CN104031237A - Extrusion grade thermoplastic polyurethane formula and preparation method thereof - Google Patents
Extrusion grade thermoplastic polyurethane formula and preparation method thereof Download PDFInfo
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- CN104031237A CN104031237A CN201410269473.1A CN201410269473A CN104031237A CN 104031237 A CN104031237 A CN 104031237A CN 201410269473 A CN201410269473 A CN 201410269473A CN 104031237 A CN104031237 A CN 104031237A
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- thermoplastic polyurethane
- antioxidant
- extrusion grade
- grade thermoplastic
- medial launder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0895—Manufacture of polymers by continuous processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
Abstract
The invention relates to a plastic material, particularly to an extrusion grade thermoplastic polyurethane formula and a preparation method thereof. The extrusion grade thermoplastic polyurethane formula is composed of the following materials in parts by weight: 45-55 parts of polyester polyol, 35-45 parts of diphenylmethane diisocyanate, 10-15 parts of butanediol, 0.2-0.5 part of an antioxidant, 0.04-0.06 part of an environment-friendly catalyst and 0.15-0.2 part of a mold-release agent. The polyester polyol is prepared from hexanedioic acid and butanediol by a polymerization esterification reaction at 220 DEG C, and the mass ratio of hexanedioic acid to butanediol is 58: 42. The antioxidant is a mixture composed of 0.1 part of antioxidant CHINOX1010 produced by Taiwan Double Bond Chemical Industry Co., Ltd and 0.1 part of antioxidant CHINOX628 produced by Taiwan Double Bond Chemical Industry Co., Ltd. The product prepared by adopting the method is applied to production of a pneumatic pipe material and is stable in quality, and the abrasion resistance and high pressure resistance are obviously improved.
Description
Technical field
The present invention relates to a kind of plastic material, specifically relate to a kind of extrusion grade thermoplastic polyurethane formula and preparation method thereof.
Background technology
This material of TPU (Polyurethane Thermoplastic Elastomer rubber) can deliquescing under certain temperature, and can remain unchanged at normal temperatures.Its main characteristic has: durometer level is wide, by changing the proportioning of each reactive component of TPU, can obtain the product of different hardness, and along with the increase of hardness, its product still keeps good elasticity and wear resistance; Good processability, TPU can adopt the working method of common thermoplastic material to process, as injection moulding, extrude, roll etc.Meanwhile, TPU and some macromolecular material are processed the polymer alloy that can access performance complement jointly; Physical strength is high, and the supporting capacity of TPU goods, shock resistance and damping performance are outstanding; Winter hardiness is outstanding, and the glass transition temperature of TPU is lower, at subzero 35 degree, still keeps good elasticity, kindliness and other physicalies; Oil resistant, water-fast, resistance to mould; Regeneration is good.
Polyurethane termoplastic elastomer is nontoxic, tasteless, dissolve in methylethylketone, pimelinketone, tetrahydrofuran (THF), dioxane, dimethyl formamide equal solvent, also can be dissolved in toluene, vinyl acetic monomer, butanone, acetone, the mixed solvent with suitable proportion composition, generally present water white transparency state, have good preservation stability.TPU is a kind of material between rubber and plastics as elastomerics, eight high-performances have been compared with general plastic: a wear resistance is strong, two tear strengths are strong, three bending properties are superior, four tensile strength and elongation at break are high, and five low temperature resistant (40 ℃) and high temperature resistant (150 ℃) performance, at the bottom of six long-term compression deformation rates, the hydrocarbon solvent of seven oil resistants and aliphatics, the eight pairs of oxygen and ozone have the ageing-resistant characteristic of resistivity.
In production for example, be applied to pneumatic tubing, thermoplastic polyurethane material's application is comparatively extensive.At present, such thermoplastic polyurethane material is being applied to pneumatic tubing, mainly exists moulding slower, and molding effect is poor, quality product time, and the problem such as output is less.
Summary of the invention
In order to solve the technical problem existing in prior art, one of object of the present invention is to provide a kind of extrusion grade thermoplastic polyurethane formula, and its technical scheme adopting is as follows:
A kind of extrusion grade thermoplastic polyurethane formula, is comprised of the raw material of following weight part:
Described polyester polyol is to be made in 220 ℃ of polymerization esterification reactions by hexanodioic acid and butyleneglycol, and mass ratio is between the two 58: 42.
Preferably, described antioxidant is the mixture of the antioxidant CHINOX1010 of the two key Chemical Groups productions in 0.1 part of Taiwan and the antioxidant CHINOX618 of 0.1 part of two key Chemical Groups production in Taiwan.
Preferably, described releasing agent is Taiwan esterified wax WAX-1220.
Two of object of the present invention is to provide a kind of extrusion grade thermoplastic polyurethane material's preparation method, and its technical scheme adopting is as follows:
1., by hexanodioic acid and butyleneglycol, be to mix at 58: 42 by weight, in 220 ℃ of polymerization esterifications reactions, make polyester polyol;
2., 45～55 parts of polyester polyols put into medial launder A store, storing temp is 90～110 ℃, nitrogen-sealed is preserved;
3., 0.2 part of antioxidant and 0.15 part of releasing agent are added in medial launder A, stir it is mixed with polyester polyol;
4., 35～45 parts of barreled diphenylmethanediisocyanates are dropped in 60～80 ℃ of hot water to medial launder B after melting and store, storing temp is 42～60 ℃, nitrogen-sealed is preserved;
5., 10～15 parts of barreled butyleneglycols are dropped in 60～80 ℃ of hot water to medial launder C after melting and store, storing temp is 42～60 ℃, nitrogen-sealed is preserved;
6., material in medial launder A, B and C is put into respectively to three bottler charging baskets of forcing machine, three bottler charging baskets keep identical temperature with medial launder A, B and C respectively, set in proportion three component groundwater increments;
7. get, in proportion tri-kinds of material assaying reactions of A, B and C active, by adding environmental protection catalyst, regulate reactive behavior in 40～50 seconds;
8., set 150～220 ℃ of extruder temperatures, 200～240 ℃ of pelletizing temperature, 40～50 ℃ of water temperatures;
9., after temperature reaches, open extruder screw, set screw speed 200～300r/min continous pouring and make three components react and extrude in forcing machine;
10., through blank, drying under water, obtain extrusion grade thermoplastic polyurethane material product pellet;
product pellet is mixed in bipyramid to oven dry, when particle moisture content is in 1000ppm, start packing warehouse-in.
Extrusion grade thermoplastic polyurethane of the present invention formula and preparation method thereof, the product of its manufacture in the production that is applied to pneumatic tubing, steady quality, wear-resistant and high voltage performance significantly improves.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1
Extrusion grade thermoplastic polyurethane formula, is comprised of the raw material of following weight part:
Extrusion grade thermoplastic polyurethane material's preparation method, comprises the steps:
1., by hexanodioic acid and butyleneglycol, be to mix at 58: 42 by weight, in 220 ℃ of polymerization esterifications reactions, make polyester polyol.
2., polyester polyol put into medial launder A store, storing temp is 90 ℃, nitrogen-sealed is preserved.
3., antioxidant and releasing agent are added in medial launder A, stir it is mixed with polyester polyol.
4., barreled diphenylmethanediisocyanate is dropped in 80 ℃ of hot water to medial launder B after melting and stores, storing temp is 42 ℃, nitrogen-sealed is preserved.
5., barreled butyleneglycol is dropped in 80 ℃ of hot water to medial launder C after melting and stores, storing temp is 60 ℃, nitrogen-sealed is preserved.
6., material in medial launder A, B and C is put into respectively to three bottler charging baskets of forcing machine, three bottler charging baskets keep identical temperature with medial launder A, B and C respectively, set in proportion three component groundwater increments.
7. get, in proportion tri-kinds of material assaying reactions of A, B and C active, by adding environmental protection catalyst, regulate reactive behavior in 50 seconds.
8., set 150 ℃ of extruder temperatures, 200 ℃ of pelletizing temperature, 50 ℃ of water temperatures.
9., after temperature reaches, open extruder screw, set screw speed 200r/min continous pouring and make three components react and extrude in forcing machine.
10., through blank, drying under water, obtain extrusion grade thermoplastic polyurethane material product pellet.
product pellet is mixed in bipyramid to oven dry, when particle moisture content is in 1000ppm, start packing warehouse-in.
Embodiment 2
Extrusion grade thermoplastic polyurethane formula, is comprised of the raw material of following weight part:
Extrusion grade thermoplastic polyurethane material's preparation method, comprises the steps:
1., by hexanodioic acid and butyleneglycol, be to mix at 58: 42 by weight, in 220 ℃ of polymerization esterifications reactions, make polyester polyol.
2., polyester polyol put into medial launder A store, storing temp is 100 ℃, nitrogen-sealed is preserved.
3., antioxidant and releasing agent are added in medial launder A, stir it is mixed with polyester polyol.
4., barreled diphenylmethanediisocyanate is dropped in 70 ℃ of hot water to medial launder B after melting and stores, storing temp is 50 ℃, nitrogen-sealed is preserved.
5., barreled butyleneglycol is dropped in 70 ℃ of hot water to medial launder C after melting and stores, storing temp is 50 ℃, nitrogen-sealed is preserved.
6., material in medial launder A, B and C is put into respectively to three bottler charging baskets of forcing machine, three bottler charging baskets keep identical temperature with medial launder A, B and C respectively, set in proportion three component groundwater increments.
7. get, in proportion tri-kinds of material assaying reactions of A, B and C active, by adding environmental protection catalyst, regulate reactive behavior in 45 seconds.
8., set 200 ℃ of extruder temperatures, 220 ℃ of pelletizing temperature, 45 ℃ of water temperatures.
9., after temperature reaches, open extruder screw, set screw speed 250r/min continous pouring and make three components react and extrude in forcing machine.
10., through blank, drying under water, obtain extrusion grade thermoplastic polyurethane material product pellet.
product pellet is mixed in bipyramid to oven dry, when particle moisture content is in 1000ppm, start packing warehouse-in.
Embodiment 3
Extrusion grade thermoplastic polyurethane formula, is comprised of the raw material of following weight part:
Extrusion grade thermoplastic polyurethane material's preparation method, comprises the steps:
1., by hexanodioic acid and butyleneglycol, be to mix at 58: 42 by weight, in 220 ℃ of polymerization esterifications reactions, make polyester polyol.
2., polyester polyol put into medial launder A store, storing temp is 110 ℃, nitrogen-sealed is preserved.
3., antioxidant and releasing agent are added in medial launder A, stir it is mixed with polyester polyol.
4., barreled diphenylmethanediisocyanate is dropped in 60 ℃ of hot water to medial launder B after melting and stores, storing temp is 60 ℃, nitrogen-sealed is preserved.
5., barreled butyleneglycol is dropped in 60 ℃ of hot water to medial launder C after melting and stores, storing temp is 42 ℃, nitrogen-sealed is preserved.
6., material in medial launder A, B and C is put into respectively to three bottler charging baskets of forcing machine, three bottler charging baskets keep identical temperature with medial launder A, B and C respectively, set in proportion three component groundwater increments.
7. get, in proportion tri-kinds of material assaying reactions of A, B and C active, by adding environmental protection catalyst, regulate reactive behavior in 40 seconds.
8., set 220 ℃ of extruder temperatures, 240 ℃ of pelletizing temperature, 40 ℃ of water temperatures.
9., after temperature reaches, open extruder screw, set screw speed 300r/min continous pouring and make three components react and extrude in forcing machine.
10., through blank, drying under water, obtain extrusion grade thermoplastic polyurethane material product pellet.
product pellet is mixed in bipyramid to oven dry, when particle moisture content is in 1000ppm, start packing warehouse-in.
Above content is only that the present invention is conceived to example and explanation; affiliated those skilled in the art make various modifications to described specific embodiment or supplement or adopt similar mode to substitute; only otherwise depart from the design of invention or do not surmount this scope as defined in the claims, all should belong to protection scope of the present invention.
Claims (6)
1. an extrusion grade thermoplastic polyurethane is filled a prescription, and it is characterized in that being comprised of the raw material of following weight part:
Described polyester polyol is to be made in 220 ℃ of polymerization esterification reactions by hexanodioic acid and butyleneglycol, and mass ratio is between the two 58: 42.
2. extrusion grade thermoplastic polyurethane formula according to claim 1, is characterized in that: described antioxidant is the mixture of the antioxidant CHINOX1010 of the two key Chemical Groups productions in 0.1 part of Taiwan and the antioxidant CHINOX618 of 0.1 part of two key Chemical Groups production in Taiwan.
3. extrusion grade thermoplastic polyurethane formula according to claim 1, is characterized in that: described releasing agent is Taiwan esterified wax WAX-1220.
4. a preparation method for extrusion grade thermoplastic polyurethane, is characterized in that step is as follows:
1., by hexanodioic acid and butyleneglycol, be to mix at 58: 42 by weight, in 220 ℃ of polymerization esterifications reactions, make polyester polyol;
2., 45～55 parts of polyester polyols put into medial launder A store, storing temp is 90～110 ℃, nitrogen-sealed is preserved;
3., 0.2 part of antioxidant and 0.15 part of releasing agent are added in medial launder A, stir it is mixed with polyester polyol;
4., 35～45 parts of barreled diphenylmethanediisocyanates are dropped in 60～80 ℃ of hot water to medial launder B after melting and store, storing temp is 42～60 ℃, nitrogen-sealed is preserved;
5., 10～15 parts of barreled butyleneglycols are dropped in 60～80 ℃ of hot water to medial launder C after melting and store, storing temp is 42～60 ℃, nitrogen-sealed is preserved;
6., material in medial launder A, B and C is put into respectively to three bottler charging baskets of forcing machine, three bottler charging baskets keep identical temperature with medial launder A, B and C respectively, set in proportion three component groundwater increments;
7. get, in proportion tri-kinds of material assaying reactions of A, B and C active, by adding environmental protection catalyst, regulate reactive behavior in 40～50 seconds;
8., set 150～220 ℃ of extruder temperatures, 200～240 ℃ of pelletizing temperature, 40～50 ℃ of water temperatures;
9., after temperature reaches, open extruder screw, set screw speed 200～300r/min continous pouring and make three components react and extrude in forcing machine;
10., through blank, drying under water, obtain extrusion grade thermoplastic polyurethane product pellet;
product pellet is mixed in bipyramid to oven dry, when particle moisture content is in 1000ppm, start packing warehouse-in.
5. according to the preparation method of the extrusion grade thermoplastic polyurethane described in claim, it is characterized in that: described antioxidant is the mixture of the antioxidant CHINOX1010 of the two key Chemical Groups productions in 0.1 part of Taiwan and the antioxidant CHINOX618 of 0.1 part of two key Chemical Groups production in Taiwan.
6. according to the preparation method of the extrusion grade thermoplastic polyurethane described in claim, it is characterized in that: described releasing agent is Taiwan esterified wax WAX-1220.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410269473.1A CN104031237A (en) | 2014-06-18 | 2014-06-18 | Extrusion grade thermoplastic polyurethane formula and preparation method thereof |
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| CN201410269473.1A CN104031237A (en) | 2014-06-18 | 2014-06-18 | Extrusion grade thermoplastic polyurethane formula and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4980445A (en) * | 1989-01-17 | 1990-12-25 | The Dow Chemical Company | Thermoplastic polyurethanes |
| CN101735596A (en) * | 2009-12-15 | 2010-06-16 | 上海联景聚氨酯工业有限公司 | Thermoplastic polyurethane elastomer and manufacturing method thereof |
| CN102558830A (en) * | 2012-02-10 | 2012-07-11 | 上海联景高分子材料有限公司 | Preparation method of transparent film-grade thermoplastic polyurethane elastomer |
| CN103059553A (en) * | 2012-12-27 | 2013-04-24 | 奥斯汀新材料（张家港）有限公司 | A method for preparing a non-blomming thermoplastic polyurethane elastomer |
-
2014
- 2014-06-18 CN CN201410269473.1A patent/CN104031237A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4980445A (en) * | 1989-01-17 | 1990-12-25 | The Dow Chemical Company | Thermoplastic polyurethanes |
| CN101735596A (en) * | 2009-12-15 | 2010-06-16 | 上海联景聚氨酯工业有限公司 | Thermoplastic polyurethane elastomer and manufacturing method thereof |
| CN102558830A (en) * | 2012-02-10 | 2012-07-11 | 上海联景高分子材料有限公司 | Preparation method of transparent film-grade thermoplastic polyurethane elastomer |
| CN103059553A (en) * | 2012-12-27 | 2013-04-24 | 奥斯汀新材料（张家港）有限公司 | A method for preparing a non-blomming thermoplastic polyurethane elastomer |
Non-Patent Citations (2)
| Title |
|---|
| 刘益军: "《聚氨酯原料及助剂手册》", 30 April 2005 * |
| 蒋平平等: "聚己二酸二元醇酯合成研究与表征", 《高校化学工程学报》 * |
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Application publication date: 20140910 |