CN107501592A - A kind of preparation method of colored TPU expanded beads - Google Patents
A kind of preparation method of colored TPU expanded beads Download PDFInfo
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- CN107501592A CN107501592A CN201710583300.0A CN201710583300A CN107501592A CN 107501592 A CN107501592 A CN 107501592A CN 201710583300 A CN201710583300 A CN 201710583300A CN 107501592 A CN107501592 A CN 107501592A
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- Prior art keywords
- tpu
- expanded beads
- pigment
- autoclave
- pressure
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/08—Supercritical fluid
-
- 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
Abstract
The present invention discloses a kind of preparation method of colored TPU expanded beads, comprises the following steps：1. by pigment and dispersant into water to prepare mixed liquor, then mixed liquor injected in autoclave；2. TPU particles, dispersant are put into autoclave successively, closing liquid and solid feed intake valve；3. high-pressure fluid is injected in autoclave, close valve, stir solid-liquid material, and it is gradually heating to predetermined temperature, pressure reaches predetermined pressure, and pigment molecule constantly diffuses to the inside of TPU particles under the entrainment effect of high-pressure fluid, and progressivelyes reach pigment concentration balance, the native staining of TPU particles is realized, while high-pressure fluid reaches solubility equilibria in TPU particles；4. opening the valve below autoclave body, pressure is discharged rapidly, the TPU particle expansions after dyeing is foamed；5. obtain colored TPU expanded beads material through separation of solid and liquid, washing, drying process.The present invention, which has, to save process, improves the characteristics of efficiency and expanded beads excellent performance.
Description
Technical field
The present invention relates to colored TPU expanded beads field, and in particular to be a kind of preparation side of colored TPU expanded beads
Method, it is diffused into inside TPU resin matrixes under supercritical fluid atmosphere by making scattered pigment in aqueous, realized
The native staining of TPU particles, by by supercritical fluid Quick Depressurization, realizing the preparation of colored TPU particles.
Background technology
TPU possess high abrasion, high resiliency, it is antifatigue, resistant to chemical etching many advantages, such as and be widely used in footwear material.With
TPU is expected to replacement EVA material expanded material for colored low-density foamed material prepared by base material and is applied to high-performance footwear material field.
The method that TPU expanded materials are prepared using CBA is known.Add and close in TPU chemical blowing systems
Suitable pigment can assign TPU expanded material a variety of colors, but the problem of similar be present to EVA resin expanded material, such as prepare
Process not environmentally with need chemical crosslinking the problem of etc..In addition, the TPU expanded materials prepared using CBA are also deposited
Foam structure is coarse, density is big, expansion multiplying power is low the problem of, therefore this technology not commercially large-scale promotion.
Patent document WO2005/066250A, WO2007/082838A, WO2010/136398A and CN103642200A are retouched
The method that using organic solvent or inert gas as physical blowing agent, TPU expanded materials are prepared by suspension process is stated.It is made
The abscess of standby TPU expanded materials is small and is evenly distributed, and density can be with as little as 0.1-0.5g/cm3.But, this method be related to by
TPU particles boil 0.5-10 hours in the water that temperature is 100-150 DEG C, and TPU resins particularly polyester-type TPU resins are easy to water
The fact that solution is a problem, and long-time boiling is easily caused TPU resins and chemical degradation and xanthochromia problem occurs, and have impact on TPU hairs
The performance of foam material and follow-up use.What is more important, the conventional pigment of TPU resins is mainly small molecule organic compound, is had
Machine small-molecule substance is easy to that interfacial migration occurs in the environment of high-pressure foam agent plasticizing, high temperature long-time boiling, face be present
The problems such as uniform expanded material surface color of material skewness inside and outside expanded material fades.
Patent document ZL201410196699.3 is described using colored TPU resins as raw material, supercritical CO2For foaming agent,
The migration of pigment is avoided using techniques such as high-pressure fluid low temperature dipping, short time foamables, it is uniform so as to be prepared for dyestuff
The TPU expanded beads being dispersed in polymer surfaces and matrix.Although it adds the work of color in realizing toward TPU expanded beads
With, but prior art still at least has the disadvantage that：
One, dyestuffs are substantially the Masterbatch using solid-state, and solid-state Masterbatch regardless of how particle is small, itself and TPU resins
Mixing can not possibly reach molecular level, TPU resins are during being foamed and then forming TPU expanded beads, these solid-state colors
Master batch does not synchronize change greatly, so that forming abscess between solid-state Masterbatch and TPU expanded beads, and then have impact on coloured silk
The final performance of color TPU expanded beads；
Two, are at present two steps carried out independently of one another and successively in the forming process of colored TPU expanded beads
Suddenly, that is, dyed and foam two steps, for example is first sufficiently mixed Masterbatch and TPU resins, and spiral shell is used again after well mixed
Revolve extruder and form the TPU resin particles with color grain, then carry out foaming operation to the particle of formation again, above-mentioned such two
Individual independent step is more complicated in process, reduces production efficiency.
The content of the invention
It is a primary object of the present invention to provide a kind of preparation method of colored TPU expanded beads, it will dyeing and foaming
Two steps are two-in-one, greatly save process, and also assure that scattered between TPU particles of pigment is in molecule rank, carry
The high performance and quality of TPU expanded beads.
In order to reach above-mentioned purpose, solution of the invention is：
A kind of preparation method of colored TPU expanded beads, wherein, comprise the following steps：
1. by pigment and dispersant into water to prepare mixed liquor, then mixed liquor injected in autoclave；
2. TPU particles, dispersant are put into autoclave successively, closing liquid and solid feed intake valve；
3. high-pressure fluid is injected in autoclave, valve is closed, stirs solid-liquid material, and is gradually heating to predetermined temperature,
Pressure reaches predetermined pressure, and pigment molecule constantly diffuses to the inside of TPU particles under the entrainment effect of high-pressure fluid, and gradually
Reach pigment concentration balance, realize the native staining of TPU particles, while high-pressure fluid reaches solubility equilibria in TPU particles；
4. opening the valve below autoclave body, pressure is discharged rapidly, the TPU particle expansions after dyeing is foamed；
5. obtaining colored TPU expanded beads material through separation of solid and liquid, washing, drying process, the mixed liquor of pigment/water is received
Collect and put into again in autoclave and recycle.
Further, in step, 1. middle pigment is disperse dyes, suspension can be formed in water, wherein pigment is in water
Mass fraction is 0.1%-4%, heatproof to 80-200 degree.
Further, in step, 2. middle TPU particles are polyether-type TPU resins, wherein contain hydrolysis agent, polyether-type TPU trees
Fat lower processing 0.5-3 hours, its molecular weight in 100-160 DEG C of water reduce not super polyether-type and cross 5%.
Further, step 3. in, the high-pressure fluid is CO2Or CO2With the fluid-mixing of organic solvent, wherein having
Solvent can be ethanol/methanol/butane/pentane etc., and predetermined temperature is 100-180 degree, predetermined pressure 5-20MPa, pigment
Concentration in aqueous is 0.01-4%.
Further, step 4. middle TPU particles expansion multiplying power be 5-10 times, foam structure is uniformly dispersed.
Further, step 3. in need carry out pressurize operation, dwell time 30min-2h.
After the above method, the present invention uses hydrolysis TPU resins, by making scattered pigment in aqueous in height
It is diffused rapidly under warm supercritical fluid atmosphere inside TPU resin matrixes, realizes the native staining of TPU particles, by faces super
Boundary's fluid Quick Depressurization, realize the preparation of colored TPU particles.The pigment concentration balance refers to that pigment is dense in high-pressure fluid
The concentration spent with pigment in TPU particles is consistent, i.e., the high pigment of concentration can be automatically mobile towards the low place of concentration, and its principle can
High temp objects and cryogenic object contact are analogous to, are finally reached equalized temperature.
Compared with prior art, method of the present invention at least has the advantages that：
Pigment is dispersed in water by the one, present invention, and the pigment so in water is formed as molecular level, when pigment enters
When in TPU particles, the foaming of TPU particles will not impact, it is ensured that the properties of product and quality of colored TPU beads.
Pigment is preferably disperse dyes by the two, present invention, and the base of TPU particles is diffused to by the entrainment effect of high-pressure fluid
In body, colored TPU particles realize and foamed that distribution of color is uniform, cell size distribution is equal so as to be prepared by quick pressure releasing
Even colored TPU expanded beads；Such pigment enters the process of TPU particles and foaming process realizes two-in-one, that is, dyes
Process be previous step positioned at foaming process, so reduce process, improve production efficiency.
Embodiment
In order to which technical scheme is explained further, the present invention is explained in detail below by specific embodiment
State.
Embodiment 1
A kind of preparation method of red TPU expanded beads, wherein, comprise the following steps：
Stirred 1. weighing and disperse red the F3BS dyestuffs 200g and anionic dispersing agents 20g of red being put into 20L water
It is even, solution pH value is adjusted to 5.5 with acetic acid, mixed liquor is prepared, mixed liquor is injected in autoclave；
2. TPU particles that the 50kg BASF trades mark are 685, dispersant are put into autoclave successively, closing liquid and solid
Body feeds intake valve；
3. high-pressure fluid is injected in autoclave, valve is closed, stirs solid-liquid material, and 2 DEG C per minute are gradually heating to
130 DEG C of temperature；Pour CO2, it is allowed to pressure and reaches 10MPa pressure, pressurize 100 minutes, pigment molecule is in high pressure CO2The folder of fluid
With constantly diffusing to the inside of TPU particles under effect, and pigment concentration balance is progressivelyed reach, realizes the native stainings of TPU particles,
High pressure CO simultaneously2Fluid reaches solubility equilibria in TPU particles；
4. opening the valve below autoclave body, pressure is discharged rapidly, obtains the red foaming that density is 0.20 or so
TPU；
5. after separation of solid and liquid, washing, drying process, after red foaming TPU particles are made into foam board, water is detected
Wash fastness, light fastness.
Above-described embodiment and non-limiting product form of the invention and style, the ordinary skill people of any art
The appropriate change or modification that member is done to it, it all should be regarded as not departing from the patent category of the present invention.
Claims (6)
1. a kind of preparation method of colored TPU expanded beads, it is characterised in that comprise the following steps：
1. by pigment and dispersant into water to prepare mixed liquor, then mixed liquor injected in autoclave；
2. TPU particles, dispersant are put into autoclave successively, closing liquid and solid feed intake valve；
3. high-pressure fluid is injected in autoclave, valve is closed, stirs solid-liquid material, and is gradually heating to predetermined temperature, pressure
Reach predetermined pressure, pigment molecule constantly diffuses to the inside of TPU particles under the entrainment effect of high-pressure fluid, and progressivelyes reach
Pigment concentration balances, and realizes the native staining of TPU particles, while high-pressure fluid reaches solubility equilibria in TPU particles；
4. opening the valve below autoclave body, pressure is discharged rapidly, the TPU particle expansions after dyeing is foamed；
5. obtaining colored TPU expanded beads material through separation of solid and liquid, washing, drying process, the mixed liquor of pigment/water is collected simultaneously
Again put into autoclave and recycle.
2. a kind of preparation method of colored TPU expanded beads as claimed in claim 1, it is characterised in that in step 1. middle face
Expect for disperse dyes, suspension can be formed in water, wherein mass fraction of the pigment in water is 0.1%-4%, and heatproof is extremely
80-200 degree.
3. a kind of preparation method of colored TPU expanded beads as claimed in claim 1, it is characterised in that in step 2. middle TPU
Particle is polyether-type TPU resins, wherein contain hydrolysis agent, polyether-type TPU resins lower processing 0.5-3 in 100-160 DEG C of water
Hour, its molecular weight reduces not super polyether-type and crosses 5%.
A kind of 4. preparation method of colored TPU expanded beads as claimed in claim 1, it is characterised in that step 3. in, institute
It is CO to state high-pressure fluid2Or CO2With the fluid-mixing of organic solvent, wherein organic solvent can be ethanol/methanol/butane/penta
Alkane etc., predetermined temperature are 100-180 degree, and predetermined pressure 5-20MPa, the concentration of pigment in aqueous is 0.01-4%.
5. a kind of preparation method of colored TPU expanded beads as claimed in claim 1, it is characterised in that in step 4. middle TPU
The expansion multiplying power of particle is 5-10 times, and foam structure is uniformly dispersed.
A kind of 6. preparation method of colored TPU expanded beads as claimed in claim 1, it is characterised in that step 3. in need
Carry out pressurize operation, dwell time 30min-2h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710583300.0A CN107501592A (en) | 2017-07-18 | 2017-07-18 | A kind of preparation method of colored TPU expanded beads |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710583300.0A CN107501592A (en) | 2017-07-18 | 2017-07-18 | A kind of preparation method of colored TPU expanded beads |
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| Publication Number | Publication Date |
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| CN107501592A true CN107501592A (en) | 2017-12-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201710583300.0A Pending CN107501592A (en) | 2017-07-18 | 2017-07-18 | A kind of preparation method of colored TPU expanded beads |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110355970A (en) * | 2018-04-04 | 2019-10-22 | 东莞市元普塑胶科技有限公司 | A method of colour TPU expanded beads being disposably made using twin screw device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5670102A (en) * | 1993-02-11 | 1997-09-23 | Minnesota Mining And Manufacturing Company | Method of making thermoplastic foamed articles using supercritical fluid |
| CN103951965A (en) * | 2014-05-09 | 2014-07-30 | 晋江国盛鞋材有限公司 | Color TPU (thermoplastic polyurethane) foam material and preparation method and application thereof as well as method for preparing molding body, sheet and shoe material by using same |
| CN105121528A (en) * | 2013-03-15 | 2015-12-02 | 耐克创新有限合伙公司 | Decorative foam and method |
-
2017
- 2017-07-18 CN CN201710583300.0A patent/CN107501592A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5670102A (en) * | 1993-02-11 | 1997-09-23 | Minnesota Mining And Manufacturing Company | Method of making thermoplastic foamed articles using supercritical fluid |
| CN105121528A (en) * | 2013-03-15 | 2015-12-02 | 耐克创新有限合伙公司 | Decorative foam and method |
| CN103951965A (en) * | 2014-05-09 | 2014-07-30 | 晋江国盛鞋材有限公司 | Color TPU (thermoplastic polyurethane) foam material and preparation method and application thereof as well as method for preparing molding body, sheet and shoe material by using same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110355970A (en) * | 2018-04-04 | 2019-10-22 | 东莞市元普塑胶科技有限公司 | A method of colour TPU expanded beads being disposably made using twin screw device |
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Application publication date: 20171222 |