CN108790227A - A kind of 2,5- furandicarboxylic acids base polyester blows the preparation method of bottle - Google Patents
A kind of 2,5- furandicarboxylic acids base polyester blows the preparation method of bottle Download PDFInfo
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- CN108790227A CN108790227A CN201810749298.4A CN201810749298A CN108790227A CN 108790227 A CN108790227 A CN 108790227A CN 201810749298 A CN201810749298 A CN 201810749298A CN 108790227 A CN108790227 A CN 108790227A
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- bottle
- furandicarboxylic acid
- base polyester
- blows
- acid base
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D22/00—Producing hollow articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/76—Measuring, controlling or regulating
- B29C45/78—Measuring, controlling or regulating of temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
- B29C49/06—Injection blow-moulding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/42—Component parts, details or accessories; Auxiliary operations
- B29C49/78—Measuring, controlling or regulating
- B29C49/783—Measuring, controlling or regulating blowing pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/42—Component parts, details or accessories; Auxiliary operations
- B29C49/78—Measuring, controlling or regulating
- B29C49/786—Temperature
-
- 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
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
- B29C2049/023—Combined blow-moulding and manufacture of the preform or the parison using inherent heat of the preform, i.e. 1 step blow moulding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
- B29C2945/76—Measuring, controlling or regulating
- B29C2945/76494—Controlled parameter
- B29C2945/76531—Temperature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/10—Applications used for bottles
Abstract
The present invention provides the preparation method that a kind of 2,5-furandicarboxylic acid base polyester blows bottle, belongs to technical field of polymer materials.This method is to react 2,5-furandicarboxylic acid base polyester and catalyst in the reaction vessel, the 2,5-furandicarboxylic acid base polyester that obtains that treated；Then addition resistance decarboxylation reagent and antioxidant in 2,5-furandicarboxylic acid base polyester after treatment, are then placed in barrel, after heating fusion plastification, by the nozzle of barrel front end, inject in Guan Bi mould cavity, after cooling and shaping, bottle base product is finally put into integrated bottle blowing machine by opening mold up to bottle base product, and bottle base, which is then sent to lamp box, is heated, bottle base is placed into and is closed in bottle mold, it is high-pressure aerated to being carried out in it, it obtains 2,5-furandicarboxylic acid base polyester and blows bottle.It is 100% bio-based materials that 2,5-furandicarboxylic acid base polyester of the present invention, which blows bottle, and oxygen transmission coefficient, carbon dioxide transmission coefficient, internal pressure resistance, thermal shock resistance and impact resistance etc. are above PET.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of 2,5-furandicarboxylic acid base polyester blows the system of bottle
Preparation Method.
Background technology
The getting worse of white pollution, oil non-renewable and by final exhausted and price continuous raising, people
The importance for developing and utilizing renewable resource is had become increasingly aware of, starts to be conceived to Green Polymer Material.2,5- furans two
Formic acid is one of the member of furans family, is its abundance based on renewable resource, is tied with terephthalic acid (TPA) (PTA)
Structure is similar, is considered a kind of novel diacid monomer and terephthalic acid (TPA) based on renewable resource by academia and industrial circle
Substitute；It is considered to establish 12 kinds of important one of chemicals of Green Chemistry industry by U.S. Department of Energy, it is graceful by Du Pont and Supreme Being
This company is described as one of " giant being sunk into sleep ".It can polymerize to obtain different 2 from the dihydric alcohol of different chain length different structure,
5- furandicarboxylic acid base polyester, such as poly- 2,5-furandicarboxylic acid glycol ester (PEF), poly- 2,5-furandicarboxylic acid -1,3- the third two
Alcohol ester (PPF), poly- 2,5- furandicarboxylic acids -1,4- butanediol esters (PBF), poly- 2,5- furandicarboxylic acids -2,2- dimethyl propyls
Ester (PDMPF), poly- 2,5- furandicarboxylic acids hexylene glycol ester (PAF), poly- 2,5- furandicarboxylic acids ethohexadiol ester (POF), poly- 2,5-
Furandicarboxylic acid nonanediol ester (PNF), poly- 2,5- furandicarboxylic acids decanediol ester (PDeF) and poly- 2,5- furandicarboxylic acids 12
Alcohol ester (PDoF) etc..
Compared with terephthalic acid groups polyester, 2,5-furandicarboxylic acid base polyester is not only 100% biology base polyester, meets
Environmental requirement, with more in superior mechanical performance, hot property, barrier property and biodegradability, such as PEF macromolecular chains
Due to furan nucleus it is difficult to overturn so that PEF barrier properties for gases is substantially better than PET, and OTR oxygen transmission rate is the 1/11 of PET, titanium dioxide
Carbon transmitance is the 1/19 of PET, and moisture-vapor transmission is the 1/2.8 of PET；According to another report, if replaced completely in bottled market PEF
For PET, the annual 440-550PJ nonrenewable resources energy will be saved, and 20-30Mt CO2 emissions will be reduced.2,
5- furandicarboxylic acid base polyester is suitable for bottled material or packaging material, but up to the present, the bottled product being often used
Material has no the report that bottled material is produced using 2,5-furandicarboxylic acid base polyester material still based on PET.
Invention content
The object of the present invention is to provide the preparation method that a kind of 2,5-furandicarboxylic acid base polyester blows bottle, which obtains
To 2,5- furandicarboxylic acid base polyester blow bottle have excellent performance.
The present invention provides the preparation method that a kind of 2,5-furandicarboxylic acid base polyester blows bottle, including：
Step 1：In a vacuum or inert atmosphere, in the reaction vessel by 2,5-furandicarboxylic acid base polyester and catalyst
Reaction, the 2,5-furandicarboxylic acid base polyester that obtains that treated；
Step 2：The addition resistance decarboxylation reagent and anti-in the step 1 2,5- furandicarboxylic acid base polyester that obtains that treated
Oxygen agent, is then placed in barrel, after heating fusion plastification, by the nozzle of barrel front end, injects in Guan Bi mould cavity, passes through
After cooling and shaping, for opening mold up to bottle base product, extruder temperature is 150-260 DEG C, and nozzle temperature is 180-260 DEG C, cooling
Preform mould medium is water, and temperature is 5-90 DEG C；
Step 3：The bottle base product that step 2 obtains is put into integrated bottle blowing machine, then bottle base be sent to lamp box into
Row heating, the bottle base having had been warmed up is placed into and is closed in bottle mold, high-pressure aerated to being carried out in it, obtains 2,5- furans
Diformyl polyester blows bottle；The lamp box temperature is 40-200 DEG C, the blowing pressure 0.05MPa-2.0MPa, cooling bottle mould
Tool medium is water, and temperature is 5-90 DEG C.
Preferably, in the step 1 structural formula of 2,5-furandicarboxylic acid base polyester as shown in formula I：
Formula I
In formula I, R isWherein, n >=2；
The reduced viscosity of the 2,5- furandicarboxylic acid base polyester is 0.5-1.5dL/g.
Preferably, catalyst is selected from tetraethyl titanate, metatitanic acid orthocarbonate, tetraisopropyl titanate, titanium in the step 1
Sour four butyl esters, tetrabutyl titanate, tetraethyl orthosilicate, silicic acid orthocarbonate, silicic acid tetra-isopropyl, tetrabutyl silicate, silicic acid four are different
Butyl ester, trimethyl phosphate, triethyl phosphate, tricresyl phosphate propyl ester, tricresyl phosphate isopropyl ester, tributyl phosphate, sodium acetate, magnesium acetate,
Aluminum acetate, zinc acetate, lanthanum acetate, germanium dioxide, antimony oxide, antimony acetate, antimony glycol, trimethyl aluminium, triethyl aluminum, three
It is one or more in aluminum ethoxide, aluminum isopropylate, stannous oxalate or stannous octoate.
Preferably, the quality of the catalyst is the 0.01-10wt% of 2,5-furandicarboxylic acid base polyester quality；
Preferably, the reaction temperature of the step one is 20-260 DEG C, reaction time 5min-240h.
Preferably, decarboxylation reagent is hindered in the step 2 be selected from SiO2、TiO2、MgO、CaO、ZnO、SnO2、ZrO2Or
CaCO3In it is one or more.
Preferably, antioxidant is phenolic antioxidant, sulphur ester antioxidant or phosphoric acid ester antioxidant in the step 2.
Preferably, the phenolic antioxidant is selected from 4,4'- dihydroxybiphenyls, 4,4'- di-2-ethylhexylphosphine oxides (2,6- di-t-butyls
Phenol), 4,4' butylidene biss (6- tertiary butyl -3- methylphenols), 4,4'- fourths pitch bis- (3 methy 6 tert butyl phenols), 4,
4'- dihydroxy-phenyl-cyclohexanes, 1,3,5- trimethyls -2,4,6- three (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene, 1,1,3-
Three (2- methyl -4- hydroxyl -5- 2-methyl-2-phenylpropanes base) butane, 2,5 di tert butyl hydroquinone, 2,5 di tert amyl hydroquinone or
It is one or more in 4,4' butylidene biss (6- tertiary butyl -3- methylphenols).
Preferably, the sulphur ester antioxidant is selected from 1,1'- thiobis (beta naphthal), 2,2'- thiobis (4- methyl-
6- tert-butyl phenols), 4,4'- thiobis (6- tertiary butyl -3- methylphenols) or bis- (3,5- di-tert-butyl-4-hydroxyl benzyls) sulphur
It is one or more in ether.
Preferably, the phosphoric acid ester antioxidant is selected from 3,5- di-tert-butyl-4-hydroxyl benzyls diethyl phosphate, double
(3,5- di-t-butyl -4- cyanobenzyls phosphonic acids mono ethyl ester) calcium, three different monooctyl ester of phosphorous acid, (the 2,4- di-tert-butyls of phosphorous acid three
Base) ester, bis- (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites or bis- (2,6- di-t-butyl -4- aminomethyl phenyls) seasons penta
It is one or more in tetrol diphosphites.
Beneficial effects of the present invention
The present invention provides the preparation method that a kind of 2,5-furandicarboxylic acid base polyester blows bottle, and this method, which passes through, controls 2,5- furans
It mutters diformyl polyester reduced viscosity, catalyst, the type for hindering decarboxylation reagent and antioxidant, and adjustment processing temperature, time
And the parameters such as tonnage, it obtains 2,5-furandicarboxylic acid base polyester and blows bottle.The 2,5- furandicarboxylic acid base polyester of the present invention is blown
Bottle can appropriate adjusting process, obtain the bottle of different purposes.A bottle material is blown with existing PET to compare, 2,5-furandicarboxylic acid base
It is 100% bio-based materials that polyester, which blows bottle, oxygen transmission coefficient, carbon dioxide transmission coefficient, internal pressure resistance, thermal shock resistance and
Impact resistance etc. is above PET.The preparation method of the present invention is easy, quick, pollution-free, at low cost, easy to control.
Description of the drawings
Fig. 1 is the practice photo figure that the 2,5- furandicarboxylic acid base polyester that the embodiment of the present invention 2 is prepared blows bottle.
Specific implementation mode
The present invention provides the preparation method that a kind of 2,5-furandicarboxylic acid base polyester blows bottle, including：
Step 1：In a vacuum or inert atmosphere, in the reaction vessel by 2,5-furandicarboxylic acid base polyester and catalyst
Reaction, the 2,5-furandicarboxylic acid base polyester that obtains that treated；
Step 2：The addition resistance decarboxylation reagent and anti-in the step 1 2,5- furandicarboxylic acid base polyester that obtains that treated
Oxygen agent, is then placed in barrel, after heating fusion plastification, by the nozzle of barrel front end, injects in Guan Bi mould cavity, passes through
After cooling and shaping, for opening mold up to bottle base product, extruder temperature is 150-260 DEG C, and nozzle temperature is 180-260 DEG C, cooling
Preform mould medium is water, and temperature is 5-90 DEG C；
Step 3：The bottle base product that step 2 obtains is put into integrated bottle blowing machine, then bottle base be sent to lamp box into
Row heating, the bottle base having had been warmed up is placed into and is closed in bottle mold, high-pressure aerated to being carried out in it, obtains 2,5- furans
Diformyl polyester blows bottle；The lamp box temperature is 40-200 DEG C, the blowing pressure 0.05MPa-2.0MPa, cooling bottle mould
Tool medium is water, and temperature is 5-90 DEG C.
According to the present invention, it is described 2,5-furandicarboxylic acid base polyester and catalyst are reacted in the reaction vessel before,
Preferentially first 2,5-furandicarboxylic acid base polyester is dried, the drying temperature is 40-220 DEG C, drying time 1-
36h；The structural formula of the 2,5- furandicarboxylic acids base polyester is as shown in formula I：
Formula I
In formula I, R isWherein, n >=2；
The reduced viscosity of the 2,5-furandicarboxylic acid base polyester is preferably 0.5-1.5dL/g, more preferably 0.7-
0.75dL/g, the present invention should rationally control the reduced viscosity of 2,5-furandicarboxylic acid base polyester, when reduced viscosity is less than 0.5dL/g
When, the mechanical performance of material, which cannot be satisfied, blows bottle needs, strong not enough, when reduced viscosity is more than 1.5dL/g, material flowability
Difference, it is difficult to process.
The source of 2,5-furandicarboxylic acid base polyester of the present invention is self-control, and preparation method refers to existing preparation side
Method, preferably：2,5-furandicarboxylic acid dimethyl ester, ethylene glycol and catalyst are placed in esterifying kettle, nitrogen is passed through,
170-190 DEG C of progress ester exchange reaction, after waiting for 4-5h ester exchange reactions, send transesterification product into batch condensation polymerization reactor, takes out
Vacuum is warming up to 230-250 DEG C, carries out polycondensation reaction, stops reaction after 4-6h, carry out granulation underwater, obtain 2,5- furans two
Formyl polyester.The molar ratio of the 2,5- furandicarboxylic acids dimethyl ester, ethylene glycol and catalyst is preferably 5：8：0.005；
The catalyst is preferably germanium dioxide or butyl titanate.
According to the present invention, in a vacuum or inert atmosphere, 2,5-furandicarboxylic acid base polyester and catalyst are held in reaction
It is reacted in device, solid-phase tack producing is carried out to 2,5-furandicarboxylic acid base polyester；The reaction temperature and time is according to catalyst kind
Depending on class difference, reaction temperature is preferably 20-260 DEG C, more preferably 100-220 DEG C, most preferably 160-180 DEG C；When reaction
Between preferably 5min-240h, more preferably 2-50h, most preferably 6-8h；The catalyst is selected from tetraethyl titanate, metatitanic acid four
Propyl ester, tetraisopropyl titanate, butyl titanate, tetrabutyl titanate, tetraethyl orthosilicate, silicic acid orthocarbonate, silicic acid tetra-isopropyl,
Tetrabutyl silicate, four isobutyl ester of silicic acid, trimethyl phosphate, triethyl phosphate, tricresyl phosphate propyl ester, tricresyl phosphate isopropyl ester, tricresyl phosphate
Butyl ester, sodium acetate, magnesium acetate, aluminum acetate, zinc acetate, lanthanum acetate, germanium dioxide, antimony oxide, antimony acetate, antimony glycol,
It is one or more in trimethyl aluminium, triethyl aluminum, aluminium ethoxide, aluminum isopropylate, stannous oxalate or stannous octoate.Catalysis
The 0.01-10wt% of the preferred 2,5- furandicarboxylic acids base polyester quality of quality of agent；More preferably 0.05-5wt%, most preferably
2wt%；
According to the present invention, addition resistance decarboxylation reagent and antioxidant two in 2,5-furandicarboxylic acid base polyester after treatment
Kind, the gross mass of the resistance decarboxylation reagent and antioxidant is preferably the 0.01- of 2,5-furandicarboxylic acid base polyester quality
20wt%；Then by 2,5-furandicarboxylic acid base polyester out of, the hopper of injector is sent into heating barrel, fusion plastification is heated
Afterwards, by the thrust of plunger or screw rod, material is compressed and is moved forward, by the nozzle of barrel front end, preferably with 0.2-5s
Speed injection Guan Bi mould cavity in, after the cooling and shaping of 1-30s, opening mold is up to bottle base product, the spiral shell
Bar temperature is 150-260 DEG C, preferably 180-240 DEG C, more preferably 225-230 DEG C；Nozzle temperature is 180-260 DEG C, preferably
It is 190-220 DEG C, more preferably 200 DEG C；Cooling preform mould medium is water, and temperature is 5-90 DEG C, preferably 10-60 DEG C, more
Preferably 40-50 DEG C.
According to the present invention, hindered decarboxylation reagent is preferably selected from SiO2、TiO2、MgO、CaO、ZnO、SnO2、ZrO2Or CaCO3In
It is one or more, the effect that resistance decarboxylation reagent is added is that diacid is avoided decarboxylation occur, to influence the purity of PEF, performance and
Color and luster.
According to the present invention, the antioxidant is preferably phenolic antioxidant, sulphur ester antioxidant or phosphoric acid ester antioxidant.
Further, the phenolic antioxidant is preferably selected from 4,4'- dihydroxybiphenyls, 4,4'- di-2-ethylhexylphosphine oxides (2,6- bis-
Tert-butyl phenol), 4,4' butylidene biss (6- tertiary butyl -3- methylphenols), 4,4'- fourths pitch bis- (3- methyl-6-tert butyl benzene
Phenol), 4,4'- dihydroxy-phenyl-cyclohexanes, 1,3,5- trimethyls -2,4,6- three (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene,
1,1,3- tri- (2- methyl -4- hydroxyl -5- 2-methyl-2-phenylpropanes base) butane, 2,5 di tert butyl hydroquinone, bis- tertiary pentyls of 2,5- are to benzene
It is one or more in diphenol or 4,4' butylidene biss (6- tertiary butyl -3- methylphenols).
The sulphur ester antioxidant is preferably selected from 1,1'- thiobis (beta naphthal), 2,2'- thiobis (4- methyl-6-tert-butyls
Base phenol), in 4,4'- thiobis (6- tertiary butyl -3- methylphenols) or bis- (3,5- di-tert-butyl-4-hydroxyl benzyls) thioethers
It is one or more.
The phosphoric acid ester antioxidant is preferably selected from 3,5- di-tert-butyl-4-hydroxyl benzyls diethyl phosphate, bis- (3,5- bis-
Tertiary butyl -4- cyanobenzyls phosphonic acids mono ethyl ester) it is calcium, three different monooctyl ester of phosphorous acid, phosphorous acid three (2,4- di-tert-butyl-phenyls) ester, double
(2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites or bis- (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythrites two are sub-
It is one or more in phosphate.
According to the present invention, bottle base product is put into integrated bottle blowing machine, by transportation sprocket, bottle base is sent to lamp box, it is right
Bottle base is heated, and the bottle base having had been warmed up is placed into the closure bottle mold being ready for, interior into horizontal high voltage to it
Inflation, blows bottle base and pulls into required bottle, the bottle after the completion of blowing takes out out of bottle blowing machine, obtains 2,5- furans diformazans
Acidic group is poly- to blow ester；The lamp box temperature is 40-200 DEG C, preferably 80-160 DEG C, more preferably 110-140 DEG C；Heating time
Preferably 30s-300s, more preferably 120-240s；The blowing pressure 0.05MPa-2.0MPa, preferably 0.08-1MPa, more preferably
For 1MPa；Cooling bottle mold medium is water, and temperature is 5-90 DEG C, preferably 10-60 DEG C, more preferably 20-30 DEG C.
Bottle blowing machine blow-molding process of the present invention is the process of a biaxial tension, in the process, 2,5- furyls
Polyester chain is in two-way extension, orientation and arrangement, and to increase the mechanical performance of bottle wall, it is strong to improve stretching, anti-tensile, anti-impact
Degree, and have good air-tightness.
Further detailed description is done to the present invention with reference to embodiment.
Embodiment 1
The preparation of poly- 2,5- furandicarboxylic acids glycol ester：By the second of the 2,5- furandicarboxylic acids dimethyl ester of 5mol, 8mol
Glycol and 0.005mol germanium dioxides are placed in esterifying kettle, and nitrogen is passed through, and ester exchange reaction is carried out at 170 DEG C, waits for 4h transesterifications
After reaction, transesterification product is sent into batch condensation polymerization reactor, vacuumized, be warming up to 230 DEG C, carried out polycondensation reaction, stop after 6h
It only reacts, carries out granulation underwater.
6h, dry temperature are dried into the poly- 2,5-furandicarboxylic acid glycol ester pelletizing that viscosity is 0.75dL/g in drying box
Degree is 120 DEG C；Then butyl titanate is added under conditions of 160 DEG C of temperature, time 8h, to 2,5- furans two under 90Pa vacuum
Formic acid glycol ester solid-phase tack producing；The quality of butyl titanate is the 2wt% of 2,5- furandicarboxylic acid base polyester quality；It obtains everywhere
2,5- furandicarboxylic acid base polyester after reason；
ZrO2 and 3,5- di-tert-butyl-4-hydroxyl benzyl phosphoric acid is added in 2,5- furandicarboxylic acid base polyester after treatment
Two kinds of additives of diethylester, the gross mass of two kinds of additives are the 5wt% of 2,5-furandicarboxylic acid base polyester quality；Then bottle processed
Base, by 2,5-furandicarboxylic acid base polyester pelletizing out of, the hopper of injector is sent into heating barrel, 230 DEG C of heating fusion plastifications
Afterwards, by the thrust of plunger or screw rod, material is compressed and is moved forward, by 200 DEG C of nozzles of barrel front end, with the speed of 2s
It spends in the Guan Bi mould cavity that implantation temperature is 10 DEG C, after the cooling and shaping of 15s, opening mold is up to bottle base product；
Most after-blow bottle, 2,5-furandicarboxylic acid base polyester bottle blank are put into integrated bottle blowing machine, by transportation sprocket, bottle base are sent
Enter to 110 DEG C of lamp boxes, heating 120s is carried out to bottle base, it is 20 DEG C that the bottle base having had been warmed up is placed into the temperature being ready for
Closure bottle mold in, high-pressure aerated to carrying out in it, the blowing pressure 0.1MPa blows bottle base and pulls into required bottle,
Bottle after the completion of blowing, takes out out of bottle blowing machine, obtains bottle.
The experimental results showed that：Bottle internal pressure resistance made from embodiment 1 is 1.7MPa, and thermal shock resistance is 50 DEG C, shock resistance
Property be 90J, internal stress is 3 grades (GB4545-84), and inner surface water resistance is HC3 grade (GB4548-95), suitable for beer bottle.
Embodiment 2
The preparation of poly- 2,5- furandicarboxylic acids glycol ester：By the second of the 2,5- furandicarboxylic acids dimethyl ester of 5mol, 8mol
In glycol and 0.005mol butyl titanate placing response devices, it is passed through nitrogen, ester exchange reaction is carried out at 190 DEG C, waits for that 5h esters are handed over
It changes after reaction, transesterification product is sent into batch condensation polymerization reactor, is vacuumized, be warming up to 230 DEG C, carry out polycondensation reaction, after 4h
Stop reaction, carries out granulation underwater.
5h, dry temperature are dried into the poly- 2,5-furandicarboxylic acid glycol ester pelletizing that viscosity is 0.70dL/g in drying box
Degree is 110 DEG C；Then butyl titanate is added under conditions of 180 DEG C of temperature, time 8h, to 2,5- furans two under 90Pa vacuum
Formic acid glycol ester solid-phase tack producing；The quality of butyl titanate is the 2wt% of 2,5- furandicarboxylic acid base polyester quality；It obtains everywhere
2,5- furandicarboxylic acid base polyester after reason；
Two kinds of additions of SiO2 and 1,1'- thiobis (beta naphthal) are added in 2,5- furandicarboxylic acid base polyester after treatment
Agent, the gross mass of two kinds of additives are the 3wt% of 2,5-furandicarboxylic acid base polyester quality；Then bottle base processed, by 2,5- furans
Diformyl polyester pelletizing is out of, the hopper of injector is sent into heating barrel, after 225 DEG C of heating fusion plastifications, by plunger or
The thrust of screw rod, material are compressed and are moved forward, by 200 DEG C of nozzles of barrel front end, with the speed implantation temperature of 1.5s
For in 40 DEG C of Guan Bi mould cavity, after the cooling and shaping of 5s, opening mold is up to bottle base product；
Most after-blow bottle, 2,5-furandicarboxylic acid base polyester bottle blank are put into integrated bottle blowing machine, by transportation sprocket, bottle base are sent
Enter to 140 DEG C of lamp boxes, heating 200s is carried out to bottle base, it is 10 DEG C that the bottle base having had been warmed up is placed into the temperature being ready for
Closure bottle mold in, high-pressure aerated to carrying out in it, the blowing pressure 0.1MPa blows bottle base and pulls into required bottle,
Bottle after the completion of blowing, takes out out of bottle blowing machine, obtains bottle.
The experimental results showed that：Bottle internal pressure resistance made from embodiment 2 is 1.2MPa, and two meters are fallen and do not rupture, can be stablized
It stands, is suitable for Coke bottle, photo pictorial diagram is as shown in Figure 1.
Embodiment 3
The preparation of poly- 2,5- furandicarboxylic acids glycol ester：By the second of the 2,5- furandicarboxylic acids dimethyl ester of 5mol, 8mol
Glycol and 0.005mol germanium dioxides are placed in esterifying kettle, and nitrogen is passed through, and ester exchange reaction is carried out at 170 DEG C, waits for 4h transesterifications
After reaction, transesterification product is sent into batch condensation polymerization reactor, vacuumized, be warming up to 230 DEG C, carried out polycondensation reaction, stop after 6h
It only reacts, carries out granulation underwater.
6h, dry temperature are dried into the poly- 2,5-furandicarboxylic acid glycol ester pelletizing that viscosity is 0.75dL/g in drying box
Degree is 120 DEG C；Then butyl titanate is added under conditions of 160 DEG C of temperature, time 8h, to 2,5- furans two under 90Pa vacuum
Formic acid glycol ester solid-phase tack producing；The quality of butyl titanate is the 2wt% of 2,5- furandicarboxylic acid base polyester quality；It obtains everywhere
2,5- furandicarboxylic acid base polyester after reason；
SnO is added in 2,5- furandicarboxylic acid base polyester after treatment2With 4,4'- dihydroxybiphenyls, two kinds of additives,
The gross mass of two kinds of additives is the 5wt% of 2,5- furandicarboxylic acid base polyester quality；Then bottle base processed, by 2,5- furans diformazans
Acid based polyester pelletizing is out of, the hopper of injector is sent into heating barrel, after 230 DEG C of heating fusion plastifications, by plunger or screw rod
Thrust, material compressed and moved forward, by 200 DEG C of nozzles of barrel front end, with the speed implantation temperature of 3s for 60 DEG C
Guan Bi mould cavity in, after the cooling and shaping of 10s, opening mold is up to bottle base product；
Most after-blow bottle, 2,5-furandicarboxylic acid base polyester bottle blank are put into integrated bottle blowing machine, by transportation sprocket, bottle base are sent
Enter to 110 DEG C of lamp boxes, heating 240s is carried out to bottle base, it is 30 DEG C that the bottle base having had been warmed up is placed into the temperature being ready for
Closure bottle mold in, high-pressure aerated to carrying out in it, the blowing pressure 0.1MPa blows bottle base and pulls into required bottle,
Bottle after the completion of blowing, takes out out of bottle blowing machine, obtains bottle.
The experimental results showed that：Bottle internal pressure resistance made from embodiment 3 is 1.7MPa, and thermal shock resistance is 50 DEG C, shock resistance
Property be 90J, internal stress is 3 grades (GB4545-84), and inner surface water resistance is HC3 grade (GB4548-95), suitable for beer bottle.
Claims (10)
1. a kind of 2,5-furandicarboxylic acid base polyester blows the preparation method of bottle, which is characterized in that including：
Step 1：In a vacuum or inert atmosphere, 2,5-furandicarboxylic acid base polyester and catalyst are reacted in the reaction vessel,
The 2,5- furandicarboxylic acid base polyester that obtains that treated；
Step 2：Addition resistance decarboxylation reagent and antioxygen in the step 1 2,5- furandicarboxylic acid base polyester that obtains that treated
Agent is then placed in barrel, after heating fusion plastification, by the nozzle of barrel front end, is injected in Guan Bi mould cavity, through supercooling
But after shaping, for opening mold up to bottle base product, extruder temperature is 150-260 DEG C, and nozzle temperature is 180-260 DEG C, cooling bottle
It is water that mold, which has medium, and temperature is 5-90 DEG C；
Step 3：The bottle base product that step 2 obtains is put into integrated bottle blowing machine, bottle base, which is then sent to lamp box, is added
The bottle base having had been warmed up is placed into and is closed in bottle mold by heat, high-pressure aerated to being carried out in it, obtains 2,5- furans diformazans
Acid based polyester blows bottle；The lamp box temperature is 40-200 DEG C, the blowing pressure 0.05MPa-2.0MPa, and cooling bottle mold is situated between
Matter is water, and temperature is 5-90 DEG C.
2. a kind of 2,5-furandicarboxylic acid base polyester according to claim 1 blows the preparation method of bottle, which is characterized in that institute
The structural formula of 2,5- furandicarboxylic acids base polyester in step 1 is stated as shown in formula I：
In formula I, R isWherein, n >=2；
The reduced viscosity of the 2,5- furandicarboxylic acid base polyester is 0.5-1.5dL/g.
3. a kind of 2,5-furandicarboxylic acid base polyester according to claim 1 blows the preparation method of bottle, which is characterized in that institute
It states catalyst in step 1 and is selected from tetraethyl titanate, metatitanic acid orthocarbonate, tetraisopropyl titanate, butyl titanate, four isobutyl of metatitanic acid
Ester, tetraethyl orthosilicate, silicic acid orthocarbonate, silicic acid tetra-isopropyl, tetrabutyl silicate, four isobutyl ester of silicic acid, trimethyl phosphate, phosphoric acid
Triethyl, tricresyl phosphate propyl ester, tricresyl phosphate isopropyl ester, tributyl phosphate, sodium acetate, magnesium acetate, aluminum acetate, zinc acetate, lanthanum acetate,
Germanium dioxide, antimony oxide, antimony acetate, antimony glycol, trimethyl aluminium, triethyl aluminum, aluminium ethoxide, aluminum isopropylate,
It is one or more in stannous oxalate or stannous octoate.
4. a kind of 2,5-furandicarboxylic acid base polyester according to claim 1 or 3 blows the preparation method of bottle, feature exists
In the quality of the catalyst is the 0.01-10wt% of 2,5-furandicarboxylic acid base polyester quality；
5. a kind of 2,5-furandicarboxylic acid base polyester according to claim 1 blows the preparation method of bottle, which is characterized in that institute
The reaction temperature of the step of stating one is 20-260 DEG C, reaction time 5min-240h.
6. a kind of 2,5-furandicarboxylic acid base polyester according to claim 1 blows the preparation method of bottle, which is characterized in that institute
It states and hinders decarboxylation reagent in step 2 selected from SiO2、TiO2、MgO、CaO、ZnO、SnO2、ZrO2Or CaCO3In it is one or more.
7. a kind of 2,5-furandicarboxylic acid base polyester according to claim 1 blows the preparation method of bottle, which is characterized in that institute
It is phenolic antioxidant, sulphur ester antioxidant or phosphoric acid ester antioxidant to state antioxidant in step 2.
8. a kind of 2,5-furandicarboxylic acid base polyester according to claim 7 blows the preparation method of bottle, which is characterized in that institute
It states phenolic antioxidant and is selected from 4,4' dihydroxy diphenyl, 4,4' methylene bis (2,6 di t butyl phenol), 4,4' butylidene biss
(6- tertiary butyl -3- methylphenols), 4,4'- fourths pitch bis- (3 methy 6 tert butyl phenols), 4,4'- dihydroxydiphenyl hexamethylenes
Alkane, 1,3,5- trimethyls -2,4,6- three (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene, (2- methyl -4- hydroxyls -5- of 1,1,3- tri-
2-methyl-2-phenylpropane base) butane, 2,5 di tert butyl hydroquinone, 2,5 di tert amyl hydroquinone or 4,4' butylidene biss (the tertiary fourths of 6-
Base -3- methylphenols) in it is one or more.
9. a kind of 2,5-furandicarboxylic acid base polyester according to claim 7 blows the preparation method of bottle, which is characterized in that institute
It states sulphur ester antioxidant and is selected from 1,1'- thiobis (beta naphthal), 2,2'- thiobis (4- methyl-6-tert-butylphenols), 4,4'-
It is one or more in thiobis (6- tertiary butyl -3- methylphenols) or bis- (3,5- di-tert-butyl-4-hydroxyl benzyls) thioethers.
10. a kind of 2,5-furandicarboxylic acid base polyester according to claim 7 blows the preparation method of bottle, which is characterized in that
The phosphoric acid ester antioxidant is selected from 3,5- di-tert-butyl-4-hydroxyl benzyls diethyl phosphate, bis- (3,5- di-t-butyl -4- cyanogen
Base benzylphosphonic acid mono ethyl ester) calcium, three different monooctyl ester of phosphorous acid, phosphorous acid three (2,4- di-tert-butyl-phenyls) ester, bis- (bis- tertiary fourths of 2,4-
Base phenyl) in pentaerythritol diphosphites or bis- (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphites
It is one or more.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142962A (en) * | 2019-06-26 | 2020-12-29 | 武汉科技大学 | Preparation method and application of high molecular weight transparent polyester |
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| CN101899145A (en) * | 2010-07-28 | 2010-12-01 | 江南大学 | Preparation method of 2, 5-furan diformyl polyester |
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Effective date of registration: 20200302 Address after: YAOGOU Industrial Zone, Wuwei County, Wuhu City, Anhui Province Applicant after: Wuhu Wanlong New Material Co., Ltd Address before: 130000 No. 5625 Renmin Street, Changchun, Jilin, Chaoyang District Applicant before: Changchun Institute of Applied Chemistry Chinese Academy of Sciences |
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Application publication date: 20181113 |