CN101092474A - Method for preparing thermoplastic polyurethane elastomer - Google Patents
Method for preparing thermoplastic polyurethane elastomer Download PDFInfo
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- CN101092474A CN101092474A CN 200710024163 CN200710024163A CN101092474A CN 101092474 A CN101092474 A CN 101092474A CN 200710024163 CN200710024163 CN 200710024163 CN 200710024163 A CN200710024163 A CN 200710024163A CN 101092474 A CN101092474 A CN 101092474A
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- thermoplastic polyurethane
- polyurethane elastomer
- preparing thermoplastic
- sodium sulfonate
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Abstract
This invention discloses a method for preparing thermoplastic polyurethane elastomer with high hardness, high modulus, high tear strength, high elongation rate and high tensile elasticity. The method comprises: adding polyester polyol and ester-type organic sulfonate at a mol. ratio of (1-30):1, and catalyst 0.01-0.5% of total weight into a reaction kettle, heating at a rate of 5-50 deg.C/min and vacuumizing until the temperature reaches 120-300 deg.C and the vacuum degree reaches 0.1-1.0 MPa, keeping for 0.5-30 h, heating one or more isocyanates and one or more C4-16 diols as the chain extender, mixing according to a certain ratio, mixing with the modified materials in the reaction kettle, casting, extracting, extruding by a double screw extruder, and granulating to obtain the final product.
Description
Technical field
The present invention relates to the preparation method of thermoplastic polyurethane (TPU).
Background technology
At present, thermoplastic polyurethane (claiming TPU again) novel material is called as " epoch-making novel high polymer material ", is one of our times six synthetic materials of having development prospect greatly.
The thermoplastic polyurethane material is that class heating can plastify, solvent can dissolved urethane, and its molecule is linear basically, does not have or chemically crosslinked is seldom arranged, but have a certain amount of physical crosslinking.The hard section formation that soft section of being formed by polyester polyol or polyether glycol of thermoplastic polyurethane and vulcabond and small molecules glycol (or diamines) chainextender form, these two portions do not have consistency.Therefore, form the segmented copolymer of so-called micro phase separation structure, soft section is determining the over-all properties of thermoplastic polyurethane with the ratio of hard section in polymkeric substance.In general, hard section concentration height, the hardness of TPU, modulus and tear strength increase, and elongation and tensile strength descend; Soft section concentration height, the hardness of TPU, modulus and tear strength reduce, and elongation and tensile strength increase.And in actual application, many occasions all need to possess simultaneously high hardness, modulus and tear strength and fabulous elongation and stretching bullet degree; And do not reach above-mentioned requirements according to the thermoplastic polyurethane of traditional preparation process method preparation at all.
Summary of the invention
Technical problem to be solved by this invention is: a kind of method for preparing thermoplastic polyurethane elastomer is provided, and can be so that the Polyurethane Thermoplastic Elastomer that generates possesses high hardness, modulus and tear strength and fabulous elongation and stretching bullet degree simultaneously.
For solving the problems of the technologies described above, the technical solution used in the present invention is: method for preparing thermoplastic polyurethane elastomer, its step gathers: polyester polyol, ester class organic sulfonate and catalyzer are put into reactor according to a certain percentage, wherein: polyester polyol, ester class organic sulfonate are according to 1～30: 1 mol ratio, catalyzer is 0.01～0.5% of a gross weight, speed with 5～50 ℃/minute slowly heats up, and intensification limit, limit vacuumizes, reach 120～300 ℃ until temperature, vacuum tightness reaches 0.1～1.0Mpa, keeps 0.5～30 hour;
Then, one or more vulcabond and one or more glycol that contains 4～16 carbon atoms as chainextender are heated the back respectively according to pouring into a mould through after the mixing of materials of modification in certain proportioning and the aforesaid reaction vessel, then under 80～250 ℃ temperature, utilize counter the extruding of twin screw limit reaction, carry out granulation at last and obtain finished product; Wherein: the add-on of vulcabond is reference with described polyester polyol, and vulcabond is in the content of NCO, and polyester polyol is in the content of-OH, and both mol ratios are 1: 1～2; The chainextender that adds accounts for 1～10% of gross weight.
Above-mentioned ester class organic sulfonate can be: the dimethyl phthalate sodium sulfonate, the dimethyl isophthalate sodium sulfonate, the dimethyl terephthalate (DMT) sodium sulfonate, the diglycol phthalate sodium sulfonate, m-phthalic acid binaryglycol ester sodium sulfonate, one or more in the diglycol terephthalate sodium sulfonate.
Above-mentioned catalyzer can be: metatitanic acid methyl esters, titanium ethanolate, titanium propanolate, butyl (tetra) titanate, two stannous octoates, one or both in the dibutyl tin laurate.
Above-mentioned vulcabond can be: tolylene diisocyanate, and isophorone diisocyanate, hexamethylene diisocyanate is in the phenyl diisocyanate one or more.
Above-mentioned chainextender can be: 1, and 4-butyleneglycol, 1, ammediol, 1, one or more in the 6-hexylene glycol.
The invention has the beneficial effects as follows: the Polyurethane Thermoplastic Elastomer through this preparation method obtains possesses high hardness, modulus and tear strength and fabulous elongation and stretching bullet degree simultaneously.
Embodiment
Embodiment 1:
In 2 liters reactor, add by hexanodioic acid and 1, polyvalent alcohol 500 grams that the polycondensation of 6-hexylene glycol forms, add positive tetrabutyl titanate 2 grams again, dimethyl isophthalate sodium sulfonate 50 grams, speed with 5 ℃/minute slowly heats up, and intensification limit, limit vacuumizes, and rises to 230 ℃ until temperature, vacuum tightness arrives 0.4MPa, reacts 1 hour;
With above-mentioned reactant 280 grams and 4,4-diphenylmethanediisocyanate 173 grams and 1, after being heated to 50 ℃ of mixing respectively, pour into a mould 4-butyleneglycol 50 grams, utilize twin screw to react while extruding, twin screw is provided with 80 ℃, 120 ℃, 180 ℃, 200 ℃, 180 ℃ and 150 ℃ of six districts altogether, and it is 55 seconds that entire reaction finds time.
Embodiment 2:
In 2 liters reactor, add by suberic acid and 1, polyvalent alcohol 500 grams that the polycondensation of 4-butyleneglycol forms, add positive tetrabutyl titanate 1.9 grams again, diglycol terephthalate sodium sulfonate 48 grams, speed with 5 ℃/minute slowly heats up, and intensification limit, limit vacuumizes, and rises to 220 ℃ until temperature, vacuum tightness arrives 0.4MPa, reacts 1.5 hours;
With above-mentioned reactant 300 grams and 4,4-diphenylmethanediisocyanate 185 grams and 1, after being heated to 50 ℃ of mixing respectively, pour into a mould 4-butyleneglycol 53 grams, utilize twin screw to react while extruding, twin screw is provided with 80 ℃, 120 ℃, 180 ℃, 200 ℃, 180 ℃ and 150 ℃ of six districts altogether, and it is 58 seconds that entire reaction finds time.
Embodiment 3:
In 2 liters reactor, add hexanodioic acid and 1, polyvalent alcohol 500 grams that the polycondensation of 4-butyleneglycol forms, add titanium propanolate 2.1 grams again, dimethyl phthalate sodium sulfonate 50 grams, speed with 6 ℃/minute slowly heats up, and intensification limit, limit vacuumizes, and rises to 210 ℃ until temperature, vacuum tightness arrives 0.45MPa, reacts 2 hours;
With above-mentioned reactant 288 grams and 4,4-diphenylmethanediisocyanate 173 grams and 1, after being heated to 50 ℃ of mixing respectively, pour into a mould 4-butyleneglycol 50 grams, utilize twin screw to react while extruding, twin screw is provided with 80 ℃, 150 ℃, 190 ℃, 220 ℃, 180 ℃ and 150 ℃ of six districts altogether, and it is 45 seconds that entire reaction finds time.
Embodiment 4:
In 2 liters reactor, add by sebacic acid and 1, polyvalent alcohol 500 grams that the polycondensation of 4-butyleneglycol forms, add positive tetrabutyl titanate 2.3 grams again, diglycol phthalate sodium sulfonate 50 grams, speed with 5 ℃/minute slowly heats up, and intensification limit, limit vacuumizes, and rises to 225 ℃ until temperature, vacuum tightness arrives 0.4MPa, reacts 1.5 hours;
With above-mentioned reactant 280 grams and tolylene diisocyanate 190 grams and 1, after being heated to 50 ℃ of mixing respectively, pour into a mould 4-butyleneglycol 50 grams, utilize twin screw to react while extruding, twin screw is provided with 80 ℃, 120 ℃, 180 ℃, 210 ℃, 180 ℃ and 150 ℃ of six districts altogether, and it is 50 seconds that entire reaction finds time.
Embodiment 5:
In 2 liters reactor, add by hexanodioic acid and 1, polyvalent alcohol 500 grams that the polycondensation of 6-hexylene glycol forms, add dibutyl tin laurate 1.5 grams again, dimethyl phthalate sodium sulfonate 50 grams, speed with 5 ℃/minute slowly heats up, and intensification limit, limit vacuumizes, and rises to 240 ℃ until temperature, vacuum tightness arrives 0.5MPa, reacts 1 hour;
With above-mentioned reactant 280 grams and 4,4-diphenylmethanediisocyanate 165 grams and 1, after being heated to 50 ℃ of mixing respectively, pour into a mould 4-butyleneglycol 50 grams, utilize twin screw to react while extruding, twin screw is provided with 80 ℃, 150 ℃, 180 ℃, 220 ℃, 180 ℃ and 150 ℃ of six districts altogether, and it is 58 seconds that entire reaction finds time.
Above-mentioned polyester polyol is made through polycondensation by di-carboxylic acid and polyhydroxy-alcohol, and its molecular weight is between 500～4000.Used di-carboxylic acid can be: aliphatic dicarboxylic acid, and as pentanedioic acid, brave amber acid, hexanodioic acid, suberic acid and sebacic acid, or aromatic binary carboxylic acid, as phthalic acid, m-phthalic acid, terephthalic acid; Used polyhydroxy-alcohol can be: glycol ether, hexylene glycol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, decamethylene-glycol and 2,2-methyl isophthalic acid, ammediol.
Claims (6)
1. method for preparing thermoplastic polyurethane elastomer, its step gathers: polyester polyol, ester class organic sulfonate and catalyzer are put into reactor according to a certain percentage, wherein: polyester polyol, ester class organic sulfonate are according to 1～30: 1 mol ratio, catalyzer is 0.01～0.5% of a gross weight, speed with 5～50 ℃/minute slowly heats up, and intensification limit, limit vacuumizes, and reaches 120～300 ℃ until temperature, vacuum tightness reaches 0.1～1.0Mpa, keeps 0.5～30 hour;
Then, one or more vulcabond and one or more glycol that contains 4～16 carbon atoms as chainextender are heated the back respectively according to pouring into a mould through after the mixing of materials of modification in certain proportioning and the aforesaid reaction vessel, then under 80～250 ℃ temperature, utilize counter the extruding of twin screw limit reaction, carry out granulation at last and obtain finished product; Wherein: the add-on of vulcabond is reference with described polyester polyol, and vulcabond is in the content of NCO, and polyester polyol is in the content of-OH, and both mol ratios are 1: 1～2; The chainextender that adds accounts for 1～10% of gross weight.
2. to show 1 described method for preparing thermoplastic polyurethane elastomer as right, its thing is levied and is: described ester class organic sulfonate can be: the dimethyl phthalate sodium sulfonate, the dimethyl isophthalate sodium sulfonate, the dimethyl terephthalate (DMT) sodium sulfonate, the diglycol phthalate sodium sulfonate, m-phthalic acid binaryglycol ester sodium sulfonate, one or more in the diglycol terephthalate sodium sulfonate.
3. will show 1 described method for preparing thermoplastic polyurethane elastomer as right, its thing is levied and is: described catalyzer can be: metatitanic acid methyl esters, titanium ethanolate, titanium propanolate, butyl (tetra) titanate, two stannous octoates, one or both in the dibutyl tin laurate.
4. to show 1 described method for preparing thermoplastic polyurethane elastomer as right, its thing is levied and is: described vulcabond can be: tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate is in the phenyl diisocyanate one or more.
5. will show 1 described method for preparing thermoplastic polyurethane elastomer as right, its thing is levied and is: described chainextender can be: 1, and 4-butyleneglycol, 1, ammediol, 1, one or more in the 6-hexylene glycol.
6. will show 1 to 5 described method for preparing thermoplastic polyurethane elastomer as right, its thing is levied and is: described elastomerics is a segmented copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710024163 CN101092474A (en) | 2007-07-18 | 2007-07-18 | Method for preparing thermoplastic polyurethane elastomer |
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| CN 200710024163 CN101092474A (en) | 2007-07-18 | 2007-07-18 | Method for preparing thermoplastic polyurethane elastomer |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952252A (en) * | 2011-08-26 | 2013-03-06 | 优泰科(苏州)密封技术有限公司 | Polyurethane with ultra-high hardness |
| CN103145946A (en) * | 2013-03-12 | 2013-06-12 | 江苏绿艳高分子材料有限公司 | Thermoplastic polyurethane elastomer and preparation method thereof |
| CN103183805A (en) * | 2011-12-28 | 2013-07-03 | 北京中能江龙科技开发有限公司 | Method for preparing novel foaming thermoplastic polyurethane elastomer material |
| CN103665302A (en) * | 2013-11-13 | 2014-03-26 | 江苏绿艳高分子材料有限公司 | Special material for TPU (Thermoplastic Polyurethane) female garden shoes and preparation method thereof |
| CN104017160A (en) * | 2014-06-17 | 2014-09-03 | 安庆市索隆新材料有限公司 | Ink-grade thermoplastic polyurethane formula and preparation method thereof |
| CN109914121A (en) * | 2017-12-12 | 2019-06-21 | 中山市卓益服饰有限公司 | A kind of production method of the ventilative baby children's underwear of moisture absorption |
| CN111285998A (en) * | 2020-03-20 | 2020-06-16 | 高鼎精细化工(昆山)有限公司 | Dyeable environment-friendly polyurethane elastomer and preparation method thereof |
| CN115215991A (en) * | 2022-08-25 | 2022-10-21 | 安庆市索隆新材料有限公司 | Thermoplastic polyurethane and production method thereof |
-
2007
- 2007-07-18 CN CN 200710024163 patent/CN101092474A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952252A (en) * | 2011-08-26 | 2013-03-06 | 优泰科(苏州)密封技术有限公司 | Polyurethane with ultra-high hardness |
| CN103183805A (en) * | 2011-12-28 | 2013-07-03 | 北京中能江龙科技开发有限公司 | Method for preparing novel foaming thermoplastic polyurethane elastomer material |
| CN103183805B (en) * | 2011-12-28 | 2015-04-29 | 北京中能江龙科技开发有限公司 | Method for preparing novel foaming thermoplastic polyurethane elastomer material |
| CN103145946A (en) * | 2013-03-12 | 2013-06-12 | 江苏绿艳高分子材料有限公司 | Thermoplastic polyurethane elastomer and preparation method thereof |
| CN103145946B (en) * | 2013-03-12 | 2015-04-15 | 江苏绿艳高分子材料有限公司 | Thermoplastic polyurethane elastomer and preparation method thereof |
| CN103665302A (en) * | 2013-11-13 | 2014-03-26 | 江苏绿艳高分子材料有限公司 | Special material for TPU (Thermoplastic Polyurethane) female garden shoes and preparation method thereof |
| CN103665302B (en) * | 2013-11-13 | 2016-02-10 | 江苏绿艳高分子材料有限公司 | Woman style garden shoe PP Pipe Compound of a kind of TPU and preparation method thereof |
| CN104017160A (en) * | 2014-06-17 | 2014-09-03 | 安庆市索隆新材料有限公司 | Ink-grade thermoplastic polyurethane formula and preparation method thereof |
| CN109914121A (en) * | 2017-12-12 | 2019-06-21 | 中山市卓益服饰有限公司 | A kind of production method of the ventilative baby children's underwear of moisture absorption |
| CN111285998A (en) * | 2020-03-20 | 2020-06-16 | 高鼎精细化工(昆山)有限公司 | Dyeable environment-friendly polyurethane elastomer and preparation method thereof |
| CN115215991A (en) * | 2022-08-25 | 2022-10-21 | 安庆市索隆新材料有限公司 | Thermoplastic polyurethane and production method thereof |
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