CN110437431A - A kind of bicyclic pentanediol copolyesters of biology base and its application - Google Patents
A kind of bicyclic pentanediol copolyesters of biology base and its application Download PDFInfo
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- CN110437431A CN110437431A CN201910717011.4A CN201910717011A CN110437431A CN 110437431 A CN110437431 A CN 110437431A CN 201910717011 A CN201910717011 A CN 201910717011A CN 110437431 A CN110437431 A CN 110437431A
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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
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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
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Abstract
It include following component the invention discloses a kind of bicyclic pentanediol copolyesters of biology base and its application, raw material: (a) terephthalic acid (TPA) or its carboxylate；(b) aliphatic dihydric alcohol；(c) bicyclic pentanediol shown in formula (I),
Description
Technical field
The invention belongs to field of material technology, and in particular to a kind of bicyclic pentanediol copolyesters of biology base and preparation method thereof
And application.
Background technique
High glass-transition temperature (Tg), impact-resistant transparent high molecular material electronics, electric appliance, baby bottles, cup,
Kitchen appliance product, food packaging, optical field, ornament materials, automobile manufacturing field have very extensive purposes, while in lightweight
Also there is specific use in bulletproof glass field.Tg is mainly bisphenol-A greater than the high molecular material of 100 DEG C, impact-resistant transparent at present
Type polycarbonate (BPA-PC), but will be slow release bisphenol-A in use process, causes infant development bad, induces cancer and new
Old metabolic disorder, European Union, which has ordered, forbids that field is packed and contacted for baby food；China forbids for baby food simultaneously
Contact container, cup, kitchen appliance product mainstream supplier be health consider, selection do not use BPA-PC.
Summary of the invention
It is bicyclic the technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a kind of novel biology base
Pentanediol copolyesters, environmental protection, will not discharge the substance being harmful to the human body, while can also have both high glass in use
Change the performances such as transition temperature and high impact-resistant toughness.
The present invention additionally provides the above-mentioned bicyclic pentanediol copolyesters of novel biology base of one kind in electronics, electric appliance, vapour simultaneously
Application in vehicle, baby bottles, cup, food packaging, optical field, ornament materials and kitchen appliance product.
In order to solve the above technical problems, a kind of technical solution that the present invention takes is as follows:
A kind of bicyclic pentanediol copolyesters of biology base, the raw material of the bicyclic pentanediol copolyesters of biology base include such as the following group
Point:
(a) terephthalic acid (TPA) or its carboxylate；
(b) aliphatic dihydric alcohol；
(c) bicyclic pentanediol shown in formula (I),
The bicyclic pentanediol copolyesters of biology base is by occurring esterification or ester friendship after said components (a), (b) and (c) mixing
Reaction is changed, is then made through polycondensation reaction.
Some preferred aspects according to the present invention, bicyclic pentanediol shown in the formula (I) is by making cis- two ring
[3.3.0] octane -3,7- diketone reacts in organic solvent with sodium borohydride to be made.
Some preferred aspects according to the present invention are reacted in cis- two ring [3.3.0] octane -3,7- diketone with sodium borohydride
During, it controls the reaction and is carried out at -10~35 DEG C.A specific aspect according to the present invention, controls the reaction
It is first carried out 1-5 hours at -10~0 DEG C, then heats to and carry out 10-30h at 20-30 DEG C.
Some specific aspects according to the present invention are reacted in cis- two ring [3.3.0] octane -3,7- diketone with sodium borohydride
During, the organic solvent is methanol.
Some preferred aspects according to the present invention are reacted in cis- two ring [3.3.0] octane -3,7- diketone with sodium borohydride
During, the mole that feeds intake of the sodium borohydride is relative to 2 times of cis- two ring [3.3.0] octane -3,7- diketone
The mole that feeds intake is excessive.
Some specific aspects according to the present invention, cis- two rings [3.3.0] octane -3,7- diketone can be by commercially available
It obtains or is made by the conventional method of this field by biology base citric acid.
The throwing of some preferred aspects according to the present invention, the bicyclic pentanediol and the terephthalic acid (TPA) or its carboxylate
Expect that molar ratio is 0.1-0.6: 1, preferably 0.2-0.6: 1.
Some preferred aspects according to the present invention, the mole that always feeds intake of the bicyclic pentanediol and the aliphatic dihydric alcohol
It is 1.2-2.0: 1, preferably 1.4-2.0: 1 with the molar ratio of the terephthalic acid (TPA) or its carboxylate, more preferably
1.5-1.9∶1。
More according to the present invention preferred and specific aspect, the esterification or ester exchange reaction are at 160-240 DEG C of temperature
It carries out, is preferably carried out at 180-220 DEG C of temperature.
More according to the present invention preferred and specific aspect, the esterification or ester exchange reaction are under inert gas atmosphere
It carries out.In certain embodiments of the present invention, the inert gas uses nitrogen；It can also adopt in other embodiments
With argon gas etc. inert gas.
More according to the present invention specific and preferred aspect, the esterification or ester exchange reaction are urged in esterification or transesterification
In the presence of agent.
More according to the present invention specific and preferred aspect, the esterification or ester exchange catalyst be selected from zinc acetate,
One of iso-butyl titanate and butyl titanate or a variety of combinations.
The inventory of some preferred aspects according to the present invention, the esterification or ester exchange catalyst is the terephthaldehyde
The 0.05-0.3% of the mole that feeds intake of acid or its carboxylate.
Some preferred aspects according to the present invention, the polycondensation reaction carry out at 260-310 DEG C of temperature, preferably 265-
It carries out at 305 DEG C, is carried out at more preferably 270-300 DEG C.
Some preferred aspects according to the present invention, the polycondensation reaction are carried out in the case where vacuum degree is less than or equal to 60Pa, preferably
It carries out in the case where vacuum degree is less than or equal to 45Pa, is more preferably carried out in the case where vacuum degree is less than or equal to 30Pa.
More according to the present invention specific and preferred aspect, the polycondensation reaction in the presence of polycondensation catalyst into
Row.
More according to the present invention specific and preferred aspect, the polycondensation catalyst are selected from antimony oxide, metatitanic acid
Isobutyl ester, butyl titanate, antimony glycol, antimony acetate, dibutyltin oxide, stannous iso caprylate, three isooctyl acid tin of monobutyl, oxygen
Change one of dioctyl tin and polyethylene glycol antimony or a variety of combinations.
Some preferred aspects according to the present invention, the inventory of the polycondensation catalyst are the terephthalic acid (TPA) or its ester
The 0.05-0.3% of the mole that feeds intake of compound.
More according to the present invention specific and preferred aspect, the aliphatic dihydric alcohol are selected from ethylene glycol, propylene glycol, fourth
One of two pure and mild cyclohexanedimethanols or a variety of combinations.
Some specific aspects according to the present invention, the terephthalic acid (TPA) or its carboxylate include terephthalic acid (TPA), to benzene
Dicarboxylic acid dimethyl ester etc..
Some specific aspects according to the present invention, the raw material further include one or both of stabilizer and antioxidant.
Some specific aspects according to the present invention, the stabilizer be selected from phosphoric acid, phosphorous acid, ortho phosphorous acid, pyrophosphoric acid,
Ammonium phosphate, trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite,
The combination of one or more of ammonium phosphite and ammonium dihydrogen phosphate.
Some specific aspects according to the present invention, the antioxidant are selected from antioxidant -1010, antioxidant -1076 and to resist
The combination of one or more of oxygen agent -168；
More according to the present invention specific and preferred aspect, the stabilizer, the antioxidant inventory be respectively
The 0.1-0.3% of the mole that feeds intake of the terephthalic acid (TPA) or its carboxylate.
Another technical solution provided by the invention: a kind of bicyclic pentanediol copolyesters of biology base described above electronics,
Application in electric appliance, automobile, baby bottles, cup, food packaging, optical field, ornament materials and kitchen appliance product.
Due to the use of above technical scheme, the invention has the following advantages over the prior art:
The present invention innovatively uses the bicyclic pentanediol of nonplanar structure shown in formula (I) as a kind of diol monomer and rouge
Fat dihydric alcohol, terephthalic acid (TPA) or its carboxylate synthesize the specific bicyclic pentanediol copolyesters of biology base, overcome first existing
The bisphenol A polycarbonate of mainstream not environmentally healthy defect；Secondly, the copolyesters not only has preferable heat resistance, (Tg can
Up to 130 DEG C or so), transparent (colorless and transparent), but also (transient absorption can be impacted when being impacted having both excellent toughness
Energy) while have solvent resistance, mechanical property is good, so that the bicyclic pentanediol copolyesters of biology base of the invention can
Replace bisphenol A polycarbonate and applies in baby bottles, food packaging etc. field.
Detailed description of the invention
Fig. 1 is the photo of the bicyclic pentanediol copolyester material of biology base prepared by the embodiment of the present invention 1；
Fig. 2 is the DSC curve of the bicyclic pentanediol copolyester material of biology base prepared by the embodiment of the present invention 1.
Specific embodiment
Above scheme is described further below in conjunction with specific embodiment；It should be understood that these embodiments are for illustrating
The basic principles, principal features and advantages of the present invention, and the present invention is not by the scope limitation of following embodiment；It is used in embodiment
Implementation condition further adjustment can be done according to specific requirement, the implementation condition being not specified is usually the item in routine experiment
Part.
In following, unless otherwise specified, all raw materials are substantially from conventional method that is commercially available or passing through this field
It is prepared.
In following embodiments, the molecular weight of all polymer is tested using Agilent PL-GPC220, and pillar is two
5 μm of Mixed-D 300*7.5mm series connection of PLgel.Mobile phase is chloroform, and test temperature is 40 DEG C, and sample dissolution solvent is neighbour
Chlorophenol: chloroform=1:1 (v/v), sample concentration 1mg/mL, flow rate 1mL/min, standard specimen are PS (3070-
258000g/mol)。
In embodiment, heat analysis is using differential scanning calorimetry (Mettler Toledo DSC) with the heating speed of 10 DEG C/min
Rate, in N2Atmosphere carries out, and temperature range is -10~300 DEG C.
Following bicyclic pentanediols used in the examples are prepared via a method which and obtain: by cis- two ring [3.3.0] of 100g
Octane -3,7- diketone is dissolved in 1000mL methanol, cools to -5 DEG C, is added with stirring 90g sodium borohydride, is reacted 3 hours, by
Step is raised to room temperature, and the reaction was continued 20 hours, and the hydrochloric acid 2L dilution of 2mol/L is added, is then neutralized with sodium hydroxide.Chloroform is added to mention
It takes, washs, distill, be dried to obtain the bicyclic pentanediol 75g of crystalline solid, be the mixture of cis-trans-isomer；Wherein, cis- different
The nuclear magnetic data of structure body are as follows:1H-NMR(400MHz,CDCl3):δ4.36-4.30(2H),2.60-2.50(2H),2.30(2H),
2.22-2.14(4H),1.80-1.70(4H)；The nuclear magnetic data of transisomer are as follows: 4.52-4.45 (1H), 4.26-4.20
(1H),2.70-2.60 2H),2.30(2H),2.20-2.12(2H),1.90-1.80(2H),1.80-1.70(2H),1.38-
1.30(2H)。
Embodiment 1
This example provides a kind of bicyclic pentanediol copolyesters of biology base, raw material include dimethyl terephthalate (DMT) 0.5mol,
Bicyclic pentanediol 0.15mol, ethylene glycol 0.65mol, triphenyl phosphate 0.00075mol and antioxidant 1010 (0.00075mol)；
It prepares as follows: dimethyl terephthalate (DMT) 0.5mol, bicyclic pentanediol 0.15mol and ethylene glycol 0.65mol is added
Enter into polymer reactor, 0.15% butyl titanate of the mole based on dimethyl terephthalate (DMT) is then added
(0.00075mol)；In a nitrogen atmosphere, 200 DEG C are warming up to, insulation reaction 3.5h obtains esterification products, is then added and is based on
0.15% triphenyl phosphate (0.00075mol) of the mole of dimethyl terephthalate (DMT) and be based on terephthalic acid (TPA) diformazan
0.15% antioxidant 1010 (0.00075mol) of the mole of ester, vacuum degree are gradually lowered to 30Pa hereinafter, gradually heating up
To 280 DEG C, insulation reaction 4h, the bicyclic pentanediol copolyesters of biology base is obtained.
Through detecting, the opposite number-average molecular weight 39600g/mol of the bicyclic pentanediol copolyesters of the biology base is relatively heavy to divide equally
Protonatomic mass 68100g/mol, the structural unit of bicyclic pentanediol and molar ratio=30:70 of ethylene glycol structure unit, gained copolymerization
As shown in Figure 1, whole in colorless and transparent, the DSC curve of copolyesters is as shown in Figure 2 for the photo of ester material；The glass of the copolyesters
Changing transition temperature is 116 DEG C, tensile strength 86MPa, stretch modulus 2400MPa, impact strength 49J/mol.Solvent resistance is surveyed
It is fixed: the 200 micron thickness copolyester films that more parts are prepared according to the method described above respectively as acetone, toluene, chloroform, ethyl alcohol,
It is placed 2 hours in dimethylbenzene, takes out drying, quality free of losses is presented in measurement, without obvious swelling and dissolution；Copolyesters has excellent
Different solvent resistance.
Embodiment 2
This example provides a kind of bicyclic pentanediol copolyesters of biology base, raw material include dimethyl terephthalate (DMT) 0.5mol,
Bicyclic pentanediol 0.25mol, ethylene glycol 0.55mol, triphenyl phosphate 0.001mol and antioxidant 1010 (0.0006mol)；
It prepares as follows: dimethyl terephthalate (DMT) 0.5mol, bicyclic pentanediol 0.25mol and ethylene glycol 0.55mol is added
Enter into polymer reactor, 0.10% butyl titanate of the mole based on dimethyl terephthalate (DMT) is then added
(0.0005mol)；In a nitrogen atmosphere, 220 DEG C are warming up to, insulation reaction 4h obtains esterification products, is then added based on to benzene
0.20% triphenyl phosphate (0.001mol) of the mole of dicarboxylic acid dimethyl ester and rubbing based on dimethyl terephthalate (DMT)
0.12% antioxidant 1010 (0.0006mol) of your amount, vacuum degree are gradually lowered to 30Pa hereinafter, being gradually warming up to 290 DEG C,
Insulation reaction 4h obtains the bicyclic pentanediol copolyesters of biology base.
Through detecting, the opposite number-average molecular weight 2850g/mol of the bicyclic pentanediol copolyesters of the biology base, relative weight average molecule
Quality 55400g/mol, the structural unit of bicyclic pentanediol and molar ratio=50:50 of ethylene glycol structure unit, the glass of copolyesters
Glass transition temperature is 125 DEG C, tensile strength 87MPa, stretch modulus 2490MPa, impact strength 55J/mol.
Embodiment 3
This example provides a kind of bicyclic pentanediol copolyesters of biology base, raw material include dimethyl terephthalate (DMT) 0.5mol,
Bicyclic pentanediol 0.30mol, ethylene glycol 0.45mol, triphenyl phosphate 0.001mol and antioxidant 1010 (0.001mol)；
It prepares as follows: dimethyl terephthalate (DMT) 0.5mol, bicyclic pentanediol 0.30mol and ethylene glycol 0.45mol is added
Enter into polymer reactor, 0.20% anhydrous zinc acetate of the mole based on dimethyl terephthalate (DMT) is then added
(0.001mol)；In a nitrogen atmosphere, 200 DEG C are warming up to, insulation reaction 5.5h obtains esterification products, then be added based on pair
0.20% antimony oxide (0.001mol) of the mole of rutgers, mole based on dimethyl terephthalate (DMT)
0.20% triphenyl phosphate (0.001mol) of amount and 0.20% antioxidant of the mole based on dimethyl terephthalate (DMT)
1010 (0.001mol), vacuum degree are gradually lowered to 30Pa hereinafter, being gradually warming up to 295 DEG C, and insulation reaction 4h obtains biology base
Bicyclic pentanediol copolyesters.
Through detecting, the opposite number-average molecular weight 28700g/mol of the bicyclic pentanediol copolyesters of the biology base is relatively heavy to divide equally
Protonatomic mass 51200g/mol, the structural unit of bicyclic pentanediol and molar ratio=58:42 of ethylene glycol structure unit, copolyesters
Glass transition temperature is 128 DEG C, tensile strength 83MPa, stretch modulus 2280MPa, impact strength 47J/mol.
Embodiment 4
This example provides a kind of bicyclic pentanediol copolyesters of biology base, raw material include dimethyl terephthalate (DMT) 0.5mol,
Bicyclic pentanediol 0.10mol, ethylene glycol 0.85mol, triphenyl phosphate 0.00053mol and antioxidant 176 (0.0005mol)；
It prepares as follows: dimethyl terephthalate (DMT) 0.5mol, bicyclic pentanediol 0.10mol and ethylene glycol 0.85mol is added
Enter into polymer reactor, 0.10% anhydrous zinc acetate of the mole based on dimethyl terephthalate (DMT) is then added
(0.0005mol)；In a nitrogen atmosphere, 180 DEG C are warming up to, insulation reaction 4.0h obtains esterification products, then be added based on pair
0.10% antimony oxide (0.0005mol) of the mole of rutgers, rubbing based on dimethyl terephthalate (DMT)
The 0.10% of 0.105% triphenyl phosphate (0.00053mol) and the mole based on dimethyl terephthalate (DMT) that you measure resists
Oxygen agent 176 (0.0005mol), vacuum degree are gradually lowered to 30Pa hereinafter, being gradually warming up to 275 DEG C, and insulation reaction 3h is given birth to
The bicyclic pentanediol copolyesters of object base.
Through detecting, the opposite number-average molecular weight 57900g/mol of the bicyclic pentanediol copolyesters of the biology base is relatively heavy to divide equally
Protonatomic mass 84200g/mol, the structural unit of bicyclic pentanediol and molar ratio=19.2:80.8 of ethylene glycol structure unit, copolymerization
The glass transition temperature of ester is 101 DEG C, tensile strength 78MPa, stretch modulus 1890MPa, impact strength 27J/mol.
Embodiment 5
This example provides a kind of bicyclic pentanediol copolyesters of biology base, raw material include dimethyl terephthalate (DMT) 0.5mol,
Bicyclic pentanediol 0.20mol, ethylene glycol 0.75mol, triphenyl phosphate 0.00053mol and antioxidant 176 (0.0005mol)；
It prepares as follows: dimethyl terephthalate (DMT) 0.5mol, bicyclic pentanediol 0.20mol and ethylene glycol 0.75mol is added
Enter into polymer reactor, 0.15% anhydrous zinc acetate of the mole based on dimethyl terephthalate (DMT) is then added
(0.00075mol)；In a nitrogen atmosphere, 180 DEG C are warming up to, insulation reaction 4.0h obtains esterification products, is then added and is based on
0.10% antimony oxide (0.0005mol) of the mole of dimethyl terephthalate (DMT), based on dimethyl terephthalate (DMT)
The 0.10% of 0.105% triphenyl phosphate (0.00053mol) of mole and the mole based on dimethyl terephthalate (DMT)
Antioxidant 176 (0.0005mol), vacuum degree are gradually lowered to 30Pa hereinafter, being gradually warming up to 285 DEG C, and insulation reaction 3h is obtained
The bicyclic pentanediol copolyesters of biology base.
Through detecting, the opposite number-average molecular weight 54200g/mol of the bicyclic pentanediol copolyesters of the biology base is relatively heavy to divide equally
Protonatomic mass 81300g/mol, the structural unit of bicyclic pentanediol and molar ratio=39.2:60.8 of ethylene glycol structure unit, copolymerization
The glass transition temperature of ester is 121 DEG C, tensile strength 88MPa, stretch modulus 2430MPa, impact strength 51J/mol.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention, it is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of bicyclic pentanediol copolyesters of biology base, which is characterized in that the raw material of the bicyclic pentanediol copolyesters of biology base
Including following component:
(a) terephthalic acid (TPA) or its carboxylate；
(b) aliphatic dihydric alcohol；
(c) bicyclic pentanediol shown in formula (I),
The bicyclic pentanediol copolyesters of biology base is anti-by generation esterification after said components (a), (b) and (c) mixing or transesterification
It answers, is then made through polycondensation reaction.
2. the bicyclic pentanediol copolyesters of biology base according to claim 1, which is characterized in that double shown in the formula (I)
Cyclopentadienyl alcohol is made by reacting cis- two ring [3.3.0] octane -3,7- diketone in organic solvent with sodium borohydride, wherein
It controls the reaction to carry out at -10~35 DEG C, the organic solvent includes methanol.
3. the bicyclic pentanediol copolyesters of biology base according to claim 1, which is characterized in that the bicyclic pentanediol and institute
The molar ratio for stating terephthalic acid (TPA) or its carboxylate is 0.1-0.6: 1, preferably 0.2-0.6: 1；And/or it is described bicyclic
Pentanediol and the aliphatic dihydric alcohol always feed intake mole and the molar ratio of the terephthalic acid (TPA) or its carboxylate is
1.2-2.0: 1, preferably 1.4-2.0: 1, more preferably 1.5-1.9: 1.
4. the bicyclic pentanediol copolyesters of biology base according to claim 1, which is characterized in that the esterification or transesterification are anti-
It should carry out at 160-240 DEG C of temperature, preferably be carried out at 180-220 DEG C of temperature；And/or the esterification or ester exchange reaction exist
It is carried out under inert gas atmosphere.
5. the bicyclic pentanediol copolyesters of biology base according to claim 1 or 4, which is characterized in that the esterification or ester are handed over
Reaction is changed in the presence of esterification or ester exchange catalyst, the esterification or ester exchange catalyst are selected from zinc acetate, metatitanic acid isobutyl
The inventory of one of ester and butyl titanate or a variety of combinations, the esterification or ester exchange catalyst is described to benzene two
The 0.05-0.3% of the mole that feeds intake of formic acid or its carboxylate.
6. the bicyclic pentanediol copolyesters of biology base according to claim 1, which is characterized in that the polycondensation reaction is in temperature
It carries out at 260-310 DEG C, is carried out at preferably 265-305 DEG C, carried out at more preferably 270-300 DEG C.
7. the bicyclic pentanediol copolyesters of biology base according to claim 1, which is characterized in that the polycondensation reaction is in vacuum
Degree is less than or equal under 60Pa carry out, and preferably carries out in the case where vacuum degree is less than or equal to 45Pa, is more preferably less than or equal in vacuum degree
It is carried out under 30Pa.
8. the bicyclic pentanediol copolyesters of biology base described according to claim 1 or 6 or 7, which is characterized in that the polycondensation reaction
It is carried out in the presence of polycondensation catalyst, the polycondensation catalyst is selected from antimony oxide, iso-butyl titanate, four fourth of metatitanic acid
Ester, antimony glycol, antimony acetate, dibutyltin oxide, stannous iso caprylate, three isooctyl acid tin of monobutyl, di-n-octyltin oxide and poly-
One of antimony glycol or a variety of combinations, the inventory of the polycondensation catalyst are the terephthalic acid (TPA) or its carboxylate
The mole that feeds intake 0.05-0.3%.
9. the bicyclic pentanediol copolyesters of biology base according to claim 1, which is characterized in that the aliphatic dihydric alcohol is choosing
From one of ethylene glycol, propylene glycol, butanediol and cyclohexanedimethanol or a variety of combinations；And/or the raw material further includes
One or both of stabilizer and antioxidant, the stabilizer are selected from phosphoric acid, phosphorous acid, ortho phosphorous acid, pyrophosphoric acid, phosphoric acid
Ammonium, trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, phosphorous
The combination of one or more of sour ammonium and ammonium dihydrogen phosphate, the antioxidant are selected from antioxidant -1010, antioxidant -1076
With the combination of one or more of antioxidant -168；
Wherein, the stabilizer, the antioxidant inventory be respectively that the terephthalic acid (TPA) or feeding intake for its carboxylate are rubbed
The 0.1-0.3% of your amount.
10. the bicyclic pentanediol copolyesters of biology base is in electronics, electricity described in a kind of any one of claim 1-9 claim
Application in device, automobile, baby bottles, cup, food packaging, optical field, ornament materials and kitchen appliance product.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101654336A (en) * | 2008-08-19 | 2010-02-24 | 朱继业 | Polyester resin impregnating agent |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101654336A (en) * | 2008-08-19 | 2010-02-24 | 朱继业 | Polyester resin impregnating agent |
Non-Patent Citations (2)
| Title |
|---|
| XIAOHAN LIU ET AL: ""Random Copolycarbonates Based on a Renewable Bicyclic Diol Derived from Citric Acid"", 《MACROMOLECULES》 * |
| YAN YU ET AL: ""Copolycarbonates Based on a Bicyclic Diol Derived from Citric Acid and Flexible 1,4-Cyclohexanedimethanol: From Synthesis to Properties"", 《ACS MACRO LETT.》 * |
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