CN104479342A - Preparation method of reinforced and toughened thermoplastic polyurethane/regenerated cellulose (TPU/RC) composite film - Google Patents
Preparation method of reinforced and toughened thermoplastic polyurethane/regenerated cellulose (TPU/RC) composite film Download PDFInfo
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Abstract
The invention discloses a preparation method of a novel regenerated cellulose (RC) in situ reinforced and toughened thermoplastic polyurethane (TPU) film. The preparation method comprises the following steps of: dissolving cellulose in a solvent, and preparing RC in a coagulation bath, wherein the mixed aqueous solution of an alkali and urea or the mixed aqueous solution of an alkali and thiourea servers as the solvent, and water serves as the coagulation bath; mixing the dried RC with a thermoplastic TPU prepolymer in the solution of N-N-dimethylformamide (DMF), and adding a chain extender to carry out in situ polymerization to obtain the TPU/RC composite film. Because the cellulose is wide in source and low in cost, and the RC is easy to prepare, the tensile strength and the elongation at break of the RC reinforced and toughened thermoplastic TPU film can be improved significantly compared with the tensile strength and the elongation at break of a thermoplastic TPU matrix, and the application range of the RC reinforced and toughened thermoplastic TPU film can be enlarged effectively.
Description
Technical field
The invention belongs to field of compound material, relate to the preparation method of a kind of Neu tuberosum element activeness and quietness Thermoplastic polyurethane composite material.
Background technology
Mierocrystalline cellulose is a kind of very abundant renewable polymeric materials, and be a kind of inexhaustible resource for our earth, its annual amount of regeneration just reaches 1.0*10
10ton.And Mierocrystalline cellulose itself has higher degree of crystallinity, intermolecular and intramolecular hydrogen bond, the performance such as mechanical property, thermostability added so cellulosic macromolecular material has significant impact.Filler as macromolecule matrix uses has unrivaled advantage, causes the concern of Many researchers.
Thermoplastic polyurethane, as a kind of widely used material of maturation, has remarkable high tensile, high-tensile strength, tough and ageing-resistant characteristic have been known as an extremely potential type material representative by industry.But the constructional feature due to TPU self makes the mechanical property of TPU be difficult to apply to some special occasions, the mechanical property therefore improving TPU has become the developing direction of TPU plastics.Numerous research in recent years adopt Mierocrystalline cellulose as reinforcing filler and TPU blended, thus improve the thermomechanical property of TPU.
At present, when application Mierocrystalline cellulose strengthens TPU as reinforcing filler, adopt nano-cellulose (CN 102604363 A more, CN 103436002 A, CN 102731990 A), although nano-cellulose has huge specific surface area, high strength and high surface, the preparation process of nano-cellulose is very loaded down with trivial details, surface modification is more difficult, and cost is higher.
In addition, be rich in the hydroxyl of strong polarity due to cellulose surface and inner strong hydrogen bonding effect can be formed, and containing carbamate (-NHCOO-) feature unit in polyurethane backbone, so for urethane/cellulose composite material, two-phase interface bonding strength is poor.The present invention utilizes the regenerated cellulose being easy to prepare with low cost as filler, by being added TPU performed polymer, the surface that in polymerization process, TPU performed polymer molecular chain is grafted to regenerated cellulose defines TPU-g-RC, reduce the polarity on regenerated cellulose surface, strengthen the interface compatibility with TPU matrix, thus prepare high performance composite.
Summary of the invention
The object of the invention is to provide a kind of preparation method of regenerated cellulose activeness and quietness compound polyurethane material.Concrete preparation method carries out as follows:
(1) preparation of regenerated cellulose:
Mierocrystalline cellulose is dissolved in alkali/urea mixed aqueous solution or alkali/thiocarbamide mixed aqueous solution, wherein Mierocrystalline cellulose and alkali/urea mixed aqueous solution or alkali/thiocarbamide mixed aqueous solution mass ratio are 1:99 to 10:90, described alkali/aqueous solution of urea is 5-12wt% alkali/8-20wt% urea mixed aqueous solution, and described alkali/thiourea solution is 6-15% alkali/3-10% thiocarbamide mixed aqueous solution.Fully disperse under stirring or ul-trasonic irradiation.Solution is carried out freezing treatment at the temperature of-12 DEG C to-20 DEG C and is no less than 1h, after mixture after to be frozen thaws, add the distilled water being no less than 2 times of volume of mixture, centrifugation obtains gel-like product, with distilled water wash products therefrom to neutral, obtain regenerated cellulose.
(2) preparation of thermoplastic polyurethane/regenerated cellulose laminated film
Be dissolved in DMF by 4,4 '-diphenylmethanediisocyanate (MDI) and polytetramethylene ether diol (PTMG), stir at least 2h under 80 DEG C of nitrogen atmospheres, react to obtain TPU prepolymer, wherein the molar mass ratio of MDI and PTMG is 2:1; After the regenerated cellulose of preparation in step (1) is dried to constant weight at 70 DEG C, be dissolved in appropriate DMF, ultrasonicly make it be uniformly dispersed; RC/DMF solution is joined in the solution of TPU prepolymer/DMF, and under 70 DEG C of conditions heated and stirred at least 1h; Add a certain amount of chainextender subsequently, under 70 DEG C of conditions heated and stirred at least 1h obtain stabilizing solution; Under described stable solution normal temperature after vacuum outgas, cast in a mold, then is taken off film and is namely obtained described TPU/RC film at 70 DEG C after dry 24h.Wherein the molar mass ratio of NCO/OH in TPU solution is 1 altogether.
Wherein, said Mierocrystalline cellulose is from least one in following cellulosic material: linters, wood pulp cellulose, Microcrystalline Cellulose.
Said alkali comprises at least one in sodium hydroxide, lithium hydroxide.
Described chainextender comprises at least one in BDO, 1,6-ethylene glycol, glycerine, Glycerin, triglycol.
The TPU/RC film prepared in described step (2), wherein RC quality accounts for 1% ~ 10% of TPU quality.
Beneficial effect:
The invention has the advantages that: regenerated cellulose is directly dissolved in the solution of TPU prepolymer by (1), and the TPU-g-RC multipolymer formed in polymerization process improves the reactive force between RC and TPU matrix, thus activeness and quietness TPU.(2) replace nano-cellulose as reinforcing filler with regenerated cellulose, reduce cost, preparation process environmental protection.
embodiment:
The present invention intends by following embodiment simple declaration feature of the present invention and advantage, it should be noted is that the present invention is not limited only to the content of embodiment.
embodiment 1:
Added in the aqueous solution of NaOH/ urea by a certain amount of linters (content of cellulose 75%), fully mix, wherein NaOH, the mass ratio of urea and distilled water is 7:12:81, and the mass ratio of the aqueous solution of linters and NaOH/ urea is 7:93.Freezing 12h under mixed solution being placed in-20 DEG C of conditions, obtains clear solution after thawing.Add distilled water in clear solution, obtain White Flocculus, wherein the volume ratio of distilled water and clear solution is 10:1.Centrifugation obtains white gels, uses deionized water wash gel to neutral, obtains regenerated cellulose, the regenerated cellulose of preparation is dried to constant weight at 70 DEG C after centrifugation.MDI and PTMG is dissolved in DMF, under 80 DEG C of nitrogen atmospheres, stirs 2h, react to obtain TPU prepolymer.Be dissolved in DMF by dried regenerated cellulose, ultrasonic disperse is even, and two kinds of solution stir 1h under mixing and being incorporated in 70 DEG C of conditions; Add Glycerin subsequently under 70 DEG C of conditions, to stir after 1h to obtain thick solution, be coated in Teflon mould under normal temperature after vacuum outgas, in baking oven, 70 DEG C of dry 24h obtain the thermoplastic polyurethane film that regenerated cellulose strengthens.Wherein the mass ratio of regenerated cellulose and TPU is 1:99.The Young's modulus of gained laminated film is 4.8MPa, and tensile strength is 15.3MPa, elongation at break 1294.3%.
embodiment 2:
Fully mixed by the aqueous solution that a certain amount of Microcrystalline Cellulose (polymerization degree 500) adds NaOH/ urea, wherein NaOH, the mass ratio of urea and distilled water is 5:8:87, and the mass ratio of the aqueous solution of cotton and NaOH/ urea is 10:90.Freezing 7h under mixed solution being placed in-20 DEG C of temperature, obtains clear solution after thawing.Add distilled water in clear solution and obtain White Flocculus, wherein the volume ratio of distilled water and clear solution is 10:1.Obtain white gels by centrifugation, use distilled water wash gel to neutral, obtain regenerated cellulose after centrifugation, under 70 DEG C of conditions, be dried to constant weight.MDI and PTMG is dissolved in DMF, under 80 DEG C of nitrogen atmospheres, reacts the TPU prepolymer of 2h; Be dissolved in by regenerated cellulose in DMF, ultrasonic disperse is even, and two kinds of solution stir 1h at mixing and being incorporated in 70 DEG C, add BDO heated and stirred 1h subsequently, obtain thick solution.Be coated in Teflon mould by under above-mentioned solution normal temperature after vacuum outgas, in baking oven, namely 70 DEG C of dry 24h obtain the thermoplastic polyurethane film that regenerated cellulose strengthens.Wherein the mass ratio of regenerated cellulose and TPU is 1:49.The Young's modulus of gained laminated film is 10.1MPa, and tensile strength is 29.5MPa, elongation at break 1366.5%.
embodiment 3:
Added in the aqueous solution of LiOH/ thiocarbamide by a certain amount of Microcrystalline Cellulose (polymerization degree 350), fully mix, wherein LiOH, the mass ratio of thiocarbamide and distilled water is 9.5:4.5:86, and the mass ratio of the aqueous solution of Microcrystalline Cellulose and LiOH/ thiocarbamide is 3:97.Freezing 7h under mixed solution being placed in-20 DEG C of conditions, obtains clear solution after thawing.Add distilled water in clear solution, obtain White Flocculus, wherein the volume ratio of distilled water and clear solution is 10:1.Centrifugation obtains white gels, uses deionized water wash gel to neutral, obtains regenerated cellulose, and be dried to constant weight after centrifugation under 70 DEG C of conditions.Be dissolved in by MDI and PTMG in DMF, the lower 80 DEG C of reaction 2h of nitrogen protection obtain TPU prepolymer; Be dissolved in by regenerated cellulose in DMF, ultrasonic disperse is even, and two kinds of solution stir 1h at mixing and being incorporated in 70 DEG C, stir 1h and obtain thick solution under adding glycerine 70 DEG C of heating conditions subsequently; To be coated in Teflon mould after the vacuum outgas at normal temperatures of above-mentioned solution, in baking oven, 70 DEG C of dry 24h obtain the thermoplastic polyurethane film that Mierocrystalline cellulose strengthens.Wherein the mass ratio of regenerated cellulose and TPU is 1:19.The Young's modulus of gained laminated film is 22.6MPa, and tensile strength is 9.8MPa, elongation at break 901.4%.
Claims (8)
1. a preparation method for Neu tuberosum element activeness and quietness thermoplastic polyurethane film, is characterized in that comprising the steps:
(1) preparation of regenerated cellulose
Taking a certain amount of alkali and urea or alkali and thiocarbamide is dissolved in distilled water, obtain the stable aqueous solution, taking a certain amount of Mierocrystalline cellulose joins in the described aqueous solution, fully disperse under stirring or ul-trasonic irradiation, make it to form stabilizing solution, solution freezing treatment at the temperature of-12 DEG C to-20 DEG C is no less than 1h, after mixture after to be frozen thaws, add the distilled water being no less than 2 times of volume of mixture, centrifugally obtain gel-like product, with product described in distilled water wash to neutral, namely obtain regenerated cellulose;
Wherein said alkali/aqueous solution of urea is 5-12wt% alkali/8-20wt% urea mixed aqueous solution, and alkali/thiourea solution is 6-15wt% alkali/3-10wt% thiocarbamide mixed aqueous solution; Described Mierocrystalline cellulose and alkali/urea mixed aqueous solution or alkali/thiocarbamide mixed aqueous solution mass ratio are 1:99 to 10:90;
(2) preparation of thermoplastic polyurethane/regenerated cellulose laminated film (TPU/RC)
Take a certain amount of 4,4 '-diphenylmethanediisocyanate (MDI) and polytetramethylene ether diol (PTMG) are dissolved in DMF, and under 80 DEG C of nitrogen protection conditions, stirring reaction at least 2h, obtains TPU performed polymer; The RC of preparation in step (1) is dried to constant weight at 70 DEG C, and redispersion, in DMF, ultrasonicly makes it be uniformly dispersed; RC/DMF solution is joined in TPU prepolymer/DMF solution, and under 70 DEG C of conditions heated and stirred at least 1h; Add a certain amount of chainextender subsequently, heated and stirred is 1h at least, obtains stable solution; Under described stable solution normal temperature after vacuum outgas, cast in a mold, then is taken off film and is namely obtained described TPU/RC film at 70 DEG C after dry 24h.
2. the mol ratio of wherein said MDI and PTMG is 2:1, and the mol ratio of NCO/OH is altogether 1 in TPU.
3. method according to claim 1, is characterized in that: in described step (1), Mierocrystalline cellulose is from least one in following cellulosic material: linters, wood pulp cellulose, Microcrystalline Cellulose.
4. method according to claim 1, is characterized in that: in described step (1), alkali comprises following middle at least one: sodium hydroxide, lithium hydroxide.
5. method according to claim 1, it is characterized in that: the alkali/aqueous solution of urea described in described step (1) is 5-12wt% alkali/8-20wt% urea mixed aqueous solution, described alkali/thiourea solution is 6-15wt% alkali/3-10wt% thiocarbamide mixed aqueous solution.
6. method according to claim 1, is characterized in that: Mierocrystalline cellulose described in described step (1) and alkali/urea mixed aqueous solution or alkali/thiocarbamide mixed aqueous solution mass ratio are 1:99 to 10:90.
7. method according to claim 1, is characterized in that: in described step (2), chainextender is at least one in BDO, 1,6-ethylene glycol, glycerine, Glycerin, triglycol.
8. method according to claim 1, is characterized in that: the TPU/RC film prepared in described step (2), wherein RC quality accounts for 1% ~ 10% of TPU quality.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109851746A (en) * | 2018-12-24 | 2019-06-07 | 山东一诺威聚氨酯股份有限公司 | Cellulose modified TPU film material and preparation method thereof |
| CN110698624A (en) * | 2019-11-15 | 2020-01-17 | 四川大学 | Preparation method of thermoplastic cellulose grafted polyurethane |
| CN111518381A (en) * | 2020-05-29 | 2020-08-11 | 叶正芬 | Two-component polyurethane stock solution for engineering tires and preparation method thereof |
| CN113248796A (en) * | 2021-06-24 | 2021-08-13 | 武汉纺织大学 | Polyurethane/cotton cellulose composite aerogel insole and preparation method thereof |
| CN113929973A (en) * | 2021-12-09 | 2022-01-14 | 北京理工大学 | Nano cellulose plastic additive, light polypropylene material and preparation method |
| CN114605685A (en) * | 2022-04-11 | 2022-06-10 | 浙江理工大学 | WPU-RCNs-PEDOT nanometer composite film with high tensile strength and high conductivity |
| CN114854180A (en) * | 2022-03-28 | 2022-08-05 | 万华化学集团股份有限公司 | Thermoplastic cellulose/PBAT composite film and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6586354B1 (en) * | 1998-12-28 | 2003-07-01 | Kimberly-Clark Worldwide, Inc. | Microlayer breathable hybrid films of degradable polymers and thermoplastic elastomers |
| CN102604363A (en) * | 2012-03-07 | 2012-07-25 | 武汉理工大学 | Preparation method of polyurethane nanometer composites |
| CN102942704A (en) * | 2012-11-20 | 2013-02-27 | 天津工业大学 | Polyurethane/cellulose composite membrane electro-active material and preparation method thereof |
| CN103012835A (en) * | 2012-12-19 | 2013-04-03 | 江南大学 | Preparation method of cellulose/ polyurethane composite aerogel |
| CN103965519A (en) * | 2014-05-16 | 2014-08-06 | 齐鲁工业大学 | Preparation method of regenerated cellulose reinforced starch film |
-
2014
- 2014-12-22 CN CN201410796458.2A patent/CN104479342A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6586354B1 (en) * | 1998-12-28 | 2003-07-01 | Kimberly-Clark Worldwide, Inc. | Microlayer breathable hybrid films of degradable polymers and thermoplastic elastomers |
| CN102604363A (en) * | 2012-03-07 | 2012-07-25 | 武汉理工大学 | Preparation method of polyurethane nanometer composites |
| CN102942704A (en) * | 2012-11-20 | 2013-02-27 | 天津工业大学 | Polyurethane/cellulose composite membrane electro-active material and preparation method thereof |
| CN103012835A (en) * | 2012-12-19 | 2013-04-03 | 江南大学 | Preparation method of cellulose/ polyurethane composite aerogel |
| CN103965519A (en) * | 2014-05-16 | 2014-08-06 | 齐鲁工业大学 | Preparation method of regenerated cellulose reinforced starch film |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109851746A (en) * | 2018-12-24 | 2019-06-07 | 山东一诺威聚氨酯股份有限公司 | Cellulose modified TPU film material and preparation method thereof |
| CN110698624A (en) * | 2019-11-15 | 2020-01-17 | 四川大学 | Preparation method of thermoplastic cellulose grafted polyurethane |
| CN111518381A (en) * | 2020-05-29 | 2020-08-11 | 叶正芬 | Two-component polyurethane stock solution for engineering tires and preparation method thereof |
| CN113248796A (en) * | 2021-06-24 | 2021-08-13 | 武汉纺织大学 | Polyurethane/cotton cellulose composite aerogel insole and preparation method thereof |
| CN113929973A (en) * | 2021-12-09 | 2022-01-14 | 北京理工大学 | Nano cellulose plastic additive, light polypropylene material and preparation method |
| CN113929973B (en) * | 2021-12-09 | 2022-09-16 | 北京理工大学 | Nano cellulose plastic additive, light polypropylene material and preparation method |
| CN114854180A (en) * | 2022-03-28 | 2022-08-05 | 万华化学集团股份有限公司 | Thermoplastic cellulose/PBAT composite film and preparation method thereof |
| CN114854180B (en) * | 2022-03-28 | 2023-05-30 | 万华化学集团股份有限公司 | Thermoplastic cellulose/PBAT composite film and preparation method thereof |
| CN114605685A (en) * | 2022-04-11 | 2022-06-10 | 浙江理工大学 | WPU-RCNs-PEDOT nanometer composite film with high tensile strength and high conductivity |
| CN114605685B (en) * | 2022-04-11 | 2023-11-14 | 浙江理工大学 | WPU-RCNs-PEDOT nano composite film with high tensile strength and high conductivity |
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