (en) * 2003-12-22 2013-05-29 伊士曼化工公司 Polymer blends with improved notched impact strength
CN104822728A (en) * 2012-09-26 2015-08-05 陶氏环球技术有限责任公司 Polyurethane based insulated glass sealant
CN104629663A (en) * 2013-11-11 2015-05-20 上海轻工业研究所有限公司 Polyester hot melt adhesive

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107254240A (en) * 2017-04-20 2017-10-17 浙江传化天松新材料有限公司 A kind of high decorative surface of curable epoxide, enhanced water resistance polyester resin for powder coating and preparation method thereof
CN107254240B (en) * 2017-04-20 2019-05-28 浙江传化天松新材料有限公司 A kind of high decorative surface of curable epoxide, enhanced water resistance polyester resin for powder coating and preparation method thereof

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Application publication date: 20161116