CN108164977A - A kind of TPU prefoam modified materials and preparation method thereof - Google Patents
A kind of TPU prefoam modified materials and preparation method thereof Download PDFInfo
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- CN108164977A CN108164977A CN201711414999.4A CN201711414999A CN108164977A CN 108164977 A CN108164977 A CN 108164977A CN 201711414999 A CN201711414999 A CN 201711414999A CN 108164977 A CN108164977 A CN 108164977A
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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
- C08J9/06—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 chemical blowing agent
- C08J9/10—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 chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
-
- 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
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- 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
- C08J9/0066—Use of inorganic compounding ingredients
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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
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
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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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
-
- 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
-
- 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
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
Abstract
The invention discloses a kind of TPU prefoam modified materials and preparation method thereof, specifically include A material and B material, and formula is respectively：A expects：TPU, 50 ~ 90 parts by weight；Foaming agent, 5 ~ 40 parts by weight；Antioxidant, 0.05 ~ 1 parts by weight；Dispersant, 0.05 ~ 5 parts by weight；B expects：TPU, 60 ~ 90 parts by weight；Activator, 5 ~ 30 parts by weight；Antioxidant, 0.05 ~ 1 parts by weight；Dispersant, 0.05 ~ 5 parts by weight.The preparation method of TPU prefoam modified materials is：A expects and B expects to carry out processing and manufacturing foamed products after mixing according still further to certain proportion after being granulated with twin-screw respectively.TPU prefoam modified materials prepared by the present invention have the advantages of machinability is good, and blowing temperature is low, expansion ratio is high, abscess is fine and closely woven uniformly, and mechanical strength is high.
Description
Technical field
The present invention relates to macromolecule foaming technical fields, and in particular to a kind of TPU prefoam modified materials and preparation method thereof.
Background technology
Common expanded material kind has polyurethane（PU）Soft and hard foam, polystyrene（PS）Foaming material
Material, polyethylene（PE）Expanded material, polypropylene（PP）Expanded material etc..Polyurethane foam material easily remains in foaming process
Isocyanates, it is harmful, and expanded material can not recycle；Polystyrol foam material degradation is difficult, is also easy to produce
" white pollution " problem, united nations environment tissue oneself through determine stop using polystyrol foam material, foam polyolefin material
High temperature resistance is poor, is not suitable for applying in high-temperature field.
Thermoplastic polyurethane（Abbreviation TPU）It is a kind of novel environment-friendly materials, is referred to as green material, has excellent
Physical mechanical property, such as elasticity is good, wearability is good, tear resistance is strong, and permanent set is low etc..And the temperature that TPU is used
Spend in extensive range, most of products can be used for a long time in the range of -40 DEG C ~ 80 DEG C, have oil resistant, corrosion-resistant, ultraviolet resistance
And the advantages that microbial resistance, and TPU is also Ke Xunhuanliyong.Original is being retained by the TPU foaming products that foam process obtains
Except some excellent properties, also with better processing performance and longer service life, soft just property also improves, because
This plays important role in polymer foaming production.It can be used as dermatine, shockproof buffer material after TPU foaming materials
Material, thermal insulation material, acoustic material, coating material etc..
The refinings such as TPU and foaming agent, filler, addition auxiliary agent uniformly form continuous glued membrane afterwards in patent CN1328076A,
It foams 80 seconds under 220 DEG C of pressurized conditions, laser heating TPU foaming bodies is made, for being used to prepare reinforcing material material.However this
Technological temperature is higher, and the time is longer, needs high-tension apparatus.The abscess of TPU expanded beads prepared by patent CN103642200A is straight
Diameter is 500 ~ 800um, and density is 0.08 ~ 0.2g/cm3, and cell diameter is very big, and has used volatile foaming agent, to ring
Border causes certain pollution, and using high-tension apparatus, technique is more complicated.
Invention content
The technical problem to be solved by the present invention is to：A kind of TPU prefoam modified materials are developed, the preparation expected using A, B
Mode prepares the raw material to react respectively, and is used after mixing according to a certain ratio when in use, prepares TPU and sends out in advance
Steep modified materials, easy to process and transport, with the TPU prefoam modified materials abscesses of its preparation are fine and closely woven uniformly, density is small, mechanical property
It is excellent.
In order to achieve the above object, present invention employs following technical schemes：A kind of TPU prefoam modified materials, feature
It is, the TPU prefoam modified materials include at least A material and B material, according to following weight：A expects：60 ~ 90 parts, B material：
10 ~ 40 parts,
The A material include
55 ~ 90 parts by weight of TPU；
5 ~ 40 parts by weight of foaming agent；
0.05 ~ 1 parts by weight of antioxidant；
0.05 ~ 5 parts by weight of lubricant；
0.05 ~ 1 parts by weight of chain extender；
The B material include
65 ~ 90 parts by weight of TPU；
5 ~ 30 parts by weight of activator；
0.05 ~ 1 parts by weight of antioxidant；
0.05 ~ 5 parts by weight of lubricant；
0.05 ~ 1 parts by weight of chain extender；
Preferably, the shore hardness of the TPU is 50A ~ 60D.
Preferably, the foaming agent is one or both of N- nitroso compounds, azo-compound, hydrazide kind compound
The mixture of any of the above ratio.Foaming agent is decomposed to form gas during product is manufactured, and plays foaming effect.
Preferably, the activator is that one or more of urea, zinc oxide, sodium bicarbonate, stearate are appointed
The mixture of meaning ratio.Activator main function is the activation temperature for reducing foaming agent, makes foaming agent at a lower temperature
It is decomposed, prevents the TPU caused by processing temperature is excessively high from degrading, so as to influence properties of product.
Preferably, the antioxidant is Hinered phenols antioxidant, suffocated amine antioxidant, phosphite ester kind antioxidant, sulphur
The mixture of one or more of esters antioxidant arbitrary proportion.Antioxidant can prevent material from processing or used
Thermo-oxidative ageing in journey improves its service life and performance.
Preferably, the lubricant be synthetic wax, one or both of metallic salt of fatty acid ester, aliphatic acid with
The mixture of upper arbitrary proportion.Lubricant can reduce the shearing force of material in process, and better protection materials are former
This performance.
Preferably, the chain extender is 1,4-butanediol, Isosorbide-5-Nitrae-cyclohexanediol, diethanol amine, diethyl toluene diamine, two
The mixture of one or more of ethyltoluene diamines arbitrary proportion.Chain extender main function is that TPU is prevented to add
Molecule chain break during work carries out chain extension, so as to improve product properties to the strand of TPU.
Second object of the present invention realized by following technical scheme, a kind of preparation of TPU prefoam modified materials
Method, the TPU prefoam modified materials are made in the steps below：
1）By TPU, foaming agent, activator, antioxidant, lubricant, chain extender is expected according to A and B material formulas ratio weighs respectively, uses
High-speed mixer is uniformly mixed, and mixing rotating speed is 300~1000rpm, and incorporation time is 5~20min；
2）A material mixture addition double screw extruders are plasticized, are disperseed and are squeezed out after pelletizing and obtain A material particles, B are expected mixed
It closes after object addition double screw extruder is plasticized, is disperseed and is squeezed out pelletizing and obtains B material particles.
）A is expected that particle and B material particles are mixed according to A, B material formula ratio up to TPU prefoam modified materials, then by double spiral shells
Bar squeezes out, and double screw extruder temperature is 120~210 DEG C, and rotating speed is 150~300rpm, and spiro rod length and diameter ratio are more than etc.
In 44:1.
TPU prefoam material provided by the invention is in a manner that A expects and B material fabricate respectively, and machinability is good, just
In transport.
Compared with the prior art, the beneficial effects of the invention are as follows：PP Pipe Compound of the present invention has that blowing temperature is low, expansion ratio
The advantages that height, abscess are fine and closely woven uniformly, and mechanical strength is high, and used additive has no toxic side effect, and there is environmental protection can return
The advantage of receipts.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, 1~6 couple of present invention with reference to embodiments
It is described further：
The formula of special material of Examples 1 to 6（Referring to table 1）.The raw material used in each embodiment for：
（1）Thermoplastic polyurethane（TPU）：Shore hardness is 70A, trade mark 1170A, and supplier is：BASF Corp. of Germany.
（2）Foaming agent：AC foaming agents, supplier are：Jiangxi Selon Industrial Co., Ltd.；Powder average grain diameter is 10
~12 microns.
（3）Activator：Urea, sodium bicarbonate, zinc stearate are according to 8:4:2 are compounded, market regular industrial grade.
（4）Antioxidant：Antioxidant -1010 and antioxidant -1098 are according to 1:1 compounding, supplier are：BASF Corp. of Germany.
（5）Lubricant：Stearic acid, supplier are：Malaysian cocoanut tree board 1801.
（6）Chain extender：1,4-butanediol, market regular industrial grade.
The formula of special material that Examples 1 to 6 uses is as shown in table 1.
1 Examples 1 to 6 formula of special material (parts by weight of table）
4 embodiment of embodiment 1 embodiment, 2 embodiment, 3 embodiment, 5 embodiment 6
A material 35 30 70 40 60 50
TPU 55 62.3 73 79.2 84 90
Foaming agent 40 36 24 20 10 5
Antioxidant 0.05 0.6 0.2 0.35 0.5 1
Lubricant 4.9 12 0.05 53
Chain extender 0.05 0.1 0.8 0.4 0.5 1
B material 65 70 30 60 40 50
TPU 65 73 74 84 87 90
Activator 30 25 20 15 10 5
Antioxidant 0.1 0.8 0.3 0.6 0.6 1
Lubricant 4.85 15 0.05 23
Chain extender 0.05 0.2 0.7 0.35 0.4 1
TPU prefoam modified materials are prepared as steps described below by the formula in table 1：
（1）By TPU, foaming agent, activator, antioxidant, lubricant, chain extender is expected according to A and B material formulas ratio weighs respectively,
It is first uniformly mixed with high-speed mixer, mixing rotating speed is 300~1000rpm, and incorporation time is 5~20min；
（2）By step（1）Obtained mixture is separately added into after double screw extruder is plasticized, is disperseed and is squeezed out pelletizing and obtains
Expect particle and B material particles, then it according to A, B material formula ratio is mixed and both obtains TPU prefoam modified materials to A；Twin-screw extrusion
Machine temperature is 120~210 DEG C, and rotating speed is 150~300rpm, and spiro rod length is more than or equal to 44 with diameter ratio:1.Spiro rod length with
Diameter than the dispersion being provided with conducive to various additives, enhance product performance.
The temperature and speed conditions of Examples 1 to 6 high mixer and twin-screw are shown in Table 2.
The temperature and speed conditions of 2 Examples 1 to 6 high mixer of table and twin-screw
4 embodiment of embodiment 1 embodiment, 2 embodiment, 3 embodiment, 5 embodiment 6
A expects
Mix rotating speed（rpm） 1000 800 700 600 400 300
Incorporation time（min） 5 8 11 14 17 20
Double screw extruder temperature（℃） 210 190 180 165 150 120
Double screw extruder rotating speed（rpm） 150 180 200 220 265 300
B expects
Mix rotating speed（rpm） 1000 800 700 600 400 300
Incorporation time（min） 5 8 11 14 17 20
Double screw extruder temperature（℃） 210 190 180 165 150 120
Double screw extruder rotating speed（rpm） 150 180 200 220 265 300
The TPU prefoam modified materials prepared using Examples 1 to 6, to its blowing temperature, apparent density, expansion ratio and mechanics
Performance is tested, and the performance test results are shown in Table 3：
3 Examples 1 to 6 TPU prefoam modified materials the performance test results of table
5 embodiment of embodiment 1 embodiment, 2 embodiment, 3 embodiment, 4 embodiment, 6 comparative sample
Blowing temperature/DEG C 165 167 170 175 175 175 195
Cell diameter/um 128 135 135 143 152 155 256
107/cm3 of cell density 12.8 11.7 10.5 9.6 8.2 7.8 2.3
Expansion ratio 3.5 3.2 2.9 2.5 2.2 1.8 1.6
Apparent density g/cm3 0.3 0.35 0.38 0.45 0.53 0.65 0.63
Tensile strength MPa 0.87 1.25 1.53 1.92 2.32 2.67 0.37
Comparative sample is the similar TPU expanded materials in market, be can be seen that from above-mentioned test result：
TPU prefoam foaming materials temperature prepared by the present invention is low, and specially 170 ± 5, it is effectively anti-less than 195 DEG C of comparative sample
Degradations of the TPU in high temperature process is stopped, therefore its Mechanical Properties of Products is excellent.In addition, in cell size and expansion ratio,
Specially half of the cell diameter for comparative sample cell diameter, product of the present invention have great advantage in embodiment 1.
The foregoing is merely the preferred embodiment of the present invention, are not intended to limit the scope of the invention, every profit
The equivalent transformation made with the present invention, in the scope of patent protection of the present invention.
Claims (7)
1. a kind of TPU prefoam modified materials, which is characterized in that the TPU prefoam modified materials include at least A material and B material, according to
Following weight：A expects：60 ~ 90 parts, B material：10 ~ 40 parts,
The A material include
55 ~ 90 parts by weight of TPU；
5 ~ 40 parts by weight of foaming agent；
0.05 ~ 1 parts by weight of antioxidant；
0.05 ~ 5 parts by weight of lubricant；
0.05 ~ 1 parts by weight of chain extender；
The B material include
65 ~ 90 parts by weight of TPU；
5 ~ 30 parts by weight of activator；
0.05 ~ 1 parts by weight of antioxidant；
0.05 ~ 5 parts by weight of lubricant；
0.05 ~ 1 parts by weight of chain extender；
TPU prefoam modified materials according to claim 1, it is characterised in that：The shore hardness of the TPU is 50A ~ 60D.
2. TPU prefoam modified materials according to claim 1, it is characterised in that：The foaming agent for N- nitroso compounds,
The mixture of one or more of azo-compound, hydrazide kind compound arbitrary proportion.
3. TPU prefoam modified materials according to claim 1, it is characterised in that：The activator for urea, zinc oxide,
The mixture of one or more of sodium bicarbonate, stearate arbitrary proportion.
4. TPU prefoam modified materials according to claim 1, it is characterised in that：The antioxidant is Hinered phenols antioxygen
One or more of agent, suffocated amine antioxidant, phosphite ester kind antioxidant, sulphur ester antioxidant arbitrary proportion
Mixture.
5. TPU prefoam modified materials according to claim 1, it is characterised in that：The lubricant is synthetic wax, aliphatic acid
Esters, aliphatic acid one or more of metallic salt arbitrary proportion mixture.
6. TPU prefoam modified materials according to claim 1, it is characterised in that：The chain extender for 1,4-butanediol, 1,
One or more of 4- cyclohexanediols, diethanol amine, diethyl toluene diamine, diethyl toluene diamine arbitrary proportion
Mixture.
7. a kind of preparation method of TPU prefoam modified materials as described in claim 1 ~ 7 any one, it is characterised in that：Institute
The TPU prefoam modified materials stated are made in the steps below：
1）By TPU, foaming agent, activator, antioxidant, lubricant, chain extender is expected according to A and B material formulas ratio weighs respectively, uses
High-speed mixer is uniformly mixed, and mixing rotating speed is 300~1000rpm, and incorporation time is 5~20min；
2）A material mixture addition double screw extruders are plasticized, are disperseed and are squeezed out after pelletizing and obtain A material particles, B are expected mixed
It closes after object addition double screw extruder is plasticized, is disperseed and is squeezed out pelletizing and obtains B material particles；
3）A is expected that particle and B material particles are mixed according to A, B material formula ratio up to TPU prefoam modified materials, then squeezed by twin-screw
Go out, double screw extruder temperature is 120~210 DEG C, and rotating speed is 150~300rpm, and spiro rod length is more than or equal to 44 with diameter ratio:
1。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113736244A (en) * | 2021-09-22 | 2021-12-03 | 佛山市发润新材料科技有限公司 | Modified foamable TPU and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131501A (en) * | 2015-09-06 | 2015-12-09 | 贵州省材料产业技术研究院 | Foaming master batch for ABS microcellular foaming material and preparation method thereof |
| CN107298847A (en) * | 2017-08-04 | 2017-10-27 | 南通德亿新材料有限公司 | A kind of micro- balloon polymer elastomeric material of thermoplasticity and preparation method thereof |
-
2017
- 2017-12-25 CN CN201711414999.4A patent/CN108164977A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131501A (en) * | 2015-09-06 | 2015-12-09 | 贵州省材料产业技术研究院 | Foaming master batch for ABS microcellular foaming material and preparation method thereof |
| CN107298847A (en) * | 2017-08-04 | 2017-10-27 | 南通德亿新材料有限公司 | A kind of micro- balloon polymer elastomeric material of thermoplasticity and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113736244A (en) * | 2021-09-22 | 2021-12-03 | 佛山市发润新材料科技有限公司 | Modified foamable TPU and preparation method thereof |
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Application publication date: 20180615 |