CN103613746A - Pure polyester resin for high weather-resistant outdoor powder coating and preparation method thereof - Google Patents
Pure polyester resin for high weather-resistant outdoor powder coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a pure polyester resin for a high weather-resistant outdoor powder coating and a preparation method thereof. The pure polyester resin is prepared from water, neopentyl glycol, trimethylolpropane, 1,4-cyclohexane dimethanol, adipic acid, purified terephthalic acid, 1,4-cyclohexane dioctyl phthalate, monobutyltin oxide, triphenyl phosphate, isophthalic acid, tri[2,4-di-tert-butylphenyl] phosphite ester, 18-carbon propionate ester and phosphorus tribromide through the following nine technological processes: a stage of feeding a first part of material, an early warming and esterified water discharge stage, a low-temperature esterification stage, a high-temperature esterification stage, a primary thermal reaction stage, a secondary feeding and secondary warming reaction stage, a vacuum decompression reaction stage, a stage of feeding an antioxidant and a curing accelerator, and a emptying stage. The production technology disclosed by the invention adopts a two-step method; the pure polyester resin has the characteristics of being narrow in molecular weight distribution, proper in glass-transition temperature, softening point, viscosity and storage stability, high in exterior durability, high in cost performance and the like.
Description
technical field:
The present invention relates to the special-purpose saturated polyester resin production technical field of powder coating, utilize formula provided by the present invention and production technique can produce a kind of high weather-proof outdoor type used for powder coating pure polyester resin.
background technology:
Development along with the industries such as building, automobile, air-conditioning, washing machine especially outdoor building material and freeway guardrail, has proposed requirements at the higher level to weathering resistance performance powder paint, and the drive of industry has promoted weathering resistance resin fast-developing.
Weathering resistance is the key property of outdoor powder coating, the aging phenomenon that causes film molecular chemistry bond rupture or destruction in ultraviolet ray, moisture, temperature variation, air, atmosphere under the composite factor effect such as chemical pollutant that refers to of filming.Filming of powder coating is comprised of resin, solidifying agent, pigment, filler, auxiliary agent etc., and the weathering resistance of therefore filming and the weather-proof stability of these several parts are contacted directly.Vibrin is as the main base-material of filming, and its weather-proof stability is maximum to the performance impact of filming.And the weather-proof stability of vibrin depends on molecular structure, the chemical stability for the synthesis of the monomer of vibrin and produces synthesis technique, control etc.
Auxiliary agent is also very large on the impact of weathering resistance, and conventional auxiliary agent has UV light absorber, free radical scavenger, the worn-out agent of optical screen, oxidation inhibitor etc.There is synergistic effect in some auxiliary agent simultaneously, adds so non-single auxiliary agent weathering resistance and have larger improvement, if use oxidation inhibitor greatly to slow down the atmospheric aging of filming, increases its weathering resistance.Therefore, How to choose auxiliary agent kind and dosage are also very important to improving coating weatherability and raising powder cost performance etc.Some auxiliary agents are more conducive to auxiliary agent and are uniformly dispersed than adding in pulverizing process in the synthetic later stage of vibrin joins resin, help raising weathering resistance.
summary of the invention:
The object of this invention is to provide a kind of high weather-proof outdoor type used for powder coating pure polyester resin and preparation method thereof.
The technical problem to be solved in the present invention is realized by following scheme: a kind of high weather-proof outdoor type used for powder coating pure polyester resin and preparation method thereof, it is by water 1, neopentyl glycol 2, TriMethylolPropane(TMP) 3, 1, 4-cyclohexane dimethyl carbinol 4, hexanodioic acid 5, pure terephthalic acid 6, 1, 4-cyclohexane dioctyl phthalate 7, Mono-n-butyltin (or not containing organotin catalysts) 8, triphenyl phosphite 9, m-phthalic acid 10, three [2.4-di-tert-butyl-phenyl] phosphorous acid ester 11, the positive octadecanol ester 12 of β-(3.5-di-tert-butyl-hydroxy phenyl) propionic acid, phosphorus tribromide 13 adopts to be thrown the First sub-material stage 14, heat up and go out the esterification water stage 15 in early stage, low temperature Esterification Stage 16, the high temperature esterification stage 17, insulation reaction stage 18 for the first time, feed intake for the second time and secondary temperature elevation step of reaction 19, vacuumize the Depressor response stage 20, throw oxidation inhibitor, curing catalyst 21, 22 9 technical process of blowing complete its preparation method, its raw-material proportioning is: water 1: neopentyl glycol 2: TriMethylolPropane(TMP) 3: 1, 4-cyclohexane dimethyl carbinol 4: hexanodioic acid 5: pure terephthalic acid 6: 1, 4-cyclohexane dioctyl phthalate 7: Mono-n-butyltin (or not containing organotin catalysts) 8: triphenyl phosphite 9: 10: three positive octadecanol esters 12 of [2.4-di-tert-butyl-phenyl] phosphorous acid ester 11: β-(3.5-di-tert-butyl-hydroxy phenyl) propionic acid of m-phthalic acid: phosphorus tribromide 13=1%～2%: 30%～40%: 0%～1%: 1%～2%: 0%～2%: 2%～3%: 40%～50%: 0%～2%: 0%～1%: 0%～1%: 5%～10%: 0%～1%: 0%～1%,
Throw First sub-material 14: when still temperature is between room temperature is with 110 ℃, in reactor, drop into water 1, neopentyl glycol 2 and TriMethylolPropane(TMP) 3, Isosorbide-5-Nitrae-cyclohexane dimethyl carbinol 4, finishes rear slow startup stirring; Drop into a part of hexanodioic acid 5 and whole pure terephthalic acid 6, Isosorbide-5-Nitrae-cyclohexane dioctyl phthalate 7 and partially catalyzed agent Mono-n-butyltin (or containing organotin catalysts) 8;
Heat up and go out the esterification water stage 15 in early stage: still temperature is persistently overheating to going out esterification water from feeding intake, and rotating speed of agitator is controlled the mode that progressively increases should taked with still temperature rise, after 124 ℃ of still temperature, and (50Hz) stirring at full speed.When still temperature reaches 180 ℃, the heat-up rate that slows down, so that temperature of charge reaches unanimity in still, will mix oar variable-frequence governor frequency and be down to 44Hz left and right, then every 30 minutes, variable-frequence governor frequency will be increased to 0.5Hz, until (50Hz) stirs at full speed.Go out after esterification water, insulation reaction 90 minutes, top temperature control is at 100 ℃～102 ℃;
Low temperature Esterification Stage 16: heat-up rate heats up by still temperature average 1 ℃/10 minutes (6 ℃/h), about 200 minutes of reaction times.Top temperature control is at 100 ℃～102 ℃, throws sub-fraction triphenyl phosphite 9 during 207 ℃ of still temperature;
The high temperature esterification stage 17: heat-up rate heats up by still temperature average 1 ℃/7～8 minutes (8～9 ℃/h), and the reaction times is about, 245 minutes～260 minutes;
Feed intake for the second time and secondary temperature elevation step of reaction 19: by still temperature drop to approximately 225 ℃ time, in reactant, add acidolysis agent hexanodioic acid 5 and m-phthalic acid 10 and remaining esterifying catalyst Mono-n-butyltin 8, react approximately 20 minutes, by still temperature rise to 246 ℃, insulation reaction 60～80 minutes, carry out sampling analysis for the second time, touch the mark scope (acid number, the 46～49mgkoH/g such as acid number, viscosity; Viscosity, 1.2～1.6pa.s(175 ℃)) carry out next-step operation;
Vacuumize the Depressor response stage 20: within 10 minutes before vacuumizing, drop into remaining triphenyl phosphite 9, while starting to draw sky, still temperature is 245 ℃～246 ℃, control vacuum pumping rate and maximum vacuum (0.092Mpa), according to analytical results for the first time, while starting to draw sky, the sky time (90 minutes～95 minutes) is drawn in the decision such as still temperature, maximum vacuum; After vacuumizing, carry out sampling analysis for the third time, touch the mark scope (acid number, the 34.5～36.5mgkoH/g such as acid number, viscosity; Viscosity, 7.0～8.5pa.s(180 ℃)) carry out next-step operation;
Throw oxidation inhibitor, curing catalyst 21: by still temperature drop to 201 ℃～205 ℃, the oxidation inhibitor that can eliminate free radical that drops into a certain amount of ratio has three [2.4-di-tert-butyl-phenyl] phosphorous acid ester 11 of the compounds such as aromatic amine and hindered phenol and derivative thereof; The oxidation inhibitor of energy hydroperoxide decomposition has the positive octadecanol ester 12 of organic compound β-(3.5-di-tert-butyl-hydroxy phenyl) propionic acid, the throwing curing catalyst phosphorus tribromide 13 of phosphorous and sulfur-bearing, stirs 20 minutes;
Blowing 22: throw curing catalyst and stir after 20 minutes, still temperature control, at 200 ℃～205 ℃, stops stirring blowing.Carrying out the 4th (finished product) sampling analysis detects.Finished product detection index is as follows: acid number, 34.5～36.5mgkoH/g; Viscosity, 7.0～8.5pa.s(180 ℃); Softening temperature, 110 ℃～115 ℃, 63 ℃ ~ 65 ℃ of second-order transition temperatures.
Owing to having adopted above technical scheme, realized preferably its goal of the invention, the outdoor used for powder coating pure polyester resin of this high weather resistant has narrow molecular weight distribution (weight-average molecular weight M
w: number-average molecular weight M
n≤ 1.3), suitable second-order transition temperature, softening temperature, viscosity, package stability and high outside durabitity, the high features such as cost performance; Polyvalent alcohol in synthetic resins of the present invention monomer used all adopts the polyvalent alcohol that does not contain β hydrogen good weatherability, as: neopentyl glycol, TriMethylolPropane(TMP), Isosorbide-5-Nitrae-cyclohexane dimethyl carbinol, hydroxypivalyl hydroxypivalate; In polyprotonic acid, increase the good weatherability such as m-phthalic acid, Isosorbide-5-Nitrae-cyclohexane dioctyl phthalate monomer consumption, add appropriate long-chain biatomic acid (as adipic acid etc.) to realize the snappiness of filming; Aspect the selection of auxiliary agent, adopt good phosphite ester kind antioxidant and Hinered phenols antioxidant the use of antioxidant effect, to bring into play its synergistic effect; Simultaneously on the selection of synthon, auxiliary agent and consumption, also consider coating weatherability, the factor such as the mechanical property of filming, cost performance; Aspect controlling of production process, adopt two-step approach.
accompanying drawing explanation:
Accompanying drawing 1 is process flow sheet of the present invention.
Accompanying drawing 2 is composition and the coating performance schematic diagram of finished product preparation outdoor type powder coating of the present invention.
Description of reference numerals is shown in specification sheets last page form.
embodiment:
Below in conjunction with embodiment, summary of the invention is described further:
embodiment 1:
From summary of the invention, a kind of high weather-proof outdoor type used for powder coating pure polyester resin and preparation method thereof, it is by water 1, neopentyl glycol 2, TriMethylolPropane(TMP) 3, 1, 4-cyclohexane dimethyl carbinol 4, hexanodioic acid 5, pure terephthalic acid 6, 1, 4-cyclohexane dioctyl phthalate 7, Mono-n-butyltin (or not containing organotin catalysts) 8, triphenyl phosphite 9, m-phthalic acid 10, three [2.4-di-tert-butyl-phenyl] phosphorous acid ester 11, the positive octadecanol ester 12 of β-(3.5-di-tert-butyl-hydroxy phenyl) propionic acid, phosphorus tribromide 13 adopts to be thrown the First sub-material stage 14, heat up and go out the esterification water stage 15 in early stage, low temperature Esterification Stage 16, the high temperature esterification stage 17, insulation reaction stage 18 for the first time, feed intake for the second time and secondary temperature elevation step of reaction 19, vacuumize the Depressor response stage 20, throw oxidation inhibitor, curing catalyst 21, 22 9 technical process of blowing complete its preparation method, its raw-material proportioning is: water 1: neopentyl glycol 2: TriMethylolPropane(TMP) 3: 1,4-cyclohexane dimethyl carbinol 4: hexanodioic acid 5: pure terephthalic acid 6: Isosorbide-5-Nitrae-cyclohexane dioctyl phthalate 7: Mono-n-butyltin (or not containing organotin catalysts) 8: triphenyl phosphite 9: 10: three positive octadecanol esters 12 of [2.4-di-tert-butyl-phenyl] phosphorous acid ester 11: β-(3.5-di-tert-butyl-hydroxy phenyl) propionic acid of m-phthalic acid: phosphorus tribromide 13=1%～2%: 30%～40%: 0%～1%: 1%～2%: 0%～2%: 2%～3%: 40%～50%: 0%～2%: 0%～1%: 0%～1%: 5%～10%: 0%～1%: 0%～1%.
Throw First sub-material 14: when still temperature is between room temperature is with 110 ℃, in reactor, drop into water 1, neopentyl glycol 2 and TriMethylolPropane(TMP) 3, Isosorbide-5-Nitrae-cyclohexane dimethyl carbinol 4, finishes rear slow startup stirring; Drop into a part of hexanodioic acid 5 and whole pure terephthalic acid 6, Isosorbide-5-Nitrae-cyclohexane dioctyl phthalate 7 and partially catalyzed agent Mono-n-butyltin (or containing organotin catalysts) 8.
Heat up and go out the esterification water stage 15 in early stage: still temperature is persistently overheating to going out esterification water from feeding intake, and rotating speed of agitator is controlled the mode that progressively increases should taked with still temperature rise, after 124 ℃ of still temperature, and (50Hz) stirring at full speed.When still temperature reaches 180 ℃, the heat-up rate that slows down, so that temperature of charge reaches unanimity in still, will mix oar variable-frequence governor frequency and be down to 44Hz left and right, then every 30 minutes, variable-frequence governor frequency will be increased to 0.5Hz, until (50Hz) stirs at full speed.Go out after esterification water, insulation reaction 90 minutes, top temperature control is at 100 ℃～102 ℃.
Low temperature Esterification Stage 16: heat-up rate heats up by still temperature average 1 ℃/10 minutes (6 ℃/h), about 200 minutes of reaction times.Top temperature control is at 100 ℃～102 ℃, throws sub-fraction triphenyl phosphite 9 during 207 ℃ of still temperature;
The high temperature esterification stage 17: heat-up rate heats up by still temperature average 1 ℃/7～8 minutes (8～9 ℃/h), and the reaction times is about, 245 minutes～260 minutes.
Feed intake for the second time and secondary temperature elevation step of reaction 19: by still temperature drop to approximately 225 ℃ time, in reactant, add acidolysis agent hexanodioic acid 5 and m-phthalic acid 10 and remaining esterifying catalyst Mono-n-butyltin 8, react approximately 20 minutes, by still temperature rise to 246 ℃, insulation reaction 60～80 minutes, carry out sampling analysis for the second time, touch the mark scope (acid number, the 46～49mgkoH/g such as acid number, viscosity; Viscosity, 1.2～1.6pa.s(175 ℃)) carry out next-step operation.
Vacuumize the Depressor response stage 20: within 10 minutes before vacuumizing, drop into remaining triphenyl phosphite 9, while starting to draw sky, still temperature is 245 ℃～246 ℃, control vacuum pumping rate and maximum vacuum (0.092Mpa), according to analytical results for the first time, while starting to draw sky, the sky time (90 minutes～95 minutes) is drawn in the decision such as still temperature, maximum vacuum; After vacuumizing, carry out sampling analysis for the third time, touch the mark scope (acid number, the 34.5～36.5mgkoH/g such as acid number, viscosity; Viscosity, 7.0～8.5pa.s(180 ℃)) carry out next-step operation.
Throw oxidation inhibitor, curing catalyst 21: by still temperature drop to 201 ℃～205 ℃, the oxidation inhibitor that can eliminate free radical that drops into a certain amount of ratio has three [2.4-di-tert-butyl-phenyl] phosphorous acid ester 11 of the compounds such as aromatic amine and hindered phenol and derivative thereof; The oxidation inhibitor of energy hydroperoxide decomposition has the positive octadecanol ester 12 of organic compound β-(3.5-di-tert-butyl-hydroxy phenyl) propionic acid, the throwing curing catalyst phosphorus tribromide 13 of phosphorous and sulfur-bearing, stirs 20 minutes.
Blowing 22: throw curing catalyst and stir after 20 minutes, still temperature control, at 200 ℃～205 ℃, stops stirring blowing.Carrying out the 4th (finished product) sampling analysis detects.Finished product detection index is as follows: acid number, 34.5～36.5mgkoH/g; Viscosity, 7.0～8.5pa.s(180 ℃); Softening temperature, 110 ℃～115 ℃, 63 ℃ ~ 65 ℃ of second-order transition temperatures.
Water 1 described in the present invention refers to: the transparent liquid of colorless and odorless; In the present invention, as solvent, play the effect of dissolved solids alcohol.
Neopentyl glycol 2 described in the present invention refers to: polyvalent alcohol, and white crystalline solid, odorless, has water absorbability; Mainly for the production of unsaturated polyester, polyester powder coating, oil-free alkyd resin, polyurethane foam plastic, be elastomeric softening agent, synthetic softening agent, tensio-active agent, insulating material, printing-ink, stopper, synthetic aircraft oil oil dope etc.
TriMethylolPropane(TMP) 3 described in the present invention refers to: branching agent; The chainextender that resin industry is conventional, product is mainly used in the fields such as Synolac, urethane, unsaturated polyester, vibrin, coating, also can be used as the thermo-stabilizer of textile auxiliary agent and polyvinyl chloride (PVC) RESINS.
Isosorbide-5-Nitrae-cyclohexane dimethyl carbinol 4 described in the present invention refers to: white waxy solid, 43 ℃ of fusing points, owing to thering is Isosorbide-5-Nitrae, replace symmetrical aliphatics ring texture, when improving hardness for polymkeric substance, certain snappiness can also be provided, and Heat stability is good, has the advantage of weathering resistance and resistance to xanthochromia.
Pure terephthalic acid 6 described in the present invention refers to: aromatic polycarboxylic acid, and white crystal or powder, low toxicity, inflammable; It can be directly and ethylene glycol esterification polycondensation obtain polyester, can also make engineering polyester plastics, also can make raw material and the dyestuff intermediate of softening agent.
Described in the present invention 1,4-cyclohexane dioctyl phthalate 7 refers to: white crystals shape solid, 164～167 ℃ of fusing points, 1,4 replace symmetrical aliphatics ring texture, be conducive to improve hardness, the pollution resistance of resin, the internal motion of alicyclic ring provides snappiness for coating, and saturated alicyclic structure is than the good weatherability of the terephthalic acid containing phenyl ring.
Mono-n-butyltin described in the present invention (or containing organotin catalysts) 8 refers to: esterifying catalyst, and water insoluble and common solvent, dissolves in the white powder of highly basic; Be applicable to synthetic saturated polyester resin, for powder coating and coil steel coating and production unsaturated polyyester, for rubber moulding coating, sheet material and mold material.Containing in the synthetic resin of organotin catalysts containing organotin, for organotin content being had in the middle of the powder coating of requirement.
M-phthalic acid 10 described in the present invention refers to: acidolysis agent is colourless crystallization by water or alcohol crystal person; For the production of Synolac, unsaturated polyester resin and other superpolymer and softening agent, also for the manufacture of cinefilm coupler, coating and trevira dyeability modifier and medicine etc.
Described in the present invention three [2.4-di-tert-butyl-phenyl] phosphorous acid ester 11 refers to: auxiliary antioxidant, white crystalline powder; This product auxiliary antioxidant, composite with primary antioxidant 1010 or 1076, there is good synergistic effect, can effectively prevent polypropylene, the thermal destruction of polyethylene in basic injection moulding, give the extra long-effective protection of polymkeric substance.
The positive octadecanol ester 12 of β described in the present invention-(3.5-di-tert-butyl-hydroxy phenyl) propionic acid refers to: primary antioxidant, white powder or particle; This product and oxidation inhibitor SONOX 168, DLTDP also use, synergistic effect is remarkable, can effectively suppress thermal destruction and the oxidative degradation of polymkeric substance, this product is widely used in polyethylene, polypropylene, polyoxymethylene, ABS resin, polystyrene, polyvinyl chloride alcohol, engineering plastics, synthetic rubber and petroleum products, and general consumption is 0.1%～0.5%.
embodiment 2:
As previously mentioned, utilize pure polyester resin that the present invention produces and TGIC, filler, pigment, auxiliary agent etc. can prepare high weather-proof outdoor type powder coating, its form with coating performance as shown in Figure 2.
Adopt artificial accelerated aging to test to judge the outdoor aging performance of the weather-proof resin of this height.UVA adopts the fluorescent tube of UVA340, and luminescence peak is 340nm, and UVA has simulated well the ultraviolet ray in sunlight and distributed, and test result and outdoor exposure have good dependency.What UVB adopted is the fluorescent tube of UVB313, and the ultraviolet ray of sending is more eager to excel in whatever one does than the ultraviolet ray of sunlight, can greatly improve trial speed, accelerates the ager process of paint film; 300 h that starting, guarantor's light rate of paint film changes very little, thereafter, guarantor's light rate of conventional polyester is trend on the way down, and through the test of 1000h, it is protected light rate and remains on more than 90%, protecting light rate with PVDF fluorocarbon coating approaches, through 2000h, the weather-proof resin-coated guarantor's light rate of this height still remains on 75% ~ 80%, has shown excellent weathering resistance.
embodiment 3:
Selecting each material rate is water: neopentyl glycol: TriMethylolPropane(TMP): 1, 4-cyclohexane dimethyl carbinol: hexanodioic acid: pure terephthalic acid: 1, 4-cyclohexane dioctyl phthalate: Mono-n-butyltin (or not containing organotin catalysts): triphenyl phosphite: m-phthalic acid: the positive octadecanol ester of three [2.4-di-tert-butyl-phenyl] phosphorous acid ester: β-(3.5-di-tert-butyl-hydroxy phenyl) propionic acid: phosphorus tribromide=1.268%: 35.654%: 0.349%: 1.188%: 2.218%: 48.062%: 1.188%: 0.095%: 0.062%: 9.286%: 0.174%: 0.349%:0.106%, be that each weight part is:
| Title | Quantity | Title | Quantity | Title | Quantity |
| Water | 80 | Neopentyl glycol | 2250 | TriMethylolPropane(TMP) | 22 |
| Isosorbide-5-Nitrae-cyclohexane dimethyl carbinol | 75 | Hexanodioic acid | 140 | Pure terephthalic acid | 3033 |
| Isosorbide-5-Nitrae-cyclohexane dioctyl phthalate | 75 | Mono-n-butyltin | 6 | Triphenyl phosphite | 3.9 |
| M-phthalic acid | 586 | Three [2.4-di-tert-butyl-phenyl] |
11 | The positive octadecanol ester of β-(3.5-di-tert-butyl-hydroxy phenyl) propionic acid | 22 |
| Phosphorus tribromide | 6.7 | ? | ? | ? | ? |
| Reference numerals | Mark title | Reference numerals | Mark title |
| 1 | Water 1 | 12 | The positive |
| 2 | Neopentyl glycol 2 | 13 | |
| 3 | TriMethylolPropane(TMP) 3 | 14 | Throw the |
| 4 | Isosorbide-5-Nitrae-cyclohexane dimethyl carbinol 4 | 15 | Heat up and go out the |
| 5 | |
16 | Low |
| 6 | Pure terephthalic acid 6 | 17 | The high |
| 7 | Isosorbide-5-Nitrae- |
18 | The |
| 8 | Mono-n- |
19 | Feed intake for the second time and secondary temperature elevation step of |
| 9 | |
20 | Vacuumize the |
| 10 | M- |
21 | Throw oxidation inhibitor, curing |
| 11 | Three [2.4-di-tert-butyl-phenyl] |
22 | Blowing 22 |
Claims (1)
1. one kind high weather-proof outdoor type used for powder coating pure polyester resin and preparation method thereof, it is characterized in that it is by water, neopentyl glycol, TriMethylolPropane(TMP), 1, 4-cyclohexane dimethyl carbinol, hexanodioic acid, pure terephthalic acid, 1, 4-cyclohexane dioctyl phthalate, Mono-n-butyltin (or not containing organotin catalysts), triphenyl phosphite, m-phthalic acid, three [2.4-di-tert-butyl-phenyl] phosphorous acid ester, the positive octadecanol ester of β-(3.5-di-tert-butyl-hydroxy phenyl) propionic acid, phosphorus tribromide adopts to be thrown the First sub-material stage, heat up and go out the esterification water stage in early stage, low temperature Esterification Stage, the high temperature esterification stage, insulation reaction stage for the first time, feed intake for the second time and secondary temperature elevation step of reaction, vacuumize the Depressor response stage, throw oxidation inhibitor, curing catalyst, nine technical process of blowing complete its preparation method, its raw-material proportioning is: water: neopentyl glycol: TriMethylolPropane(TMP): 1, 4-cyclohexane dimethyl carbinol: hexanodioic acid: pure terephthalic acid: 1, 4-cyclohexane dioctyl phthalate: Mono-n-butyltin (or not containing organotin catalysts): triphenyl phosphite: m-phthalic acid: the positive octadecanol ester of three [2.4-di-tert-butyl-phenyl] phosphorous acid ester: β-(3.5-di-tert-butyl-hydroxy phenyl) propionic acid: phosphorus tribromide=1%～2%: 30%～40%: 0%～1%: 1%～2%: 0%～2%:2%～3%: 40%～50%: 0%～2%: 0%～1%: 0%～1%: 5%～10%: 0%～1%: 0%～1%,
Throw First sub-material: when still temperature is between room temperature is with 110 ℃, in reactor, drop into water, neopentyl glycol and TriMethylolPropane(TMP), Isosorbide-5-Nitrae-cyclohexane dimethyl carbinol, finishes rear slow startup stirring; Drop into a part of hexanodioic acid and whole pure terephthalic acid, Isosorbide-5-Nitrae-cyclohexane dioctyl phthalate and partially catalyzed agent Mono-n-butyltin (or containing organotin catalysts);
Heat up and go out the esterification water stage in early stage: still temperature is persistently overheating to going out esterification water from feeding intake, and rotating speed of agitator is controlled the mode that progressively increases should taked with still temperature rise, after 124 ℃ of still temperature, and (50Hz) stirring at full speed; When still temperature reaches 180 ℃, the heat-up rate that slows down, so that temperature of charge reaches unanimity in still, will mix oar variable-frequence governor frequency and be down to 44Hz left and right, then every 30 minutes, variable-frequence governor frequency will be increased to 0.5Hz, until (50Hz) stirs at full speed; Go out after esterification water, insulation reaction 90 minutes, top temperature control is at 100 ℃～102 ℃;
Low temperature Esterification Stage: heat-up rate heats up by still temperature average 1 ℃/10 minutes (6 ℃/h), about 200 minutes of reaction times; Top temperature control is at 100 ℃～102 ℃, throws sub-fraction triphenyl phosphite during 207 ℃ of still temperature;
The high temperature esterification stage: heat-up rate heats up by still temperature average 1 ℃/7～8 minutes (8～9 ℃/h), and the reaction times is about, 245 minutes～260 minutes;
Insulation reaction stage for the first time: throw half of residue triphenyl phosphite during 245 ℃ of still temperature, control the highest still temperature and be no more than 248 ℃, enter the insulation reaction stage for the first time, 80 minutes～100 minutes insulation reaction time;
When finishing, insulation carries out sampling analysis for the first time, touch the mark scope (acid number, the 6～8mgkoH/g such as acid number, viscosity; Viscosity, 1.0～1.4pa.s(175 ℃)) carry out next-step operation;
Feed intake for the second time and secondary temperature elevation step of reaction: by still temperature drop to approximately 225 ℃ time, in reactant, add acidolysis agent hexanodioic acid and m-phthalic acid and remaining esterifying catalyst Mono-n-butyltin, react approximately 20 minutes, by still temperature rise to 246 ℃, insulation reaction 60～80 minutes, carry out sampling analysis for the second time, touch the mark scope (acid number, the 46～49mgkoH/g such as acid number, viscosity; Viscosity, 1.2～1.6pa.s(175 ℃)) carry out next-step operation;
Vacuumize the Depressor response stage: within 10 minutes before vacuumizing, drop into remaining triphenyl phosphite, while starting to draw sky, still temperature is 245 ℃～246 ℃, control vacuum pumping rate and maximum vacuum (0.092Mpa), according to analytical results for the first time, while starting to draw sky, the sky time (90 minutes～95 minutes) is drawn in the decision such as still temperature, maximum vacuum; After vacuumizing, carry out sampling analysis for the third time, touch the mark scope (acid number, the 34.5～36.5mgkoH/g such as acid number, viscosity; Viscosity, 7.0～8.5pa.s(180 ℃)) carry out next-step operation;
Throw oxidation inhibitor, curing catalyst: by still temperature drop to 201 ℃～205 ℃, the oxidation inhibitor that can eliminate free radical that drops into a certain amount of ratio has three [2.4-di-tert-butyl-phenyl] phosphorous acid ester of the compounds such as aromatic amine and hindered phenol and derivative thereof; The oxidation inhibitor of energy hydroperoxide decomposition has the positive octadecanol ester of organic compound β-(3.5-di-tert-butyl-hydroxy phenyl) propionic acid, the throwing curing catalyst phosphorus tribromide of phosphorous and sulfur-bearing, stirs 20 minutes;
Blowing: throw curing catalyst and stir after 20 minutes, still temperature control, at 200 ℃～205 ℃, stops stirring blowing; Carry out the 4th (finished product) sampling analysis and detect, finished product detection index is as follows: acid number, 34.5～36.5mgkoH/g; Viscosity, 7.0～8.5pa.s(180 ℃); Softening temperature, 110 ℃～115 ℃, 63 ℃ ~ 65 ℃ of second-order transition temperatures.
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