CN105860456A - Degradable polyester type waterproof material and method for preparing same - Google Patents

Degradable polyester type waterproof material and method for preparing same Download PDF

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Publication number
CN105860456A
CN105860456A CN201610302556.5A CN201610302556A CN105860456A CN 105860456 A CN105860456 A CN 105860456A CN 201610302556 A CN201610302556 A CN 201610302556A CN 105860456 A CN105860456 A CN 105860456A
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acid
waterproof material
type waterproof
aliphatic
dicarboxylic acid
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仇影
姜海东
郭兆来
郑春扬
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Jiangsu China Railway ARIT New Materials Co Ltd
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Jiangsu China Railway ARIT New Materials Co Ltd
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/46—Applications of disintegrable, dissolvable or edible materials
    • B65D65/466—Bio- or photodegradable packaging materials
    • 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
    • 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
    • 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
    • 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
    • C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
    • C08G63/187—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
    • C08G63/189—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings containing a naphthalene ring
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention relates to a degradable polyester type waterproof material. The degradable polyester type waterproof material is characterized by comprising, by weight, 20%-89% of aliphatic dicarboxylic acid-aromatic dicarboxylic acid-aliphatics or cycloaliphatic diol copolyester, 1%-50% of polycarbonate di-propyl ester, 1%-30% of starch, 0.5%-1% of coupling agents, 0.5%-1% of end-capping agents and 0.5%-1% of plasticizers. A method for preparing the degradable polyester type waterproof material includes sufficiently mixing raw materials with one another in a high-speed mixing machine to obtain mixtures; extruding and molding the mixtures by the aid of an extruding machine to obtain the degradable polyester type waterproof material. The degradable polyester type waterproof material and the method have the advantage that the degradable polyester type waterproof material prepared by the aid of the method can be applied to waterproof materials and has a biodegradable function.

Description

A kind of degradable poly ester type waterproof material and preparation method thereof
Technical field
The invention belongs to the synthetically prepared field of macromolecule polymer material, relate to a kind of waterproof material of degradable poly ester type Material and preparation method thereof, is specifically related to a kind of main by aliphatic dicarboxylic acid-aromatic dicarboxylic acid-binary aliphatic The degradable poly ester type waterproof material of the sub-propyl ester/starch of alcohol copolyesters/poly-carbonic acid two/other auxiliary agents composition and system thereof Preparation Method.
Background technology
Along with the garbage produced in the quickening of process of industrialization, human being's production and life process is on the increase, place The main method of reason garbage is landfill method, will the pollutant such as waste or used plastics deliver to treat after landfill yard is buried its from So degraded.But, the amount of landfill of the material such as waste or used plastics is far longer than natural degradation amount, causes landfill yard quantity Constantly reducing, refuse processing cost is continuously increased, and environmental pollution is the most serious.
Thus, it is necessary to a kind of plastics that can be directly degraded by environment, microorganism etc., these plastics are especially suitable In disposable fast-moving consumer goods, when these plastics use terminate after, can nature microorganism such as antibacterial, Resolving into micromolecular compound under mycete, fungus and Algal Effects, these micromolecular compounds again can be by plant profit With, so that material defines the green circulatory of closing, it is achieved human being's production, life and the harmony of natural environment Get along.
The biodegradable plastic of most study is aliphatic polyester at present, and it can be by nature under composting conditions Microorganism will resolve into water and CO through the several months2Deng material, again participate in the photosynthesis of plant.This The advantages such as its excellent biocompatibility outer, polymer and catabolite are nontoxic also make it of increasing concern.So And the mechanical property that this kind polyester is poor, relatively low fusing point and glass transition temperature (the most respectively lower than 65 DEG C With-30 DEG C) it is difficult to the requirement to each side such as material properties in satisfied reality application, only it is used in only a few Occasion.
In order to give full play to the biological degradability of aliphatic polyester and realize large-scale application, the research work of various countries Person has carried out a lot of research work.Wherein, relatively successful example is aliphatic polyester and aromatic polyester to be entered Row copolymerization, thus obtained this fat/aromatic copolyesters combine aliphatic polyester biodegradable and The machinery of aromatic polyester excellence and processing characteristics, therefore show one's talent in biodegradable field.BASF Patent CN 1075527 C discloses the preparation process of a kind of biodegradable polymers, by adipic acid, right Phthalic acid and 1,4-butanediol copolymerization obtain the copolyesters of adipic acid-p-phthalic acid and 1,4-butanediol.Du Nation's patent CN 200480022043.4 discloses the preparation process of its copolyesters, utilize aromatic dicarboxylic acid, Aliphatic dicarboxylic acid, poly-(alkylene ether) glycol and glycol copolymerization obtain aliphatic-aromatic polyether ester.This A little copolyesters preferably combine the mechanical property of aromatic polyester and the biodegradability of aliphatic polyester, but It is that they are usually present following shortcoming: (1) production cost is higher；(2) very hydrophobic chain structure, lack Few active reaction point；(3) degradation rate is slower so that it the most extensively applies limited, it is therefore necessary to right Degradable polyester is modified research.
The sub-propyl ester [Poly (Propylene carbonate), be abbreviated as PPC] of poly-carbonic acid two is a kind of by epoxy Propane (PO) and carbon dioxide (CO2) novel thermoplastic of fully biodegradable of alternating copolymerization Material, can be applicable to the fields such as fresh-keeping bag for food, waterproof plastic bag, Disposable paper cup.
Summary of the invention
It is an object of the invention to provide a kind of environmental protection, degradable, mechanical property one good, low cost can drop Solving polyester-type waterproof material, it is a further object of the present invention to provide the preparation method of above-mentioned material, the present invention will be from " white pollution " that fundamentally environment is caused by solution conventional plastic goods or Disposable paper cup, and to plastics system The water resistance of product and Disposable paper cup strengthens to be improved.
The technical scheme is that a kind of degradable poly ester type waterproof material, it is characterised in that raw material components and Each component accounts for the mass percent of raw material total amount and is respectively as follows: aliphatic dicarboxylic acid-aromatic dicarboxylic acid-aliphatic Or cycloaliphatic diols copolyesters: 20%～89%；The sub-propyl ester 1%～50% of poly-carbonic acid two；Starch 1%～30%； Coupling agent 0.5%～1%；End-capping reagent 0.5%～1%；Plasticizer 0.5%～1%.
Institute in the most above-mentioned aliphatic dicarboxylic acid-aromatic dicarboxylic acid-aliphatic or cycloaliphatic diols copolyesters Stating aliphatic dicarboxylic acid is ethanedioic acid, malonic acid, succinic acid, dimethyl succinic acid, 1,3-propanedicarboxylic acid, 2-methylpent two Acid, 3-methylglutaric acid, 1,2-cyclohexane cyclohexanedimethanodibasic, adipic acid, 3-methyl adipic acid, 2,2,5,5-tetramethyl Adipic acid, 1,5-pentanedicarboxylic acid., suberic acid, Azelaic Acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid or tridecane One or more in diacid；Described aromatic dicarboxylic acid is M-phthalic acid, p-phthalic acid, O-phthalic Acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4 '-biphenyl dicarboxylic acid or 3,4 '-biphenyl One or more in dioctyl phthalate；Described aliphatic dihydroxy alcohol is ethylene glycol, 1,2-propylene glycol, 1,3-the third two Alcohol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6- Hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,7-heptandiol, 1,8-ethohexadiol, 1,9-nonyl two One or more in alcohol, 1,10-decanediol, 1,11-undecane or 1,12-dodecanediol；Described fat Ring race dihydroxylic alcohols is 1,2-cyclohexanedimethanol or 1,4 cyclohexane dimethanol.
The sub-propyl ester (PPC) of the most above-mentioned poly-carbonic acid two be weight average molecular weight be the polymer of 1500～3000. The most above-mentioned starch is in corn starch, tapioca, potato starch, esterification starch or etherification starch One or more.The most above-mentioned coupling agent is silane coupler, titanium system coupling agent, aluminum system coupling agent or aluminum titanium One or more in composite coupler.The most above-mentioned end-capping reagent is in maleic anhydride or caprolactam One or more.The most above-mentioned plasticizer is ethylene glycol, glycerol or sorbitol, tributyl citrate (TBC), trioctyl lemon acid (TOC), tributyl 2-acetylcitrate (ATBC) or ATOC (ATOC) one or more in.
Present invention also offers the preparation method of above-mentioned degradable poly ester type waterproof material, its concrete steps are such as Under:
A, aliphatic dicarboxylic acid-aromatic dicarboxylic acid-aliphatic or the preparation of cycloaliphatic diols copolyesters；
(1) by aromatic dicarboxylic acid, aliphatic dicarboxylic acid, aliphatic dihydroxy alcohol or cycloaliphatic diols and chlorine Imitative by mass percentage for 1:(0.5～1.5): (0.4～1.8): (0.2～0.5) is placed in reaction vessel, rise Temperature carries out constant temperature esterification reaction, is then carrying out negative pressure esterification, is obtaining primary esterification product；
(2) by above-mentioned primary esterification product, add account for esterification products mass percent be 0.01～0.15% take off Water preparation and to account for esterification products mass percent be 0.1～0.5% catalyst, under high temperature, negative pressure, polycondensation reaction obtains To high molecular biodegradable copolyester；
B, the preparation of degradable poly ester type waterproof material: by the aliphatic dicarboxylic acid-fragrance obtained by step A Race's dicarboxylic acids-aliphatic or cycloaliphatic diols copolyesters propyl ester, starch, coupling agent, envelope sub-with poly-carbonic acid two After end agent and plasticizer addition high mixer are sufficiently mixed, carry out extrusion molding by extruder, obtain degradable Polyester-type waterproof material.
In preferred steps (1), heating rate is 5～1010 DEG C/min；Constant temperature esterification reaction temperature is 120～200 DEG C, response time 2～3 hours；The pressure of negative pressure esterification is 40～100KPa, and negative pressure esterification is anti- Between Ying Shi 0.5～2 hour.
In preferred steps (2), polycondensation reaction temperature controls at 220～260 DEG C；Stress control is 10～50kPa In；Response time 2～5 hours；Heating rate is 5～1010 DEG C/min.
The preferably rotating speed of the high mixer described in above-mentioned steps B is 1000～2000 revs/min；Incorporation time is 10～30 minutes；Described extruder is double screw extruder, and technological parameter is: temperature of charge is at 35-200 DEG C Between, screw speed 80-350 rev/min.
The most above-mentioned dehydrant is diethyl carbodiimide salt, DIC salt or dicyclohexyl carbon One in diimmonium salt；Described catalyst is tetraethyl titanate, tetraisopropyl titanate, butyl titanate, titanium Acid four different monooctyl esters, titanium potassium oxalate, stannous octoate, two fourth stannum dilaurates, dibutyltin diacetate, positive silicon At least one in acid methyl ester or tetraethyl orthosilicate.
Beneficial effect:
1. the present invention is total to by adjusting aliphatic dicarboxylic acid-aromatic dicarboxylic acid-aliphatic or cycloaliphatic diols Polyester and PPC ratio, prepared Biodegradable polymer material can adapt to various different condition and ring Use under border, biodegradable properties and water resistance are excellent, and production cost is low；
2. the Biodegradable polymer material degraded prepared by the present invention uniformly and thoroughly, noresidue, without two Secondary pollution, degradation speed is very fast under proper condition；
3. the Biodegradable polymer material excellent in mechanical performance prepared by the present invention, and meet Related product Mechanics, thermal property requirement.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further described (non-specified otherwise in following instance, addition is equal For mass fraction):
Embodiment 1
First in 20 parts of chloroform solvents, add 100 parts of p-phthalic acids, 50 parts of succinic acid and 40 part 1, 2-butanediol, stirs, and is brought rapidly up to 165 DEG C with 10 DEG C/min speed, is esterified, constant temperature React 2 hours.Then under 40KPa pressure, carry out negative pressure esterification, 0.5 hour time, then with 5 DEG C/min It is warming up to 240 DEG C, adds 0.21 part of tetrabutyl titanate catalyst, 0.021 portion of dicyclohexylcarbodiimide salt Dehydrant, is decompressed to 45KPa and carries out polycondensation reaction 4 hours, i.e. obtains p-phthalic acid/succinic acid-fourth two Alcohol copolyesters.
The PPC that weight average molecular weight is 2000 that 1 part of Jiangsu ZhongKe JinLong chemical engineering Co., Ltd is produced, Copolyester product that 89 parts of above steps obtain, 8.5 parts of corn starchs, 0.5 part of aluminum system coupling agent, 0.5 part Maleic anhydride and 0.5 part of tributyl 2-acetylcitrate, be slowly added into height and stir stirring in machine after preliminary mixing 20min, high mixer rotating speed is 1000 revs/min, and uniform compound is extruded in double screw extruder, made Grain, extruder temperature is set as 110 DEG C, and speed setting is 250 revs/min.
The raw material blown film using this example prepares the packing film that thickness is 0.03mm, and soil buries at normal temperatures, root Examine according to the standard test method of ASTM D5338-92 plastics aerobic biological degradation under the conditions of controlled composting Survey its degradation property.Test pellet in an oven with obtained pellet and start tacky temperature, use gained simultaneously To pellet in injector, carry out sample preparation by the requirement of GB/T17037-1997, then press GB/T The requirement of 1040-2006 and GB/T 2918-1998 carries out tensile property test, records test result.Use The test method measuring degradation plastic aerobic biological degradation under the conditions of ASTM D538-92 controlled composting is surveyed Fixed output quota product degradation property.
Embodiment 2
First in 50 parts of chloroform solvents, add 100 parts of M-phthalic acids, 80 parts of 1,2-cyclohexane cyclohexanedimethanodibasics With 180 parts of ethylene glycol, stir, and be brought rapidly up to 120 DEG C with 10 DEG C/min speed, be esterified, Isothermal reaction 2.5 hours.Then negative pressure esterification is carried out under 100KPa pressure, 1 hour time, then with 5 DEG C / min is warming up to 220 DEG C, adds 1.23 parts of metatitanic acid four different monooctyl ester catalyst, and 0.205 part of diethyl carbon two is sub- Amine salt dehydrant, is decompressed to 50KPa and carries out polycondensation reaction 5 hours, i.e. obtains p-phthalic acid/1,2-hexamethylene Alkane dioctyl phthalate-glycol copolyester.
The PPC that weight average molecular weight is 3000 that 50 parts of Jiangsu ZhongKe JinLong chemical engineering Co., Ltd are produced, Copolyester product that 20 parts of above steps obtain, 27 portions of tapiocas, 1 part of titanium system coupling agent, 1 part in oneself Amide and 1 part of ethylene glycol are slowly added into height and stir stirring 20min, high mixer rotating speed 2000 in machine after tentatively mixing Rev/min, uniform compound to be extruded in double screw extruder, pelletize, extruder temperature is set as 35 DEG C, Speed setting is 100 revs/min.
Carry out performance test according to method described in embodiment one, and record data.
Embodiment 3
First in 30 parts of chloroform solvents, add 100 parts of phthalic acids, 110 parts of ethanedioic acids and 120 part 1, 6-hexanediol, stirs, and is brought rapidly up to 200 DEG C with 5 DEG C/min speed, is esterified, and constant temperature is anti- Answer 3 hours.Then carry out negative pressure esterification, time 2 h under 60KPa pressure, then heat up with 5 DEG C/min To 260 DEG C, add 1.6 parts of methyl silicate catalyst, 0.48 part of DIC dehydration of salt agent, It is decompressed to 45KPa and carries out polycondensation reaction 4.5 hours, i.e. obtain M-phthalic acid/succinic acid-hexanediol copolyesters.
The weight average molecular weight 17.9 parts of Jiangsu ZhongKe JinLong chemical engineering Co., Ltd produced is 1500 The copolyester product that PPC, 50 parts of above steps obtain is combined together with 30 parts of potato starch, 0.8 part of aluminum titanium Coupling agent, 0.6 part of maleic anhydride and 0.7 part of glycerol, be slowly added into height after preliminary mixing and stir in machine Stirring 20min, high mixer rotating speed is 1500 revs/min, uniform compound is extruded in double screw extruder, Pelletize, extruder temperature is set as 200 DEG C, and speed setting is 160 revs/min.
Carry out performance test according to method described in embodiment one, and record data.
Embodiment 4
First in 40 parts of chloroform solvents, 100 part 2 is added, 7-naphthalenedicarboxylic acid, 150 parts of adipic acids and 60 parts 1,3-PD, stirs, and is brought rapidly up to 150 DEG C with 10 DEG C/min speed, is esterified, permanent Temperature reaction 2 hours.Then negative pressure esterification is carried out under 50KPa pressure, 1.5 hours time, then with 10 DEG C/min Being warming up to 235 DEG C, add 1.4 part of two acetic acid butyl ester catalyst, 0.35 portion of dicyclohexylcarbodiimide salt takes off Water preparation, is decompressed to 10KPa and carries out polycondensation reaction 2 hours, i.e. obtains naphthalenedicarboxylic acid/adipic acid-propylene glycol common Polyester.
The PPC that weight average molecular weight is 3000 that 40 parts of Jiangsu ZhongKe JinLong chemical engineering Co., Ltd are produced, Copolyester product that 57 parts of above steps obtain, 1 part of etherification starch, 0.6 part of silane coupler, 0.5 part oneself Lactams and 0.9 part of tributyl citrate, be slowly added into height and stir stirring 30min in machine after preliminary mixing, high Mixed machine rotating speed is 1000 revs/min, is extruded by uniform compound, pelletize in double screw extruder, extruder Temperature is set as 90 DEG C, and speed setting is 200 revs/min.
Carry out performance test according to method described in embodiment one, and record data.
For comparing plastic alloy of the present invention waterproof degradation modification effect, elite to take commercially available molecular weight be 12.4 × 104, Glass transition temperature is that the pure PBS and the pure PPC of employing in the present invention of-15.4 DEG C are according to embodiment one institute The method of stating carries out same performance test, and concrete test result is as follows:
Table 1. result of the test
By above-mentioned experimental data: the degradation time of the degradable poly ester type waterproof material of the present invention is purer PPC is slightly longer, but is shorter than pure PBS, in the experimental data of mechanical property, hot strength than pure PPC and Pure PBS improves more；Elongation at break is in bigger excursion, has widened degradable poly ester type waterproof The range of application of material.
The several specific embodiments being only the application disclosed above, but the application is not limited to this, Ren Heshi Change that matter is identical or a combination thereof, all should fall in the protection domain of the application.

Claims (10)

1. a degradable poly ester type waterproof material, it is characterised in that its raw material components and each component account for raw material total amount Mass percent be respectively as follows: aliphatic dicarboxylic acid-aromatic dicarboxylic acid-aliphatic or cycloaliphatic diols altogether Polyester: 20%～89%；The sub-propyl ester 1%～50% of poly-carbonic acid two；Starch 1%～30%；Coupling agent 0.5%～1%； End-capping reagent 0.5%～1%；Plasticizer 0.5%～1%.
Degradable poly ester type waterproof material the most according to claim 1, it is characterised in that described fat Described in race's dicarboxylic acids-aromatic dicarboxylic acid-aliphatic or cycloaliphatic diols copolyesters, aliphatic dicarboxylic acid is Ethanedioic acid, malonic acid, succinic acid, dimethyl succinic acid, 1,3-propanedicarboxylic acid, 2-methylglutaric acid, 3-methylglutaric acid, 1,2-cyclohexane cyclohexanedimethanodibasic, adipic acid, 3-methyl adipic acid, 2,2,5,5-tetramethyl adipic acid, 1,5-pentanedicarboxylic acid., pungent One or more in diacid, Azelaic Acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid or tridecandioic acid； Described aromatic dicarboxylic acid is M-phthalic acid, p-phthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5- One or more in naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4 '-biphenyl dicarboxylic acid or 3,4 '-biphenyl dicarboxylic acid； Described aliphatic dihydroxy alcohol be ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-HD, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,7-heptandiol, 1,8-ethohexadiol, 1,9-nonanediol, 1,10-decanediol, 1,11-ten One or more in one alkane glycol or 1,12-dodecanediol；Described cycloaliphatic diols is 1,2-hexamethylene Dimethanol or 1,4 cyclohexane dimethanol.
Degradable poly ester type waterproof material the most according to claim 1, it is characterised in that described poly-carbon The weight average molecular weight of the sub-propyl ester of acid two is 1500～3000.
Degradable poly ester type waterproof material the most according to claim 1, it is characterised in that described starch For one or more in corn starch, tapioca, potato starch, esterification starch or etherification starch.
Degradable poly ester type waterproof material the most according to claim 1, it is characterised in that described coupling Agent is one or more in silane coupler, titanium system coupling agent, aluminum system coupling agent or aluminium titanium composite coupler； Described end-capping reagent is one or more in maleic anhydride or caprolactam；Described plasticizer is second two Alcohol, glycerol or sorbitol, tributyl citrate, trioctyl lemon acid, tributyl 2-acetylcitrate or acetyl One or more in trioctyl lemon acid.
6. the method preparing degradable poly ester type waterproof material as claimed in claim 1, its concrete steps As follows:
A, aliphatic dicarboxylic acid-aromatic dicarboxylic acid-aliphatic or the preparation of cycloaliphatic diols copolyesters；
(1) by aromatic dicarboxylic acid, aliphatic dicarboxylic acid, aliphatic dihydroxy alcohol or cycloaliphatic diols and chlorine Imitative by mass percentage for 1:(0.5～1.5): (0.4～1.8): (0.2～0.5) is placed in reaction vessel, rise Temperature carries out constant temperature esterification reaction, is then carrying out negative pressure esterification, is obtaining primary esterification product；
(2) by above-mentioned primary esterification product, add account for esterification products mass percent be 0.01～0.15% take off Water preparation and to account for esterification products mass percent be 0.1～0.5% catalyst, under high temperature, negative pressure, polycondensation reaction obtains To high molecular biodegradable copolyester；
B, the preparation of degradable poly ester type waterproof material: by the aliphatic dicarboxylic acid-fragrance obtained by step A Race's dicarboxylic acids-aliphatic or cycloaliphatic diols copolyesters propyl ester, starch, coupling agent, envelope sub-with poly-carbonic acid two After end agent and plasticizer addition high mixer are sufficiently mixed, carry out extrusion molding by extruder, obtain degradable Polyester-type waterproof material.
Method the most according to claim 6, it is characterised in that the heating rate in step (1) is 5～1010 DEG C/min；Constant temperature esterification reaction temperature is 120～200 DEG C, response time 2～3 hours；Negative pressure ester The pressure changed is 40～100KPa, negative pressure reaction time of esterification 0.5～2 hours.
Method the most according to claim 6, it is characterised in that polycondensation reaction temperature control in step (2) System is at 220～260 DEG C；Stress control is in 10～50kPa；Response time 2～5 hours；Heating rate is 5～1010 DEG C/min.
Method the most according to claim 6, it is characterised in that the rotating speed of the high mixer described in step B It it is 1000～2000 revs/min；Incorporation time is 10～30 minutes；Described extruder is twin-screw extrusion Machine, technological parameter is: temperature of charge between 35-200 DEG C, screw speed 80-350 rev/min.
Method the most according to claim 6, it is characterised in that the dehydrant described in step (2) is One in diethyl carbodiimide salt, DIC salt or dicyclohexylcarbodiimide salt；Described Catalyst be tetraethyl titanate, tetraisopropyl titanate, butyl titanate, the different monooctyl ester of metatitanic acid four, titanium potassium oxalate, In stannous octoate, two fourth stannum dilaurates, dibutyltin diacetate, methyl silicate or tetraethyl orthosilicate At least one.
CN201610302556.5A 2016-05-09 2016-05-09 Degradable polyester type waterproof material and method for preparing same Pending CN105860456A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114196220A (en) * 2021-12-27 2022-03-18 深圳百市达生物技术有限公司 Preparation method of fully-degradable biomass fiber-based waterproof dinner plate
CN114734692A (en) * 2022-04-19 2022-07-12 深圳市利星彩印刷包装有限公司 Waterproof environment-friendly packaging bag and preparation method thereof

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CN102993655A (en) * 2012-11-23 2013-03-27 金发科技股份有限公司 Starch-containing biodegradable barrier thin film, as well as preparation method and application thereof
CN102993656A (en) * 2012-11-23 2013-03-27 金发科技股份有限公司 Biodegradable barrier thin film, as well as preparation method and application thereof

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CN102165013A (en) * 2008-09-29 2011-08-24 巴斯夫欧洲公司 Biodegradable polymer mixture
CN102993655A (en) * 2012-11-23 2013-03-27 金发科技股份有限公司 Starch-containing biodegradable barrier thin film, as well as preparation method and application thereof
CN102993656A (en) * 2012-11-23 2013-03-27 金发科技股份有限公司 Biodegradable barrier thin film, as well as preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114196220A (en) * 2021-12-27 2022-03-18 深圳百市达生物技术有限公司 Preparation method of fully-degradable biomass fiber-based waterproof dinner plate
CN114734692A (en) * 2022-04-19 2022-07-12 深圳市利星彩印刷包装有限公司 Waterproof environment-friendly packaging bag and preparation method thereof

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