CN1274770A - Making method of high-performance elastic polyurethane fiber - Google Patents
Making method of high-performance elastic polyurethane fiber Download PDFInfo
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- CN1274770A CN1274770A CN 99107422 CN99107422A CN1274770A CN 1274770 A CN1274770 A CN 1274770A CN 99107422 CN99107422 CN 99107422 CN 99107422 A CN99107422 A CN 99107422A CN 1274770 A CN1274770 A CN 1274770A
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- polyurethane fiber
- elastic polyurethane
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Abstract
High-performance polyurethane elastomer is first produced through polymerization in special formulation, then dried and solid-state polymerized to reach the standard of melt spinning, and finally molten spinned to obtain the elastic fiber. Using higher carbon polyglycol and aromatic compound in the reaction, the present invention can produce elastic fiber with relatively higher melting point, high hydrolysis resistance, high weather resistance and high oxidation stability for the need of high-quality elastic fiber product.
Description
The present invention is a kind of manufacture method of polyurethane elaster and elastomer of suitable melt spinning, especially refer to a kind of polyurethane elaster of producing special formulation with continous mode, its special formula can make the elastomer of production be applicable to the melt spinning processing procedure, use making the elastomer of producing, have preferable hydrolytic resistance, heat resistance and weatherability than general Polyurethane fiber.Belong to the artificial fibre technical field.
Polyurethane elaster (Polyurethane Elastomer, PU) be in the thermoplastic elastomer, the most widely used a kind of, generally be called TPU again, it has the thermoplasticity processing characteristics of plastic material and the elasticity of elastomeric material simultaneously, therefore apply to ejection formation, extrusion molding, moulded section, processing aspect such as blow-molded widely, its product includes all kinds of pipe fittings, part, sports equipment, electronic component and fibre etc.
The elastomer of present tradition, the most well-known person is the dry process processing procedure of E.I.Du Pont Company, these method for makings at first must be synthesized polyurethane elaster, make the solution mode again, spin mouth through extruding out, then blow away solvent with heated nitrogen, stay elastomer and form elastomer, this kind method for making is because relate to the problem of solvent [as dimethyl amide (DMF) or dimethyl ethanamide (DMAC)] volatilization, all can work the mischief for human body and environment, make it need drop into the recovery that huge fund is carried out solvent, cause the elastomer cost that utilizes this kind method too high, be unfavorable for applying and competing of market.
Develop the technology of making elastomer with the fusion method spinning in Japan advancing year, it is different from the dry process mode of production of E.I.Du Pont Company, utilize the elastomer processing procedure of fusion method production, the problem that does not have solvent recovery, can be so that production cost be lower, but because the heat resistance of general polyurethane elaster is not good, after through the high-temperature fusion spinning, its rerum natura can greatly fail, and the elastomer of making is on procedure thereafter, also can be through heating, steps such as dyeing and finishing, must accept variations such as high temperature and hydrolysis, this feasible melt spinning method that is developed out by Japan, its product is subjected to many restrictions on purposes, and is lower than the elastomer that E.I.Du Pont Company produces with dry process in physics and chemical property aspect.
Main purpose of the present invention is: provide a kind of and produce making method of high-performance elastic polyurethane fiber with the continuity processing procedure, it is to carry out the prepolymerization reaction with reactive tank earlier, with twin screw extruder machine prepolymer, chain elongation agent and additive etc. are reacted extrusion again, and remove moisture content, unreacted reactant and low polymer with high vacuum, product is through the pelletizing of twin screw extruder machine outlet tie rod, the polyurethane elaster of finishing just can be used for carrying out the processing operation of melt spinning after drying.
A kind of making method of high-performance elastic polyurethane fiber of the present invention, the prescription system that polyurethane elaster manufacturing is wherein adopted carries out the prepolymerization reaction earlier with polyester diol and diisocyanate, again with prepolymerization product and chain elongation agent, be pumped into twin screw extruder machine with measurement gear and react extrusion, produce polyurethane elaster, use the utilization melt spinning and make elastic polyurethane fiber with high-performance physics and chemical property.
Polyester diol system wherein adopts A, B two classes to mix and uses;
The composition of category-A is ploy (tetramethylene adipate) glycol or the ploy (glycol of ε-caprolactone);
The composition of category-B reacts the polyester diol of making for 36 carbon dimeric dibasic acids and the glycol that contains high-purity; Wherein the polyester diol molecular weight of A, B two classes is 500g/mole-3000g/mole, and wherein the chemical constitution of 36 carbon dimeric dibasic acids of category-B polyester diol is:
The not ear ratio that the present invention adopts A, B two kind polyester dihydroxylic alcohols to mix the mixing of using is 95: 5～5: 95.
Wherein, the temperature of prepolymerization reaction is that 60～80 ℃, reaction time are 0.5～2 hour, and charges into the prepolymerization reactive tank with nitrogen during reaction.
Formula rate wherein is roughly:
Polyester diol: chain elongation agent: MDI=1: 1: 2～1: 10: 11; Principle is the not ear number that the not ear number of polyester diol+chain elongation agent equals MDI (diisocyanate).
Chain elongation agent wherein is a glycols, can be divided into A, B two parts;
A partly is 1.4-butanediol, 1.6-hexylene glycol or 1.2-ethylene glycol,
B partly is an aromatic dicarboxylic family, and its chemical constitution is:
Its m, n are integer 1,2,3,4,5, and m+n=2～10.
Wherein A, B two class glycolss mix the mixing used not the ear ratio be 95: 5～5: 95.
Wherein the baking temperature of polyurethane elaster usually system ℃ carry out drying with over dry air heat to 70～100 of dew point-60 ℃.
Advantage of the present invention is: the present invention quotes multinomial material and process set, effectively improves the general prescription of producing elastic polyurethane, and the characteristic of its prescription and processing procedure is as follows:
1. containing the polyester diol that the dimeric dibasic acid of 36 carbon and glycol reaction make by high-purity is the Polyurethane soft segments of part, can improve elastomeric heat-resisting and hydrolysis character.
2. be the chain elongation agent of Polyurethane by containing the glycol that aromatic structure forms, can increase elastomeric heat-resisting character and improve fusing point.
3. extrude with continous mode twin-screw reaction and make polyurethane elaster, the ratio of its hard segment and soft segments can be adjusted arbitrarily, makes the stay in grade of product.
4. the elastomer according to special formulation carries out melt spinning, can have excellent heat resistance, hydrolytic resistance and weatherability.
The present invention utilizes unique prescription to make high performance polyurethane elaster, and further this polyurethane elaster is applied to the manufacturing production of elastomer, and the processing procedure that it used is simple and easy and product property stable; Particularly the prescription of its uniqueness can produce excellent innovation effect.
The present invention has following accompanying drawing:
Fig. 1 is the manufacturing flow chart of the relevant polyurethane elaster of the present invention.
Fig. 2 is the manufacturing equipment schematic diagram of the relevant polyurethane elaster of the present invention.
Fig. 3 is the manufacturing flow chart of the relevant elastic polyurethane fiber of the present invention.
Fig. 4 is the manufacturing equipment schematic diagram of the relevant elastic polyurethane fiber of the present invention.
Number in the figure is as follows:
1. the 2. polyester diol preheatings of diisocyanate fore-warmer tank remove tank
3. additive fore-warmer tank 4. prepolymerization reactive tanks
5. prepolymer medial launder 6. chain elongation agent fore-warmer tanks
7. chain elongation agent medial launder 8. measurement gear pumps
9. measurement gear pump 10. measurement gear pumps
11. measurement gear pump 12. measurement gear pumps
13. material outlet 14. twin screw extruder machines
15. the vacuum extract exports 16. boshes
17. pelleter 18. elastomer dry slots
19. elastomer medial launder 20. extruders
21. spin mouthful group 22. cool wind box
23. spin duct 24. first breast wheels
25. second breast wheel, 26. coiling machines
Now lift preferred embodiment and conjunction with figs. is described in detail as follows:
The present invention is a kind of manufacture method about polyurethane elaster and elastomer, sees also shown in each accompanying drawing, item by item manufacturing production procedure of the present invention is illustrated:
A: diisocyanate preheating
See also Fig. 2, shown in Figure 2, diisocyanate (diisocyanate) composition that the present invention adopts is Methylene bis-(phenylisocynate), be called for short MDI, its purity is about 97%, fusing point is 42-44 ℃, general is in the icebox that is stored in below 0 ℃, use and guarantee its security, MDI need be placed 50 ℃ diisocyanate fore-warmer tank 1 to be dissolved during use, precisely because the temperature during dissolving can not be higher than more than 65 ℃, the retention time of its molten can not surpass one hour simultaneously, uses preventing that MDI itself from carrying out polymerisation.
B: the polyester diol heating vacuumizes and dewaters
The polyester diol that the present invention adopts can be divided into A, B two classes; Wherein, the composition of category-A is ploy (tetramethylene adipate) glycol or the ploy (glycol of ε-caprolactone); The composition of category-B reacts the polyester diol of making for 36 carbon dimeric dibasic acids and the glycol that contains high-purity; The polyester diol molecular weight of A, B two classes is 500g/mole-3000g/mole, and category-B wherein can provide the high low temperature stability of elastomer, hydrolytic resistance, weatherability and oxidation stability owing to contain 36 carbon structures.
Wherein, the chemical constitution of 36 carbon, two polyester is:
The present invention adopts A, B two kind polyester dihydroxylic alcohols to mix and uses; the not ear ratio of its mixing is 95: 5～5: 95; can select according to client's demand; because polyester diol regular meeting absorbs aqueous vapor; therefore need remove tank 2 heating for dissolving prior to the polyester diol preheating before using; it need be heated to more than 100 ℃, and it is standby to remove the moisture content that is absorbed with vacuum.
C: additive preheating
The present invention reaches target rapidly for making reaction when carrying out, and makes the character of product in the future stable, adds catalyst, thermal stabilizer and antioxidant especially in reactant, and required reactant all dissolves standby in additive fore-warmer tank 3 in.
D: prepolymerization reaction
Diisocyanate, polyester diol and additive that the present invention adopts, send into prepolymerization reactive tank 4 through the metering of measurement gear pump and carry out the prepolymerization reaction, it is that 60～80 ℃, reaction time are 0.5～2 hour that needed temperature is reacted in prepolymerization, charge in the prepolymerization reactive tank 4 with nitrogen during reaction, use the generation of anti-oxidation.
E: prepolymer medial launder
React the prepolymer of finishing polymerization via prepolymerization, once deliver to polymer medial launder 5, prepolymerization reactive tank 4 can carry out the reaction of another batch.
F: chain elongation agent preheating
The chain elongation agent that the present invention adopts is a glycols, can be divided into A, B two parts; A partly is 1.4-butanediol, 1.6-hexylene glycol or 1.2-ethylene glycol, and the chemical constitution of B part is:
Its m, n is an integer 1,2,3,4,5, and the structure of m+n=2～10B part is an aromatic dicarboxylic family, provide polymer outstanding heat-resisting character, this polymerisation adopts two kinds of glycolss of A, B to mix and uses, and respectively gets a kind of by A, B, its not the ear ratio be 95: 5～5: 95, can select according to customer demand, this glycol needs heat in chain elongation agent fore-warmer tank 6 to mix, and be warming up to 80 ℃ standby.
G: chain elongation agent medial launder
It is standby that the chain elongation agent that is mixed by the chain elongation agent is passed to chain elongation agent medial launder 7, and chain elongation agent fore-warmer tank 6 can carry out the preparation of next batch simultaneously.
H: twin screw extruder machine is set
The present invention adopts the continous mode polymerisation, precalculated ratio is complied with in control for product characteristics fully, required raw material metering is reacted, for example: the MDI of prepolymerization reaction and polyester diol not ear than or the not ear ratio of prepolymer and chain elongation agent, all can be by in addition accurate control of measurement gear pump 8,9,10,11,12.
The formula rate that the present invention adopts is roughly:
Polyester diol: chain elongation agent: MDI=1: 1: 2～1: 10: 11; More than adopt not ear ratio, its principle is the not ear number that the not ear number of polyester diol+chain elongation agent equals MDI, but in order to try to achieve reaching of high molecular, the not ear error that each measurement gear pump 8,9,10,11,12 causes must not surpass 1%, otherwise can cause the problem of the low and bad of molecular weight.
The medial launder reactant of above-mentioned E and G step, through accurate measurement gear pump, prepolymer and chain elongation agent are sent into to scale the feed(raw material)inlet 13 of twin screw extruder machine 14, the temperature of twin screw extruder machine 14 is set according to different prescriptions and slightly variant, the scope that its temperature is set is 170～240 ℃, the reaction required time of extrusion can be controlled by screw speed, the extrusion reaction time that reactant carried out is 1 to 10 minute, gas that produces during reaction (carbon dioxide or water vapour) and small-molecular weight be reactant not, can extract out by vacuum extract outlet 15, make that product can be perfect still, and send by twin screw extruder machine 14 outlets.
I: elastomer extrudes cooling and dicing
The product that the present invention is sent by twin screw extruder machine 14 is cooled off rapidly by bosh 16, and carries out pelletizing by pelleter 17, just can make the polyurethane elaster product of providing unique formula and good physics and chemical property.
J: elastomer drying
See also Fig. 3, shown in Figure 4, because the glass transition point of polyurethane elaster is lower than room temperature, therefore the baking temperature of setting is unsuitable too high, usually system ℃ carries out drying with over dry air heat to 70～100 of dew point-60 ℃, when this dry-heat air passes through polyurethane elaster, polyurethane elaster can be stirred by the agitator in the elastomer dry slot 18, dry-heat air can promptly moisture content be taken away, simultaneously dry via 4～20 hours continue, polyurethane elaster can carry out the solid-state polymerization reaction, make the molecular weight of polyurethane elaster, reach the standard of melt spinning.
K: extruder is set
Composition difference according to polyurethane elaster, the fusing point of polyurethane elaster is 165～200 ℃, therefore the temperature of extruder 20 is set at that 190～230 ℃, pressure are set at 50～200kg/cm, speed setting is 2～50rpm, set according to the specification of being spun, and the time of staying of polyurethane elaster in extruder 20 is advisable to be no more than 15 minutes, optimum can prevent that for being no more than 5 minutes polyurethane elaster from cracking reaction at high temperature taking place.
L: the spinning road is set
The length that the spinning road is established can be adjusted according to need, and only the cooling air temperature of required cool wind box 22 is advisable with 20～25.
M: intermediate speed is set
The rotating ratio of first breast wheel 24 and second breast wheel 25 is 1: 1～1: 3, extends the fiber tool with this and forward acts on, and can improve the degree of crystallinity and the intensity of elastic polyurethane fiber.
N: finished product batches
Because the high-performance polyamine ester elastomer that the present invention produces has higher viscosity and fusing point, very be suitable for high speed spinning, the speed that its running is batched can reach 1000～2500m/min, effectively improve productive rate, reduce cost, reviewing general polyurethane elaster can only be under low speed (300～500m/min) runnings, production capacity is quite low; Therefore, the present invention makes elastic polyurethane fiber with the polyurethane elaster of producing, and the physics of not only low cost of manufacture, and product and chemical property all obviously surmount the elastic polyurethane fiber of conventional process production.
Claims (10)
1. making method of high-performance elastic polyurethane fiber, it is characterized in that: the prescription system that polyurethane elaster manufacturing is wherein adopted carries out the prepolymerization reaction earlier with polyester diol and diisocyanate, again with prepolymerization product and chain elongation agent, be pumped into twin screw extruder machine with measurement gear and react extrusion, produce polyurethane elaster, use the utilization melt spinning and make elastic polyurethane fiber with high-performance physics and chemical property.
2. a kind of making method of high-performance elastic polyurethane fiber according to claim 1 is characterized in that: polyester diol system wherein adopts A, B two classes to mix and uses;
The composition of category-A is ploy (tetramethylene adipate) glycol or the ploy (glycol of ε-caprolactone);
The composition of category-B reacts the polyester diol of making for 36 carbon dimeric dibasic acids and the glycol that contains high-purity.
3. a kind of making method of high-performance elastic polyurethane fiber according to claim 2 is characterized in that: wherein the polyester diol molecular weight of A, B two classes is 500g/mole-3000g/mole.
4. a kind of making method of high-performance elastic polyurethane fiber according to claim 2 is characterized in that: the chemical constitution of 36 carbon dimeric dibasic acids of category-B polyester diol wherein is:
5. a kind of making method of high-performance elastic polyurethane fiber according to claim 2 is characterized in that: wherein the not ear ratio of the mixing of A, B two kind polyester dihydroxylic alcohols mixing use is 95: 5～5: 95.
6. a kind of making method of high-performance elastic polyurethane fiber according to claim 1 is characterized in that: wherein, the temperature of prepolymerization reaction is that 60～80 ℃, reaction time are 0.5～2 hour, and charges into the prepolymerization reactive tank with nitrogen during reaction.
7. a kind of making method of high-performance elastic polyurethane fiber according to claim 1, it is characterized in that: formula rate wherein is:
Polyester diol: chain elongation agent: MDI=1: 1: 2～1: 10: 11; Principle is the not ear number that the not ear number of polyester diol+chain elongation agent equals MDI (diisocyanate).
8. according to claim 1 or 2 described a kind of making method of high-performance elastic polyurethane fiber, it is characterized in that: chain elongation agent wherein is a glycols, can be divided into A, B two parts;
A partly is 1.4-butanediol, 1.6-hexylene glycol or 1.2-ethylene glycol,
B partly is an aromatic dicarboxylic family, and its chemical constitution is:
Its m, n are integer 1,2,3,4,5, and m+n=2～10.
9. described according to Claim 8 a kind of making method of high-performance elastic polyurethane fiber is characterized in that: wherein A, B two class glycolss mix the mixing used not the ear ratio be 95: 5～5: 95.
10. a kind of making method of high-performance elastic polyurethane fiber according to claim 1 is characterized in that: wherein the baking temperature of polyurethane elaster usually system ℃ carry out drying with over dry air heat to 70～100 of dew point-60 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99107422 CN1274770A (en) | 1999-05-20 | 1999-05-20 | Making method of high-performance elastic polyurethane fiber |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99107422 CN1274770A (en) | 1999-05-20 | 1999-05-20 | Making method of high-performance elastic polyurethane fiber |
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| CN1274770A true CN1274770A (en) | 2000-11-29 |
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| CN 99107422 Pending CN1274770A (en) | 1999-05-20 | 1999-05-20 | Making method of high-performance elastic polyurethane fiber |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1100896C (en) * | 1998-01-30 | 2003-02-05 | 日清纺绩株式会社 | Process for producing polyurethane elastomer and elastic filament |
| CN105593463A (en) * | 2013-12-26 | 2016-05-18 | 株式会社吴羽 | Downhole tool or downhole tool member, degradable resin composition, and method for recovering hydrocarbon resources |
| TWI811788B (en) * | 2020-09-11 | 2023-08-11 | 日商旭化成股份有限公司 | Polyurethane elastic fibers, gathering parts containing them, and hygienic materials |
-
1999
- 1999-05-20 CN CN 99107422 patent/CN1274770A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1100896C (en) * | 1998-01-30 | 2003-02-05 | 日清纺绩株式会社 | Process for producing polyurethane elastomer and elastic filament |
| CN105593463A (en) * | 2013-12-26 | 2016-05-18 | 株式会社吴羽 | Downhole tool or downhole tool member, degradable resin composition, and method for recovering hydrocarbon resources |
| TWI811788B (en) * | 2020-09-11 | 2023-08-11 | 日商旭化成股份有限公司 | Polyurethane elastic fibers, gathering parts containing them, and hygienic materials |
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