CN102002170A - Coupling agent composite and method for improving intrinsic viscosity of polyethylene terephthalate by utilizing same - Google Patents
Coupling agent composite and method for improving intrinsic viscosity of polyethylene terephthalate by utilizing same Download PDFInfo
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- CN102002170A CN102002170A CN2009101720263A CN200910172026A CN102002170A CN 102002170 A CN102002170 A CN 102002170A CN 2009101720263 A CN2009101720263 A CN 2009101720263A CN 200910172026 A CN200910172026 A CN 200910172026A CN 102002170 A CN102002170 A CN 102002170A
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Abstract
The invention relates to a coupling agent composite which comprises an epoxy compound and a tertiary amine compound. The invention also provides a method for improving intrinsic viscosity of polyethylene terephthalate. The method comprises the following steps: mixing the polyethylene terephthalate and a coupling agent composite to form a mixture, wherein the coupling agent comprises the epoxy compound and the tertiary amine compound; and carrying out melt-mixing on the mixture to form the polyethylene terephthalate with high intrinsic viscosity.
Description
Technical field
The present invention relates to a kind of coupling agent (coupling agent), particularly relates to a kind of coupling agent composition and utilizes this coupling agent composition to promote the method for polyethylene terephthalate limiting viscosity.
Background technology
(poly (ethylene terephthalate) is the maximum and the most inexpensive macromolecular material of output in domestic PET) to polyethylene terephthalate, has the superior mechanical property and the transparency, is widely used in the fine and PET bottle product of people.Whole world PET annual production reaches 6,0,000,000 tons, with people's fibre and PET bottle serves as that application is large, and only the quantum of output of disabled person's fibre and PET bottle product is more surprising, is gold if can change rubbish, this disabled person's fibre and PET bottle product are reclaimed, and upgrading and promote its rerum natura, to be applied to high-valued product scope, this not only can reduce the Carbon emission equivalent, and can meet the environmental protection demand of 3R (decrement, recovery, utilize again), can reach energy-conservation effect again simultaneously.Only in the process of recycling PET, the processing procedure of high-temperature fusion can cause the degraded of PET, the stability of lower molecular weight PET and rigidity are all relatively poor, therefore, for how to recover or promote limiting viscosity (intrinsic viscosity again, IV) and molecular weight, be to reclaim the required major issue of facing of PET.The general IV that reclaims PET is approximately 0.60, reach more than 0.74 even higher if IV can be improved, and can satisfy the demand of mechanical property and machine-shaping.
At present, the commercialization volume production only can be utilized the solid-state polycondensation (solid-statepolycondensation of lower temperature reaction, SSPC) processing procedure, this is because if use pyritous molten state polymerization processing procedure, to bring out PET and produce pyrolysis, and the high sticking PET of fusion also is unfavorable for reacting the devolatilization of the EG condenses in being, cause and can't promote IV, right SSPC processing procedure is from drying, the pre-crystallization of ester grain and solid-state polycondensation supervisor is quite consuming time, energy consumption and problem on the processing procedure cost of investment such as nitrogen recycling purifying is arranged.
Summary of the invention
The object of the present invention is to provide a kind of coupling agent composition, can with PET fusion polycondensation reaction latter stage remaining carboxyl and hydroxyl carry out coupled reaction, thereby realize the utilization again of the high performance that useless polyester resource reclaims.
The invention provides a kind of coupling agent composition, comprising: an epoxy compounds; And tertiary amine (tertiaryamine) compound.
The invention provides a kind of method that promotes the polyethylene terephthalate limiting viscosity, comprise: mix a polyethylene terephthalate and a coupling agent composition, to form a mixture, wherein this coupling agent composition comprises an epoxy compounds and a tertiary amine compound; And this mixture carried out a melting mixing processing procedure, to form a polyethylene terephthalate with high inherent viscosity.
High clayization fusion coupled reaction process technique of the present invention be utilize PET fusion polycondensation reaction latter stage (about IV=0.6) remaining carboxyl and hydroxyl, can remaining therewith carboxyl by adding, hydroxyl reaction has the coupling agent of difunctionality base, to carry out the quick high clayization fusion coupled reaction (can finish in several minutes) of PET, its advantage is for can (for example: carry out the quick high vicious coupling reaction of PET twin screw extruder) and extrude generally having traditional reactive tank that high torsion stirs or forcing machine, and the coupling agent addition is few (generally≤5wt%), and can block remaining carboxyl of PET and hydroxyl, so, can promote hydrolysis and the thermostability of PET, also can give up PET bottle or waste silk is that raw material is to carry out high vicious coupling reaction, to realize the utilization again of the high performance that useless polyester resource reclaims, its processing procedure elasticity is big, and process apparatus and running cost are also lower.
For above-mentioned purpose of the present invention, feature and advantage can be become apparent, a preferred embodiment cited below particularly is described in detail below:
Embodiment
One embodiment of the invention provide a kind of coupling agent composition, comprise an epoxy compounds, and a tertiary amine compound.
When being used to promote the PET limiting viscosity, among per 100 parts of PET, epoxy compounds is 0.1～5 weight part, is preferably 0.5～4 weight part, and tertiary amine is 0.01～5 weight part, is preferably 0.01～0.5 weight part.
Above-mentioned epoxy compounds for example can comprise 1,4-butanediol diglycidyl ether (1,4-Butanedioldiglycidyl ether), 1,6-hexanediol diglycidyl ether (1,6-Hexanediol diglycidyl ether), neopentylglycol diglycidyl ether (Neopentyl glycol diglycidyl ether), polypropylene glycol diglycidyl ether (Polypropylene glycol diglycidyl ether), 4,4-bisphenol A diglycidyl ether (4,4-Isopropylidenediphenol diglycidyl ether), 1,4-two (oxidation Racemic glycidol) benzene (1,4-Bis (glycidyloxy) benzene) or the di-epoxy compounds of dihydroxyphenyl propane NOVOLAC Resins, epoxy (Bisphenol-ANovolac Epoxy), trihydroxymethylpropanyltri diglycidyl ether (Trimethylolpropane triglycidyl ether) for example, T 55 (Glycerol triglycidyl ether), the glycerine third oxygen acid esters triglycidyl ether (Glycerol propoxylate triglycidyl ether), N, N-2-glycidyl-4-oxidation Racemic glycidol aniline (N, N-Diglycidyl-4-glycidyloxyaniline), three (2, the 3-epoxypropyl) (Tris (2 for chlorinated isocyanurates, 3-epoxypropyl) isocyanurate), three epoxy compoundss of three hydroxyphenyl methane triglycidyl ether (Triphenylol methane triglycidly ether) or o-cresol epoxy resin (O-Cresol NovolakEpoxy Resin) or N for example, N, N ', N '-Fourth Ring oxygen propyl group-4,4 '-diaminodiphenylmethane (4,4 '-the Fourth Ring oxygen compound of Methylenebis (N, N-diglycidylaniline)) or four hydroxyphenyl ethane glycidyl ethers (Tetraphenylolethane glycidyl ether).
Above-mentioned tertiary amine compound can comprise 3-Ben Jia Ji oxazole pyridine (3-Benzyloxazolidine), { 1-phenmethyl-piperidines-3-yl }-dimethyl-amine (1-Benzyl-Pyrrolidin-3-YL}-Dimethyl-amine), 2,2 '-dimorpholine base diethyl-ether (2,2 '-Dimorpholinyldiethyl-ether), 4-dimethyl amine yl pyridines (4-Dimethylaminopyridine), N, N-diethyl cyclo-hexylamine (N, N-Diethylcyclohexylamine), N, N-dimethyl stearyl amine (N, N-Dimethylstearylamine), 1,8-two azos two rings [5,4,0] 11-7-alkene (1,8-Diazabicyclo[5,4,0]-UnDec-7-ENE).
Coupling agent composition of the present invention also can comprise one for example B-110 (by three (2,4-two-tert-butyl-phenyl) (Tris (2 for phosphoric acid salt, 4-di-tert-butylphenyl) phosphate) with four-[methylene radical (3 ', 5 '-two-tert-butyl-hydroxy phenyl) propionic ester] methane (Tetrakis-[Methylene (3 ', 5 '-Di-tert-Butyl-4-Hydroxylphenyl) Propionate] methane) form with 1 to 1 ratio), B-210 is (by three (2,4-two-tert-butyl-phenyl) (Tris (2 for phosphoric acid salt, 4-di-tert-butylphenyl) phosphate) with four-[methylene radical (3 ', 5 '-two-tert-butyl-hydroxy phenyl) propionic ester] methane (Tetrakis-[Methylene (3 ', 5 '-Di-tert-Butyl-4-Hydroxylphenyl) Propionate] methane) form with 2 to 1 ratios), B310 is (by three (2,4-two-tert-butyl-phenyl) (Tris (2 for phosphoric acid salt, 4-di-tert-butylphenyl) phosphate) with four-[methylene radical (3 ', 5 '-two-tert-butyl-hydroxy phenyl) propionic ester] methane (Tetrakis-[Methylene (3 ', 5 '-Di-tert-Butyl-4-Hydroxylphenyl) Propionate] methane) form than l ratio with 3), B410 is (by three (2,4-two-tert-butyl-phenyl) (Tris (2 for phosphoric acid salt, 4-di-tert-butylphenyl) phosphate) with four-[methylene radical (3 ', 5 '-two-tert-butyl-hydroxy phenyl) propionic ester] methane (Tetrakis-[Methylene (3 ', 5 '-Di-tert-Butyl-4-Hydroxylphenyl) Propionate] methane) form with 4 to 1 ratios), B401 is (by three (2,4-two-tert-butyl-phenyl) (Tris (2 for phosphoric acid salt, 4-di-tert-butylphenyl) phosphate) with octadecyl-3-(3 ', 5 '-two-tert-butyl-hydroxy phenyl) (Stearyl-3-(3 ' for propionic ester, 5 '-di-tert-butyl-4-Hydroxyphenyl)-Propionate) with 4 to 1 prescription compositions), B201 is (by three (2,4-two-tert-butyl-phenyl) (Tris (2 for phosphoric acid salt, 4-di-tert-butylphenyl) phosphate) with octadecyl-3-(3 ', 5 '-two-tert-butyl-hydroxy phenyl) propionic ester (Stearyl-3-(3 ', 5 '-di-tert-butyl-4-Hydroxyphenyl)-Propionate) with 2 to 1 ratios composition), the antioxidant of B-561 (production of UNIBROM company) or Topanol (the full skill in Taiwan company buys) etc.
One embodiment of the invention provide a kind of method that promotes the polyethylene terephthalate limiting viscosity, comprise the following steps.At first, mix a polyethylene terephthalate and a coupling agent composition, to form a mixture.The coupling agent composition comprises an epoxy compounds and a tertiary amine compound.Afterwards, mixture is carried out a melting mixing processing procedure, to form a polyethylene terephthalate with high inherent viscosity.
Above-mentioned epoxy compounds for example can comprise 1,4-butanediol diglycidyl ether (1,4-Butanedioldiglycidyl ether), 1,6-hexanediol diglycidyl ether (1,6-Hexanediol diglycidyl ether), neopentylglycol diglycidyl ether (Neopentyl glycol diglycidyl ether), polypropylene glycol diglycidyl ether (Polypropylene glycol diglycidyl ether), 4,4-bisphenol A diglycidyl ether (4,4-Isopropylidenediphenol diglycidyl ether), 1,4-two (oxidation Racemic glycidol) benzene (1,4-Bis (glycidyloxy) benzene) or the di-epoxy compounds of dihydroxyphenyl propane NOVOLAC Resins, epoxy (Bisphenol-A NovolacEpoxy), trihydroxymethylpropanyltri diglycidyl ether (Trimethylol propanetriglycidyl ether) for example, T 55 (Glycerol triglycidyl ether), the glycerine third oxygen acid esters triglycidyl ether (Glycerol propoxylate triglycidyl ether), N, N-2-glycidyl-4-oxidation Racemic glycidol aniline (N, N-Diglycidyl-4-glycidyloxyaniline), three (2, the 3-epoxypropyl) (Tris (2 for chlorinated isocyanurates, 3-epoxypropyl) isocyanurate), three epoxy compoundss of three hydroxyphenyl methane triglycidyl ether (Triphenylolmethane triglycidly ether) or o-cresol epoxy resin (O-Cresol Novolak Epoxy Resin), or N for example, N, N ', N '-Fourth Ring oxygen propyl group-4,4 '-diaminodiphenylmethane (4,4 '-the Fourth Ring oxygen compound of Methylenebis (N, N-diglycidylaniline)) or four hydroxyphenyl ethane glycidyl ethers (Tetraphenylolethane glycidyl ether).
Above-mentioned tertiary amine compound can comprise 3-Ben Jia Ji oxazole pyridine (3-Benzyloxazolidine), { 1-phenmethyl-piperidines-3-yl }-dimethyl-amine (1-Benzyl-Pyrrolidin-3-YL}-Dimethyl-amine), 2,2 '-dimorpholine base diethyl-ether (2,2 '-Dimorpholinyldiethyl-ether), 4-dimethyl amine yl pyridines (4-Dimethylaminopyridine), N, N-diethyl cyclo-hexylamine (N, N-Diethylcyclohexyl amine), N, N-dimethyl stearyl amine (N, N-Dimethylstearylamine), 1,8-two azos two rings [5,4,0] 11-7-alkene (1,8-Diazabicyclo[5,4,0]-UnDec-7-ENE).
Coupling agent composition of the present invention also can comprise one for example B-110 (by three (2,4-two-tert-butyl-phenyl) (Tris (2 for phosphoric acid salt, 4-di-tert-butylphenyl) phosphate) with four-[methylene radical (3 ', 5 '-two-tert-butyl-hydroxy phenyl) propionic ester] methane (Tetrakis-[Methylene (3 ', 5 '-Di-tert-Butyl-4-Hydroxylphenyl) Propionate] methane) form with 1 to 1 ratio), B-210 is (by three (2,4-two-tert-butyl-phenyl) (Tris (2 for phosphoric acid salt, 4-di-tert-butylphenyl) phosphate) with four-[methylene radical (3 ', 5 '-two-tert-butyl-hydroxy phenyl) propionic ester] methane (Tetrakis-[Methylene (3 ', 5 '-Di-tert-Butyl-4-Hydroxylphenyl) Propionate] methane) form with 2 to 1 ratios), B310 is (by three (2,4-two-tert-butyl-phenyl) (Tris (2 for phosphoric acid salt, 4-di-tert-butylphenyl) phosphate) with four-[methylene radical (3 ', 5 '-two-tert-butyl-hydroxy phenyl) propionic ester] methane (Tetrakis-[Methylene (3 ', 5 '-Di-tert-Butyl-4-Hydroxylphenyl) Propionate] methane) form with 3 to 1 ratios), B410 is (by three (2,4-two-tert-butyl-phenyl) (Tris (2 for phosphoric acid salt, 4-di-tert-butylphenyl) phosphate) with four-[methylene radical (3 ', 5 '-two-tert-butyl-hydroxy phenyl) propionic ester] methane (Tetrakis-[Methylene (3 ', 5 '-Di-tert-Butyl-4-Hydroxylphenyl) Propionate] methane) form with 4 to 1 ratios), B401 is (by three (2,4-two-tert-butyl-phenyl) (Tris (2 for phosphoric acid salt, 4-di-tert-butylphenyl) phosphate) with octadecyl-3-(3 ', 5 '-two-tert-butyl-hydroxy phenyl) (Stearyl-3-(3 ' for propionic ester, 5 '-di-tert-butyl-4-Hydroxyphenyl)-Propionate) with 4 to 1 prescription compositions), B201 is (by three (2,4-two-tert-butyl-phenyl) (Tris (2 for phosphoric acid salt, 4-di-tert-butylphenyl) phosphate) with octadecyl-3-(3 ', 5 '-two-tert-butyl-hydroxy phenyl) propionic ester (Stearyl-3-(3 ', 5 '-di-tert-butyl-4-Hydroxyphenyl)-Propionate) with 2 to 1 ratios composition), the antioxidant of B-561 (production of UNIBROM company) or Topanol (the full skill in Taiwan company buys) etc.
In said mixture, the part by weight of polyethylene terephthalate and epoxy compounds is substantially between 100: 0.1～5, preferable between 100: 0.5～4, the part by weight of polyethylene terephthalate and tertiary amine compound is substantially between 100: 0.01～5, preferable between 100: 0.01～0.5, the part by weight of polyethylene terephthalate and antioxidant is substantially between 100: 0.01～5, and is preferable between 100: 0.01～0.3.
The present invention carries out the temperature of melting mixing processing procedure substantially between 250～290 ℃, is approximately higher than about 10～30 ℃ of PET fusing points.The time of melting mixing processing procedure is substantially between 1～3 minute.It should be noted that the present invention's formed polyethylene terephthalate behind the melting mixing processing procedure, its limiting viscosity is the highest even can reach more than 0.78.
Because primary amine (NR
1H
2) and secondary amine (NR
1R
2H) all have the NH functional group, can be with acid-base reaction become acid amides (amide), so primary amine and secondary amine do not possess catalyzed reaction.Therefore, the present invention select not can with the tertiary amine (NR of acid-base reaction
1R
2R
3) as coupling agent.
High clayization fusion coupled reaction process technique of the present invention be utilize PET fusion polycondensation reaction latter stage (about IV=0.6) remaining carboxyl and hydroxyl, can remaining therewith carboxyl by adding, hydroxyl reaction has the coupling agent of difunctionality base, to carry out the quick high clayization fusion coupled reaction (can finish in several minutes) of PET, its advantage is for can (for example: carry out the quick high vicious coupling reaction of PET twin screw extruder) and extrude generally having traditional reactive tank that high torsion stirs or forcing machine, and the coupling agent addition is few (generally≤5wt%), and can block remaining carboxyl of PET and hydroxyl, so, can promote hydrolysis and the thermostability of PET, also can give up PET bottle or waste silk is that raw material is to carry out high vicious coupling reaction, to realize the utilization again of the high performance that useless polyester resource reclaims, its processing procedure elasticity is big, and process apparatus and running cost are also lower.
The preparation (time processing) of [comparing embodiment 1] polyethylene terephthalate (PET)
Polyethylene terephthalate (PET, environmental protection company of Taiwan Norcent provides) is added a twin screw extruder to be processed.Processing conditions is as follows: input speed is 16.0, and screw speed is 200rpm, and extrusion temperature is 250 ℃, and Torque is 22.27.This comparing embodiment is formed polyethylene terephthalate after time processing, and its limiting viscosity is 0.5488, and is as shown in table 1.
The preparation (6) of [comparing embodiment 2] polyethylene terephthalate (PET)
At first, with 100: 0.3 weight part mixing polyethylene terephthalate (PET) with B-561 (production of UNIBROM company).Afterwards, said mixture is added a twin screw extruder, to carry out a melting mixing processing procedure.The melting mixing process conditions is as follows: input speed is 16, and screw speed is 200rpm, and extrusion temperature is 250 ℃, and the reaction times is 1～2 minute, and Torque is 22.93.Present embodiment is formed polyethylene terephthalate behind the melting mixing processing procedure, and its limiting viscosity is 0.5925, and is as shown in table 1.
The preparation (7) of [embodiment 1] polyethylene terephthalate (PET)
At first, with 100: 1.0: 0.2: 0.3 weight part mixing polyethylene terephthalate (PET), o-cresol epoxy resin (O-Cresol Novolak Epoxy Resin), N, (N is N-Dimethylstearylamine) with B-561 (production of UNIBROM company) for N-dimethyl stearyl amine.Afterwards, said mixture is added a twin screw extruder, to carry out a melting mixing processing procedure.The melting mixing process conditions is as follows: input speed is 18, and screw speed is 200rpm, and extrusion temperature is 250 ℃, and the reaction times is 1～2 minute, and Torque is 26.01.Present embodiment is formed polyethylene terephthalate behind the melting mixing processing procedure, and its limiting viscosity is 0.655, and is as shown in table 1.
The preparation (8) of [embodiment 2] polyethylene terephthalates (PET)
At first, with 100: 3.0: 0.2: 0.3 weight part mixing polyethylene terephthalate (PET), o-cresol epoxy resin (O-Cresol Novolak Epoxy Resin), N, (N is N-Dimethylstearylamine) with B-561 (production of UNIBROM company) for N-dimethyl stearyl amine.Afterwards, said mixture is added a twin screw extruder, to carry out a melting mixing processing procedure.The melting mixing process conditions is as follows: input speed is 18, and screw speed is 200rpm, and extrusion temperature is 250 ℃, and the reaction times is 1～2 minute, and Torque is 25.24.Present embodiment is formed polyethylene terephthalate behind the melting mixing processing procedure, and its limiting viscosity is 0.745, and is as shown in table 1.
Table 1
| Blank test | Comparing embodiment 1 | Comparing embodiment 2 | Embodiment 1 | Embodiment 2 | |
| PET | 100 | ?100 | ?100 | 100 | 100 |
| Three epoxy compoundss | - | ?- | ?- | 1.0 | 3.0 |
| Tertiary amine compound | - | ?- | ?- | 0.2 | 0.2 |
| Antioxidant | - | ?- | ?0.3 | 0.3 | 0.3 |
| Extrusion temperature (℃) | - | ?250 | ?250 | 250 | 250 |
| Input speed (ampere) | - | ?16 | ?16 | 18 | 18 |
| Screw speed (rpm) | - | ?200 | ?200 | 200 | 200 |
| Torque | - | ?22.27 | ?22.93 | 26.01 | 25.24 |
| IV | 0.64 | ?0.5488 | ?0.5925 | 0.655 | 0.745 |
The IV of fusion PET is not 0.64, because the hot shearing effect of twin screw extruder, making PET produce thermooxidizing slightly decomposes, cause IV to drop to 0.5488, yet after comparing embodiment 2 was added coupling agent, its IV only dropped to 0.59, therefore, antioxidant can suppress the thermooxidizing decomposition of PET really.In addition in embodiment 1 and embodiment 2 adds tertiary amine compounds (catalyzer) and with antioxidant after, formed coupling PET constituent, its IV can reach 0.745, confirmation can make PET carry out quick high clayization reaction.
The preparation of [comparing embodiment 3] polyethylene terephthalate (PET) (Ba catalyzer)
At first, with 100: 2: 0.2: 0.3 weight part mixing polyethylene terephthalate (PET), o-cresol epoxy resin (O-Cresol Novolak Epoxy Resin), Ba catalyzer and B-561 (production of UNIBROM company).Afterwards, said mixture is added a twin screw extruder, to carry out a melting mixing processing procedure.The melting mixing process conditions is as follows: input speed is 16, and screw speed is 200rpm, and extrusion temperature is 250 ℃, and Torque is 23.59.This comparing embodiment is formed polyethylene terephthalate behind the melting mixing processing procedure, and its limiting viscosity is 0.607, and is as shown in table 2.
The preparation of [comparing embodiment 4] polyethylene terephthalate (PET) (Ba catalyzer)
At first, with 100: 3: 0.3: 0.3 weight part mixing polyethylene terephthalate (PET), o-cresol epoxy resin (O-Cresol Novolak Epoxy Resin), Ba catalyzer and B-561 (production of UNIBROM company).Afterwards, said mixture is added a twin screw extruder, to carry out a melting mixing processing procedure.The melting mixing process conditions is as follows: input speed is 16, and screw speed is 200rpm, and extrusion temperature is 250 ℃, and Torque is 23.55.This comparing embodiment is formed polyethylene terephthalate behind the melting mixing processing procedure, and its limiting viscosity is 0.643, and is as shown in table 2.
The preparation of [comparing embodiment 5] polyethylene terephthalate (PET) (Ca/Zn catalyzer)
At first, with 100: 2: 0.2: 0.3 weight part mixing polyethylene terephthalate (PET), o-cresol epoxy resin (O-Cresol Novolak Epoxy Resin), Ca/Zn catalyzer and B-561 (production of UNIBROM company).Afterwards, said mixture is added a twin screw extruder, to carry out a melting mixing processing procedure.The melting mixing process conditions is as follows: input speed is 16, and screw speed is 200rpm, and extrusion temperature is 250 ℃, and Torque is 23.71.This comparing embodiment is formed polyethylene terephthalate behind the melting mixing processing procedure, and its limiting viscosity is 0.595, and is as shown in table 2.
The preparation of [comparing embodiment 6] polyethylene terephthalate (PET) (Ca/Zn catalyzer)
At first, with 100: 3: 0.3: 0.3 weight part mixing polyethylene terephthalate (PET), o-cresol epoxy resin (O-Cresol Novolak Epoxy Resin), Ca/Zn catalyzer and B-561 (production of UNIBROM company).Afterwards, said mixture is added a twin screw extruder, to carry out a melting mixing processing procedure.The melting mixing process conditions is as follows: input speed is 16, and screw speed is 200rpm, and extrusion temperature is 250 ℃, and Torque is 23.15.This comparing embodiment is formed polyethylene terephthalate behind the melting mixing processing procedure, and its limiting viscosity is 0.684, and is as shown in table 2.
The preparation (9) of [embodiment 3] polyethylene terephthalates (PET)
At first, with 100: 2: 0.2 weight part mixing polyethylene terephthalates (PET), o-cresol epoxy resin (O-Cresol Novolak Epoxy Resin) and 4-dimethyl amine yl pyridines (4-Dimethylaminopyridine).Afterwards, said mixture is added a twin screw extruder, to carry out a melting mixing processing procedure.The melting mixing process conditions is as follows: input speed is 16, and screw speed is 200rpm, and extrusion temperature is 250 ℃, and the reaction times is 1～2 minute, and Torque is 27.03.Present embodiment is formed polyethylene terephthalate behind the melting mixing processing procedure, and its limiting viscosity is 0.713, and is as shown in table 2.
The preparation (10) of [embodiment 4] polyethylene terephthalates (PET)
At first, with 100: 3: 0.2 weight part mixing polyethylene terephthalates (PET), o-cresol epoxy resin (O-Cresol Novolak Epoxy Resin) and 4-dimethyl amine yl pyridines (4-Dimethylaminopyridine).Afterwards, said mixture is added a twin screw extruder, to carry out a melting mixing processing procedure.The melting mixing process conditions is as follows: input speed is 16, and screw speed is 200rpm, and extrusion temperature is 250 ℃, and the reaction times is 1～2 minute, and Torque is 27.42.Present embodiment is formed polyethylene terephthalate behind the melting mixing processing procedure, and its limiting viscosity is 0.785, and is as shown in table 2.
Table 2
When prescription is selected three epoxy compound compound coupling agents for use and is used metal catalyst and antioxidant, the viscosity that can find PET promotes DeGrain, but observe tertiary amine compound is extruded effect to the PET high vicious coupling reaction influence, even if can find out and not add antioxidant, also can make more than the PET viscosity fast lifting to 0.78, this has proved that also (catalysis) speed of response of using tertiary amine catalyst is more than fast (being meant that here catalysis speed is not the time at screw extrusion press) of using the metallic salt catalyzer.Tradition uses metallic salt as catalyzer, and its reaction times is 20～50 minutes (in same reactor).And the present invention uses twin screw equipment, be about 1～2 minute from being fed to extrude according to the rotating speed differential responses time, from comparative example, the same reaction times (be fed to and extrude spended time), use the metallic salt catalyzer that the effect that PET viscosity promotes is not had the many of tertiary amine catalyst, this represents that promptly the catalyzed reaction of metallic salt catalyzer does not have the fast of tertiary amine catalyst really.
Though the present invention discloses as above with preferred embodiment; right its is not in order to limiting the present invention, anyly has the knack of this skill person, without departing from the spirit and scope of the present invention; when can doing to change and retouching, so protection scope of the present invention is as the criterion when looking the scope that the accompanying Claim book defined.
Claims (24)
1. coupling agent composition comprises:
One epoxy compounds; And
One tertiary amine compound.
2. coupling agent composition according to claim 1, wherein this epoxy compounds is di-epoxy compounds, three epoxy compoundss or Fourth Ring oxygen compound.
3. coupling agent composition according to claim 2, wherein this di-epoxy compounds is 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentylglycol diglycidyl ether, polypropylene glycol diglycidyl ether, 4,4-bisphenol A diglycidyl ether, 1,4-two (oxidation Racemic glycidol) benzene or dihydroxyphenyl propane NOVOLAC Resins, epoxy.
4. coupling agent composition according to claim 2, wherein this three epoxy compounds is trihydroxymethylpropanyltri diglycidyl ether, T 55, the glycerine third oxygen acid esters triglycidyl ether, N, N-2-glycidyl-4-oxidation Racemic glycidol aniline, three (2, the 3-epoxypropyl) chlorinated isocyanurates, o-cresol epoxy resin, three hydroxyphenyl methane triglycidyl ether or o-cresol epoxy resins.
5. coupling agent composition according to claim 2, wherein this Fourth Ring oxygen compound is N, N, N ', N '-Fourth Ring oxygen propyl group-4,4 '-diaminodiphenylmethane or four hydroxyphenyl ethane glycidyl ethers.
6. coupling agent composition according to claim 1, wherein this tertiary amine compound is the pyridine of 3-Ben Jia Ji oxazole, { 1-phenmethyl-piperidines-3-yl }-dimethyl-amine, 2,2 '-dimorpholine base diethyl-ether, 4-dimethyl amine yl pyridines, N, N-diethyl cyclo-hexylamine, N, N-dimethyl stearyl amine, 1,8-two azos two ring [5,4,0] 11-7-alkene.
7. coupling agent composition according to claim 1 also comprises an antioxidant.
8. coupling agent composition according to claim 7, wherein this antioxidant is B-110, B-215, B-210, B-225, B310, B410, B401, B201, B-561 or Topanol.
9. method that promotes the polyethylene terephthalate limiting viscosity comprises:
Mix a polyethylene terephthalate and a coupling agent composition, to form a mixture, wherein this coupling agent composition comprises an epoxy compounds and a tertiary amine compound; And
This mixture is carried out a melting mixing processing procedure, to form a polyethylene terephthalate.
10. the method for lifting polyethylene terephthalate limiting viscosity according to claim 9, wherein this epoxy compounds is di-epoxy compounds, three epoxy compoundss or Fourth Ring oxygen compound.
11. the method for lifting polyethylene terephthalate limiting viscosity according to claim 10, wherein this di-epoxy compounds is 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentylglycol diglycidyl ether, polypropylene glycol diglycidyl ether, 4,4-bisphenol A diglycidyl ether, 1,4-two (oxidation Racemic glycidol) benzene or dihydroxyphenyl propane NOVOLAC Resins, epoxy.
12. the method for lifting polyethylene terephthalate limiting viscosity according to claim 10, wherein this three epoxy compounds is trihydroxymethylpropanyltri diglycidyl ether, T 55, the glycerine third oxygen acid esters triglycidyl ether, N, N-2-glycidyl-4-oxidation Racemic glycidol aniline, three (2, the 3-epoxypropyl) chlorinated isocyanurates, o-cresol epoxy resin, three hydroxyphenyl methane triglycidyl ether or o-cresol epoxy resins.
13. the method for lifting polyethylene terephthalate limiting viscosity according to claim 10, wherein this Fourth Ring oxygen compound is N, N, N ', N '-Fourth Ring oxygen propyl group-4,4 '-diaminodiphenylmethane or four hydroxyphenyl ethane glycidyl ethers.
14. the method for lifting polyethylene terephthalate limiting viscosity according to claim 9, wherein this tertiary amine compound is the pyridine of 3-Ben Jia Ji oxazole, { 1-phenmethyl-piperidines-3-yl }-dimethyl-amine, 2,2 '-dimorpholine base diethyl-ether, 4-dimethyl amine yl pyridines, N, N-diethyl cyclo-hexylamine, N, N-dimethyl stearyl amine, 1,8-two azos two ring [5,4,0] 11-7-alkene.
15. the method for lifting polyethylene terephthalate limiting viscosity according to claim 9 also comprises and mixes an antioxidant.
16. the method for lifting polyethylene terephthalate limiting viscosity according to claim 15, wherein this antioxidant is B-110, B-215, B-210, B-225, B310, B410, B401, B201, B-561 or Topanol.
17. the method for lifting polyethylene terephthalate limiting viscosity according to claim 9, wherein the part by weight of this polyethylene terephthalate and this epoxy compounds is between 100: 0.1～5.
18. the method for lifting polyethylene terephthalate limiting viscosity according to claim 9, wherein the part by weight of this polyethylene terephthalate and this epoxy compounds is between 100: 0.5～4.
19. the method for lifting polyethylene terephthalate limiting viscosity according to claim 9, wherein the part by weight of this polyethylene terephthalate and this tertiary amine compound is between 100: 0.01～5.
20. the method for lifting polyethylene terephthalate limiting viscosity according to claim 9, wherein the part by weight of this polyethylene terephthalate and this tertiary amine compound is between 100: 0.01～0.5.
21. the method for lifting polyethylene terephthalate limiting viscosity according to claim 15, wherein the part by weight of this polyethylene terephthalate and this antioxidant is between 100: 0.01～5.
22. the method for lifting polyethylene terephthalate limiting viscosity according to claim 15, wherein the part by weight of this polyethylene terephthalate and this antioxidant is between 100: 0.01～0.3.
23. the method for lifting polyethylene terephthalate limiting viscosity according to claim 9, wherein the temperature of this melting mixing processing procedure is between 250～290 ℃.
24. the method for lifting polyethylene terephthalate limiting viscosity according to claim 9, wherein the time of this melting mixing processing procedure was between 1～3 minute.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104250432A (en) * | 2013-06-25 | 2014-12-31 | 财团法人工业技术研究院 | Polyester composition and polyester product prepared from same |
| CN105385155A (en) * | 2015-12-31 | 2016-03-09 | 祥兴(福建)箱包集团有限公司 | Nylon plastic bearing retainer for draw-bar box and preparation method of nylon plastic bearing retainer |
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2009
- 2009-09-03 CN CN2009101720263A patent/CN102002170A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104250432A (en) * | 2013-06-25 | 2014-12-31 | 财团法人工业技术研究院 | Polyester composition and polyester product prepared from same |
| CN104250432B (en) * | 2013-06-25 | 2016-03-23 | 财团法人工业技术研究院 | Polyester composition and polyester product prepared from same |
| CN105385155A (en) * | 2015-12-31 | 2016-03-09 | 祥兴(福建)箱包集团有限公司 | Nylon plastic bearing retainer for draw-bar box and preparation method of nylon plastic bearing retainer |
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