CN106916280A - No-solvent type polyurethane nano hydrotalcite composite membrane and preparation method thereof - Google Patents
No-solvent type polyurethane nano hydrotalcite composite membrane and preparation method thereof Download PDFInfo
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- CN106916280A CN106916280A CN201710244873.0A CN201710244873A CN106916280A CN 106916280 A CN106916280 A CN 106916280A CN 201710244873 A CN201710244873 A CN 201710244873A CN 106916280 A CN106916280 A CN 106916280A
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to no-solvent type polyurethane nano hydrotalcite composite membrane and preparation method thereof, taking polyethylene glycol and hydrotalcite nano particle are added to heating stirring in the there-necked flask equipped with agitating device and reflux condensate device, and ultrasound or emulsion dispersion are uniform；Emulsion to be composite is cooled to room temperature, adds toluene di-isocyanate(TDI) high-speed stirred uniform；Complex emulsions are coated and is fixed in the release liners of level board；Release liners are removed, film forming is dried in baking oven.The present invention instead of conventional organic solvents production technology and aqueous production technology, and the volatilization of a large amount of organic solvents for preventing to be used in production process causes serious ecological environmental pollution problem；On this basis, by nano hydrotalcite is modified make its with bigger specific surface area, physical and mechanical properties is obviously improved.
Description
Technical field
The present invention relates to a kind of production technology of polyurethane film, and in particular to a kind of no-solvent type polyurethane nano hydrotalcite
Composite membrane and preparation method thereof.
Background technology
Traditional solvent borne polyurethane film production process, the volatilization of a large amount of organic solvents used in its production process is caused
Serious ecological environmental pollution, and with polyurethane from thickening property it is poor, solid content is low, resistance to elevated temperatures is not good, poor water resistance and
The defect such as relatively costly.
The content of the invention
It is an object of the invention to provide a kind of no-solvent type polyurethane nano hydrotalcite composite membrane and preparation method thereof, overcome
Existing polyurethane/nano technology of composite film preparation defect, and the mechanical performance of film forming is improved to a greater degree.
The technical solution adopted in the present invention is：
The preparation method of no-solvent type polyurethane nano hydrotalcite composite membrane, it is characterised in that：
Realized by following steps：
The hydrotalcite nano particle of the polyethylene glycol and 4 ~ 8 mass parts that weigh 5 mass parts is added to equipped with agitating device and backflow
In the there-necked flask of condensing unit, heating stirring 1h ~ 1.5h at 40 DEG C ~ 65 DEG C, with ultrasonic cell disruptor ultrasonic disperse or
Mulser emulsion dispersion 5min ~ 15min, makes nano-particle dispersed；
Emulsion to be composite is cooled to room temperature, adds the toluene di-isocyanate(TDI) that mass fraction is 3 mass parts, and high-speed stirred is uniform；
Complex emulsions are coated and is fixed in the release liners of level board；
Release liners are removed, film forming is dried in 100 DEG C ~ 110 DEG C of baking oven.
Hydrotalcite nano particle is anion type laminated compound of the interlamellar spacing in 0.79 nm.
No-solvent type polyurethane nano hydrotalcite composite membrane obtained in preparation method as mentioned.
The present invention has advantages below：
No-solvent type polyurethane nano hydrotalcite composite membrane prepared by the present invention, instead of conventional organic solvents production technology and water
Property production technology, the volatilization of a large amount of organic solvents for preventing to be used in production process causes serious ecological environmental pollution problem；
Simultaneously in aqueous polyurethane production technology, polyurethane from thickening property it is poor, solid content is low, resistance to elevated temperatures is not good, poor water resistance and
It is relatively costly.Present invention seek to address that the environmental pollution of synthetic leather industry and product safety problem, prevent the generation of pollution sources, it is real
The now whole flow process environmental protection from producing to using, improves the mechanical performance of composite membrane, and has prevented production efficiency, under low cost
The defects such as drop.On this basis, by nano hydrotalcite is modified make its with bigger specific surface area, reaction high
Active and larger interlamellar spacing, then introduces polyurethane（PU）In, prepare a kind of environment-friendly solvent-free polyurethane nano neatly
Stone composite membrane, the physical and mechanical properties for comparing composite membrane with conventional urethane synthesis technique is obviously improved, and tensile strength is improved
140%, elongation at break improves 30%.
Specific embodiment
With reference to specific embodiment, the present invention will be described in detail.
The general principle of no-solvent polyurethane synthetic leather manufacturing technology foundation is fast reaction injection moulding（RM）, this work
The raw material that skill is used is not polymer, but by 2 kinds or liquid polyurethane prepolymer of more than two kinds, is distinguished in certain proportion
Mixing head is transported to, is well mixed under elevated pressure, and be injected on base material immediately, the coating film forming by way of blade coating, then
Into drying tunnel, now being swift in response between liquid prepolymer is carried out, and polymer molecule quality is sharply increased, at a terrific speed
Polyurethane of the generation containing new characteristic group structure, until completing last curing shaping.
Hydrotalcite (LDHs) is made up of on side altogether the octahedron that metal ion and six hydroxyls are constituted, and is that a class has double hydroxyls
The new inorganic material of layer structure, part M in its octahedra layer structure2+By M3+Same order elements and make laminate positively charged,
The anion of interlayer filling plays balancing charge.This structures shape hydrotalcite can be widely used in absorption, ion exchange,
The aspects such as synthetic material, daily-use chemical industry, catalysis, superconduction and environmental protection, to realize the industrialization low cost of nano hydrotalcite
Production and application lay the foundation.
Nano hydrotalcite material is widely studied in recent years, and it is combined to form into organic-inorganic nano with organic matter
Composite membrane, its advantage for having had inorganic matter and organic polymer concurrently gives full play to the excellent mechanical property of inorganic matter molecule, heat-resisting
The characteristic such as property, anticorrosive.
Current many researchers are modified result and show using hydrotalcite to PVC and PU, using surface modified hydrotalcite
PVC in-situ suspension polymerizations are carried out, have been synthesized PVC/ hydrotalcite nanos compound resin and has been processed further obtaining nano composite material,
The stretching of its composite and shock strength are greatly improved.
The preparation method of no-solvent type polyurethane nano hydrotalcite composite membrane of the present invention, is realized by following steps：
The hydrotalcite nano particle of the polyethylene glycol and 4 ~ 8 mass parts that weigh 5 mass parts is added to equipped with agitating device and backflow
In the there-necked flask of condensing unit, heating stirring 1h ~ 1.5h at 40 DEG C ~ 65 DEG C, with ultrasonic cell disruptor ultrasonic disperse or
Mulser emulsion dispersion 5min ~ 15min, makes nano-particle dispersed；
Emulsion to be composite is cooled to room temperature, adds the toluene di-isocyanate(TDI) that mass fraction is 3 mass parts, and high-speed stirred is uniform；
Complex emulsions are coated and is fixed in the release liners of level board；
Release liners are removed, film forming is dried in 100 DEG C ~ 110 DEG C of baking oven.
Hydrotalcite nano particle is anion type laminated compound of the interlamellar spacing in 0.79 nm.
Example 1
Weigh the polyethylene glycol of 5 mass parts（PEG）It is added to the hydrotalcite of 5 mass parts and is filled equipped with agitating device and reflux condensation mode
In the there-necked flask put, heating stirring 65min at 45 DEG C, with ultrasonic cell disruptor ultrasonic disperse or mulser emulsion dispersion
10min, disperses hydrotalcite nano uniform particle.Emulsion to be composite is cooled to room temperature, adds the toluene diisocynate of 3 mass parts
Ester（TDI）, high-speed stirred is uniform.Complex emulsions are coated and is fixed in the release liners of level board.Release liners are removed, 105
DEG C baking oven in dry film forming.
Example 2
Weigh the polyethylene glycol of 5 mass parts（PEG）It is added to the hydrotalcite of 6 mass parts and is filled equipped with agitating device and reflux condensation mode
In the there-necked flask put, heating stirring 70min at 50 DEG C, with ultrasonic cell disruptor ultrasonic disperse or mulser emulsion dispersion
15min, disperses hydrotalcite nano uniform particle.Emulsion to be composite is cooled to room temperature, adds the toluene diisocynate of 3 mass parts
Ester（TDI）, high-speed stirred is uniform.Complex emulsions are coated and is fixed in the release liners of level board.Release liners are removed, 110
DEG C baking oven in dry film forming.
Example 3
Weigh the polyethylene glycol of 5 mass parts（PEG）It is added separately to equipped with agitating device and returned cold with the hydrotalcite of 7 mass parts
In the there-necked flask of solidifying device, heating stirring 75min at 55 DEG C is emulsified with ultrasonic cell disruptor ultrasonic disperse or mulser
Dispersion 15min, disperses hydrotalcite nano uniform particle.Emulsion to be composite is cooled to room temperature, adds the toluene two of 3 mass parts different
Cyanate（TDI）, high-speed stirred is uniform.Complex emulsions are coated and is fixed in the release liners of level board.Release liners are removed,
Film forming is dried in 110 DEG C of baking oven.
Environment-friendly solvent-free polyurethane nano hydrotalcite composite membrane prepared by the present invention, compares with conventional urethane synthesis technique
The physical and mechanical properties of composite membrane is obviously improved, and tensile strength improves 140%, and elongation at break improves 30%.
Present disclosure is not limited to cited by embodiment, and those of ordinary skill in the art are by reading description of the invention
And any equivalent conversion taken technical solution of the present invention, it is claim of the invention and is covered.
Claims (3)
1. the preparation method of no-solvent type polyurethane nano hydrotalcite composite membrane, it is characterised in that：
Realized by following steps：
The hydrotalcite nano particle of the polyethylene glycol and 4 ~ 8 mass parts that weigh 5 mass parts is added to equipped with agitating device and backflow
In the there-necked flask of condensing unit, heating stirring 1h ~ 1.5h at 40 DEG C ~ 65 DEG C, with ultrasonic cell disruptor ultrasonic disperse or
Mulser emulsion dispersion 5min ~ 15min, makes nano-particle dispersed；
Emulsion to be composite is cooled to room temperature, adds the toluene di-isocyanate(TDI) that mass fraction is 3 mass parts, and high-speed stirred is uniform；
Complex emulsions are coated and is fixed in the release liners of level board；
Release liners are removed, film forming is dried in 100 DEG C ~ 110 DEG C of baking oven.
2. the preparation method of no-solvent type polyurethane nano hydrotalcite composite membrane according to claim 1, it is characterised in that：
Hydrotalcite nano particle is anion type laminated compound of the interlamellar spacing in 0.79 nm.
3. no-solvent type polyurethane nano hydrotalcite composite membrane obtained in preparation method as claimed in claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710244873.0A CN106916280A (en) | 2017-04-14 | 2017-04-14 | No-solvent type polyurethane nano hydrotalcite composite membrane and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710244873.0A CN106916280A (en) | 2017-04-14 | 2017-04-14 | No-solvent type polyurethane nano hydrotalcite composite membrane and preparation method thereof |
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| CN106916280A true CN106916280A (en) | 2017-07-04 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201710244873.0A Pending CN106916280A (en) | 2017-04-14 | 2017-04-14 | No-solvent type polyurethane nano hydrotalcite composite membrane and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109666287A (en) * | 2018-12-25 | 2019-04-23 | 陕西科技大学 | A kind of no-solvent type aqueous polyurethane/Sulfonated calixarenes modified hydrotalcite nanocomposite and preparation method thereof |
| CN110577653A (en) * | 2019-09-10 | 2019-12-17 | 陕西科技大学 | Emulsion nano composite emulsion based on electrostatic self-assembly and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104725596A (en) * | 2015-03-26 | 2015-06-24 | 浙江工商大学 | Nano-silver/carbon nano tube/polyurethane hybrid membrane and preparation method thereof |
| CN105219066A (en) * | 2015-10-09 | 2016-01-06 | 北京化工大学 | A kind of have polyurethane/nano hydrotalcite composite material of high damping, uv-absorbing and toughness reinforcing performance and preparation method thereof |
-
2017
- 2017-04-14 CN CN201710244873.0A patent/CN106916280A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725596A (en) * | 2015-03-26 | 2015-06-24 | 浙江工商大学 | Nano-silver/carbon nano tube/polyurethane hybrid membrane and preparation method thereof |
| CN105219066A (en) * | 2015-10-09 | 2016-01-06 | 北京化工大学 | A kind of have polyurethane/nano hydrotalcite composite material of high damping, uv-absorbing and toughness reinforcing performance and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 吴键儒等: "聚氨酯(PU)/凹凸棒土(AT)原位复合材料制备及表征", 《化工新型材料》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109666287A (en) * | 2018-12-25 | 2019-04-23 | 陕西科技大学 | A kind of no-solvent type aqueous polyurethane/Sulfonated calixarenes modified hydrotalcite nanocomposite and preparation method thereof |
| CN109666287B (en) * | 2018-12-25 | 2021-04-06 | 陕西科技大学 | Solvent-free waterborne polyurethane/sulfonated calixarene modified hydrotalcite nanocomposite and preparation method thereof |
| CN110577653A (en) * | 2019-09-10 | 2019-12-17 | 陕西科技大学 | Emulsion nano composite emulsion based on electrostatic self-assembly and preparation method thereof |
| CN110577653B (en) * | 2019-09-10 | 2022-04-26 | 陕西科技大学 | Emulsion nano composite emulsion based on electrostatic self-assembly and preparation method thereof |
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Application publication date: 20170704 |
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